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Polymer Notes

The document outlines the syllabus for the Polymer Chemistry course (17CHP305A) at Karpagam Academy of Higher Education for the II M.Sc. Chemistry program. It covers the scope, objectives, and methodology of the course, detailing key topics such as polymerization mechanisms, molecular weight, polymer processing, and properties of commercial polymers. The syllabus includes suggested readings and a lecture plan divided into five units, each focusing on different aspects of polymer chemistry.

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0% found this document useful (0 votes)

17 views190 pages

Polymer Notes

Uploaded by

Eric Yiu

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Download as PDF, TXT or read online on Scribd

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2017 -2019

Syllabus Batch

KARPAGAM ACADEMY OF HIGHER EDUCATION

(Deemed to be University)
(Established Under Section 3 of UGC Act 1956)
Coimbatore – 641 021.
(For the candidates admitted from 2018 onwards)
DEPARTMENT OF CHEMISTRY
SUBJECT NAME: POLYMER CHEMISTRY SUBJECT CODE: 17CHP305A
SEMESTER: III CLASS: II M. Sc CHEMISTRY

Scope
Polymer chemistry frames much of our understanding of the natural world and continues to bring
new technologies that are useful to every aspect of human life. Polymer chemistry is an exciting
and challenging course, which helps us to understand the various aspects of compounds used in
our day to day life. Polymer chemistry interfaces with a myriad of other disciplines and fields. It
is fundamental to understand other areas of chemistry, biology and medicine. Due to highly
prized nature of Polymer chemistry and its diverse topics, it lays the foundation for extremely
productive and exciting career in variety of disciplines as pharmaceutical, agrochemical,
mineralogy, molecular biology, biotechnology, nanotechnology, polymer technology, teaching
research, scientific publication and so on. The importance of this subject would not diminish over
time, so it will remain a promising career path. This course presents the basic principles of
polymerization, coordination polymerization, determination of molecular weight of polymers,
properties of polymers.

Objectives

1. To learn about the basic concepts of kinetics and mechanism of polymerization.

2. To learn about the coordination polymerization.
3. To understand the Molecular weight of the polymers and their properties.
4. To learn about the processing of polymers.

Methodology
Blackboard teaching, Powerpoint presentation and group discussion.

UNIT – I
Polymer Basic Concepts: Monomers, repeat units, degree of polymerization, linear, branched
and network polymers. Condensation polymerization: Mechanism of stepwise polymerization.
Kinetics and statistics of linear stepwise polymerization. Addition polymerization: Free radical,
cationic and anionic polymerization. Polymerization conditions. Polymerization in homogeneous
and heterogeneous systems.

UNIT – II
Co-ordination Polymerization: Kinetics, mono and bimetallic mechanism of co-ordination
polymers. Zeigler Natta catalyst, co-polymerization: Block and graft co-polymers, kinetics of
copolymerization. Types of co-polymerization. Reactivity ratio.

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 1/1

2017 -2019
Syllabus Batch

UNIT–III
Molecular Weight and Properties: Polydispersion – average molecular weight concept, number,
weight and viscosity average molecular weights. Measurement of molecular weights. Viscosity,
light scattering, osmotic and ultracentrifugation methods. Polymer structure and physical
properties – crystalline melting point Tm. The glass transition temperature. Determination of Tg.
Relationship between Tm and Tg.

UNIT – IV
Polymer Processing: Plastics, elastomers and fibres. Compounding, processing techniques:
calendering, die casting, rotational casting, film casting, injection moulding, blow moulding
extrusion, moulding, thermoforming, foaming, reinforcing and fibre spinning.

UNIT – V
Properties of Commercial Polymers: Polyethylene, polyvinyl chloride, polyamides, polyesters,
phenolic resins, epoxy resins and silicone polymers. Functional polymers, fire retarding polymers
and electrically conducting polymers. Biomedical polymers – contact lens, dental polymers,
artificial heart, kidney, skin and blood cells.

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 2/1

2017 -2019
Lecture Plan Batch

KARPAGAM ACADEMY OF HIGHER EDUCATION

(Deemed to be University)
(Established Under Section 3 of UGC Act 1956)
Coimbatore - 641 021.
(For the candidates admitted from 2017 onwards)
DEPARTMENT OF CHEMISTRY
SUBJECT NAME: POLYMER CHEMISTRY SUBJECT CODE: 17CHP305A
SEMESTER: III CLASS: II M. Sc CHEMISTRY

LECTURE PLAN
UNIT-1
Polymer Basic Concepts Total no. of hours: 10

LECTURE
S.NO TOPICS TO BE COVERED SUPPORT MATERIALS
DURATION

Monomers, repeat units, degree of T1: 9-12,; T2: 4-5 ,239

1. 1
polymerization T1: 96-98; T2: 139-141
T1: 142-143; T2: 5-8, T1:
2. 1 Linear, branched and network polymers
142-143
Condensation polymerization: Mechanism of
3. 1 T2: 25-26, 26-32
stepwise polymerization
4. 1 Kinetics of linear step wise polymerization T2: 33-35
5. 1 Statistics of linear step wise polymerization T2: 35-38
T1: 105,116-120; T2: 50-53,
6. 1 Addition polymerization: Free radical,
85-88, 89-90
T1: 105,116-120; T2: 50-53,
7. 1 Cationic and anionic polymerization
85-88, 89-90
8. 1 Polymerization conditions T2: 126
Polymerization in homogenous and
9. 1 T2: 127-133
heterogeneous systems
10. 1 Discussion of important questions

Reference book
R1: M.S Bhatnagar,2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 1/4

2017 -2019
Lecture Plan Batch

UNIT-2
Co-ordination Polymerization Total no. of hours: 10

LECTURE SUPPORT
S.NO TOPIC TO BE COVERED
DURATION MATERIALS

1. 1 Co-ordination polymerization T2: 91

2. 1 Kinetics of co-ordination polymerization T2: 94-96

Mono metallic mechanism of co-ordination T1: 47-52; T2: 92-
3. 1
polymers 93
bimetallic mechanism of co-ordination T1: 47-52; T2: 92-
4. 1
polymers 93
5. 1 Ziegler Natta catalyst T1: 46; T2: 91-94
Co-polymerization: Block and graft co- T1: 120-122; T2:
6. 1
polymers 142-144
7. 1 Kinetics of copolymerization T1: 101,107-108
T1: 103-106, T2:
8. 1 Types of co-polymerization
182,206
9. 1 Reactivity ratio T1: 106-107

10. 1 Discussion of important questions

Reference book
R1: M.S Bhatnagar,2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 2/4

2017 -2019
Lecture Plan Batch

UNIT -3
Molecular Weight and Properties Total no. of hours: 10

S.NO LECTURE TOPIC TO BE COVERED SUPPORT

DURATION MATERIALS

1 1 Polydispersion- Average molecular weight T1:86-88,

concept, number
2 1 Weight and viscosity average molecular T1: 89-92,
weights
3 1 Measurements of molecular weights T2: 208-213, 198

4 1 Viscosity, light scattering T2: 208, T1: 404-

408,
T1: 413-419
5 1 Osmotic method T2: 205-206,
T1: 392-401
6 1 Ultracentrifugation methods T2: 207, T1: 409-
413
7 1 Polymer structure and physical properties- T1: 100-104;
Crystalline melting point Tm T2:331-336
8 1 The glass transition temperature Tg T2: 337

9 1 Determination of Tg, Relation between Tm T1: 423-426

and Tg. T2: 337-340
10 1 Discussion of important questions

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 3/4

2017 -2019
Lecture Plan Batch

UNIT -4
Polymer Processing Total no. of hours: 09

LECTURE
S.NO TOPIC TO BE COVERED SUPPORT MATERIALS
DURATION

T1: 14,221, 225, 429,229,449

1 1 Plastics, elastomers and fibres.
T2: 351, 371,486,471-475
2 1 Compounding T1: 450-451

3 1 Process techniques: Calendering, T1: 452-453; T2:464-466

4 1 Die casting T1: 453-454; T2:464-466

5 1 rotational casting, film casting T1: 454-456; T2: 465-466

injection moulding, blow moulding, T1: 457-462;

6 1
Extrusion moulding T2: 458-461, 461-464
T1: 462-464;
7 1 Thermoforming
T2: 467-469
T1: 462-464;
8 1 Foaming
T2: 467-469
T1: 465-469, T1: 470-474;
9 1 Reinforcing, Fiber spinning
T2: 491-496
10 1 Discussion of important questions

Text book:
T1: Gowariker, V. R., N. V. Viswanathan and J. Sreedhar, 1986(2014 re-print). “Polymer
Science”, New Age International Private Ltd., New Delhi.
T2: Billmeyer, F.W., 2008(Re-print). “Text Book of Polymer Science”. III Edition, John
Wiley, New York.
Reference book
R1: M.S Bhatnagar, 2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 4/4

2017 -2019
Lecture Plan Batch

UNIT -5
Properties of Commercial Polymers Total no. of hours: 09
LECTURE
S.NO TOPIC TO BE COVERED SUPPORT MATERIALS
DURATION
T1: 215-217, 236-238,
1 1 Polyethylene, Polyvinyl chloride
227-229
T1: 215-217, 236-238,
2 1 Polyamides
227-229
T1: 221-223,255-256;
3 1 Polyesters and Silicon polymers
T2: 442-445,448-450
T1: 251-254; T2: 436-
4 1 Phenolic resins, Epoxy resins
440,445-446
5 1 Functional polymers, Fire retarding Polymers W1

6 1 Electrically conducting polymers W1

Bio-medical polymers- contact lens, dental
7 1 W2, Journals
polymers
8 1 Artificial heart, kidney, skin and blood cells. W2, W3
Recapitulation and discussion of Previous year
9 1 question

Text book:
T1: Gowariker, V. R., N. V. Viswanathan and J. Sreedhar, 1986. Polymer Science, New Age
International Private Ltd., New Delhi.
T2: Billmeyer, F.W., 2003. Text Book of Polymer Science. III Edition, John Wiley, New
York
Reference book
R1: M.S Bhatnagar, 2004, “A text book of polymers”. Ist Edition, S.Chand & Company.
Web Address:
W1: https://en.wikipedia.org/wiki/Fire-safe_polymers or Functional or Electrically
conducting polymers.
W2: https://en.wikipedia.org/wiki/ Artificial-heart or https://biomedical
polymers/applications.
W3: https://en.wikipedia.org/wiki/ Artificial-kidney
Journals: Applications of polymers in the biomedical field, Current-Trends in Biomedical eng
& biosensors, vol.4, issue.4 (2017), Ibrahim et al (mini review)

Prepared by Dr. S. Manickasundaram, Department of Chemistry, KAHE 5/4

KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE:17CHP305A UNIT: I (POLYMER BASIC CONCEPTS) BATCH: 2017-2019

UNIT-1

SYLLABUS

Monomers, repeat units, degree of polymerization, Linear, branched and network Polymers.
Condensation Polymerization: Mechanism of stepwise polymerization. Kinetics and statistics of
linear stepwise polymerization. Addition polymerization: Free radical, cationic and anionic
polymerization. Polymerization conditions. Polymerization in homogeneous and heterogeneous
systems.

Polymer Basic Concepts

INTRODUCTION

Polymer

Appearance of real linear polymer chains as recorded using an atomic force microscope on a
surface, under liquid medium. Chain contour length for this polymer is ~204 nm; thickness is
~0.4 nm.
IUPAC definition
Substance composed of macromolecules. Applicable to substance macromolecular in nature like
cross-linked systems that can be considered as one macromolecule.
A polymer (/ˈpɒlɪmər/; Greek poly-, "many" + -mer, "parts") is a large molecule,
or macromolecule, composed of many repeated subunits. Because of their broad range of
properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday
life. Polymers range from familiar synthetic plastics such as polystyrene to
natural biopolymers such as DNA and proteins that are fundamental to biological structure and
function. Polymers, both natural and synthetic, are created via polymerization of many small
molecules, known as monomers. Their consequently large molecular mass relative to small

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 1/25

molecule compounds produces unique physical properties, including toughness, viscoelasticity,
and a tendency to form glasses and semicrystalline structures rather than crystals.
The term "polymer" derives from the ancient Greek word πολύς (polus, meaning "many, much")
and μέρος (meros, meaning "parts"), and refers to a molecule whose structure is composed of
multiple repeating units, from which originates a characteristic of high relative molecular
mass and attendant properties. The units composing polymers derive, actually or conceptually,
from molecules of low relative molecular mass. The term was coined in 1833 by Jöns Jacob
Berzelius, though with a definition distinct from the modern IUPAC definition. The modern
concept of polymers as covalently bonded macromolecular structures was proposed in 1920
by Hermann Staudinger, who spent the next decade finding experimental evidence for this
hypothesis.
Polymers are studied in the fields of biophysics and macromolecular science, and polymer
science (which includes polymer chemistry and polymer physics). Historically, products arising
from the linkage of repeating units by covalent chemical bonds have been the primary focus
of polymer science; emerging important areas of the science now focus on non-covalent
links. Polyisoprene of latex rubber is an example of a natural/biological polymer, and
the polystyrene of styrofoam is an example of a synthetic polymer. In biological contexts,
essentially all biological macromolecules—i.e., proteins (polyamides), nucleic
acids (polynucleotides), and polysaccharides—are purely polymeric, or are composed in large
part of polymeric components—e.g., isoprenylated/lipid-modified glycoproteins, where small
lipidic molecules and oligosaccharide modifications occur on the polyamide backbone of the
protein.
The simplest theoretical models for polymers are ideal chains.
Monomer
A monomer (/ˈmɒnəmər/ MON-ə-mər) (mono-, "one" + -mer, "part") is a molecule that, as a
unit, binds chemically or supramolecularly to other molecules to form
a supramolecularpolymer. Large numbers of monomer units combine to form polymers in a
process called polymerization. It is a small molecule of an organic substance. A double bond
exist between the individual molecule which is weak. Molecules of a small number of monomer
units (up to a few dozen) are called oligomers. The term "monomeric protein" may also be used
to describe one of the proteins making up a multiprotein complex.
Biopolymer groupings, and the types of monomers that create them:

 For lipids (Diglycerides, triglycerides)*, the monomers are glycerol and fatty acids.
 For proteins (Polypeptides), the monomers are amino acids.
Repeat unit
A repeat unit or repeating unit is a part of a polymer whose repetition would produce the
complete polymer chain (except for the end-groups) by linking the repeat units together
successively along the chain, like the beads of a necklace.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 2/25

A repeat unit is sometimes called a mer or mer unit. "Mer" originates from the Greek word
"meros," which means part. The word polymer derives its meaning from this, which means
"many mers." A repeat unit (or mer), is not to be confused with the term monomer, which refers
to the small molecule from which a polymer is synthesized.
One of the simplest repeat units is that of the addition polymer polyvinyl chloride, -[CH2-
CHCl]n-, whose repeat unit is -[CH2-CHCl]-. In this case the repeat unit has the same atoms as
the monomer vinyl chloride CH2=CHCl. When the polymer is formed, the C=C double bond in
the monomer is replaced by a C-C single bond in the polymer repeat unit, which links by two
new bonds to adjoining repeat units.
In condensation polymers (see examples below), the repeat unit contains fewer atoms than the
monomer or monomers from which it is formed.
The subscript "n" denotes the degree of polymerisation, that is, the number of units linked
together. The molecular mass of the repeat unit, MR, is simply the sum of the atomic masses of
the atoms within the repeat unit. The molecular mass of the chain is just the product nMR. Other
than monodisperse polymers, there is normally a molar mass distributioncaused by chains of
different length.
In copolymers there are two or more types of repeat unit, which may be arranged in alternation,
or at random, or in other more complex patterns.
Degree of polymerization

The degree of polymerization, or DP, is the number of monomeric units in

a macromolecule or polymer or oligomer molecule.
For a homopolymer, there is only one type of monomeric unit and the number-average degree of
polymerization is given by DPn = Xn = Mn / M0, where Mn is the number-average molecular
weight and M0 is the molecular weight of the monomer unit. For most industrial purposes,
degrees of polymerization in the thousands or tens of thousands are desired. This number does
not reflect the variation in molecule size of the polymer that typically occurs, it only represents
the mean number of monomeric units.
Some authors, however, define DP as the number of repeat units, where for copolymers the
repeat unit may not be identical to the monomeric unit. For example, in nylon-6,6, the repeat unit
contains the two monomeric units —NH(CH2)6NH— and —OC(CH2)4CO—, so that a chain of
1000 monomeric units corresponds to 500 repeat units. The degree of polymerization or chain
length is then 1000 by the first (IUPAC) definition, but 500 by the second.

Classification of polymers:

copolymer - a polymer prepared from more than one monomer

addition polymer - a polymer that consists of a repeat unit equivalent to its monomer - generally
vinyl polymers, e.g., polyethylene, or ring-opening polymers, e.g., poly(ethylene oxide)

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 3/25

condensation polymer - a polymer that differs from its monomer(s) by the elimination of a
small molecule during polymerization (Carothers' original definition) e.g., polyamides and
polyesters

the definition has been expanded to include any polymer that incorporates new functional
group(s) in the chain that were not present in the monomers
(to allow inclusion of polyurethanes)

Descriptions of polymer structure:

linear polymer - a polymer consisting of a single continuous chain of repeat units

branched polymer - a polymer that includes side chains of repeat units connecting onto the
main chain of repeat units (different from side chains already present in the monomers)

crosslinked polymer - a polymer that includes interconnections between chains, either formed
during polymerization (by choice of monomer) or after polymerization (by adding a specific
reagent)

network polymer - a crosslinked polymer that includes numerous interconnections between

chains such that the entire sample is (or could be) a single molecule

Condensation polymerization

The monomers that are involved in condensation polymerization are not the same as those in
addition polymerization. The monomers for condensation polymerization have two main
characteristics:.
Instead of double bonds, these monomers have functional groups (like alcohol, amine, or
carboxylic acid-groups).
Each monomer has at least two reactive sites, which usually means two functional groups.

The Amide Linkage:

When a carboxylic acid and an amine react, a water molecule is removed, and an amide molecule
is formed.

Because of this amide formation, this bond is known as an amide linkage.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 4/25

The Ester Linkage:
When a carboxylic acid and an alcohol react, a water molecule is removed, and an ester molecule
is formed.

Because of this ester formation, this bond is known as an ester linkage.

Monomers involved in condensation polymerization have functional groups. These functional

groups combine to form amide and ester linkages. When this occurs, a water molecule in
removed. Since water is removed, we call these reactions condensation reactions (water
condenses out.). When a condensation reaction involves polymerization, we call it condensation
polimarization.

Examples: The Mechanism of Condensation Polymerization

That the monomers are joined by condensation polymerization have two functional groups. You
also know (from Part 6) that a carboxylic acid and an amine can form an amide linkage, jand a
carboxylic acid and an alcohol can form an ester linkage. Since each monomer has two reactive
sites, they can form long-chain polymers by making many amide or ester links. Let's look at two
examples of common polymers made from the monomers we have studied.

Example 1:
A carboxylic acid monomer and an amine monomer can join in an amide linkage.

As before, a water molecule is removed, and an amide linkage is formed. Notice that an acid
group remains on one end of the chain, which can react with another amine monomer. Similarly,
an amine group remains on the other end of the chain, which can react with another acid
monomer. Thus, monomers can continue to join by amide linkages to form a long chain. Because
of the type of bond that links the monomers, this polymer is called a polyamide. The polymer
made from these two six-carbon monomers is known as nylon-6,6. (Nylon products include
hosiery, parachutes, and ropes.)

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 5/25

Example 2:
A carboxylic acid monomer and an alcohol monomer can join in an ester linkage.

A water molecule is removed as the ester linkage is formed. Notice the acid and the alcohol
groups that are still available for bonding.

Because the monomers above are all joined by ester linkages, the polymer chain is a polyester.
This one is called PET, which stands for poly(ethylene terephthalate). (PET is used to make soft-
drink bottles, magnetic tape, and many other plastic products.)

Stepwise polymerization

A number of different chemical reactions may be used to synthesize polymeric materials by step
polymerization. These include esteriﬁcation, amidation, the formation of urethanes, aromatic
substitution, and others. Polymerization usually proceeds by the reactions between two different
functional groups, for example, hydroxyl and carboxyl groups, or isocyanate and hydroxyl
groups.All step polymerizations fall into two groups depending on the type of
monomer(s)employed. The ﬁrst involves two different bifuncti onal and/or polyfunctional
monomers in which each monomer possesses only one type of functional group. (A
polyfunctional monomer is a monomer with more than one functional group per molecule. A
bifunctional monomeris one with two functional groups per molecule.) The second involves a
single monomer containing both types of functional groups. The synthesis of polyamides
Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 6/25
illustrates both groups of polymerization reactions. Thus polyamides can be obtained from the
reaction of diamines with diacids.
nH2N-R-NH2 + nHO2C-R’-CO2H → -(-NH-R-NHCO-R’-CO-)-nOH + (2n-1)H2O
or from the reaction of amino acids with themselves:

nH2N-R-CO2H → H-(-NH-R-CO-)-nOH + (n-1)H2O

The two groups of reaction can be represented in a general manner by the equations
nA-A + nB-B → -(-A-AB-B-)-n

nA-B → -(-A-B-)-n

where A and B are the two different types of functional groups. The characteristics of these two
polymerization reactions are very similar. The successful synthesis of high polymers (i.e.,
polymer of sufﬁciently high molecular weight to be useful from the practical viewpoint) using
any step polymerization reaction generally is more difﬁcult than the corresponding small
molecule reaction, since high polymers can be achieved only at very high conversions (>98–
99%). A conversion of 90%, which would be considered excellent for the synthesis of ethyl
acetate or methyl benzamide, is a disaster for the synthesis of the corresponding polyester or
polyamide. The need for very high conversions to synthesize high polymer places several
stringent requirements on any reaction to be used for polymerization—a favorable equilibrium
and the absence of cyclization and other side reactions. These stringent requirements are met by
a relatively small fraction of the reactions familiar to and used by chemists to synthesize small
molecules. An additional requirement for achieving high molecular weights is the need for the A
and B functional groups to be present at very close to stoichiometric amounts.

Kinetics of Stepwise Polimerisation:

Consider the polyesterification of a diacid and a diol to illustrate the general form of the
kinetics of a typical step polymerization. Simple esterification is a well -known acidcatalyzed
reaction and polyesterification follows the same course [Otton and Ratton, 1988; Vancso-
Szmercsanyi and Makay-Bodi, 1969]. The reaction involves protonation of the carboxylic acid,

(C-OH) + HA K2
K1
──(HO-C+ -OH(A-) 1
followed by reaction of the protonated specie with the alcohol to yield the ester
OH OH
C+-OH + ─( OH) K3
C OH 2
(A−) K4
O+H) (A-)
II
OH O

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 7/25

│ ║
K5
C─OH C-O + H2O + HA 3
│
O+H (A−)

In the above equations and are used to indicate all acid or alcohol species in the
reaction mixture (i.e., monomer, dimer, trimer, . . . , n-mer). Species I and II are shown in the
form of their associated ion pairs since polymerization often takes place in organic media of low
polarity. (A-) is the negative counter ion derived from the acid HA. Polyesterifications, like many
other step polymerizations, are equilibrium reactions. However, from the practical viewpoint of
obtaining high yields of high-molecular-weight product such polymerizations are run in a
manner so as to continuously shift the equilibrium in the direction of the polymer. In the case of
a polysterification this is easily accomplished by removal of the water that is a by-product of the
reaction species II (Eq. 3).
Under these conditions the kinetics of polymerization can be handled by considering the
reactions in Eqs. 2 and 3 to be irreversible.
The rate of a step polymerization is conveniently expressed in terms of the concentrations
of the reacting functional groups. Thus the polyesterification can be experimentally followed by
titrating for the unreacted carboxyl groups with a base. The rate of polymerization Rp can then
be expressed as the rate of disappearance of carboxyl groups -d[COOH]/dt. For the usual
polyesterification, the polymerization rate is synonomous with the rate of formation of species II;
that is, k4 is vanishingly small (since the reaction is run under conditions that drive Eqs. 2 and 3
to the right), and k1, k2, and k5 are large compared to k3. An expression for the reaction rate can
be obtained following the general procedures for handling a reaction scheme with the
characteristics described [Moore and Pearson, 1981]. The rate of polymerization is given by

R= -d[COOH]/dt] = k3[C+ (OH)2][OH] 4

Where [COOH], [OH], and [C+ (OH)2] represent the concentrations of carboxyl, hydroxyl, and
protonated carboxyl (I) groups, respectively. The concentration terms are in units of moles of the
particular functional group per liter of solution. Equation 4 is inconvenient in that the
concentration of protonated carboxylic groups is not easily determined experimentally. One can
obtain a more convenient expression for Rp by substituting for C + (OH)2 from the equilibrium
expression

K =k1/k2 = [C+(OH)2] / [COOH][HA] 5

for the protonation reaction (Eq. 1). Combination of Eqs. 4 and 5 yields

-d[COOH]/dt = k3K[COOH][OH][HA] 6

Two quite different kinetic situations arise from Eq. 6 depending on the identity of HA,
that is, on whether a strong acid such as sulfuric acid or p-toluenesulfonic acid is added as an
external catalyst.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 8/25

Self-Catalyzed Polymerization

In the absence of an externally added strong acid the diacid monomer acts as its own
catalyst for the esterification reaction. For this case [HA] is replaced by [COOH] and Eq. 6 can
be written in the usual form [Flory, 1953]

-d[COOH]/dt = k[COOH]2 [OH] 7

where K and k3 have been combined into the experimentally determined rate constant k.
Equation 2-18 shows the important characteristic of the self-catalyzed polymerization- the
reaction is third-order overall with a second-order dependence on the carboxyl concentration.
The second-order dependence on the carboxyl concentration is comprised of two first-order
dependencies—one for the carboxyl as the reactant and one as the catalyst.
For most polymerizations the concentrations of the two functional groups are very nearly
stoichiometric, and Eq. 7 can be written as

-d[M]/dt = k[M]3 8a

-d[M]/[M]3 = kdt 8b

where [M] is the concentration of hydroxyl groups or carboxyl groups.

Integration of Eq. 8b yields

2kt =1/[M]2-1/[M0]2 9

where [M0] is the initial (at t = 0) concentration of hydroxyl or carboxyl groups. It is convenient
at this point to write Eq. 9 in terms of the extent or fraction of reaction p defined as the fraction
of the hydroxyl or carboxyl functional groups that has reacted at time t. p is also referred to as
the extent or fraction of conversion. (The value of p is calculated from a determination of the
amount of unreacted carboxyl groups.) The concentration [M] at time t of either hydroxyl or
carboxyl groups is then given by

[M] = [M0]- [M0]p = [M0](1-p) 10

Combination of Eqs. 9 and 10 yields

1/(1- p)2 = 2[M0]2kt+1 11

Experimental Observations

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 9/25

Equation 11 indicates that a plot of 1/(1-p)2 versus t should be linear. This behavior has
been generally observed in polyesterifications. Figure 2-1 shows the results for the
polymerization of diethylene glycol, (HOCH2CH2)2O, and adipic acid [Flory, 1939; Solomon,
1967and 1972]. The results are typical of the behavior observed for polyesterifications.
Although various authors agree on the experimental data, there has been considerable
disagreement on the interpretation of the results. At first glance the plot does not appear to
exactly follow the relationship. The experimental points deviate from the third-order plot in the
initial region below 80% conversion and in the later stages above 93% conversion. These
deviations led various workers [Amass, 1979; Fradet and Marechal, 1982a,b; Solomon, 1967,
1972] to suggest alternate kinetic expressions based on either 1- or 3 /2-order dependencies of

the reaction rate on the carboxyl concentration, that is, 2- and 2(1/ 2)-order dependencies
according to

-d[COOH]/dt = k[COOH][OH] 12a

And
-d[COOH]/dt =k[COOH]3/2[OH] 12b
However, a critical evaluation shows that both kinetic possibilities leave much to be desired. The
experimental rate data fits Eq. 12a well only in the region between 50 and 86% conversion with
an excessively poor fit above 86% conversion. On the other hand, a plot according to Eq. 12b fits
reasonably well up to about 80% conversion but deviates badly above that point. Neither of the
two alternate kinetic plots comes close to being as useful as the third-order plot in Fig. 2-1. The
third-order plot fits the experimental data much better than does either of the others at the higher
conversions. The fit of the data to the third-order plot is reasonably good over a much greater
range of the higher conversion region. The region of high conversion is of prime importance,
since, high-molecular-weight polymer is obtained only at high conversions. From the practical
viewpoint, the low conversion region of the kinetic plot is of little significance.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 10/25

External Catalysis of Polymerization

The slow increase in molecular weight was mistakenly thought originally to be due to the
low reactivity of functional groups attached to large molecules. It is, however, simply a
consequence of the third-order kinetics of the direct polyesterification reaction. The realization
of this kinetic situation led to the achievement of high-molecular-weight products in reasonable
reaction times by employing small amounts of externally added strong acids (such as sulfuric
acid or p-toluenesulfonic acid) as catalysts. Under these conditions, [HA] in Eq. 2-17 is the
concentration of the catalyst. Since this remains constant throughout the course of the
polymerization, Eq. 2-17 can be written as,

-d[M]/dt = Kʼ [M]2 13
where the various constant terms in Eq. 11 have been collected into the experimentally
determinable rate constant Kʹ. Equation 13 applies to reactions between stoichiometric
concentrations of the diol and diacid. Integration of Eq. 13 yields

Kʹ t =1/[M]-1/[M0] 14

Combining Eqs. 14 and 10 yields the dependence of the degree of polymerization on reaction
time as

[Mo]kʹt =1/(1 – p) - 1 15
Or

Xn̅ = 1 + [Mo]kʹt 15b

Data for the polymerization of diethylene glycol with adipic acid catalyzed by p-toluene
sulfonic acid are shown in Fig. 2-2. The plot follows Eq. 15 with the degree of polymerization
increasing linearly with reaction time. The much greater rate of increase of Xn with reaction time
in the catalyzed polyesterification (Fig. 2-2) relative to the uncatalyzed reaction (Fig. 2-1) is a
general and most significant phenomenon. The polyesterification becomes a much more
economically feasible reaction when it is catalyzed by an external acid. The selfcatalyzed
polymerization is not a useful reaction from the practical viewpoint of producing high polymers
in reasonable reaction times.
Equations 2-27 and 2-33 and Fig. 2-2 describe the much greater difficulty of performing a
successful polymerization compared to the analogous small-molecule reaction (such as the
synthesis of ethyl acetate from acetic acid and ethanol).
Consider the case where one needs to produce a polymer with a degree of polymerization
of 100, which is achieved only at 99% reaction. Running the polymerization to a lower
conversion such as 98%, an excellent conversion for a small-molecule synthesis, results in no
polymer of the desired molecular weight. Further, one must almost double the reaction time
(from _450 min to 850 min in (Fig. 2-2) to achieve 99% reaction and the desired polymer
molecular weight. For the small molecule reaction one would not expend that additional time to

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 11/25

achieve only an additional 1% conversion. For the polymerization one has no choice other than
to go to 99% conversion. The nonlinearity in the initial region of Fig. 2-2 is, like that in Fig. 2-1,
a characteristic of esterifications in general and not of the polymerization reaction. The general
linearity of the plot in the higher conversion region is a strong confirmation of the concept of
functional group reactivity independent of molecular size. Figure 2-2 shows that the
polyesterification.

continues its second-order behavior at least up to a degree of polymerization of 90 corresponding

to a molecular weight of _10,000. There is no change in the reactivities of the hydroxyl and
carboxyl groups in spite of the large increase in molecular size (and the accompanying large
viscosity increase of the medium). Similar results have been observed in many other
polymerizations. Data on the degradation of polymers also show the same effect. Thus in the
acid hydrolysis of cellulose there is no effect of molecular size on hydrolytic reactivity up to a
degree of polymerization of 1500 (molecular weight 250,000) [Flory, 1953]. The concept of
functional group reactivity independent of molecular size has been highly successful in allowing
the kinetic analysis of a wide range of polymerizations and reactions of polymers. Its validity,
however, may not always be quite rigorous at very low or very high conversions.

Addition polymerization
Polymers are long chain giant organic molecules are assembled from many smaller molecules
called monomers. Polymers consist of many repeating monomer units in long chains. A
polymer is analogous to a necklace made from many small beads (monomers). Many monomers
are alkenes or other molecules with double bonds which react by addition to their unsaturated
double bonds.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 12/25

have been turned into single bonds. No atoms have been lost and you can see that the monomers
have just been joined in the process of addition. A simple representation is -[A-A-A-A-A]-.
Polyethylene is used in plastic bags, bottles, toys, and electrical insulation.

 LDPE - Low Density Polyethylene: The first commercial polyethylene process used
peroxide catalysts at a temperature of 500 C and 1000 atmospheres of pressure. This
yields a transparent polymer with highly branched chains which do not pack together
well and is low in density. LDPE makes a flexible plastic. Today most LDPE is used for
blow-molding of films for packaging and trash bags and flexible snap-on lids. LDPE is
recyclable plastic #4.
 HDPE - High Density Polyethylene: An alternate method is to use Ziegler-Natta
aluminum titanium catalysts to make HDPE which has very little branching, allows the
strands to pack closely, and thus is high density. It is three times stronger than LDPE and
more opaque. About 45% of the HDPE is blow molded into milk and disposable
consumer bottles. HDPE is also used for crinkly plastic bags to pack groceries at grocery
stores. HDPE is recyclable plastic #2.
Examples
 PVC (polyvinyl chloride), which is found in plastic wrap, simulated leather, water pipes,
and garden hoses, is formed from vinyl chloride (H2C=CHCl). The reaction is shown in
the graphic on the left. Notice how every other carbon must have a chlorine attached.
 Polypropylene: The reaction to make polypropylene (H2C=CHCH3) is illustrated in the
middle reaction of the graphic. Notice that the polymer bonds are always through the
carbons of the double bond. Carbon #3 already has saturated bonds and cannot participate
in any new bonds. A methyl group is on every other carbon.
 Polystyrene: The reaction is the same for polystrene where every other carbon has a
benzene ring attached. Polystyrene (PS) is recyclable plastic #6. In the following
illustrated example, many styrene monomers are polymerized into a long chain
polystyrene molecule. The squiggly lines indicate that the polystyrene molecule extends
further at both the left and right ends.

 Blowing fine gas bubbles into liquid polystyrene and letting it solidify
produces expanded polystyrene, called Styrofoam by the Dow Chemical Company.
 Polystyrene with DVB: Cross-linking between polymer chains can be introduced into
polystyrene by copolymerizing with p-divinylbenzene (DVB). DVB has vinyl groups (-

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 13/25

CH=CH2) at each end of its molecule, each of which can be polymerized into a polymer
chain like any other vinyl group on a styrene monomer.

Polymers from conjugated dienes usually give elastomer polymers having rubber-like properties.

Addition homopolymers from conjugated dienes

Monomer Polymer name Trade name Uses
H2C=CH-C(CH3)=CH2 polyisoprene natural or some synthetic rubber applications similar
to natural rubber
H2C=CH-CH=CH2 polybutadiene polybutadiene synthetic rubber select synthetic
rubber applications
H2C=CH-CCl=CH2 polychloroprene Neoprene chemically-resistant
rubber
Ring opening polymerization
In this kind of polymerization, molecular rings are opened in the formation of a polymer. Here
epsilon-caprolactam, a 6-carbon cyclic monomer, undergoes ring opening to form a Nylon 6
homopolymer, which is somewhat similar to but not the same as Nylon 6,6 alternating
copolymer.

Cationic polymerization
Cationic polymerization is a type of chain growth polymerization in which a cationic initiator
transfers charge to a monomer which then becomes reactive. This reactive monomer goes on to
react similarly with other monomers to form a polymer. The types of monomers necessary for
cationic polymerization are limited to olefins with electron-donating substituents and
heterocycles. Similar to anionic polymerization reactions, cationic polymerization reactions are
very sensitive to the type of solvent used. Specifically, the ability of a solvent to form free ions
will dictate the reactivity of the propagating cationic chain. Cationic polymerization is used in
the production of polyisobutylene (used in inner tubes) and poly(N-vinylcarbazole) (PVK).

Monomers
Monomer scope for cationic polymerization is limited to two main
types: olefins and heterocyclic monomers. Cationic polymerization of both types of monomers
occurs only if the overall reaction is thermally favorable. In the case of olefins, this is due
to isomerization of the monomer double bond; for heterocycles, this is due to release of
monomer ring strain and, in some cases, isomerization of repeating units. Monomers for cationic
polymerization are nucleophilic and form a stable cation upon polymerization.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 14/25

Olefins
Cationic polymerization of olefin monomers occurs with olefins that contain electron-donating
substituents. These electron-donating groups make the olefin nucleophilic enough to
attack electrophilic initiators or growing polymer chains. At the same time, these electron-
donating groups attached to the monomer must be able to stabilize the resulting cationic charge
for further polymerization. Some reactive olefin monomers are shown below in order of
decreasing reactivity, with heteroatom groups being more reactive than alkyl or aryl groups.
Note, however, that the reactivity of the carbenium ion formed is the opposite of the monomer
reactivity.[5]

Heterocyclic monomers

Heterocyclic monomers that are cationically polymerized are lactones, lactams, and
cyclic amines. Upon addition of an initiator, cyclic monomers go on to form linear polymers.
The reactivity of heterocyclic monomers depends on their ring strain. Monomers with large ring
strain, such as oxirane, are more reactive than 1,3-dioxepane which has considerably less ring
strain. Rings that are six-membered and larger are less likely to polymerize due to lower ring
strain.

Synthesis
Initiation
Initiation is the first step in cationic polymerization. During initiation, a carbenium ion is
generated from which the polymer chain is made. The counterion should be non-nucleophilic,
otherwise the reaction is terminated instantaneously. There are a variety of initiators available for
cationic polymerization, and some of them require a coinitiator to generate the needed cationic
species.[7]

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 15/25

Classical protonic acids
Strong protic acids can be used to form a cationic initiating species. High concentrations of the
acid are needed in order to produce sufficient quantities of the cationic species.
The counterion (A−) produced must be weakly nucleophilic so as to prevent early termination
due to combination with the protonated olefin. Common acids used are phosphoric, sulfuric,
fluro-, and triflic acids. Only low molecular weight polymers are formed with these initiators.

Lewis acids/Friedel-Crafts catalysts

Lewis acids are the most common compounds used for initiation of cationic polymerization. The
more popular Lewis acids are SnCl4, AlCl3, BF3, and TiCl4. Although these Lewis acids alone
are able to induce polymerization, the reaction occurs much faster with a suitable cation source.
The cation source can be water, alcohols, or even a carbocation donor such as an ester or
an anhydride. In these systems the Lewis acid is referred to as a coinitiator while the cation
source is the initiator. Upon reaction of the initiator with the coinitiator, an intermediate complex
is formed which then goes on to react with the monomer unit. The counterion produced by the
initiator-coinitiator complex is less nucleophilic than that of the Brønsted acid A− counterion.
Halogens, such as chlorine and bromine, can also initiate cationic polymerization upon addition
of the more active Lewis acids.[1]

Carbenium ion salts

Stable carbenium ions are used to initiate chain growth of only the most reactive olefins and are
known to give well defined structures. These initiators are most often used in kinetic studies due
to the ease of being able to measure the disappearance of the carbenium ion absorbance.
Common carbenium ions are trityl and tropylium cations.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 16/25

Ionizing radiation
Ionizing radiation can form a radical-cation pair that can then react with a monomer to start
cationic polymerization. Control of the radical-cation pairs are difficult and often depend on the
monomer and reaction conditions. Formation of radical and anionic species are often observed.

Effect of temperature
The temperature of the reaction has an effect on the rate of propagation. The overall activation
energy for the polymerization (E) is based upon the activation energies for the initiation (Ei),
propagation (Ep), and termination (Et) steps:
E = Ei + Ep - Et

Generally, is larger than the sum of and , meaning the overall activation
energy is negative. When this is the case, a decrease in temperature leads to an increase in the
rate of propagation. The converse is true when the overall activation energy is positive.
Chain length is also affected by temperature. Low reaction temperatures, in the range of 170–190
K, are preferred for producing longer chains. This comes as a result of the activation energy for
termination and other side reactions being larger than the activation energy for propagation. As
the temperature is raised, the energy barrier for the termination reaction is overcome, causing
shorter chains to be produced during the polymerization process.
Effect of solvent and counterion
The solvent and the counterion (the gegen ion) have a significant effect on the rate of
propagation. The counterion and the carbenium ion can have different associations according
to intimate ion pair theory; ranging from a covalent bond, tight ion pair (unseparated), solvent-
separated ion pair (partially separated), and free ions (completely dissociated).
〰〰RXcovalent 〰〰R+
X−
tight ion pair 〰〰R+

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 17/25

/X−
solvent-separated
ion pair 〰〰R+
+X−
free ions

The association is strongest as a covalent bond and weakest when the pair exists as free ions.[6] In
cationic polymerization, the ions tend to be in equilibrium between an ion pair (either tight or
solvent-separated) and free ions. The more polar the solvent used in the reaction, the better the
solvation and separation of the ions. Since free ions are more reactive than ion pairs, the rate of
propagation is faster in more polar solvents.
The size of the counterion is also a factor. A smaller counterion, with a higher charge density,
will have stronger electrostatic interactions with the carbenium ion than will a larger counterion
which has a lower charge density. Further, a smaller counterion is more easily solvated by a
polar solvent than a counterion with low charge density. The result is increased propagation rate
with increased solvating capability of the solvent.
Termination
Termination generally occurs via unimolecular rearrangement with the counterion. In this
process, an anionic fragment of the counterion combines with the propagating chain end. This
not only inactivates the growing chain, but it also terminates the kinetic chain by reducing the
concentration of the initiator-coinitiator complex.

Chain transfer
Chain transfer can take place in two ways. One method of chain transfer is hydrogen abstraction
from the active chain end to the counterion. In this process, the growing chain is terminated, but
the initiator-coinitiator complex is regenerated to initiate more chains.

Chain transfer by hydrogen abstraction to the counterion

The second method involves hydrogen abstraction from the active chain end to the monomer.
This terminates the growing chain and also forms a new active carbenium ion-counterion
complex which can continue to propagate, thus keeping the kinetic chain intact.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 18/25

Chain transfer by hydrogen abstraction to the monomer
Cationic ring-opening polymerization
Cationic ring-opening polymerization follows the same mechanistic steps of initiation,
propagation, and termination. However, in this polymerization reaction, the monomer units are
cyclic in comparison to the resulting polymer chains which are linear. The linear polymers
produced can have low ceiling temperatures, hence end-capping of the polymer chains is often
necessary to prevent depolymerization.

Cationic ring-opening polymerization of oxetane involving (a and b) initiation, (c) propagation,

and (d) termination with methanol

Kinetics
The rate of propagation and the degree of polymerization can be determined from an analysis of
the kinetics of the polymerization. The reaction equations for initiation, propagation, termination,
and chain transfer can be written in a general form:
I+ + M ki M+
M+ + M kp M+
M+ kt M

M+ + M ktr M + M+
In which I+ is the initiator, M is the monomer, M+ is the propagating center, and ki, kp, kt, and ktr
are the rate constants for initiation, propagation, termination, and chain transfer, respectively.
For simplicity, counterions are not shown in the above reaction equations and only chain
transfer to monomer is considered. The resulting rate equations are as follows, where brackets
denote concentrations:
Rate (initiation) = ki [I+][M]
Rate (propagation) = kp [M+][M]
Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 19/25
Rate (termination) = kt [M+]
Rate (chain transfer) = ktr [M+][M]
Assuming steady-state conditions, i.e. the rate of initiation = rate of termination
[ ][ ]
=

This equation for [M+] can then be used in the equation for the rate of propagation

[ ] [ ]
( )=

From this equation, it is seen that propagation rate increases with increasing monomer and
initiator concentration.
The degree of polymerization, Xn, can be determined from the rates of propagation and
termination.

( ) [ ]
= ( )
=

If chain transfer rather than termination is dominant, the equation for Xn becomes
( )
= =
( ℎ )
Anionic addition polymerization
Anionic addition polymerization is a form of chain-growth polymerization or addition
polymerization that involves the polymerization of vinyl monomers with strong electronegative
groups. This polymerization is carried out through a carbanion active species. Like all chain-
growth polymerizations, it takes place in three steps: chain initiation, chain propagation,
and chain termination. Living polymerizations, which lack a formal termination pathway, occur
in many anionic addition polymerizations. The advantage of living anionic addition
polymerizations is that they allow for the control of structure and composition.
Anionic polymerizations are used in the production of polydiene synthetic rubbers, solution
styrene/butadiene rubbers (SBR), and styrenic thermoplastic elastomers.

Monomer characteristics
In order for polymerization to occur with vinyl monomers, the substituents on the double
bond must be able to stabilize a negative charge. Stabilization occurs through delocalizationof
the negative charge. Because of the nature of the carbanion propagating center, substituents that
react with bases or nucleophiles either must not be present or be protected.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 20/25

Vinyl monomers with substituents that stabilize the negative charge through charge
delocalization, undergo polymerization without termination or chain transfer.[4] These monomers
include styrene, dienes, methacrylate, vinyl pyridine, aldehydes, epoxide, episulfide,
cyclic siloxane, and lactones. Polar monomers, using controlled conditions and low
temperatures, can undergo anionic polymerization. However, at higher temperatures they do not
produce living stable, carbanionic chain ends because their polar substituents can undergo side
reactions with both initiators and propagating chain centers. The effects of counterion, solvent,
temperature, Lewis base additives, and inorganic solvents have been investigated to increase the
potential of anionic polymerizations of polar monomers.[4] Polar monomers
include acrylonitrile, cyanoacrylate, propylene oxide, vinyl ketone, acrolein, vinyl sulfone,
vinyl sulfoxide, vinyl silane and isocyanate.

Solvent
The solvent used in anionic addition polymerizations are determined by the reactivity of both the
initiator and carbanion of the propagating chain end. Anionic species with low reactivity, such
as heterocyclic monomers, can use a wide range of solvents.

Initiation
The reactivity of initiators used in anionic polymerization should be similar to that of the
monomer that is the propagating species. The pKa values for the conjugate acids of the
carbanions formed from monomers can be used to deduce the reactivity of the monomer. The
least reactive monomers have the largest pKa values for their corresponding conjugate acid and
thus, require the most reactive initiator. Two main initiation pathways involve electron transfer
(through alkali metals) and strong anions.
Initiation by electron transfer
Szwarc and coworkers studied the initiation of polymerization through the use of aromatic
radical-anions such as sodium naphthenate. In this reaction, an electron is transferred from the
alkali metal to naphthalene. Polar solvents are necessary for this type of initiation both for

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 21/25

stability of the anion-radical and to solvate the cation species formed. The anion-radical can then
transfer an electron to the monomer.

Initiation can also involve the transfer of an electron from the alkali metal to the monomer to
form an anion-radical. Initiation occurs on the surface of the metal, with the reversible transfer of
an electron to the adsorbed monomer.
Initiation by strong anions
Nucleophilic initiators include covalent or ionic
metal amides, alkoxides, hydroxides, cyanides, phosphines, amines and organometallic
compounds (alkyllithium compounds and Grignard reagents). The initiation process involves the
addition of a neutral (B:) or negative (B:-) nucleophile to the monomer.

The most commercially useful of these initiators has been the alkyllithium initiators. They are
primarily used for the polymerization of styrenes and dienes.
Monomers activated by strong electronegative groups may be initiated even by weak anionic or
neutral nucleophiles (i.e. amines, phosphines). Most prominent example is the curing
of cyanoacrylate, which constitutes the basis for superglue. Here, only traces of basic impurities
are sufficient to induce an anionic addition polymerization or zwitterionic addition
polymerization, respectively.

Propagation

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 22/25

Propagation in anionic addition polymerization results in the complete consumption of monomer.
It is very fast and occurs at low temperatures. This is due to the anion not being very stable, the
speed of the reaction as well as that heat is released during the reaction. The stability can be
greatly enhanced by reducing the temperatures to near 0˚C. The propagation rates are generally
fairly high compared to the decay reaction, so the overall polymerization rates is generally not
affected.

Termination
Anionic addition polymerizations have no formal termination pathways because proton transfer
from solvent or other positive species does not occur. However, termination can occur through
unintentional quenching due to trace impurities. This includes trace amounts of oxygen, carbon
dioxide or water. Intentional termination can occur through the addition of water or alcohol.
Another method of termination, chain transfer, can occur when an agent can act as a Brønsted
acid. In this case, the pKa value of the agent is similar to the conjugate acid of the propagating
carbanionic chain end. Spontaneous termination occurs because the concentration of carbanion
centers decay over time and eventually results in hydride elimination. Polar monomers are more
reactive because they are stabilized by their polar substituents. These polar substituents can react
with nucleophiles which results in termination as well as side reactions that compete with both
initiation and propagation.

Kinetics
The kinetics of anionic addition polymerization depend on whether or not a termination pathway
occurs.
In general, the reaction mechanism for living anionic addition polymerization are as follows:
I- + M k
init M-
M- + M k
prop M-
where I = initiator, kinit = the initiation reaction rate constant, M = monomer, M−= propagating
species, and kprop = the propagation reaction rate constant.
As most polymerizations of this type do not have a termination pathway, the rate of
polymerization is the rate of propagation:
Rate (prop) = kp [M-][M]
where kp is the rate of constant of propagation, [M−] is the total concentration of propagating
centers, and [M] is the concentration of monomer. Since there is no termination pathway in
living polymerizations, the concentration of propagating centers is equal to the concentration of
initiator ([I]). Thus,
rate (prop) = kp [I][M]
The degree of polymerization, Xn is also affected by no termination pathway. It is the ratio of
concentration of reacted monomer ([M]o) to initiator([I]o) times the percent conversion p. In this
case, the chain length (ν) is equal to X n.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 23/25

[ ]
=
[ ]
When conversion, p = 1 (100% conversion), chain length is simply the ratio of reacted monomer
[ ]
to initiator. = [ ] .

Kinetics: termination due to impurities

When termination occurs due to impurities, the impurities must be taken into account in
determining the reaction rate. The reaction mechanisms would begin the same as that of a living
anionic addition (initiation and propagation). However, there would now be a termination step to
account for the effect of the impurities on the reaction.
M- + HX k
term M-H + X-
where M−= propagating species, HX = impurity and kterm = the termination reaction rate
constant.
Using the steady-state approximation, the rate of propagation becomes
[ ][ ]
( )=
[ − ]

Since
( ) [ ]
= =
( ) [ − ]

Thus chain length and rate of propagation are negatively impacted by the presence of impurities
in the reaction.
Free-Radical polymerization
Initiation The initiation reaction produces free radicals. There are several ways to do this: •
Chemical initiation The decomposition of the initiator (e.g. AIBN) forms free radicals:

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 24/25

Propagation
Propagation is the addition of a monomer molecule to a radical chain.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 25/25

Chain Transfer
• Chain transfer to monomer

The reactants are the same as for the propagation reaction, but the activation energy is much
larger. Accordingly, kfm is usually at least 103 times smaller than kp. This reaction

leads to the formation of a polymer chain with a terminal double bond. This can induce chain
branching through the terminal double bond propagation reaction.
• Chain transfer to chain transfer agent

A chain transfer agent, S is a molecule containing a weak bond that can be broken to lead to
radical transfer, similarly as in the case of monomer above (e.g. CCl4, CBr4, mercaptans).
• Chain transfer to polymer

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 26/25

In this reaction the growing radical chain, R• n extracts a hydrogen from the dead chain, Pm.
Since this extraction can occur on any of the m monomer units along the chain, the rate of this
reaction is proportional to the length of Pm.
General observations on the role of chain transfer reactions:
- The concentration of radicals is not affected and therefore the rate of monomer consumption is
also unchanged.
- The growth of polymer chains is stopped and therefore shorter chains are produced.
- Each transfer event leaves a different end-group on the chain that can be detected (NMR,
titration) so as to identify and quantify the corresponding chain transfer reaction.
- Nonlinear (branched) polymer chains are produced: directly by chain transfer to polymer or
indirectly through the propagation of the terminal double bond left by a chain transfer to
monomer event.

Reference book
R1: M.S Bhatnagar,2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 27/25

KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHU305A UNIT: I (Coordination Chemistry) BATCH-2017-2019

Questions Opt-1 Opt-2 Opt-3 Opt-4 Answers

1 Which is obtained from the Polyamides polyester Acrylicfibre poly vinyl chloride Polyamides
reaction of diamines with diacids?

2 In step polymerization the The collision b. diffusion rate Nature of the Size of the group The collision
reactivity of a functional group frequency of the of the whole functional group frequency of the
depends on? group molecule group
3 The alkyl resins are condensation phenol formaldehyde Acetaldehyde Glycol Phenol
polymers obtained from dibasic
acids and
4 Reactivity of a functional group Collision diffusion rate Size Molecular weight Collision
depends on ? frequency frequency

5 In a polymer chain the functional the different Tautomeric Optical activity The
group has appreciable mobility due conformational stereochemical arrangements conformational
to rearrangements forms rearrangements
6 The ﬁrst step in the reaction of the dimer trimer Pentamer Tetramer Dimer
diol and diacid monomer is to form
?
7 The rate of a step polymerization is Concentrations concentration of Concentration of Concentration of Concentration of
conveniently expressed in terms of of the reacting the monomeric monomer and the functional the functional
the functional the solvent groups and groups and
groups. monomers monomers
8 A dimer reacts with a monomer to Trimer Dimer Pentamer Tetramer Trimer
give
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In thermal catalyzed Homolytic Heterolytic Decomposition Association of the Homolytic

9 polymerizations the most widely dissociation of dissociation of of the initiator initiator dissociation of
used mode of generating radicals initiators initiators initiators
to initiate polymerization ?
10 The Polyesterification of a diol and Step Ionic Radical Self catalysted Step
a diacid will illustrate the general polymerization polymerization polymerization polymerization polymerization
kinetics of a typical ?
11 The carboxyl concentration is Product Reactant Reagent Catalyst Catalyst
comprised of two first-order
dependencies, one for the carboxyl
as the reactant and another one
as?
12 The polyesterification becomes a Base Acid Alkali Neutral Acid
much more economically feasible
reaction when it is catalyzed by an
?
13 Example for radical sources for the Peroxides Epoxides Nitrenes Carbenes Peroxides
polymerization reactions?

14 A titanium atom at the surface is Five chlorines Six chlorines Three chlorines Two chlorines Five chlorines
bonded by?

15 In free radical vinyl polymerization The electrons in The electrons in Non bonding Electrons from the The electrons in
the pi bond split the sigma bond electrons are functional group the pi bond split
up split up used splits. up
16 The general linearity of the plot in Frequency Molecular Density Molecular size Molecular size
the higher conversion region is a Weight
strong confirmation of the concept
of functional group reactivity
independent of?
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17 In the acid hydrolysis of cellulose Frequency Molecular wight Density Molecular size Molecular size
there is no effect of ?

18 Isotactic polymerization depends Crystal structure Surface area of Volume of the Concentration of Crystal structure
intimately on the ? of the initiator the initiator initiator the initiator of the initiator
surface surface
19 In isotactic polymerization the Edges (surfaces) Edges of the Corners of the Inside the pores of Edges (surfaces)
polymerization occurs at active of elementary basal planes basal planes the catalyst of elementary
sites found on the ? sheets of the sheets of the
crystal crystal
20 Which find extensive use as radical Peroxides Epoxides Nitrenes Carbenes Peroxides
sources?

21 The enantiomorphic site control Isoselective Isotactic Free radical Ionic Isoselective
model attributes stereo control in ? polymerization polymerization polymerization polymerization polymerization

22 The C ~ 190 kJ mol -1 ~ 390 kJ mol -1 ~ 290 kJ mol -1 ~ 360 kJ mol -1 ~ 290 kJ mol -1
is?

23 The various initiators are used at Reaction Decomposition Composition Entropy Decomposition
different temperatures depending
on their rates of
24 The azobisisobutyronitrile (AIBN) is 60-70 OC 50–70OC 80-90 OC 40-50 OC 50–70OC
commonly used at?

25 Teflon is a polymer of the Monofloroethene Difloroethene Trifloroethene Tetrafloroethene Tetrafloroethene

monomer or Teflon is obtained by
the polymerisation of ?
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26 Which of the following is an PVC Polyamide Terylene Polyester Terylene

example of condensation polymer?

27 two trimers react together to form Trimer Hexamer Monomer Heptamer Hexamer

28 Ionic vinyl polymerizations are very Free radical vinyl Step Self catalysted Free radical Free radical vinyl
similar to polymerizations polymerizations vinyl polymerizations polymerizations
polymerization
29 A tetramer reacts with a trimer to Trimer Dimer Pentamer Heptamer Heptamer
form

30 A pentamer reacts with a trimer to Trimer Dimer Pentamer Octamer Octamer

form

31 Monomer concentration decreases Step Ionic Radical Self catalysted Ionic

steadily throughout reaction in? polymerization polymerization polymerization polymerization polymerization

32 Polymer molecular weight rises Step Ionic Radical Self catalysted Step
steadily throughout reaction in ? polymerization polymerization polymerization polymerization polymerization

33 In which step of cationic Initiation propagation termination transfermation termination

polymerization follows the first
order kinetics
34 A simple termination or chain chain growth degree of kinetics polymer degree of
transfer depending to polymerization deformation polymerization
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35 The temperature would decreases molecular weight chain formation initiator monomer molecular weight
the of polymer of polymer

36 In the radical polymerization, the monomer concentration of concentration of reaction rate concentration of
propagation rate depends on monomer radical catalyst monomer radical

37 In Cationic vinyl polymerization Same direction Same and Opposite Same or opposite Opposite
electron flow is ? opposite direction direction direction
direction
38 Ionic polymerization necessarily Counter ion Cation Anion Cation or anion Counter ion
carry along a?

39 The fraction of the radicals Initiator High efficiency Low efficiency Closer efficiency Initiator
produced in the homolysis reaction efficiency efficiency
that initiate polymer chains is
defined as?
40 A dimer react with another dimer Trimer Dimer Pentamer Tetramer Tetramer
to form a

41 In most polymerizations, the Much faster than Much slower Less faster than Slower than the Much faster than
second step is? the first step than the first the first step first step the first step
step
42 Which is impossible under any and Cationic vinyl Ionic Polymerization Wastage reactions Polymerization
all reaction conditions if it does not polymerization polymerization
pass the test of thermodynamic
feasibility?
43 which of the following is a example methyl isonate acetylene malic acid glycine glycine
of bifunctional monomer
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44 Which of the following is the monofunctional bifunctional tetra functional tri functional tetra functional
functionality of Gallic acid

45 Monomers show high selectivity Cationic initiators Cationic and Ionic initiators Anionic initiators Ionic initiators
towards? anionic initiators

46 Most monomers will undergo Varying rates Reliable rates Stable rates Positive rates Varying rates
polymerization with a radical
initiator, although at?
47 Polymerization is possible only if Positive Negative Both negative Neither negative Negative
the free-energy difference -G and positive nor positive
between monomer and polymer is?
48 The property of fabric which Tensile Compressional Shear Surface Shear
influences drape the most is?

49 The Q–e scheme is best considered Qualitative basis Quantitative Qualitative Quantitative Quantitative
as an empirical approach to placing basis radical radical basis
monomer reactivity on a?
50 To remove the residual metals, a Ashing Reashing Ashing and Deashing Deashing
process referred as ? reashing

51 3,4-Difluorophenylamine is a Phenylamine Phenylacetate Phenol Henepthyl alcohol Phenylamine

weaker base than ?

52 What method would you use to Free radical Anionic Using a Ziegler Condensation Free radical
synthesize a triblock copolymer? polymerization polymerization Natta catalyst polymerization polymerization
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53 Suspension free radical Branching Cross-linking Stereo- Polymeric Branching

polymerization of styrene would be isomerism impurities
preferred over bulk polymerization
to overcome the problem of ?
54 Polymers are ? Large molecule Small molecule Small chain Large chain Large chain
molecule molecule molecule

55 Polymers are high molecular 104 to 107 103 to 107 102 to 107 105 to 107 103 to 107
weight in the range of ?

56 Tetramer + monomer is ? Trimer Dimer Pentamer Tetramer Pentamer

57 Which one is not a polymer? Carbohydrates Proteins Carboxylic acid Nucleic acid Carboxylic acid

58 Due to the presence of carbon Ionic bond Covalent bond Triple bond Metalic bond Covalent bond
atom in polymers all large
biological molecules are made of ?
59 Amino acids are building blocks of ? Carbohydrates Proteins Carboxylic acid Lipids Proteins

60 polyethylene is ? Colourless liquid Colourless gas Gas Liquid Colourless gas

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UNIT – II
Co-ordination Polymerization

Co-ordination Polymerization: Kinetics, mono and bimetallic mechanism of co-ordination

polymers. Zeigler Natta catalyst, co-polymerization: Block and graft co-polymers, kinetics of
copolymerization. Types of co-polymerization. Reactivity ratio.

Coordination polymerization
Coordination polymerisation is a form of addition polymerization in which monomer adds to a
growing macromolecule through an organometallic active center. The development of
this polymerization technique started in the 1950s with heterogeneous Ziegler-Natta
catalysts based on titanium tetrachloride and an aluminium co-catalyst such
as methylaluminoxane. Coordination polymerization has a great impact on the physical
properties of vinyl polymers such as polyethylene and polypropylene compared to the same
polymers prepared by other techniques such as free-radical polymerization. The polymers tend to
be linear and not branched and have much higher molar mass. Coordination type polymers are
also stereoregular and can be isotactic or syndiotactic instead of just atactic.
This tacticity introduces crystallinity in otherwise amorphous polymers. From these differences
in polymerization type the distinction originates between low-density
polyethylene (LDPE), high-density polyethylene (HDPE) or even ultra-high-molecular-weight
polyethylene (UHMWPE).
Polymerizations catalysed by metallocenes occur via the Cossee-Arlman mechanism. The active
site is usually anionic but cationic coordination polymerization also exists.
In many applications Ziegler-Natta polymerization is succeeded by metallocene catalysis
polymerization. This method is based on homogeneous metallocene catalysts such as
the Kaminsky catalyst discovered in the 1970s. The 1990s brought forward a new range of post-
metallocene catalysts.
Typical monomers are nonpolar ethylene and propylene. The development of coordination
polymerization that enables copolymerization with polar monomers is more recent. Examples of
monomers that can be incorporated are methyl vinyl ketones methyl acrylate and acrylonitrile.
Kinetics
A case of heterogeneous polymerization.
It is defined : H is the surface of the transition-metal compound,
AR is the metal alkyl,
M is the monomer,
MX is the polymer.
Adsorption of metal alkyl from solution to form the active site
K1 H AR
H + AR

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 1/19

Adsorption of M from solution
K2
H + M M H
Initiation
Ki
M H AR H A M R
Propagation
KP
M H A MX R H MX+1 R
Termination
(transfer)
Ktr
M H A MX R H A M R + MX
Termination
(monomer forms an inactive site)
K1
M H A MX R H A M + MX R

It is assumed that the process occurs in Langmuir isotherm condition and it is defined that :
ƟA and Ɵ M are the fractions of the available surface covered by AR and M respectively,
[C*] is the concentration of growing chains,
Then the overall rate can be determined.
K1 [AR] K2 [M]
A = M =
1 + K1 [AR] + K2 [M] 1 + K1 [AR] + K2 [M]

The overall rate :

d [M]
R =  = (kp + ktr ) M [C*]
dt
Assume that [C*] reaches steady state so that the initiation rate is similar to the termination rate.
ki A M = kt [C*] M
The overall rate :
d [M] ( kp + ktr ) ki
K1 K2 [AR] [M]
R =  =
dt kt (1 + K1 [AR] + K2 [M] )2

Ziegler–Natta catalysis and polymerization

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 2/19

section the mechanistic features of Ziegler–Natta polymerizations are considered with emphasis
on those features that hold for most initiator systems.
The major interest will be on the titanium–aluminum systems for isoselective
polymerization, more specifically, TiCl3 with Al(C2H 5)2Cl and TiCl4 with Al(C2H 5)3—
probably the most widely studied systems, and certainly the most important systems for
industrial polymerizations. Before proceeding with the mechanistic consideration it is useful to
review the evolution of the Ti-Al initiator system for industrial applications. The original
initiator used by Ziegler for ethylene polymerization was obtained in situ as a precipitate on
mixing the components TiCl4 and Al(C2H 5)3 in a hydrocarbon solvent. The mixture was used
directly for initiating polymerization. Natta, recognizing that the major product of the reaction
was b-TiCl3 (brown in color), explored various methods of preforming it outside the
polymerization system, for example, by reduction of TiCl4 with hydrogen, aluminum, and
various alkylaluminum compounds. The stereoselectivity of these early initiator systems was low
with isotactic indices of only 20–40% for polypropene. The isotactic index, a measure of the
isotactic content of a polymer, is the percentage of the sample insoluble in a hydrocarbon solvent
such as boiling n-heptane. This is not as informative a technique as high-resolution NMR since
insoluble molecules may contain some syndiotactic and atactic sequences and soluble molecules
may contain some isotactic sequences. It does, however, give a simple measure of isotacticity
that is usually within about 10% of the value obtained from NMR,
especially for highly isotactic samples.
There was a dramatic increase in stereoselectivity when the α-, δ-,or γ-crystalline form of
TiCl3 (all violet in color) was used directly. The early generations of industrial processes used
TiCl3 together with Al(C2H 5)3 and/or Al(C2H 5)2Cl. Over a two decade period starting in the
late 1950s, the isotactic indices for polypropene increased to the low 90 percentile range. The
initiator activity was enhanced by various ball milling and heat treatments of the initiator
components before and after mixing. Ball milling involves mechanical grinding and not only
increases surface area but also facilitiates reactions between the initiator components.
However, the activities were too low to allow the polymer products to be used
without purification (by treatment with base or acid) to remove the residual metals,
a process referred to as deashing. Also, optimization of the physical properties of the
product often required removal of the atactic fraction. The initiator systems were inefficient with
less than 1% of the Ti being active in polymerization. The later generations of initiators, starting
in the late 1970s, increased initiator efficiency and activity without sacrificing stereoselectivity
[Bohm, 2001; Busico and Cipullo, 2001; Cecchin et al., 2001; Chadwick, 2001; Chadwick et al.,
2001; Chien et al., 1982; Hu and Chien, 1988]. The effective surface area of the active
component of the initiator system was increased by close to 2 orders of magnitude by using
MgCl2 as a solid support in which TiCl4 is finely dispersed. Stereoselectivity was kept high and
actually increased by the addition of electron-donor additives.
A typical recipe for a present-day superactive or high-mileage initiator system involve
ball milling of MgCl2 (or the alkoxide) and TiCl4 followed by the addition of Al(C2H 5)3 with an
electron donor (such as dialkyl phthalate and alkoxysilane) usually added in each step of
preparation. Activity is 50–200 kg polymer per gram of initiator system. Typically, the initiator
system is no more than 2–4% Ti, which makes the activity about 1500–6000 kg polymer per

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 3/19

gram of Ti. The high activity not only minimizes initiator and production costs but also avoids
the costly task of initiator removal from the polymer product (except possibly for food- and
medical-grade products). Isotactic indices for polypropene have been increased to 98% or higher
with (mmmm) pentad fractions up to 98% and higher. This not only improves the product’s
physical properties but also avoids the need to remove the a tactic fraction.
Chemical Nature of Propagating Species
Some early polymerizations reported as Ziegler–Natta polymerizations were conventional
free-radical, cationic, or anionic polymerizations proceeding with low stereoselectivity.Some
Ziegler–Natta initiators contain components that are capable of initiating conventional ionic
polymerizations of certain monomers, such as anionic polymerization of methacrylates by
alkyllithium and cationic polymerization of vinyl ethers by TiCl4. Most Ziegler–Natta
components participate in a complex set of reactions involving alkylation and reduction of the
transition-metal component by the group I–III component as shown below for TiCl4 + AlR3:
TiCl4 + AlR3 ───› TiCl3 R + AlR2 Cl

TiCl4 + AlR2Cl ───› TiCl3R + AlRCl2

TiCl3R + AlR3 ───› TiCl2 R2 + AlRCl2

TiCl3 R ───› TiCl3 + R•

TiCl3 + AlR3 ───› TiCl2 R + AlR2 Cl

R• ───› combination + disproportionation

Radicals produced in Eq. 8-31 are capable of initiating radical polymerizations with some
monomers, for example, vinyl chloride.The mechanism for the tereoselective polymerization of
a-olefins and other nonpolar alkenes is a p-complexation of monomer and transition metal
(utilizing the latter’s d-orbitals) followed by a four-center anionic coordination insertion process
in which monomer is inserted into a metal–carbon bond as described in Fig. 8-10. Support for the
initial p-complexation has come from ESR, NMR, and IR studies [Burfield, 1984]. The insertion
reaction has both cationic and anionic features. There is a concerted nucleophilic attack by the
incipient carbanion polymer chain end on the a-carbon of the double bond together with an
electrophilic attack by the cationic counterion on the alkene p-electrons.The anionic character of
the polymerization is consistent with the polymerization rate decreasing in the order ethylene >
propene > 1-butene [Bier, 1961; Boor, 1967].
The reverse order is expected for a polymerization involving the conversion of a
monomer into the corresponding carbocation. For addition of a carbanion to the monomers,
attack occurs at the a-carbon to form the less substituted (and more stable) carbanion. Further, a-
substituents sterically hinder the approach of a carbanion and/or counterion with the result that
reactivity decreases with increasing substituent size. Evidence for the anionic nature of
propagation also comes from studies in which labeled methanol is used to terminate chain
growth. The terminated polymer is radioactive when CH3 O3 H is used, while termination by
14
CH3 OH yields a nonradioactive polymer.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 4/19

Mechanism of Isoselective Propagation
A variety of structures have been proposed for the active species in Ziegler–Natta
initiator systems [Allegra, 1971; Arlman and Cossee, 1964; Corradini et al., 1989; Natta,
1960a,b; Patat and Sinn, 1958; Rodriguez and van Looy, 1966; Tait and Watkins, 1989].
Structure XX is generally considered as the active species formed from titanium chloride and
alkylaluminum components..

R Cl

Cl ─ Ti─□

Cl Cl

The Cl in the structure represents an unoccupied (vacant) site of the octahedral titanium
complex. XX represents an active titanium site at the surface of a TiCl3 crystal after modification
by reaction with the alkylaluminum component. The titanium atom shares four chloride ligands
with its neighboring titanium atoms and has an alkyl ligand (incorporated via exchange of alkyl
from the alkylaluminum for chloride) and a vacant orbital.
There are molecular mechanics calculations that indicate dimeric Ti2Cl6 may be the active
species instead of monomeric TiCl3 [Monaco et al., 2000]. Other proposals for the active species
include bimetallic species that contain both titanium and aluminum [Liu et al., 2002]. To
simplify matters, our discussions will center on the monomeric and monometallic titanium
species, especially since the mechanistic details of stereoselectivity and activity are essentially
the same for both monomeric and dimeric titanium species as well as titanium–aluminum
species. The high-mileage supported initiators previously mentioned involve a species similar to
XX as part of a mixed titanium–magnesium–chloride lattice, usually involving Mg-Cl-Ti bonds.
Ti and Mg are interchangeable within the metal lattice.
Figure 8-11 shows the proposed mechanism for isoselective propagation. Monomer coordinates
at the vacant site of titanium, resulting in a four-center transition state and subsequent insertion
of monomer into the polymer–transition metal bond. The insertion is referred to as migratory
insertion since the polymer chain migrates from its original site to that occupied by monomer.
The whole polymer chain does not migrate, only the active end of the polymer chain migrates.
This follows the principle of least nuclear motions. For the polymer chain to remain at its
original coordination site after monomer insertion, all or at least most of the polymer chain atoms
must move, specifically back away from the coordination site. For Cossee-Arlman mechanism, .

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 5/19

Fig. Mechanism for catalyst site control model of isoselective polymerization. migratory
insertion only the atoms of the first few repeat units move. This regenerates a vacant site with its
configuration opposite from the original vacancy.
If propagation continued with this species, the result might be syndioselective
propagation. Isoselective propagation requires migration of the polymer chain to its original
position with regeneration of the original configuration of the vacant site, often referred to as
back skip or back-flip. The chain migrates twice for insertion of each monomer unit, and the
overall process can also be regarded as a site epimerization. This mechanism, referred to as the
Cossee-Arlman mechanism, is based on the observed stereoselectivity and molecular modeling
tudies [Arlman and Cossee, 1964; Ewen, 1999; Rappe et al., 2000; Resconi et al., 2000]. A
variation on this mechanism involves a lowering of the transition state barrier to insertion by an
a-agostic interaction, specifically, an attractive interaction between titanium and a hydrogen on
the first carbon attached to Ti.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 6/19

Isotactic polymerization depends intimately on the crystal structure of the initiator
surface.For a coordination lattice, as opposed to a molecular crystal lattice, the crystal contains
a number of ligand vacancies in order to achieve overall electrical neutrality of the crystal.
a-TiCl3 crystals are made up of elementary crystal sheets of alternating titanium and chlorine
layers aligned along the principal crystal axis [Natta et al., 1961a,b,c,d]. Figure 8-12 is a
representation of a portion of the crystal [Corradini et al., 1989]. The titanium and chlorine
atoms are represented by solid black and open spheres, respectively. The titaniums are at the
octahedral interstices of the chlorine lattice while chlorines are hexagonally close-packed.
Every third titanium in the lattice is missing, that is, there is a vacancy in between pairs
of titanium atoms. Vacancies are represented by & in Fig. 8-12.
Polymerization occurs at active sites found on the edges (surfaces) of elementary sheets
of the crystal and not in the basal planes. This is supported by microscopic observations of
polymer growth at the crystal edges [Cossee, 1967; Kollar et al., 1968a,b; Rodriguez and van
Looy, 1966]. A titanium atom at the surface is bonded to only five chlorines instead of six
because of the imposed requirement of electroneutrality. Of the five chlorines, four are more
strongly bonded since they are bridged to other titanium atoms. The fifth, nonbridged chlorine
may be replaced by an alkyl group when the titanium component interacts with the group
I–III component. The octahedral vacancy remains as a vacancy.Neighboring metal atoms
(bridged by two chlorines) have opposite chirality [Allegra, 1971]. The two enantiomeric
titaniums can be represented as XXI and XXII where one of the chlorine ligands has been
i Cl □ □ Cl
Ti
Cl Ti Cl Cl Ti Cl
R R
Cl Ti Ti Cl

XXI XXII

replaced by R via alkylation by the group I–III metal component.Propagation occurs by

coordination of monomer at the vacancy, migratory insertion into the Ti__R bond, and migration
of the newly formed bond to regenerate the vacancy in the original configuration. Considering
either XXI or XXII, coordination of monomer can occur through either of the two monomer
enantiofaces (si or re), which results in two diastereomeric transition states. The two
diasteromeric states give rise to the two possible placements of monomer units in the
polymerchain—meso and racemo [Corradini et al., 1984,1985; Zambelli et al., 1978, 1980].
The driving force for isoselective propagation results from steric and electrostatic interactions
between the substituent of the incoming monomer and the ligands of the transition metal. The
chirality of the active site dictates that monomer coordinate to the transition metal vacancy
primarily through one of the two enantiofaces. Actives sites XXI and XXII each yield isotactic
polymer molecules through nearly exclusive coordination with the re and si monomer
enantioface, respectively, or vice versa. That is, we may not know which enantioface will
coordinate with XXI and which enantioface with XXII, but it is clear that only one of the
enantiofaces will coordinate with XXI while the opposite enantioface will coordinate with XXII.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 7/19

This is the catalyst (initiator) site control or enantiomorphic site control model for isoselective
polymerization.
The enantiomorphic site control model attributes stereocontrol in isoselective
polymerization to the initiator active site with no influence of the structure of the propagating
chain end. The mechanism is supported by several observations:
1. 13C NMR of isotactic polypropene shows the main error is pairs of racemic dyads
instead of isolated racemic dyads (Table 8-3) [Heatley et al., 1969; Resconi et al., 2000;
Wolfsgruber et al., 1975]. A stereoerror in the addition of a monomer molecule is
immediately corrected when stereocontrol is by the chiral active site. If stereocontrol was due
to the propagating chain end, an error would continue to propagate in an isotactic manner to
yield a polymer, referred to as an isotactic stereoblock, containing long isotactic all-R and
all-S stereoblocks on each side of the error.
2. 13C NMR of ethylene-propene copolymers of low ethylene content produced by
initiators that yield isotactic polypropene shows that the isotactic propene units on each side
of an ethylene unit have the same configuration (i.e., all-R or all-S) [Zambelli et al., 1971,
1978, 1979]. For stereocontrol by the propagating chain end, the amount of polymer in which
the polypropene blocks on either side of an ethylene unit have the same configuration would
equal that in which the blocks have the opposite configuration.
3. Statistical analysis of the stereochemical sequence distributions (Table 8-3 and Sec. 8-
16) also supports the enantiomorphic site control model.
Isotactic Polymerization Mechanism

Suface titanium wants to fill its orbitals. But first, Al(C2H5)2Cl enters the picture. It donates one
of its ethyl groups to the impoverished titanium, but kicks out one of the chlorines in the process.
We still have an empty orbital. But more about that in a moment.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 8/19

As you can see in this picture, the aluminum has a hard time letting go. It stays coordinated,
though not covalently bonded, to the CH2 carbon atom of the ethyl group it just donated to the
titanium. Not only that, but it also coordinates itself to one of the chlorine atoms adjacent to the
titanium. But titanium still has one empty orbital left to be filled.
So then a vinyl monomer like propylene comes along. There are two electrons in the π-system of
a carbon-carbon double bond. Those electrons can be used to fill the empty orbital of the
titanium. We say that the propylene and the titanium form a complex, and we draw it like this:

Natta- Bimetallic Polymerization mechanism

Copolymerization
Copolymerization of ethylene and α-olefins have been demonstrated soon after the discovery
that Ziegler-Natta catalysts homopolymerize α-olefins. Copolymers have gained much interest in
polymer field due to their elastomeric characteristics. Therefore, many research works were
carried out to prepare better catalyst systems and to obtain more interesting elastomeric
copolymers. The properties of the copolymers formed can be controlled by operating conditions,
chemical composition and physical state of catalyst and comonomers structure. The most
Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 9/19
important copolymer is prepared from ethylene and propylene. The production of ethylene-
propylene copolymers were traditionally carried out with homogenous Ziegler-Natta catalyst
based on vanadium compounds. The application of the Ziegler-Natta heterogenous catalytic
system based on titanium compounds for the production of copolymers has recently become
more important, due to high activity of the catalyst systems and low production costs. The best
coordinated anionic type catalyst suitable for the production of ethylene-propylene copolymers
are obtained by reaction of alklyaluminium compounds with transition metals such as vanadium,
chromium, niobium and titanium. Recently, Soga and coworkers53 successfully copolymerized
ethylene and propylene using a soluble chromium catalytic system composed of
Cr(C17H35COO)3 and AlEt2Cl. The catalytic system produced random copolymer with a narrow
molecular weight distribution.
Kinetics of Copolymerization
Although radical copolymerization has been more extensively studied and is more
important than ionic copolymerization, we will consider the general case without specification as
to whether the mode of initiation is by a radical, anionic, or cationic species. Copolymerization
of the two monomers leads to two types of propagating species—one with M1 at the propagating
end and the other with M2. These can be represented by M1* and M2* where the asterisk
represents either a radical, a carbocation, or a carbanion as the propagating species depending on
the particular case. If it is assumed that the reactivity of the propagating species is dependent
only on the monomer unit at the end of the chain (referred to as the end or ultimate unit), four
propagation reactions are then possible. Monomers M1 and M2 can each add either to a
propagating chain ending in M1 or to one ending in M2, that is,

K11
M1 * + M1 → M1* 1

k12
M1 * + M2 → M2* 2

k21
M2 * + M1 → M1* 3

K22
M2 * + M2 → M2 * 4

where k11 is the rate constant for a propagating chain ending in M1 adding to monomer
M1, k12 that for a propagating chain ending in M1 adding to monomer M2, and so on. The
propagation of a reactive center by addition of the same monomer (i.e., Reaction1-4) is often
referred to as homopropagation or self-propagation; propagation of a reactive center by addition
of the other monomer (Reactions 2 and 3) is referred to as cross propagation or a crossover
reaction. All propagation reactions are assumed to be irreversible.
Monomer M1 disappears by Reactions 1 and 3, while monomer M2 disappears by
Reactions 6-3 and 6-5. The rates of disappearance of the two monomers, which are synonymous
with their rates of entry into the copolymer, are given by

-d[M1]/dt = k11[M1][M1] + k21[M2][M1] 5

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 10/19

-d[M2]/dt = k12[M1 *][M2] + k22[M2*][M2] 6

Dividing Eq. 6-6 by Eq. 6-7 yields the ratio of the rates at which the two monomers enter the
copolymer, that is, the copolymer composition, as

d[M1]/d[M2] = (k11[M1][M1] + k21[M2][M1]) / ( k12[M1][M2] + k22[M2][M2]) 7

In order to remove the concentration terms in M1* and M2* from Eq. 7, a steady-
state concentration is assumed for each of the reactive species M1* and M2* separately. For the
concentrations of M1* and M2* ro remain constant, their rates of interconversion must be equal.
In other words, the rates of Reactions 2 and 3 must be equal:

K21[M2*][M1*] = k12[M1*][M2] 8

Equation 8 can be rearranged and combined with Eq. 7 to yield

d[M1] / d[M2]=((k11k21[M2][M1]2 / k12[M2])+k21[M2][M1])/k22[M2][M2] + k21[M2][M1] 9

Dividing the top and bottom of the right side of Eq. 6-10 by k21[M2*][M1] and combining the
result with the parameters r1 and r2, which are defined by
r1=k11/k12 and r2=k22 / k21 10
one finally obtains
d[M1] / d[M2] = [M1] (r1[M1] + [M2]) / [M2] ( [M1] + r2 [M2]) 11

Equation 11 is known as the copolymerization equation or the copolymer composition

equation. The copolymer composition, d[M1] = d[M2], is the molar ratio of the two monomer
units in the copolymer. d[M1] = d[M2] is expressed by Eq. 6-12 as being related to the
concentrations of the two monomers in the feed, [M1] and [M2], and the parameters r1 and r2. The
parameters r1 and r2 are termed the monomer reactivity ratios. Each r as defined above in Eq. 6-
11 is the ratio of the rate constant for a reactive propagating species adding tis own type of
monomer to the rate constant for its additon of the other monomer.The tendency of two
monomers to copolymerize is noted by r values between zero and unity. An r1 value greater than
unity means that M1* preferentially adds M1 instead of M2, while an r1 value less than unity
means that M1* preferentially adds M2. An r1 value of zero would mean that M1 is incapable of
undergoing homopolymerization.
The copolymerization equation can also be expressed in terms of mole fractions instead
of concentrations. If f1 and f2 are the mole fractions of monomers M1 and M2 in the feed, and F1
and F2 are the mole fractions of M1 and M2 in the copolymer, then
f1 = 1 - f2 = [M1] / ([M1] + [M2]) 12
and
F1 = 1 - F2= d[M1] / (d[M1] + d[M2]) 13
Combining Eqs. 12 and 13 with above Eq. yields
F1 = (r1f12 + f1f2) / (r1f12 +2f1f2 + r2 f22)
or

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 11/19

f1 / f2 = f1(r1f1+ f2) / f2 (r2f2+ f1) 14
The equation 14 gives the copolymer composition as the mole fraction of monomer M 1 in the
copolymer and is often more convenient to use than the previous form of the copolymerization
equation.

Types of copolymers

Different types of copolymers

Since a copolymer consists of at least two types of constituent units (also structural units),
copolymers can be classified based on how these units are arranged along the chain.[3] These
include:

 Alternating copolymers with regular alternating A and B units (structure 2 in diagram)

 Periodic copolymers with A and B units arranged in a repeating sequence (e.g. (A-B-A-B-
B-A-A-A-A-B-B-B)n)
 Statistical copolymers are copolymers in which the sequence of monomer residues follows
a statistical rule. If the probability of finding a given type monomer residue at a particular
point in the chain is equal to the mole fraction of that monomer residue in the chain, then the
polymer may be referred to as a truly random copolymer[4] (structure 3).
 Block copolymers comprise two or more homopolymer subunits linked by covalent bonds
(structure 4). The union of the homopolymer subunits may require an intermediate non-
repeating subunit, known as a junction block. Block copolymers with two or three distinct
blocks are called diblock copolymers and triblock copolymers, respectively.
Copolymers may also be described in terms of the existence of or arrangement of branches in
the polymer structure. Linear copolymers consist of a single main chain whereas branched
copolymers consist of a single main chain with one or more polymeric side chains.
Other special types of branched copolymers include star copolymers, brush copolymers,
and comb copolymers. In gradient copolymers the monomer composition changes gradually
along the chain.
A terpolymer is a copolymer consisting of three distinct monomers. The term is derived
from ter (Latin), meaning thrice, and polymer.

 Stereoblock copolymers
Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 12/19
A special structure can be formed from one monomer where now the distinguishing feature is
the tacticity of each block.
Statistical copolymers
Statistical copolymers are dictated by the reaction kinetics of the two chemically distinct
monomer reactants, and are commonly referred to interchangeably as “random” in the polymer
literature. As with other types of copolymers, random copolymers can have interesting and
commercially desirable properties that blend those of the individual homopolymers. Examples of
commercially relevant random copolymers include rubbers made from styrene-butadiene
copolymers and resins from styrene-acrylic or methacrylic acidderivatives.[6] Copolymerization
is particularly useful in tuning the glass transition temperature, which is important in the
operating conditions of polymers; it is assumed that each monomer occupies the same amount of
free volume whether it is in a copolymer or homopolymer, so the glass transition temperature
falls between the Tg of each homopolymer and is dictated by the mole or mass fraction of each
component.
A number of parameters are relevant in the composition of the polymer product; namely, one
must consider the reactivity ratio of each component. Reactivity ratios describe whether the
monomer reacts preferentially with a segment of the same type or of the other type. For example,
a reactivity ratio that is less than one for component 1 indicates that this component reacts with
the other type of monomer more readily. Given this information, which is available for a
multitude of monomer combinations in the “Wiley Database of Polymer Properties”, the Mayo-
Lewis equation can be used to predict the composition of the polymer product for all initial mole
fractions of monomer. This equation is derived using the Markov model, which only considers
the last segment added as affecting the kinetics of the next addition; the Penultimate Model
considers the second-to-last segment as well, but is more complicated than is required for most
systems. When both reactivity ratios are less than one, there is an azeotropic point in the Mayo-
Lewis plot. At this point, the mole fraction of monomer equals the composition of the component
in the polymer.
There are several ways to synthesize random copolymers. The most common synthesis method
is free radical polymerization; this is especially useful when the desired properties rely on the
composition of the copolymer rather than the molecular weight, since free radical polymerization
produces relatively disperse polymer chains. Free radical polymerization is less expensive than
other methods, and produces high-molecular weight polymer quickly. Several methods offer
better control over dispersity. Anionic polymerization can be used to create random copolymers,
but with several caveats: if carbanions of the two components do not have the same stability,
only one of the species will add to the other. Additionally, anionic polymerization is expensive
and requires very clean reaction conditions, and is therefore difficult to implement on a large
scale.[5] Monodisperse random copolymers are also synthesized by ″living″ controlled radical
polymerization methods, such as atom-transfer radical-polymerization (ATRP), nitroxide
mediated radical polymerization(NMP), or Reversible addition−fragmentation chain-transfer
polymerization (RAFT). These methods are favored over anionic polymerization because they
can be performed in conditions similar to free radical polymerization. The reactions require

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 13/19

longer experimentation periods than free radical polymerization, but still achieve reasonable
reaction rates.
Graft copolymers
Graft copolymers are a special type of branched copolymer in which the side chains are
structurally distinct from the main chain. The illustration (structure 5) depicts a special case
where the main chain and side chains are composed of distinct homopolymers. However, the
individual chains of a graft copolymer may be homopolymers or copolymers. Note that different
copolymer sequencing is sufficient to define a structural difference, thus an A-B diblock
copolymer with A-B alternating copolymer side chains is properly called a graft copolymer.
For example, suppose we perform a free-radical polymerization of styrene in the presence
of polybutadiene, a synthetic rubber, which retains one reactive C=C double bond per residue.
We get polystyrene chains growing out in either direction from some of the places where there
were double bonds, with a one-carbon rearrangement. Or to look at it the other way around, the
result is a polystyrene backbone with polybutadiene chains growing out of it in both directions.
This is an interesting copolymer variant in that one of the ingredients was a polymer to begin
with.
As with block copolymers, the quasi-composite product has properties of both "components". In
the example cited, the rubbery chains absorb energy when the substance is hit, so it is much less
brittle than ordinary polystyrene. The product is called high-impact polystyrene, or HIPS.
Block copolymers
One kind of copolymer is called a "block copolymer". Recently the terminology "block polymer"
has been used. Block copolymers are made up of blocks of different polymerizedmonomers and
is usually made by first polymerizing styrene, and then subsequently polymerizing methyl
methacrylate (MMA) from the reactive end of the polystyrene chains. This polymer is a "diblock
copolymer" because it contains two different chemical blocks. Triblocks, tetrablocks,
multiblocks, etc. can also be made. Diblock copolymers are made using living
polymerization techniques, such as atom transfer free radical polymerization (ATRP), reversible
addition fragmentation chain transfer (RAFT), ring-opening metathesis polymerization (ROMP),
and living cationic or living anionic polymerizations.[11] An emerging technique is chain
shuttling polymerization.
The "blockiness" of a copolymer is a measure of the adjacency of comonomers vs their
statistical distribution. Many or even most synthetic polymers are in fact copolymers, containing
about 1-20% of a minority monomer. In such cases, blockiness is undesirable.

Copolymer Composition
Terminal Model; Monomer Reactivity Ratios
The instantaneous copolymer composition—the composition of the copolymer formed at
very low conversions (about <5%)—is usually different from the composition of the comonomer
feed from which the copolymer is produced, because different monomers have differing
tendencies to undergo copolymerization. It was observed early that the relative copolymerization
tendencies of monomers often bore little resemblance to their relative rates of
homopolymerization [Staudinger and Schneiders, 1939]. Some monomers are more reactive in

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 14/19

copolymerization than indicated by their rates of homopolymerization; other monomers are less
reactive. Further, and most dramatically, a few monomers, such as maleic anhydride and
stilbene undergo facile copolymerization with radical initiation, although they have very little or
no tendency to undergo homopolymerization.
The composition of a copolymer thus cannot be determined simply from a knowledge of
the homopolymerization rates of the two monomers. The determinants of copolymerization
composition have been elucidated by several workers by assuming the chemical reactivity of the
propagating chain (which may be a free radical, carbocation, or carbanion) in a copolymerization
is dependent only on the identity of the monomer unit at the growing end and independent of the
chain composition preceding the last monomer unit [Alfrey and Goldfinger, 1944; Mayo and
Lewis, 1944; Wall, 1944; Walling, 1957]. This is referred to as the firstorder Markov or terminal
model of copolymerization. Consider the case for the copolymerization of the two monomers M1
and M2.

Q–e Scheme
Various attempts have been made to place the radical–monomer reaction on a quantitative
basis in terms of correlating structure with reactivity. Success in this area would give a better
understanding of copolymerization behavior and allow the prediction of the monomer reactivity
ratios for comonomer pairs that have not yet been copolymerized. A useful correlation is the Q –
e scheme of Alfrey and Price [1947], who proposed that the rate constant for a radical–monomer
reaction, for example, for the reaction of M1• radical with M2 monomer, be written as

K12 = P1Q2 exp(-e1e2) 15

where P1 represents the intrinsic reactivity of M1• radical, Q2 represents the intrinsic reactivity of
M2 monomer, e1 represents the polarity of M1• radical, and e2 represents the polarity of M2
monomer. By assuming that the same e value applies to both a monomer and its corresponding
radical (i.e., e1 defines the polarities of M1 and M1•, while e2 defines the polarities of M2 and
M2•), one can write expressions for k11, k22, k21 analogous to Eq. 15. These can be appropriately
combined to yield the monomer reactivity ratios in the forms
r1 =Q1/ Q2 exp[-e1(e1 - e2)] 16
r2 = Q2/ Q1 exp[-e2(e2 – e1)] 17
which correlate monomer–radical reactivity with the parameters Q1, Q2, e1, and e2. The basis of
the Q–e scheme (Eqs. 15 to 17) is the theoretically unsatisfactory suggestion that the alternating
tendency is due to ground-state electrostatic interactions between permanent charges in the
monomer and radical [Price, 1948].
Although there have been attempts to place it on a solid theoretical basis [Colthup, 1982;
O’Driscoll and Yonezawa, 1966], the Q–e scheme is best considered as an empirical approach to
placing monomer reactivity on a quantitative basis. Monomer reactivity is separated into the
parameter Q, which describes the resonance factor (and to a slight extent the steric factor)
present in the monomer, and the parameter e, which describes the polar factor.
Consider now the use of the Q–e shceme to predict monomer reactivity ratios. Values of
Q and e have been assigned to monomers on the basis of their r values and the arbitrarily chosen
reference values of Q = 1 and e = - 80 for styrene [Greenley, 1989b, 1999]. Table 6-7 shows the

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 15/19

average Q and e values for some common monomers. The practical success of the Q–e scheme
in predicting the r1 and r2 values for comonomer pairs not previously copolymerized has been
limited in its quantitative aspects. The reason for this is that the Q and e values for a monomer
are not unique values for both experimental and theoretical reasons. The precision of the
calculated Q and e values is often poor as a result of inaccuracies in the experimentally
determined r values. Further, the Q and e values for a monomer vary considerably depending on
the monomer with which it is copolymerized as a result of inherent deficiencies of the Q–e
scheme. It does not explicitly take into account steric factors that may affect monomer reactivity
ratios for certain radical–monomer combinations. The assumption of the same e value for a
monomer and its corresponding radical is also inadequate. Attempts to refine the Q–e scheme by
using separate e values for monomer and radical have not been successful.
In spite of these deficiencies the Q–e scheme is a reasonable qualitative and even semi
quantitative approach to the effect of structure on monomer reactivity. It can be used to give a
general idea of the behavior to be expected from a comonomer pair that has not been studied.
The Q–e values can be used to more quantitatively discuss reactivity data such as those in Table
6-4 and 6-6. The monomers are lined up in Table 6-6 in order of their e values. This order
defines the polarities of the various monomers. The relative importance of resonance and polar
factors in determining monomer reactivity can be discussed by considering the data in Table 6-4
in terms of the Q and e values of the monomers.
The various reference radicals can be divided into two groups: one composed of the
relatively unreactive radicals and the other composed of reactive radicals. For the reactive
radicals, such as vinyl chloride and vinyl acetate, monomer reactivity depends on Q with k12
increasing with increasing Q and polar effects are too subtle to discern. The unreactive radicals
from styrene and, 3-butadiene show the same trends except that one can discern the polar effects.
There is enhanced reactivity of these radicals (processing negative e values) toward a onomer
such as acrylonitrile with relatively high positive e values. The resonance factor is, however,
more important than the polar factor; the former determines the magnitude of monomer
reactivity. Thus monomer reactivities toward the 1,3-butadiene and styrene radicals fall into two
groups—one group of monomers with high Q values and high reactivities and another group
with low Q values and low reactivities.
A number of useful generalizations are possible regarding which pairs of monomers will
copolymerize and the behavior to be expected. Copolymerization proceeds poorly with
monomers whose Q values are very different, since copolymer formation would require the
energetically unfavorable conversion of a resonance-stabilized radical to a less stabilized radical
and vice versa . Thus vinyl chloride and vinyl acetate do not copolymerize well with styrene or
1,3-butadiene. Copolymerization is more suitable between monomers of similar Q values,
preferably high Q values, for example, styrene and 1,3-butadiene. Ideal copolymerization occurs
between two monomers having similar Q and e values, for example, styrene–1,3-butadiene, vinyl
chloride–vinyl acetate, and acrylonitrile–methyl acrylate. The tendency toward alternation is
greatest for monomers having the same Q values with high e values of opposite sign.
TABLE: Q and e Values for Monomersa; a Data from Greenley [1989b, 1999].
Monomer Q e
Ethyl vinyl ether 0.018 -1.80

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 16/19

Propene 0.009 -1.69
N-Vinylpyrrolidone 0.088 -1.62
n-Butyl vinyl ether 0.038 -1.50
p-Methoxystyrene 1.53 -1.40
Isobutylene 0.023 -1.20
Vinyl acetate 0.026 -0.88
α-Methylstyrene 0.97 -0.81
Styrene 1.00 -0.80
Isoprene 1.99 -0.55
1,3-Butadiene 1.70 -0.50
Ethylene 0.016 0.05
Vinyl chloride 0.056 0.16
Vinylidene chloride 0.31 0.34
Methyl methacrylate 0.78 0.40
Acrylamide 0.23 0.54
Methacrylic acid 0.98 0.62
Methyl acrylate 0.45 0.64
Methacrylonitrile 0.86 0.68
Vinyl fluoride 0.008 0.72
4-Vinylpyridine 2.47 0.84
Acrylic acid 0.83 0.88
Methyl vinyl ketone 0.66 1.05
Diethyl maleate 0.053 1.08
Acrylonitrile 0.48 1.23
Tetrafluoroethylene 0.032 1.63
Diethyl fumarate 0.25 2.26
Fumaronitrile 0.29 2.73
Maleic anhydride 0.86 3.69

Reference book
R1: M.S Bhatnagar,2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

POSSIBLE QUESTIONS

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 17/19

Multiple choice questions (Each Carry 1 Marks)

1. The polyethene polymer formed by the addition polymerisation process using the Ziegler-
Natta catalyst is a?
a. High density and high melting point b. Low density and high melting point
c. High density and low melting point d. Low density and low melting point
2. The catalyst used for the Ziegler–Natta polymerizations?
a. TiCl3 with Al(C2H5)2Cl b. BCl3 with Al(C2H5)2Cl c. TiCl3 with Fe(C2H5)2Cl
d. TiF3 with Al(C2H5)2F
3. Melting Point of Low Density Polyethylene (LDPE) is?
a. ~115º C b. ~116 ºC c. ~117ºC d.~118ºC
4. Which polymer is not an copolymer?
a. CCDDDCCDDDCCD b. AAAAAAAAAAA c. BBBBBBBAAAAAAA
d. CCCDDCCCDDCCC
5. The metal in the co-catalyst is come from
a. I to III b. III to IV c. IV and V d. IV-VIII
6. R-Ti-Cl4 is an
a. bi-metallic catalyst b. mono metallic catalyst c. tri metallic catalyst
d. alkyl catalyst
7. Monometallic mechanism proposed by
a. Natta b. Cossee c. Robert d. Wilson
8. The Ti metal have a ---- number of co-ordination
a. 5 b. 4 c. 7 d. 6
9. Ti halide is acting as a
a. adsorbate b. co-catalyst c. secondary catalyst d. Surface catalyst
10. In the zieglar-natta catalyst the aluminium halide ------- on Ti halide
a. chemisorbed b. physisorbed c. bonded d. absorped
11. The insertition of monomer in the alternative spatial arrangement form the
a. isotactic polymer b. syndiotactic polymer c. copolymer d. radical polymer
12. Which of the following is not depend on the formation of vaccant sites
a. coming monomeric unit b. chlorine atom of catalyst c. substituent of monomer unit
d. Transition metal atom
13. Which is the step to form the activesite catalyst in co-ordination polymerization
a. initiation b. propagation c. termination d. transfermation
14. In the monometallic mechanism monmer attacks the
a. Ti-Cl bond b. Al-R bond c. Ti-R bond d. Al-Cl bond
15. Who fractionated the vinyl chloride-vinyl acetate co-polymer
a. Cossee b. Natta c. Staudinger d. Zieglar
16. Two or more monomers are combined to form
a. Co-ordination polymer b. Co-polymer c. Crystalline polymer d. Homo polymer
17. The polymer production in the co-polymerisation depends on the
a. anyone monomer unit b. reactivity ratio c. reaction path d. two monomers
18. The reactivity ratio is represented as
a. r1 b. r2 c. r1/r2 d. m1/m2
19. [m1] and [m2] represents the
a. mole fraction b. molar concentration c. molecular mass d. number of moles

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 18/19

20. The plot between r1(assumed values) Vs r2 (calculated values) is drawn in the method of
a. Mayo-Lewis method b. Fineman-Rose method c. Lewis method d. molecular method

Questions (Each carry 6 Marks)

1. Derive the kinetic equation of co-ordination polymerization?

2. Explain the kinetics of co-polymerisation?
3. What is Co-polymer and explain its types?
4. Explain the most useful co-ordination catalyst?
5. Explain the types of co-polymerisation?
6. What is Zieglar-Natta catalyst explain it briefly?
7. Give an account about reactivity ratio?
8. Derive the kinetic equation of co-polymerization?
9. What is reactivity ratio and explain it concepts?
10. How to determine the reactivity ratio of the polymers?

Compulsory Questions (Each carry 10 Marks)

1. Explain the mono and bi metallic mechanism of co-ordination catalyst?
2. Explain the influence of reactivity ratio in the co-polymerization?

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 19/19

KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: II (CO-ORDINATION POLYMERIZATION) BATCH-2017-2019

Questions Opt-1 Opt-2 Opt-3 Opt-4 Answers

The alternating copolymer 2 monomer 3 monomer

1 4 monomer units 1 monomer units 2 monomer units
contains ? units units

2 The copolymer is not an? Alloy Trimer Monomer Initiator Alloy

The polyethene polymer

formed by the addition High density Low density and
High density and low Low density and High density and
3 polymerisation process and high high melting
melting point low melting point high melting point
using the Ziegler- Natta melting point point
catalyst is a?
The catalyst used for the
TiCl3 with BCl3 with TiCl3 with Fe(C2H TiF3 with Al(C2H TiCl3 with Al(C2H
4 Ziegler–Natta
Al(C2H 5)2Cl Al(C2H 5)2Cl 5)2Cl 5)2F 5)2Cl
polymerizations?
Melting Point of Low
5 Density Polyethylene (LDPE) ~115o C ~116 oC ~117oC ~118 oC ~115o C
is?

Which polymer is not an CCDDDCCDDDC

6 AAAAAAAAAAA BBBBBBBAAAAAAA CCCDDCCCDDCCC AAAAAAAAAAA
copolymer? CD

Which, speeds up the

7 oxidation process in Heat Catalyst Initiator Reactants Heat
polymerization?
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Highly unsaturated
8 polymers are much more Reduction Addition Oxidation Redox oxidation
sensitive to ?

Stability of a polymer Physical Chemical Chemical

Physical properties Chemical structure
9 depends on? structure properties structure

10 Most polymers are? Thermally stable Physically stable Chemically stable Unstable Thermally stable

Carbon Black and other

11 colorants may also protect Temperature Melting point Pressure Light Light
plastics from the effects of?
2-
Hydroxybenzop Hydroxybenzophen
12 Ultraviolet absorber is? hydroxyphenyl Hindered amines Benzophenones
henones ones
benzotriazoles
Any of a group of
substances that are used in
plastics to impart viscosity,
13 Light stabilizers Colouarants Plasticizers Flame retardents Plasticizers
flexibility, softness to the
finished product is defined
as?
Which of the following is
Zieglar-natta
14 used to form a stereo co-polymer Acid catalyst Zieglar-natta catalyst alkyl catalyst
catalyst
regular polymer

higher alpha olefins form isotactic syndiotactic

15 stereo polymer copolymer isotactic polymer
the polymer polymer
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Polymerization reaction
done by the presence of co-ordinaion co- addition chain co-ordinaion
16
organo-metallic compounds polymerisation polymerization polymerisation polymerization polymerisation
is
In the zieglar-natta catalyst,
17 I to III III to IV IV and V IV-VIII I to III
the alkyl metals from group

The metal in the co-catalyst

18 I to III III to IV IV and V IV-VIII IV-VIII
is come from

bi-metallic mono metallic mono metallic

19 R-Ti-Cl4 is an tri metallic catalyst alkyl catalyst
catalyst catalyst catalyst

Monometallic mechanism
20 natta cossee Robert Wilson cossee
proposed by

The Ti metal have a ----

21 5 4 7 6 5
number of co-ordination

22 Ti halide is acting as a adsorbate co-catalyst secondary catalyst Surfae catalyst Surfae catalyst

In the zieglar-natta catalyst

23 the aluminium halide ------- chemisorbed physisorbed bonded absorption chemisorbed
on Ti halide

In the Zieglar-natta catalyst,

24 vacant d-orbital vacant p-orbital filled d-orbitals filled p-orbitals vacant d-orbital
the Ti halide have a
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Which of the following is the

metal in I-III only in II group metal in IV-VIII
25 active site of the zieglar- metal in I group metal in IV-VIII group
group metal group
natta catalyst

In the bi metallic mechanism intermediate

26 bi-complex intermediate ion Catalyst bi-complex
forms the compound

Which of the following

27 metal is not present in the Ti Mo V Li Li
zieglar-natta catalyst

The metal present in the

28 non-metal semi metal taransition metal radio-active metal taransition metal
zieglar-natta catalyst is

Which of the following is

zieglar-natta zieglar-natta
29 used for the stereo-regular Acid catalyst basic catalyst intermediate
catalyst catalyst
polymer
The insertition of monomer
isotactic syndiotactic
30 in the same spatial copolymer radical polymer isotactic polymer
polymer polymer
arrangement form the
The insertition of monomer
isotactic syndiotactic syndiotactic
31 in the alternative spatial copolymer radical polymer
polymer polymer polymer
arrangement form the
which of the following is not
coming chlorine atom substituent of Transition metal Transition metal
32 depent on the formation of
monomeric unit of catalyst monomer unit atom atom
vaccant sites
In the syndiotactic polymer,
33 the substituent monomer alternative sites same position opposit position regular postion alternative sites
units are insert in the
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In the isotactic polymer, the

opposite either same or
34 monomer insertition in the - Same direction alternative direction Same direction
direction alternative
-- spatial arrangements

Which is the step to form

35 initiation propagation termination transfermation propagation
the activesite catalyst

In the monometallic
36 mechanism monmer attacks Ti-Cl bond Al-R bond Ti-R bond Al-Cl bond Ti-R bond
the
Who fractionated the vinyl
37 chloride-vinyl acetate co- Cossee natta Staudinger Zieglar Staudinger
polymer

Two or more monomers are co-ordination

38 co-polymer crystalline polymer homo polymer co-polymer
combined to form polymer

The polymer production in

anyone
39 the co-polymerisation reactivity ratio reaction path two monomers reactivity ratio
monomer unit
depends on the

The reactivity ration is

40 r1 r2 r1/r2 m1/m2 r1/r2
represented as

The r1>1 means the neither M1 nor

41 M1 monomer M2 monomer either M1 or M2 M1 monomer
preference of the add M2

The r2 > 1 prefer the neither M1 nor

42 M1 monomer M2 monomer either M1 or M2 M2 monomer
addition of M2
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: II (CO-ORDINATION POLYMERIZATION) BATCH-2017-2019

The two monomers in the

co-polymerisation have ideal co- alternative co-
43 block polymer non-ideal polymer ideal co-polymer
same prefernce of addition polymer polymer
to produce
In the ideal co-polymer, the
44 1 0 not equal to 0 not equal to unity 1
reactivity ratio is equal to

In the alternating co-

45 polymer, the reactivity ratio 0 1 not equal to 0 above 1 0
is equal to
In which of the following
46 condition form the block co- r1/r2 = 1 r1/r2 = 0 r1,r2<1 r1,r2>1 r1,r2>1
polymer
The over all rate of co-
propagation both inition and both inition and
47 polymerization depends on inition step only termination step only
step only termination termination
the

Most of the graft polymers chain co-ordination Ionic radical

48 radical polymerization
are formed by polymerization polymerization polymerization polymerization

[m1] and [m2] represents molar

49 mole fraction molecular mass number of moles mole fraction
the concentration

the plot between

r1(assumed values) Vs r2 Mayo-Lewis Finemann-Rose Mayo-Lewis
50 Lewis method molecular method
(calculated values) is drawn method method method
in the method of
Mayo-Lewis Finemann-Rose Finemann-Rose
51 equation belongs to the Lewis method molecular method
method method method
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the slope of graph in the

52 fineman-ross method give M P r1 r2 r1
the value of
In the fineman-Ross
negative r1
53 method, the ordinate r1 value negative r2 value positive r1 value negative r2 value
value
intercept give the
Which of the following
condition make the M1
radical prefers to add M2
54 r1/r2 = 0 r1,r2<1 r1,r2>1 r1=r2=0 r1=r2=0
monomer and the M2
radical prefer to add M1
monomer
Which of the following
condition make the both M1
55 and M2 radical have same r1=r2 = 1 r1,r2<1 r1,r2>1 r1=r2=0 r1=r2 = 1
preference for M1 and M2
monomers
The composition of two an azeotropic
azeotropic co- alternating co- azeotropic co-
56 monomers are constant co- block co-polymer
polymerisation polymerization polymerisation
means it forms polymerisation
Which of the following
57 conditions form the M1 r1,r2<1 r1,r2>1 r1=r2=0 r1>1 , r2<1 r1>1 , r2<1
richer co-polymer
M1 radical prefer
M1 radical prefer
M1 radical prefer to to M1 and
M1 radical M2 radical to M2 monomer
The condition r1<1 and r2>1 M2 monomer and M2 monomer and M2
58 prefer to M1 prefer to the and M2 radical
condition preferse the radical prefer the M1 radical prefer the
monomer M2 monomer prefer the M1
monomer M1 and M2
monomer
monomer
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The r1 is less than r2, the

first increases
59 azeotropic composition increases decreases constant decreases
then decreases
should be
The r1 < 1 and r2 > 1
60 condition to form the M1 monomer M2 monomer M1 radical M2 radical M2 monomer
polymer richer in
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UNIT–III

SYLLABUS

Polydispersion – average molecular weight concept, number, weight and viscosity average
molecular weights. Measurement of molecular weights. Viscosity, light scattering, osmotic and
ultracentrifugation methods. Polymer structure and physical properties – crystalline melting
point Tm. The glass transition temperature. Determination of Tg. Relationship between Tm and
Tg.

Polydispersion

A uniform (monodisperse) collection A non-uniform (polydisperse) collection

In physical and organic chemistry, the dispersity is a measure of the heterogeneity of sizes of
molecules or particles in a mixture. A collection of objects is called uniform if the objects have
the same size, shape, or mass. A sample of objects that have an inconsistent size, shape and mass
distribution is called non-uniform. The objects can be in any form of chemical dispersion, such
as particles in a colloid, droplets in a cloud, crystals in a rock, or polymer macromolecules in a
solution or a solid polymer mass. Polymers can be described by molecular mass distribution; a
population of particles can be described by size, surface area, and/or mass distribution; and thin
films can be described by film thickness distribution.

IUPAC has deprecated the use of the term polydispersity index, having replaced it with the term
dispersity, represented by the symbol Đ (pronounced D-stroke) which can refer to either
molecular mass or degree of polymerization. It can be calculated using the equation ĐM =
Mw/Mn, where Mw is the weight-average molar mass and Mn is the number-average molar mass.
It can also be calculated according to degree of polymerization, where ĐX = Xw/Xn, where Xw is
the weight-average degree of polymerization and Xn is the number-average degree of
polymerization. In certain limiting cases where ĐM = ĐX, it is simply referred to as Đ. IUPAC

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 1/21

has also deprecated the terms monodisperse, which is considered to be self-contradictory, and
polydisperse, which is considered redundant, preferring the terms uniform and non-uniform
instead.

The dispersity index, or formerly polydispersity index (PDI), or heterogeneity index, or simply
dispersity (Đ), is a measure of the distribution of molecular mass in a given polymer sample. Đ
(PDI) of a polymer is calculated:

PDI = Mw/ Mn

Where Mwis the weight average molecular weight and Mnis the number average molecular
weight. Mnis more sensitive to molecules of low molecular mass, while Mwis more sensitive to
molecules of high molecular mass. The dispersity indicates the distribution of individual
molecular masses in a batch of polymers. Đ has a value equal to or greater than 1, but as the
polymer chains approach uniform chain length, Đ approaches unity

Since molecular weight is central to the entire polymer field, students in this short course are
assumed to understand the need for measuring polymer molecular weight and to be familiar,
from textbooks or course notes, with the basic principles underlying the most common molecular
weight measurement techniques - light scattering, osmometry, GPC, end group analysis, and
intrinsic viscosity. For some polymer samples, textbook familiarity with a method and an
instrument manual are all that is needed to make a meaningful measurement. For others, matters
are not so simple, especially if a target polymer is of a new chemistry and/or not a linear neutral
homopolymer that dissolves in an ordinary solvent.

After going through common methods in some detail, “problem” polymers and a few less common
measurement methods will be discussed. In this first handout, principles and terminology
associated with molecular weight and its distribution will be overviewed.

Methods - Some variation of the following table [adapted from Elias et al., Adv. Polym. Scil11
(1973), 111] is cited in many introductory polymer textbooks. This table lists measurement
methods by type (A=absolute, R=relative, E=equivalent), by applicable molecular weight range,
and if a specific mean molecular weight value is determined, by the type of average produced.

Molecular
Weight
Mean Value
Range, g/mol Measured
Method Typ
e

1. Membrane osmometry A 104-106 Mn

2. Ebullioscopy (boiling point elevation) A <104 Mn

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 2/21

3. Cryoscopy (freezing point depression) A <104 Mn

4. Isothermal distillation A <104 Mn

5. Vapor Phase osmometry A* <105 Mn

6. End group analysis E <105 Mn

7. Static light scattering A 102-108 Mw

8. Sedimentation equilibrium A <106 Mw, Mz, Mz=1

9. Sedimentation in a density gradient A >105 depends

10. Sedimentation velocity/diffusion A 103-108 depends

11. Solution viscosity R 102-108 M

12. Gel Permeation Chromatography R 102-107 different values

“absolute” – the measurement is directly related to the molecular weight without assumptions
about chemical and/or physical properties of the polymer

“equivalent” – the chemical structure of the polymer must be known to obtain molecular weight

“relative” – the quantity measured depends on the physical structure of the tested polymer and so
a calibration curve relating measurement and molecular weight values must be known a priori;
typically, this molecular weight calibration is established by companion measurements on a
series narrow molecular weight polydispersity standards of the same chemical and physical
structure as the tested polymer

Classification of Methods -

Calibration: The terms “absolute”, “relative”, and “equivalent” are not always distinct. GPC, for
example, may be absolute or relative, depending on the method of calibration. Vapor phase
osmometry, as presented in the method’s underlying theory, is an absolute method, but in actual
practice, the instrument requires calibration with a standard compound of known molecular
weight, making the method relative. Even an absolute method such as mass spectrometry is
usually calibrated by molecular weight standards.

Molecular Weight Range: Molecular weight ranges for each method are limited by constraints
unique to that method. These limits will be discussed separately as methods are introduced.

Molecular Weight Averages: The common molecular weight averages (Mn, Mw, Mz, Mz+1) are
well understood by polymer students; they are associated with increasingly higher moments of

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 3/21

the molecular weight distribution. However, students often do not grasp why different
experimental methods are sensitive to different averages.

1.3 Why Different Methods Provide Different Molecular Weight Averages

If the quantity measured by a given method directly manifests the number of polymer molecules
- but not their molecular weights - this quantity can only be used to deduce Mn.

As an example, consider vapor phase osmometry. In a thermodynamically ideal solution, vapor

pressure  is lowered by kT/V as each nonvolatile solute molecule of molecular mass M is added
to volume V of volatile solvent. The lowered vapor pressure  of N polymer solutes is thus
NkT/V, a combination independent of M but dependent on N. Upon writing this product in
terms of c, the mass concentration of the solutes, M merges as a measurable parameter,

N c
  kT = kT
V M

so that

c
M = kT


For the polydisperse molecular weight case, suppose that Ni polymers of molecular weight Mi
are added to the solvent, each molecular weight fraction i in the mixture present at mass
concentration ci. Only the total mass concentration c [=ci] is known and only  measured,
the latter parameter summing contribution kT/V from each molecule irrespective of M i,

kT
 =  Ni
V

Applying the formula previously analyzed for monodisperse M now yields

ckT V  ci  Vc i  Ni M i
= = = = Mn
  Ni Ni  Ni

This is the “true” average molecular weight as the word “average” is used in nontechnical
contexts.

In essence, vapor phase osmometry allows a “count” of the number of molecules in a known
mass of polymer. The same concept of molecular counting applies to all colligative property-
based measurements (colligative properties are measured in osmometry, freezing point

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 4/21

depression, boiling point elevation, etc.), which detect the solvent activity in the presence of
solute.

Contrarily, other methods manifest not just the number of dissolved molecules but also their
molecular weight.Consider static light scattering. In the absence of optical interference, each
polymer molecule dissolved in a fixed volume of solution contributes equally to the measured
quantity, the reduced scattered intensity R (R=Rayleigh factor or ratio),

N c
R k = k
V M

where k is a molecular contrast factor (reflecting the optical contrast between polymer and
solvent surroundings, the property ultimately responsible for all light scattering phenomena).
Without inter- and intramolecular interference of scattered light, k is given by the Rayleigh
scattering formula,

16 2 2no4
k
o 4

whereno is the solvent refractive index, o is the wavelength of incident light in vacuum, and 
is the molecular polarizability.

If all subunits of a linear polymer (i.e., its repeat units) contribute equally to the polymer’s net
polarizability, as expected for a homopolymer,  is proportional to M: a longer polymer scatters
more light than a shorter one. It then follows from the above formulas that the reduced scattered
intensity R is proportional to the product of c and M.

R=KcM

where the proportionality constant K is known as the optical constant; it has no dependence on
M. By simple rearrangement,

R
M =
Kc

Contrasting vapor phase osmometry with light scattering, the contribution of individual
molecules to the measured signals are quite distinct,

N N 2
  kT vs. R M K
V V

In light scattering, each molecule contributes to the overall measurement according to the square of
its molecular weight. In osmometry, all molecules contribute equally, independently of molecular

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 5/21

weight.Turning to the analogous polydisperse molecular weight case, and using the same notation
as before, contributions to R by each molecular weight fraction simply add,

R = KciMi

The M formula for the monodisperse sample now yields

R  ci Mi  Ni M i 2
= = = Mw
Kc  ci  Ni M i

In essence, light scattering “sums” the product of the number of polymer molecules multiplied
by the square of their molecular weight.

One could naively imagine a measurement method exactly intermediate to the two just evaluated,
i.e., a method based on a property sensitive to the product of N and M. This product, however, is
simply the total mass of polymer; it could not be employed to calculate M.

Because in vapor phase osmometry and similar techniques each molecule contributes to the overall
measurement a constant, universal quantity independent of chemistry or structure, these techniques
require, at least in theory, no calibration. As the previous discussion reveals, light scattering does
require calibration, i.e., the value of K must be known to calculate M from R.

K is typically obtained by measuring the refractive index increment dn/dc as polymer is added to
solvent, and as a consequence, I would prefer the light scattering method instead be termed the
light scattering-refractive index method. The standard formula for K is written,

4 2no2 dn2
K =
 o4 N A dc 

This formula, offering K via measurement of dn/dc, is derived through an optical model that
supposes a polymer consists of independent, identical, and isotropic scattering sites immersed an
optically homogeneous medium of infinite extent. The scattering from such sites is then
proportional to the square of the scattering site-solvent optical mismatch [~(dn/dc)2], while the
contribution from such sites to solution refraction index is linearly proportional to the same
quantity [~(dn/dc]. These assumptions, due to Debye, are far from obvious. The local symmetry
of a polymer chain is cylindrical, not spherical (i.e., not isotropic); also, the interaction of light
with a single scattering site could be influenced by neighboring scattering sites. If one represents
the chain as an optically mismatched cylinder rather than a string of isotropic, optically
independent scattering sites, a slightly different prefactor appears in the theoretical formula for K.
The difference can be associated with depolarized light scattering, which fortunately, is usually
small for high M polymers.

Molecular Weight Distributions -

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 6/21

Consider ways that this molecular weight distribution might be graphically presented. Most
commonly, the distribution is shown as the raw GPC trace, which is given next. A single, well-
defined molecular weight peak is noted. [To define the molecular weight distribution better, there
should be more data points spread over the peak; I didn’t want to do more hand calculations, so the
table has only enough data to illustrate trends clearly.]
100

h i 50

0
0 10 20 30 40 50
V i (ml)

Despite this sample’s large PDI, the peak looks relatively narrow. This trace, termed the
chromatogram, is by itself is pretty meaningless, since we don’t know how M i and Viare related:
the poorer the molecular weight separation, for example, the narrower is the chromatogram peak.
Notwithstanding this trivial fact, raw GPC traces are frequently cited when arguing for low
polydispersity.

In this instance, the relationship between Mi and Vi is known by a calibration with polystyrene
standards, so we can do much better than the chromatogram. Given below are the weight and
number fraction distributions derived above.
20

x(M)

w(M), x(M) 10

w(M)
5

0
0.00 0.25 0.50 0.75 1.00 1.25

M x10 -6 (g/mol)

These bear no resemblance to the raw trace, and the significant polydispersity of the sample is
amply evident. Indeed, the x(M) curve shows that the most common polymer species has a
molecular weight of 7,200 g/mol even though Mn and Mw both exceed 100,000 g/mol.
Approximately 10% of the molecules by weight have molecular weights in excess of 800,000

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 7/21

g/mol, while 10% by weight have molecular weights less than 50,000 g/mol. The value of Mn
falls slightly above the maximum of w(M), whereas the value of Mw lies well above this
maximum, a fact commonly mentioned in introductory polymer texts. The difference between
x(M) and w(M) simply manifests that it takes many small chains to balance the mass of a few
larger chains. By number, the short chains dominate, while by weight, the converse is true.
Surveying a whole year of Macromolecules, one is likely to never see a x(M) curve and just a
handful of w(M) curves.

In most polymer situations, greatest interest lies in the logarithmic spread of M. This is the
case, for example, if we are interested in the power law exponents of polymer physics, where
an increase from 10,000 g/mol to 100,000 g/mol leads to property changes comparable to
those for an increase from 100, 000 g/mol to 1,000,000 g/mol. Unfortunately, the logarithmic
spread of M is too often incorrectly displayed in a plot that simply switches the x-axis variable
from M to log M, leaving the y-axis magnitude unchanged. [Unfortunately, my name is listed
on a paper with such an error; I didn’t see the paper until it was too late to make a correction.]

To make the logarithmic plot properly, one must recognize that the plotted functions are
distributions. Thus, the y-axis variable reflects the number of occurrences per unit change of
x-axis variable. Here, for example, w(M)dM represents the number of chains with M in the
range between M and M+dM. In logarithmic form, the y-axis variable must represent the
number of chains with log M in the range between log M and log M+dlogM. The y-axis
variable in a logarithmic plot of a distribution thus has a different functional form than the y-
axis variable in a linear plot of this same distribution. To avoid the spontaneous creation of
chains in converting plotting formats, the new y-axis variable y must be related to the old y-
axis variable y by,
y dx = ydlog(x)

Solving,

y = yx

Thus, to present the weight fraction distribution in its logarithmic form, one must plot w(M)M
vs. log M. Similarly, x(M), the number fraction distribution, must be plotted as x(M)M vs. log
M. Don’t simply check the log(x) box in the plotting software!

For the distribution of the example, these plots are given next.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 8/21

0.5

w(M)M
0.4

0.3

0.2
x(M)M

0.1

0.0
0.0 0.0 0.1 1.0

M x10 -6 (g/mol)

The peak in the logarithmic weight fraction distribution is at 430,000 g/mol, well above M w.
This value nicely corresponds to the “peak molecular weight” M p defined by the maximum of the
GPC trace. When plotted in linear rather than logarithmic form, the peak is at 80,000 g/mol,
which is quite different. Mp, although often used in GPC characterization, has no fundamental
significance unless the distribution of molecular weights is very narrow. Loose definition of M p
creates confusion. This parameter usually represents the molecular weight position of the peak in
the GPC trace.

Because the calibration curve in GPC offers an almost semi-logarithmic relationship between Vi
and Mi, the function w(M)M, the weight fraction distribution in its logarithmic form, appears
similar to a horizontal reflection of the original GPC trace.

End Group Method

The molecular weight of polymers which have an end group amenable to analysis could be
principally analyzed by an end-group assay [42]. The biggest drawback of this method is the
decrease in sensitivitywith an increased chain length. The first measurements with this method
were performed by Staudinger and Eder and gave determination limits of about 15,000 g·mol−1.
Weber and Husemann treated cellulose with an alkaline copper sulfate solution to oxidize
aldehydes to aldonic acids. Afterwards, they determined the so-called “Monosezahl” (number of
glucose units per carboxyl group). With this method, they were able to determine molecular
weights up to 200,000 g·mol−1. However, due to processing, cellulose usually already contains
oxidized end groups and additional carbonyl groups. Hence, a direct relationship between
carboxyl groups (aldonic acid) and molecular weight determined with a high rate of accuracy.

Osmotic Pressure
Osmometry is among the methods for determining molecular mass which rely on colligative
properties (from the Latin word colligerefor “collect”), meaning that only the number of
dissolved molecules influences the properties of a solution [46]. In addition, the osmotic
pressure, boiling point elevation, vapor pressure reduction, and the freezing point depression are

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 9/21

based on colligative properties. Out of the four colligative methods, only membrane osmometry
(MO) is of interest for cellulosic samples.
However, vapor pressure osmometry (VPO) is superior for analyzing samples with Mn < 20,000
g·mol−1. This is because the diffusion of low molecular weight molecules through the membrane
limits the utility of membrane osmometry for this especially low molecular weight region. Only
a few publications address the use of VPO experiments on directly-dissolved cellulose and these
will be discussed at the end of this chapter.
Since the osmotic pressure of a solution depends on molecular weight and concentration c, the
following equation can be used to determine the number average of the molecular weight

whereП is the osmotic pressure, c is the solute concentration, R is the ideal gas constant, T the
temperature, Mn is the number average, and A2 and A3 are the second and third virial
coefficients. The most common method of osmometry is membrane osmometry. In membrane
osmometry, the osmotic pressure is measured directly using a semi-permeable membrane [42]. In
experiments, the osmotic pressure must be measured at several different concentrations. By
extrapolating the П/c versus c plot to zero, the intercept gives the molecular weight, whereas
slope yields A2. Note, that A2 is an empirical constant for a given solute/solvent system and it
depends on the temperature. It represents the interaction of a single molecule with the solvent.
For the fundamental theory of osmometry.
Using osmometry for cellulose molecular weight determination creates a few problems. First, the
osmotic pressure is inversely proportional to molecular weight, so molecules with a high
molecularweight contribute very little. Therefore, the sample must be free of low molecular
compounds when applying osmometry. This is especially true for salts and, therefore, for
aqueous cellulose solutions. This is the main reason that osmometry is ordinarily used with
cellulose derivatives in organic solvents.
In most cases, cellulose-based membranes such as cellophane or bacterial cellulose are used for
membrane osmometry. However, these membranes are not completely resistant against solvents
used for cellulose. Hence, the usual cellophane membrane gels which are used in an osmometer
would dissolve in, for example, cuen solutions.
Working with those membranes, they measured the molecular weights of two cellulose samples
directly. Since cellulose in cuen behaves as a polyelectrolyte, they faced another problem beyond
membrane instability. However, by proper conditioning of the membranes, the polyelectrolyte
character of the solution can be compensated and allow for a valid measurement. Immergut’s
paper is one of the few dealing with the direct osmometry of pure cellulose.
This method continues to play a minor role today, even for derivatized cellulose.
It is worth noting that osmometry was originally used to determine the relationship between
intrinsic viscosity and molecular weight. It has been shown that under mild conditions, the
degradation during cellulose nitration is negligible. In his pioneering work, Staudinger used the
osmometry of cellulose nitrates in acetone to determine the constant Kcmof the Staudinger
Equation:

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 10/21

whereηris the relative viscosity (see Chapter 2.4), M is the molecular weight, and Kcmis the
molecular weight-concentration constant. The Staudinger equation was later the basis for the
Mark-Houwinkequation (see Chapter 2.4).
Using VPO instruments with increased sensitivity, Kamideet al. detected an upper limit of 1 ×
105 g·mol−1. Compared with the results for cellulose acetate obtained by MO and SEC, VPO
values differed by only a small percentage.

Ultracentrifugation
When polymer chemistry was in its early stages in the 1920s, analytical ultracentrifugation
experiments played an important role. Svedberg introduced two analytical ultracentrifugation
methods: the sedimentation velocity method and the sedimentation equilibrium method [56]. The
sedimentation velocity method (performed at, for example, 70,000 RPM) provides information
on the physical homogeneity of a sample, its conformation, interaction or co-sedimentation, and
flexibility information.
The sedimentation equilibrium, which is carried out at lower rotor speeds such as 15,000 RPM,
yields information on absolute weight averages (Mw, and Mz) and molecular weight
distributions.
Ultracentrifugation is also capable of measuring the molecular charge in polysaccharides.
Diffusion parameters can also be obtained by ultracentrifugation experiments; however, strictly
speaking, diffusion has nothing to do with ultracentrifugation, though it is very closely connected
to the theoretical and practical background. See Vollmert [57] for a detailed theoretical
discussion.
The first studies of cellulose in which ultracentrifugation was used were performed by Stamm
between 1926 and 1930. Stamm investigated cellulose dissolved in cuprammonium
(tetraaminecopper(II) sulfate) and cellulose xanthogenate in diluted alkali solutions. He and his
coworkersinvestigated the state of dispersion of cellulose in cuprammonium solutions. They
found diffusioncoefficients of cellulose and also claimed that cellulose was uniform with a
molecular weight of 55,000 ± 7000 g·mol−1. However, they realized that under an oxygen
atmosphere, the cellulose is degraded.
A typical equilibrium run time was 190 h; therefore, severe degradation of the molecule during
the measurements can be assumed.
Gralén and Svedberg measured cellulose in cuprammonium solutions under a nitrogen
atmosphere.
In the area of synthetic polymers, ultracentrifugation experiments have been nearly completely
replaced by other techniques. For biopolymers, especially cellulose, ultracentrifugation still plays
a minor role in analytics. Two recent review articles published by Harding et al. discuss the
possibilities of ultracentrifugation experiments in polysaccharide analysis today; especially in
combination with SEC and MALLS, it can provide complementary information such as the
heterogeneity of materials. Like SEC-MALLS, the sedimentation equilibrium method provides a
molecular weight distribution, although there is no column or separation device and therefore no
limitations concerning the column’s medium inertness or available pore sizes.
Today, the ultracentrifuge is used to obtain fundamental biophysical information about solutions
of cellulose rather than to determine molecular weight. In his perspective papers, however,
Harding demonstrated that sedimentation equilibrium is a powerful and valuable independent
check on the results generated with other methods such as SEC-MALLS experiments.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 11/21

Viscosity Method
Polymers are, in general, less soluble than their corresponding monomers. Dissolving polymers
in solvents leads to an increase in viscosity; the longer the average chain length of the polymer
molecules, the more the viscosity changes (known as positive viscosity). The viscosity of a
solution can be easily measured; therefore, viscosity measurements are widely used in
determining the average DP of cellulose.
In 1930, Hermann Staudinger was the first to recognize an empirical relationship between the
relative magnitude of the increase in viscosity and the molecular weight of the polymer [27]. The
simplest method for determining the viscosity of a polymer solution is by capillary viscometry,
using the Ubbelohde U-tube viscometer. Here, the flow time t of the polymer solution and of
pure solvent t0are recorded. The ratio of the flow time of a polymer solution t to that of pure
solvent is equal to the ratio of their viscosities (η/η0) if their densities are equal. This is only
feasible for dilute solutions (in which density differences level out). Because unity is the lower
limit of the relative viscosity ηr, the specific viscosity ηspis more useful, as it depicts the relative
increase brought about by the dissolved polymer.
Relating the specific viscosity to concentration gives the reduced viscosity. The intrinsic
viscosity is expressed as the limit of the reduced viscosity at zero concentrations. The inherent
viscosity is given as the natural logarithm of the relative viscosity divided by the concentration.
At concentration zero the inherent viscosity becomes equal to the intrinsic viscosity. Thus, either
the extrapolation of the reducedviscosity or the inherent viscosity gives the intrinsic viscosity:

For a given polymer-solvent pair the intrinsic viscosity is a unique function of molecular mass.
The Mark-Houwink (or Kuhn-Mark-Houwink-Sakurada) equation then relates the molecular
weight of the polymer plus solvent at a specified temperature to the intrinsic viscosity

Kv(or sometimes KM) and v (sometimes notated a) must be established by calibrating with
polymers of known molecular weights. Once this has been performed, only [η] will give the
molecular weight for an unknown molecule, which is normally done by plotting log [η] against
log M and subsequent interpolation.
For a theta solvent, v = 0.5, and as the solvent becomes thermodynamically better, v increases.
For most practical systems, these values can be found in data handbooks. The extrapolation
factors for cellulose to zero concentration are also listed. Under these assumptions, it is possible
to calculate the intrinsic viscosity by measuring only one concentration of the sample. Molecular
weights derived via the

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 12/21

Mark-Houwink equation and viscometry yield the viscosity average molar mass [Mv], which is
given by:

whereniis the number of molecules of molar mass Miand the exponent v is the exponent of the
Mark-Houwink equation. It should be noted that the viscosity average is not an absolute average
and depends on solvent and/or temperature; therefore, viscosity measurements yield relative
values. Mvis not a fixed quantity—it depends on v. If v becomes unity, viscosity and weight
average are equal; Mvlies therefore, in between Mn and Mw in magnitude but will be usually
closer to Mw.
Viscometry is the leading method for determining average molecular weight in industrial
applications. As a standalone method, it delivers Mvvalues, typically by using an Ubbelohde
capillary viscometer. In industrial applications, the measurement of [η] provides a quick and easy
route to the molecular weight. For viscosity measurements, a minimum requirement is the
knowledge of the dependence of [η] on (M).
The solvent most commonly used for viscometry measurements is the complex-forming solvent
cuen, largely because of its rapidity and simplicity in dissolving cellulose. One drawback of cuen
lies in the cuen solution’s high alkalinity, which may induce degradation reactions at oxidized
functionalities.
Cellulose solutions in cuen are not very stable, and the solubility for cellulose with high
molecular weight (DP > 5000) is relatively poor.
Viscometry was actually one of the first methods used to determine polymer molecular weights.
It was Hermann Staudinger who applied viscometry to cellulose analytics in the 1930s.
Staudinger described the Km value (for the Staudinger equation) of cellulose in cuen with 1 ×
10−4; in 1938 he published the Km values for cellulose in Schweizer’s Reagent as 5 × 10 −4.
It is important to remember that Kvand v are empirical constants. There are several standard
methodsfor estimating the degree of polymerization of a cellulose sample from its intrinsic
viscosity in cuensolution. In process control practices in industrial environments, the intrinsic
viscosity is often estimated from a single viscosity measurement. There are several published
warnings when using such standard methods. Evans et al. showed that the Mark-Houwink-
Sakurada (MHS) equations used in the SCAN.
The relationship between intrinsic viscosity and the DP (or the molecular weight) is very often
derived from osmometric measurements of cellulose trinitratesamples in acetone. Such
measurements date back to very early experiments and should be evaluated with modern
methods. It is commonly assumed that the molecular weight average determined by viscosity is
very close to Mw and that Mvtherefore is an approximation of Mw. In fact, Mvcan often be very
far from Mw, depending on the MHS parameters used and on the molecular weight distribution
of the sample. Only if the sample is very narrowly distributed or if uniform standards are used
can Mvbe used as an approximation of Mw. MHS parameters found in the literature can be
excessively variable, with Kvvalues ranging from 0.42 to 1.87 and v values ranging from 0.771
to 0.905.
In spite of these factors, viscometry remains a primary method for obtaining cellulose molecular
weight averages because it does not require calibration. It is also a feasible method for

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 13/21

monitoring cellulose degradation during process steps, which results in relative data. This is
mainly because it does not require advanced equipment, the method is relatively simple, and it is
specifically recommended by industrial standards. It is essential to remember that the parameters
for the Mark-Houwink equations arespecified for cellulose and that it is problematic to use such
parameters for samples with, for example, high lignin or hemicellulose content.
The equations also depend on the expected DP range; a DP larger than 950 requires a different
equation than the equation used for lower DPs. According to the current knowledge, there is no
equation available for cellulose with a large oligomeric portion, so the cuen-DP values in such
cases may be prone to error. It is standard practice to use linear fits for data when drawing a log
[n]-log Mw plot. In general, there is no justification for the linearity, and it is questionable
whether such fits are applicable forcellooligomers or samples containing oligomers in such high
amounts.
Thus far, most Mark-Houwink equations for cellulose were established for cellulose in cuen or
cadoxen solutions [68–70] because these solvents demonstrate beneficial properties for the rapid
dissolution of cellulose. However, the instability of cellulose in this solvent must be noted, as
should the limited dissolving power for very large molecules.
. The viscosity of cellulose in NMMO, a very important solvent within the technology sector,
was first measured by Eckeltet al., who reported the following equation

The Kuhn Mark-Houwink plot for cellulose in NMMO·H2O shows a non-linear behavior of the
fit. After reaching a critical value, the straight line deviates. Thus far, this study is the only paper
in which the cellulose viscosity in NMMO solutions is addressed. For analytical purposes, this
solvent system has no practical importance because of the elevated temperature it requires.

Light Scattering Methods

Scattering methods are some of the most popular methods for determining molecular weight
averages Mw. The fundamentals of the light scattering phenomena were expounded by Lord
Rayleigh in 1871.
Light scattering (LS) is one of the few absolute methods that provide access to molecular weight
and structure. Light scattering is often used as a tandem technique together with separation using
SEC [74]. As a standalone technique, it delivers the weight average Mw, the corresponding z-
average square radii < r2g >z, and the second virial coefficient A2 of cellulose. Since it is an
absolute method, it does not require calibration. One limitation of the LS method is that for a
given concentration c (g·mL−1), the scattered light signal is proportional to c × Mw, such that
molecules below a few thousand g·mol−1need relatively high concentrations in order to produce
a detectable signal. Raising the concentration of, for example, a broad distributed sample, leads
to problems, especially in the SEC portion of the process in which cellulose is analyzed. Dust
will also scatter light and contribute to the intensity; therefore, dust has to be removed using
ultra-fine filters or centrifugation prior to measurements. The source of radiation is, in most
cases, visible light from a laser; therefore, using colored solvents (e.g., Cu- and Fe-containing
complexes) is challenging and cellulose is often derivatized and dissolved in an organic solvent
or colorless solvent instead. Thus far, DMAc/LiCl is the solvent of choice for an LS experiment
coupled to an SEC.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 14/21

Measuring cellulosic samples with fluorescence activity (e.g., pulp with high lignin content) also
poses some challenges. Due to the laser excitation, even small amounts of fluorophores will
disrupt a measurement. There are two types of LS experiments: the batch mode and the
chromatographic (online) measurement. In the batch mode (off-line), MALLS detector can be
used as a standalone instrument to characterize an unfractionated polymer sample; the online use
of an LS detector is described in
In this static light scattering experiment (SLS), a vertically polarized (laser) light is scattered by
the macromolecules of a polymer in solution. The scattered light is detected by a photometer or a
photodiode: either one photometer is used to encircle the sample in a horizontal plane or several
photodiodes are placed around the measurement cell, which detects the scattered light from
several positions and angles.
The ratio:

depends on:

• The concentration of solution c;

• The specific refractive increment obtained at chemical equilibrium dn/dc or, more accurately,
(dn/dc)μ;
• The molecular weight of dissolved particles (M);
• Scattering angle θ.
The scattering intensity is dependent on the angle and reflects the diminution of the light
intensity by intra-particular interference. For light scattering experiments, the Zimm equation
forms for calculating the molecular weight:

Where K* is the optical constant, R(θ, c) is the excess Rayleigh ratio of the solution as a function
ofscattering angle θ and concentration c, Mw is the molar mass weight average, P(θ) is the
angular dependence of the scattered light, A2 is the second virial coefficient, and c is the
concentration of the solute.
The optical constant is described by the following equation:

Where dn/dc is the specific refractive increment at chemical equilibrium, Na is the Avogadro’s
Number, λ0 is the wavelength of the incident light, and n0 is the solvent refractive index.
The measured data can be extrapolated to zero concentration and zero-degree scattering angle,
which can be achieved for the batch mode by using the so-called Zimm-plot to derive three
valuable quantities: the weight average Mw, the second virial coefficient of osmotic pressure A2

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 15/21

(both with extrapolation to zero angle), and the radius of gyration (z-average) by extrapolating
the concentration to zero. The specific refractive increment at chemical equilibrium must be
measured separately by using a differential refractometer.

Polymer morphology
Polymer morphology generally describes the arrangement and microscale ordering of polymer
chains in space.
Crystallinity
When applied to polymers, the term crystalline has a somewhat ambiguous usage. In some cases,
the term crystalline finds identical usage to that used in conventional crystallography. For
example, the structure of a crystalline protein or polynucleotide, such as a sample prepared for x-
ray crystallography, may be defined in terms of a conventional unit cell composed of one or
more polymer molecules with cell dimensions of hundreds of angstroms or more.
A synthetic polymer may be loosely described as crystalline if it contains regions of three-
dimensional ordering on atomic (rather than macromolecular) length scales, usually arising from
intramolecular folding and/or stacking of adjacent chains. Synthetic polymers may consist of
both crystalline and amorphous regions; the degree of crystallinity may be expressed in terms of
a weight fraction or volume fraction of crystalline material. Few synthetic polymers are entirely
crystalline.
The crystallinity of polymers is characterized by their degree of crystallinity, ranging from zero
for a completely non-crystalline polymer to one for a theoretical completely crystalline polymer.
Polymers with microcrystalline regions are generally tougher (can be bent more without
breaking) and more impact-resistant than totally amorphous polymers.
Polymers with a degree of crystallinity approaching zero or one will tend to be transparent, while
polymers with intermediate degrees of crystallinity will tend to be opaque due to light scattering
by crystalline or glassy regions. Thus for many polymers, reduced crystallinity may also be
associated with increased transparency.
Chain conformation
The space occupied by a polymer molecule is generally expressed in terms of radius of gyration,
which is an average distance from the center of mass of the chain to the chain itself.
Alternatively, it may be expressed in terms of pervaded volume, which is the volume of solution
spanned by the polymer chain and scales with the cube of the radius of gyration.
Phase behavior
Melting point
The term melting point, when applied to polymers, suggests not a solid–liquid phase transition
but a transition from a crystalline or semi-crystalline phase to a solid amorphous phase. Though
abbreviated as simply Tm, the property in question is more properly called the crystalline melting
temperature. Among synthetic polymers, crystalline melting is only discussed with regards
to thermoplastics, as thermosetting polymers will decompose at high temperatures rather than
melt.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 16/21

Glass transition temperature
A parameter of particular interest in synthetic polymer manufacturing is the glass
transition temperature (Tg), at which amorphous polymers undergo a transition from a rubbery,
viscous liquid, to a brittle, glassy amorphous solid on cooling. The glass transition temperature
may be engineered by altering the degree of branching or crosslinking in the polymer or by the
addition of plasticizer
Glass transition
The glass–liquid transition or glass transition for short is the reversible transition
in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard
and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is
increased. An amorphous solid that exhibits a glass transition is called a glass. The reverse
transition, achieved by supercooling a viscous liquid into the glass state, is called vitrification.
The glass-transition temperature Tg of a material characterizes the range of temperatures over
which this glass transition occurs. It is always lower than the melting temperature, Tm, of the
crystalline state of the material, if one exists.
Hard plastics like polystyrene and poly(methyl methacrylate) are used well below their glass
transition temperatures,that is in their glassy state. Their Tg values are well above room
temperature, both at around 100 °C (212 °F). Rubber elastomers
like polyisoprene and polyisobutylene are used above their Tg, that is, in the rubbery state, where
they are soft and flexible.
Despite the change in the physical properties of a material through its glass transition, the
transition is not considered a phase transition; rather it is a phenomenon extending over a range
of temperature and defined by one of several conventions. Such conventions include a constant
cooling rate (20 kelvins per minute (36 °F/min)) and a viscosity threshold of 1012 Pa·s, among
others. Upon cooling or heating through this glass-transition range, the material also exhibits a
smooth step in the thermal-expansion coefficient and in the specific heat, with the location of
these effects again being dependent on the history of the material.
Relationship between Tg and Tm
In polymers the glass transition temperature, Tg, is often expressed as the temperature at which
the Gibbs free energy is such that the activation energy for the cooperative movement of 50 or so
elements of the polymer is exceeded. This allows molecular chains to slide past each other when
a force is applied. From this definition, we can see that the introduction of relatively stiff
chemical groups (such as benzene rings) will interfere with the flowing process and hence
increase Tg. The stiffness of thermoplastics decreases due to this effect (see figure.) When the
glass temperature has been reached, the stiffness stays the same for a while, i.e., at or near E2,
until the temperature exceeds Tm, and the material melts. This region is called the rubber plateau.
In ironing, a fabric is heated through this transition so that the polymer chains become mobile.
The weight of the iron then imposes a preferred orientation. Tg can be significantly decreased by
addition of plasticizers into the polymer matrix. Smaller molecules of plasticizer embed
themselves between the polymer chains, increasing the spacing and free volume, and allowing
them to move past one another even at lower temperatures. The "new-car smell" is due to the
initial outgassing of volatile small-molecule plasticizers (most commonly known as phthalates)

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 17/21

used to modify interior plastics (e.g., dashboards) to keep them from cracking in the cold of
winter weather. The addition of nonreactive side groupsto a polymer can also make the chains
stand off from one another, reducing Tg. If a plastic with some desirable properties has a Tg that
is too high, it can sometimes be combined with another in a copolymer or composite
material with a Tg below the temperature of intended use. Note that some plastics are used at
high temperatures, e.g., in automobile engines, and others at low temperatures.

Stiffness versus temperature

In viscoelastic materials, the presence of liquid-like behavior depends on the properties of and so
varies with rate of applied load, i.e., how quickly a force is applied. The silicone toy Silly
Putty behaves quite differently depending on the time rate of applying a force: pull slowly and it
flows, acting as a heavily viscous liquid; hit it with a hammer and it shatters, acting as a glass.
On cooling, rubber undergoes a liquid-glass transition, which has also been called a rubber-glass
transition.
Determination of Tg
The glass transition temperature (Tg) of a polymer adhesive is actually a range of temperatures
during which the solid polymer material experiences some substantial changes in its physical
properties (transitions from glassy to rubbery solid).

Differential Scanning Calorimetry (DSC)

The basic concept of this method is that as a polymer transitions from a glassy to a rubbery state,
one of the physical properties of the material that substantially changes is its heat capacity - the
amount of heat it takes to raise the temperature of the material by one degree.
A DSC gradually adds more and more heat to a sample of a polymer material and at the same
time measures how much the material changes its temperature as a result. When the polymer
reaches the lower end of its glass transition temperature its heat capacity will spike up and the
DSC will use this information to ultimately estimate the glass transition temperature of the
material (Tg is point B on the graph below).

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 18/21

Estimating the Tg of a material using a DSC is a cost effective method, however, it is not always
accurate. Many materials will only have a small increase in heat capacity, making the transition
hard to identify.
Thermo Mechanical Analysis (TMA)
TMA estimates the glass transition temperature of a material by tracking its coefficient of
thermal expansion (CTE). In many cases the CTE of a polymer material will increase 3-5x as it
transitions from the glassy to the rubbery state.
Similar to DSC testing, TMA involves slowly adding heat to a sample material and
simulataneously tracking changes in physical properties. In the case of TMA, the physical
dimensions of the material are tracked and the Tg is identified as the temperature where there is a
dramatic change in these dimensions.
TMA testing is slightly more involved than DSC testing, however, this method generally yields
more accurate results.
Dynamic Mechanical Analysis (DMA)
One of the most immediate and obvious differences between a glassy and a rubbery material is of
course the stiffness. DMA testing uses this fundmental physical differentiator as a guide and
tracks the stiffness of a polymeric material over a range of temperatures in order to determine its
Tg. The graph below plots stiffness vs. temperature and points out

"Rubber plateau"
This method is extremely accurate and sensitive, however, is also very time consuming and
costly compared to the other two methods described.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 19/21

Reference book
R1: M.S Bhatnagar,2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

POSSIBLE QUESTIONS
Multiple choice questions (Each carry 1 Marks)

1. The freezing point depression depends on the

a. Number of dissolved solutes b. Average weight of solute c. Size and nature of solute
d. solvent nature
2. The difference temperature between the freezing point of solute and solvent in the range of
a. 10ºC b. 0.01ºC c. 0.001ºC d. 0.1ºC
3. By this method, accurately determine the molecular weights upto
a. 10,000 b. 20,000 c. 30,000 d. 50,000
4. The method based on observation of boiling point of a solution and solvent is known as
a. cryoscopic b. Ebuliometry c. membarane Osmometry
d. Equlibrium Osmometry

5. the equation belongs to

a. Number-average concept b. Weight average concept c. Viscosity concept

d. Osmostric concept
6. The weight average molecular degree of polymerisation indicates as
a. Dp b. (Dp)w c. (Dp)n d. D
7. A simple chemical compounds which have same molecular weight to form
a. monodispersion b. bi dispersion c. poly dispersion d. polymer solution
8. The symbol M̅v represents the
a. Number-average molecular weight b. Weight average molecular weight

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 20/21

c. Viscosity average molecular weight d. Vapour pressure molecular weight
9. A polymer contains different molecular weight compounds to form
a. monodispersion b. bi dispersion c. poly dispersion d. polymer solution
10. The symbol M̅w represents the
a. Number-average molecular weight b. Weight average molecular weight
c. Viscosity average molecular weight d. Vapour pressure molecular weight
11. The symbol M̅v represents the
a. Number-average molecular weight b. Weight average molecular weight
c. Viscosity average molecular weight d. Vapour pressure molecular weight
12. The phenomenon of depressing the freezing point of a liquid by the addition of solute is
known as
a. Cryoscopy b. Ebuliometry c. Osmometry d. Vapour phase Osmometry
13. The freezing point depression depends on the
a. Number of dissolved solutes b. Average weight of solute c. Size and nature of solute
d. solvent nature
14. The difference temperature between the freezing point of solute and solvent in the range of
a. 10ºC b. 0.01ºC c. 0.001ºC d. 0.1ºC
15. By this method, accurately determine the molecular weights upto
a. 10,000 b. 20,000 c. 30,000 d. 50,000
16. The method based on observation of boiling point of a solution and solvent is known as
a. cryoscopic b. Ebuliometry c. membarane Osmometry
d. Equlibrium Osmometry
17. [η], dl/g is equal to the
a. specific viscosity b. reduced viscosity c. inherent viscosity d. intrinsic viscosity
18. The intrinsic viscosity is also known as
a. specific viscosity b. reduced viscosity c. inherent viscosity d. Staudinger viscosity
19. The rpm maintained for minute in the sedimentation equilibrium method is
a. 30,000 b. 50,000 c. 15,000 d. 65,000
20. The error occurred in the viscometer due to the measurement of
a. level of solute b. density c. nature d. flow time

Questions (Each Carry 6 Marks)

1. How to calculate the molecular weight of the polymer based on the number average
method. Explain anyone of its experimental method?
2. Give an account of viscosity methods?
3. How to calculate the molecular weight of the polymer based on viscocity?
4. Give an account of light scattering method?
5. How to calculate the molecular weight of the polymer based on the weight average
method. Explain anyone of its experimental method?
6. Give an account of vapour phase osmometry methods?
7. How to determine the molecular weight by osmometry?
8. Give an account of viscosity methods?
9. How to calculate the molecular weight of the polymer by Cryoscopic and Ebuliometric
method?

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 21/21

10. What are the difference between Tg and Tm?
11. What is Glass Transition Temperature? How to determine it experimently?

Compulsory Questions (Each Carry 10 Marks)

1. What is glass transition temperature and how will you determine the Tg by experimently?
2. How to calculate the polymer weight of the polymer based on weight average method?
3. What is number average method? Explain its experimental methods to determine the
molecular weight of the polymers?

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 22/21

KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: III (MOLECULAR WEIGHT AND PROPERTIES) BATCH-2017-2019

Questions Opt-1 Opt-2 Opt-3 Opt-4 Answers

Number- Weight
Viscosity Number-average
1 average average Osmostric concept
the equation belongs to concept concept
concept concept

The weight average molecular degree of

2 Dp (Dp)w (Dp)n D (Dp)w
polymerisation indicates as

A simple chemical compounds which monodispersi

3 bi dispersion poly dispersion polymer solution monodispersion
have same molecular weight to form on

A polymer contains different molecular monodispersi

4 bi dispersion poly dispersion polymer solution poly dispersion
weight compounds to form on

Number- Weight Viscosity

average average average Vapour pressure Number-average
5 The symbol Ṁn represents the
molecular molecular molecular molecular weight molecular weight
weight weight weight
Number- Weight Viscosity
average average average Vapour pressure Weight average
6 The symbol Ṁw represents the
molecular molecular molecular molecular weight molecular weight
weight weight weight
Number- Weight Viscosity
average average average Vapour pressure Viscosity average
7 The symbol Ṁv represents the
molecular molecular molecular molecular weight molecular weight
weight weight weight
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CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: III (MOLECULAR WEIGHT AND PROPERTIES) BATCH-2017-2019

Number- Weight Viscosity

The experiments based on viscosity yield average average average Vapour pressure Viscosity average
8
the molecular molecular molecular molecular weight molecular weight
weight weight weight
The phenomenon of depressing the
Vapour phase
freezing point of a liquid by the addition Cryoscopy Ebuliometry Osmometry Cryoscopy
9 Osmometry
of solute is known as
Number of Average
The freezing point depression depents solvent Number of
10 dissolved weight of solvent nature
on the concentration dissolved solutes
solutes solute
size and
The freezing point depression not to nature of number of size and nature of
11 nature of weight of solvent
depents on the solvent solutes solute
solute
Weight Number- Viscosity
Cryoscopic method is applied to average average average Vapour pressure Number-average
12
determine the molecuar molecular molecular molecular weight molecular weight
weight weight weight
The freezing point of the solvent
13 F TF Tf Ts Tf
indicates the

freezing point freezing point

freezing the temperature freezing point
between between
14 ∆Tf is the difference of point of between solute between solute
solute and solvent
solutes and solvent and solvent
solvent molecules

In the cryoscopic method, the error weight of

15 temperature freezing point melting point temperature
occurred to measure the monomer

The difference temperature between

16 the freezing point of solute and solvent 10ºC 0.01ºC 0.001ºC 0.1ºC 0.001ºC
in the range of
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CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: III (MOLECULAR WEIGHT AND PROPERTIES) BATCH-2017-2019

By this method, accurately determine

17 10,000 20,000 30,000 50,000 30,000
the molecular weights upto

The method based on observation of

membarane Equlibrium
18 boiling point of a solution and solvent is cryoscopic Ebuliometry Ebuliometry
Osmometry Osmometry
known as

The Ebuliometry is a method based on

19 freezing point boiling point meltinf point crystalline point boiling point
the observation of

The difference in the heat of

20 ∆Hv ∆Sv ∆Tv ∆Gv ∆Hv
vapourisation is indicates as

freezing point boiling point meltinf point of crystalline point of boiling point of
21 The Tb is the symbol for
of solvent of solvent solvent solvent solvent

membrane membrane
22 The osmosis based method is known as Ebuliometry Cryoscopic Viscometry
osmometry osmometry

The membrane osmometry method osmotic

23 freezing point boiling point crystaline point osmotic pressure
based on pressure

In the membrane osmometry, the

nature of flow of nature of concentration of
24 pressure applied to the solution should flow of solvent
solvent solvent solute solvent
prevent

25 The osmotic pressure is represented as σ Ɵ µ π π

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CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: III (MOLECULAR WEIGHT AND PROPERTIES) BATCH-2017-2019

Weight Number- Viscosity

average average average Vapour pressure Number-average
26 The osmotic pressure is related to the
molecuar molecular molecular molecular weight molecular weight
weight weight weight
The Ebuliomrtry method, the boiling higher than less than same to the decrease than
27 higher than solvent
point of solution is solvent solvent solvent solvent

The Ebuliometry method is applicable non-volatile low molecular

28 volatile solute ionised solute non-volatile solute
for solute weight solute

The solution and solvent levels are

29 cathetometer anometer thermometer osmometry cathetometer
measured by using

height of density of Viscosity of

The cathetometer is used to measure concentration of height of solute
30 solute and solute and solute and
the solute and solvent and solvent
solvent solvent solvent

1033 g 1110 g
31 1 atmosphere is equal to the 1200 g wt/cm2 1040 g wt/cm2 1033 g wt/cm2
wt/cm2 wt/cm2

The membrane osmometry is used to

30,000 to 30,000 to
32 measure the molecular weight in the 30,000 50,000 to 100000 30,000 to 1000000
40,000 1000000
range of

The vapour pressure of a solution is ---

33 more less same constant less
than pure solvent

The total rise in temperature is molecular mole fraction number of mole fraction of
34 nature of solute
proportional to the weight of solute solutes solute
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The ratio between the functionality

35 divided by functional group equivalent is Ṁn Ṁw Ṁv Ṁs Ṁn
known as

The viscosity of the polymer solution is

36 solute solvent monomer catalyst solvent
high compared to

37 The relative viscosity is equal to the ᵑ/ᵑ0 = t/t0 = ᵑr ηsp ηred ln ηr /C ᵑ/ᵑ0 = t/t0 = ᵑr

38 The specific viscosity is equal t the ηr - 1 ηr ηred ln ηr /C ηr - 1

39 The reduced viscosity is equal to the ηsp /C = ηred ηr - 1 ηr ln ηr /C ηsp /C = ηred

specific reduced inherent

40 ln ηr /C is the intrinsic viscosity inherent viscosity
viscosity viscosity viscosity

specific reduced inherent

41 [η], dl/g is equal to the intrinsic viscosity intrinsic viscosity
viscosity viscosity viscosity

specific reduced inherent Staudinger Staudinger

42 The intrinsic viscosity is also known as
viscosity viscosity viscosity viscosity viscosity

specific reduced inherent

43 The limiting viscosity number known as intrinsic viscosity intrinsic viscosity
viscosity viscosity viscosity
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: III (MOLECULAR WEIGHT AND PROPERTIES) BATCH-2017-2019

44 The USLV is the osmometer viscometer cathetometer speedometer viscometer

45 The viscosity highly depends on the temperature density size nature temperature

The range of constant temperature

46 0.01ºC ± 0.001ºC ± 0.1ºC ± 0.01ºC ± 0.01ºC
maintained at viscometer is

The error occurred in the viscometer dur

47 level of solute density nature flow time flow time
to the measurement of

Number of
All the solutions are free from
48 dissolved yield error density error
impurities, it reduces the
solutes

Which one of the following is most ultracentrifuga

49 viscometry osmometry light scattering ultracentrifugation
complex method tion

In the ultracentrifugation, which force is magnetic centrifugal

50 kinetic force vanderwalls force centrifugal force
used for polymer separation force force

The sedimentation velocity depends on nature of size of molecular

51 number of solute molecular weight
the polymer polymer weight

The sedimentation velocity method has -

52 30,000 60,000 65,000 50,000 65,000
---- revolution per minute
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CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: III (MOLECULAR WEIGHT AND PROPERTIES) BATCH-2017-2019

angular angular
53 The symbol ω represents the pressure angular velocity angular velocity
viscosity moment

The sedimentation constant is denoted

54 ω0 S0 A0 C0 S0
as

sedimentation sedimentatio sedimentation sedimentation

The molecular weight distribution form Osmometric
55 velocity n viscosity equilibrium equilibrium
a heterogenous system in the method
method method method method

The sedimentation equilibrium method time

56 easy method low cost accurate time consumuing
is one of the consumuing

The rpm maintained for minute in the

57 30,000 50,000 15,000 65,000 15,000
sedimentation equilibrium method is

intensity of intensity of intensity of intensity of both intensity of

58 The symbol iƟis the equation
scattered light incident light solvent solute and solvent scattered light

59 The symbol ƫ is equal to the viscosity velosity turbidity density turbidity

Number- Weight
Viscosity Number-average
60 the equation belongs to average average Osmostric concept
concept concept
concept concept
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE:17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH: 2017-2019

Unit-IV

SYLLABUS

Polymer Processing: Plastics, elastomers and fibres. Compounding, processing techniques: calendering,
die casting, rotational casting, film casting, injection moulding, blow moulding extrusion, moulding,
thermoforming, foaming, reinforcing and fibre spinning.

Plastics- Introduction
Property Low Density Polyethylene High Density Polyethylene
(LDPE) (HDPE)
o o
Melting Point ~115 C ~135 C
Crystallinity low crystallinity (50-60% highly crystalline (>90% crystalline)
crystalline) contains less than 1 side chain per 200
Main chain contains many side carbon atoms in the main chain leading
chains of 2-4 carbon atoms leading to long linear chains that result in
to irregular packing and low regular packing and high crystallinity
crystallinity (amorphous)
Flexibility more flexible than HDPE due to more rigid than LDPE due to higher
lower crystallinity crystallinity
Strength not as strong as HDPE due to strong as a result of regular packing of
irregular packing of polymer chains polymer chains
Heat retains toughness & pliabilty over a useful above 100oC
Resistance wide temperature range, but density
drops off dramatically above room
temperature.
Transparency good transparency since it is more less transparent than LDPE because it is
amorphous (has non-crystalline more crystalline
regions) than HDPE
Density 0.91-0.94 g/cm3 0.95-0.97 g/cm3
lower density than HDPE higher density than LDPE
Chemical chemically inert chemically inert
Properties Insolvent at room temperature in
most solvents.
Good resistance to acids and alkalis.
Exposure to light and oxygen results
in loss of strength and loss of tear
resistance.
Schematic
diagram

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 1/20

Uses sandwich bags, cling wrap, car freezer bags, water pipes, wire and cable
covers, squeeze bottles, liners for insulation, extrusion coating
tanks and ponds, moisture barriers
in construction

Elastomer
An elastomer is a polymer with viscoelasticity (having both viscosity and elasticity) and very
weak inter-molecular forces, generally having low Young's modulus and high
failure strain compared with other materials.[1] The term, which is derived from elastic polymer,
is often used interchangeably with the term rubber, although the latter is preferred when referring
to vulcanisates. Each of the monomers which link to form the polymer is usually made
of carbon, hydrogen, oxygen or silicon. Elastomers are amorphous polymers existing above
their glass transition temperature, so that considerable segmental motion is possible. At ambient
temperatures, rubbers are thus relatively soft (E~3MPa) and deformable. Their primary uses are
for seals, adhesives and molded flexible parts. Application areas for different types of rubber are
manifold and cover segments as diverse as tires, shoe soles, and damping and insulating
elements.
Rubber like solids with elastic properties are called elastomers. Polymer chains are held together
in elastomers by weak intermolecular forces. These weak binding forces permit the polymers to
be stretched. Natural rubber, neoprene rubber, buna-s and buna-n are elastomers.
Fibres
Fiber

A bundle of optical fibers

Fiber or fibre (from the Latin fibra[1]) is a natural or synthetic substance that is significantly
longer than it is wide.[2] Fibers are often used in the manufacture of other materials. The
strongest engineering materials often incorporate fibers, for example carbon fiber and ultra-high-
molecular-weight polyethylene.
Synthetic fibers can often be produced very cheaply and in large amounts compared to natural
fibers, but for clothing natural fibers can give some benefits, such as comfort, over their synthetic
counterparts.
Compounding

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 2/20

Pharmaceutical compounding (done in compounding pharmacies) is the creation of a
particular pharmaceutical product to fit the unique need of a patient. To do this, compounding
pharmacists combine or process appropriate ingredients using various tools. This may be done
for medically necessary reasons, such as to change the form of the medication from a solid pill to
a liquid, to avoid a non-essential ingredient that the patient is allergic to, or to obtain the exact
dose(s) needed or deemed best of particular active pharmaceutical ingredient(s). It may also be
done for more optional reasons, such as adding flavors to a medication or otherwise altering taste
or texture. Compounding is most routine in the case of intravenous/parenteral medication,
typically by hospital pharmacists, but is also offered by privately owned compounding
pharmacies and certain retail pharmacies for various forms of medication. Whether routine or
rare, intravenous or oral, etc., when a given drug product is made or modified to have
characteristics that are specifically prescribed for an individual patient, it is known
as "traditional" compounding.
Due to the rising cost of compounding and the shortage of drugs, many hospitals have shown a
tendency to rely more upon large-scale compounding pharmacies to meet their regular
requirement, particularly of sterile-injectable medications. When compounding is done on bulk
production of a given formulation rather than patient-specific production, it is known as "non-
traditional" compounding (which, as discussed below, is arguably not "compounding" but rather
"manufacturing"). This development raises concerns about patient safety and makes a case for
proper regulatory control and monitoring.

Roles
During research and development
Pharmaceutical compounding is a branch of pharmacy that continues to play the crucial role
of drug development. Compounding pharmacists and medicinal chemists develop and test
combinations of active pharmaceuticals and delivery systems for new pharmaceutical
formulations so that the active ingredients are effective, stable, easy to use, and acceptable to
patients. However, for actual clinical trials, production of drug products is generally
considered manufacturing because compounding is typically defined as being for small batch or
single individual patient production only.
Patients with unique or unusual medication needs
Physicians may prescribe an individually compounded medication for a patient with an unusual
health need. This allows the physician to tailor a prescription to each individual. Compounding
preparations are especially prevalent for:

 Patients requiring an individualized compounded formulation to be developed by the

pharmacist[4]
 Patients who cannot take commercially prepared prescriptions[4]
 Patients requiring limited dosage strengths, such as a very small dose for infants
 Patients requiring a different formulation, such as turning a pill into a liquid or transdermal
gel for people who cannot swallow pills due to disability
 Patients requiring an allergen-free medication, such as one without gluten or colored dyes
 Patients who absorb or excrete medications abnormally[5]
 Patients who need drugs that have been discontinued by pharmaceutical manufacturers
because of low profitability
 Patients facing a supply shortage of their normal drug

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 3/20

 Children who want flavored additives in liquid drugs, usually so that the medication tastes
like candy or fruit
 Veterinary medicine, for a change in dose, change to a more easily administered form (such
as from a pill to a liquid or transdermal gel), or to add a flavor more palatable to the animal.
In the United States, compounded veterinary medicine must meet the standards set forth in
the Animal Medicinal Drug Use Clarification Act (AMDUCA)
 Many types of bioidentical hormone replacement therapy

Polymer processing Techniques

Plastics are mainly organic polymers of high molecular mass, but they sometimes contain other
substances as well. Plastics are usually synthetic, most commonly derived from petrochemicals,
but many are partially natural. Plastics are usually classified by their chemical structure of the
polymer's backbone and side chains. Some important groups in these classifications are
the acrylics, polyesters, silicones, polyurethanes, and halogenated plastics. There are a variety of
methods used to process plastic. Each method has its advantages and disadvantages and are
better suited for specific applications. There are various plastic processing techniques.

1. Calendering

Calendering is a continuous process which works in much the same way as an old-fashioned
clothes mangle. For plastics, there are usually four heated rollers of different sizes rotating at
slightly different speeds. The material is fed into these rollers, heated and melted, then shaped
into a sheet or film. This is then cooled and rolled up. The sheets can be mono-oriented during
this process. The most commonly calendered material is PVC.

2. Casting Process

Casting is a manufacturing process in which a liquid material is usually poured into a mold,
which contains a hollow cavity of the desired shape, and then allowed to solidify. The solidified
part is also known as a casting, which is ejected or broken out of the mold to complete the
process. Casting materials are usually metals or various cold setting materials that cure after
mixing two or more components together; examples are epoxy, concrete, plaster and clay.
Casting is most often used for making complex shapes that would be otherwise difficult or
uneconomical to make by other methods.
1. Die casting
2. Rotational casting
3. Film casting

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 4/20

2.1 Die casting
Die casting is a metal casting process that is characterized by forcing molten metal under high
pressure into a mold cavity. The mold cavity is created using two hardened tool steel dies which
have been machined into shape and work similarly to an injection mold during the process. Most
die castings are made from non-ferrous metals,
specifically zinc, copper, aluminium, magnesium, lead, pewter and tin-based alloys. Depending
on the type of metal being cast, a hot- or cold-chamber machine is used.
The casting equipment and the metal dies represent large capital costs and this tends to limit the
process to high-volume production. Manufacture of parts using die casting is relatively simple,
involving only four main steps, which keeps the incremental cost per item low. It is especially
suited for a large quantity of small- to medium-sized castings, which is why die casting produces
more castings than any other casting process. Die castings are characterized by a very
good surface finish (by casting standards) and dimensional consistency.
Two variants are pore-free die casting, which is used to eliminate gas porosity defects; and direct
injection die casting, which is used with zinc castings to reduce scrap and increase yield.
Equipment
There are two basic types of die casting machines: hot-chamber machines and cold-chamber
machines. These are rated by how much clamping force they can apply. Typical ratings are
between 400 and 4,000 st (2,500 and 25,400 kg).
Hot-chamber die casting

Schematic of a hot-chamber machine

Hot-chamber die casting, also known as gooseneck machines, rely upon a pool of molten metal
to feed the die. At the beginning of the cycle the piston of the machine is retracted, which allows
the molten metal to fill the "gooseneck". The pneumatic- or hydraulic-powered piston then forces
this metal out of the gooseneck into the die. The advantages of this system include fast cycle
times (approximately 15 cycles a minute) and the convenience of melting the metal in the casting
machine. The disadvantages of this system are that it is limited to use with low-melting
point metals and that aluminium cannot be used because it picks up some of the iron while in the
molten pool. Therefore, hot-chamber machines are primarily used with zinc-, tin-, and lead-based
alloys.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 5/20

Cold-chamber die casting

A schematic of a cold-chamber die casting machine.

These are used when the casting alloy cannot be used in hot-chamber machines; these include
aluminium, zinc alloys with a large composition of aluminium, magnesium and copper. The
process for these machines start with melting the metal in a separate furnace.[14]Then a precise
amount of molten metal is transported to the cold-chamber machine where it is fed into an
unheated shot chamber (or injection cylinder). This shot is then driven into the die by a hydraulic
or mechanical piston. The biggest disadvantage of this system is the slower cycle time due to the
need to transfer the molten metal from the furnace to the cold-chamber machine.

Advantages and disadvantages

Advantages of die casting:
 Excellent dimensional accuracy (dependent on casting material, but typically 0.1 mm for the
first 2.5 cm (0.005 inch for the first inch) and 0.02 mm for each additional centimeter
(0.002 inch for each additional inch).
 Smooth cast surfaces (Ra 1–2.5 micrometres or 0.04–0.10 thou rms).
 Thinner walls can be cast as compared to sand and permanent mold casting (approximately
0.75 mm or 0.030 in).
 Inserts can be cast-in (such as threaded inserts, heating elements, and high strength bearing
surfaces).
 Reduces or eliminates secondary machining operations.
 Rapid production rates.
 Casting tensile strength as high as 415 megapascals (60 ksi).
 Casting of low fluidity metals.
The main disadvantage to die casting is the very high capital cost. Both the casting equipment
required and the dies and related components are very costly, as compared to most other casting
processes. Therefore, to make die casting an economic process, a large production volume is
needed. Other disadvantages are that the process is limited to high-fluidity metals, and casting
weights must be between 30 grams (1 oz) and 10 kg (20 lb). In the standard die casting process
the final casting will have a small amount of porosity. This prevents any heat treating or welding,
because the heat causes the gas in the pores to expand, which causes micro-cracks inside the part
and exfoliation of the surface. Thus a related disadvantage of die casting is that it is only for
parts in which softness is acceptable. Parts needing hardening (through hardening or case
hardening) and tempering are not cast in dies.

2.2 Rotational Casting

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 6/20

Rotational Molding (BrE moulding) involves a heated hollow mold which is filled with a
charge or shot weight of material. It is then slowly rotated (usually around two perpendicular
axes), causing the softened material to disperse and stick to the walls of the mold. In order to
maintain even thickness throughout the part, the mold continues to rotate at all times during the
heating phase and to avoid sagging or deformation also during the cooling phase. The process
was applied to plastics in the 1940s but in the early years was little used because it was a slow
process restricted to a small number of plastics. Over the past two decades, improvements in
process control and developments with plastic powders have resulted in a significant increase in
usage.

Rotocasting (also known as rotacasting), by comparison, uses self-curing resins in an unheated

mould, but shares slow rotational speeds in common with rotational molding. Spin
casting should not be confused with either, utilizing self-curing resins or white metal in a high-
speed centrifugal casting machine.
2.3 Film Casting
Polymer solution casting is a technique that can replace film extrusion to deliver high-quality
films with superior optical, mechanical and physical film properties.
In polymer solution casting, polymer is dissolved or dispersed in solution, coated onto a carrier
substrate, and then the water or solvent is removed by drying to create a solid layer on the
carrier. The resulting cast layer can be stripped from the carrier substrate to produce a standalone
film. Before or after stripping, the cast film can be laminated with other webs or coated with
other materials to create multi-layer products.

Manufacturing process advantages of polymer solution casting over traditional film extrusion
methods include:
 Processing at low temperatures, which is valuable for thermally activated films or applications
incorporating temperature-sensitive active ingredients.
 Ability to produce high-temperature resistant films from non-thermoplastic but soluble raw
materials.
 Simplified incorporation of additives and fillers.
 Quicker changeovers for platforms with many part numbers that are differentiated based on
formula.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 7/20

 Single pass manufacturing of multi-layer films (g. the ability to cast a free film, then coat an
adhesive and laminate release liner on one side, and coat a top coat on the other side).
 Wider range of material choices with casting from either aqueous or solvent-based solutions.
Advantages of the resulting film include:
 Greater film thickness uniformity, as tight as +/-2%.
 Wider range of film thickness, from 150 microns down to less than 12 microns.
 Films that are gel and pinhole free.
 Excellent flatness and dimensional stability.
 Isotropic orientation (mechanical and optical) as film is not stretched during manufacture.
 Absence of typical extrusion process lubricants.
3. Moulding

Moulding is one of the most relavent technology to form a plastic products. They are various
types. Few of them are Given below
1. Injection molding
2. Extrusion
3. Blow Molding
4. Compression molding
5. Rotational molding

3.1 Injection molding

Injection molding is a manufacturing process for producing parts by injecting material into a
mold. The main method used for processing plastic is injection molding. With this process, the
plastic is placed into a hopper. The hopper then feeds the plastic into a heated injection unit,
where it is pushed through a long chamber with a reciprocating screw. Here, it is softened to a
fluid state. A nozzle is located at the end of the chamber. The fluid plastic is forced through the
nozzle into a cold, closed mold. The halves of the mold are held shut with a system of clamps.
When the plastic is cooled and solidified, the halves open and the finished product is ejected
from the press.
3.2 Extrusion

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 8/20

Plastics extrusion is a high volume manufacturing process in which raw plastic material is melted
and formed into a continuous profile. The process of extrusion is usually used to make products
such as film, continuous sheeting, tubes, profile shapes, rods, coat wire, filaments, cords, and
cables. As with injection molding, dry plastic material is placed into a hopper and fed into a long
heating chamber. At the end of the chamber, however, the material is forced out of a small
opening or a die in the shape of the desired finished product. As the plastic exits the die, it is
placed on a conveyor belt where it is allowed to cool. Blowers are sometimes used to aid in this
process, or the product may be immersed in water to help it cool.
3.3 Blow Molding

Stretch Blow Molding process is mainly used when the plastic product that needs to be created
should be hollow. A molten tube is created with blow molding by using compressed air, which
blows up the tube and forces it to conform to the chilled mold. Variations of blow molding
include injection, injection-stretch, and extrusion blow molding.
3.4 Compression molding

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 9/20

desired shape. The amount temperature, amount of pressure, and length of time utilized during
the process depends on the desired outcome.

3.5 Rotational molding

Rotational molding is an extremely popular and well-used process for producing items that are
usually hollow. The mold is closed and then spun both vertically and horizontally and moved
into an oven. As the powder starts to melt and the mold continues rotating, it is flung onto the
walls of the mold by centrifugal force where it forms a skin. After a fixed period, the mold is
removed from the oven and allowed to cool carefully to avoid the product shoring.

4. Thermoforming

Thermoforming is a manufacturing process where a plastic sheet is heated to a pliable forming

temperature, formed to a specific part shape in a mold, and trimmed to create a usable product.
The sheet, or film when referring to thinner gauges and certain material types, is heated in an
oven to a high-enough temperature that it can be stretched into or onto a mold and cooled to a
finished shape. The second animation shows the twin sheet thermoforming process whereby two
individual components are fused together through the application of tremendous pressure which
forces two molds together, thereby fusing the materials together.
4.1 Vacuum forming

Vacuum forming is a simplified version of thermoforming, whereby a sheet of plastic is heated

to a forming temperature, stretched onto a convex, or into a concave, single-surface mold, and
forced against the mold by a vacuum (suction of air).

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 10/20

5. Polymeric Foams
The most of the polymeric foams are formed by a process involving nucleation and growth of
gas bubbles in a polymer matrix, except in the syntactic foam where micro−beads of
encapsulated gas are compounded into a polymer system or latex. According to the nucleation
mechanism, the fundamental principle for the formation of polymeric foam involves three
different important stages such as, bubble formation, bubble growth and bubble stability. The
foam is expanded by increasing the bubble size before stabilizing the system. As the bubbles
grow, the foam structure changes through number of stages.5 These are the following
characteristics observed during the formation of foam. ƒInitially, small dispersed spherical
bubbles are produced in a liquid polymer matrix, with a small reduction in density. The further
growth of cells leads to lower foam density, which involves distortion of cells to form polyhedral
structures, sometimes idealized as pentagonal dodecahedrons. ƒEffects of viscosity and surface
tension subsequently cause materials to flow towards the uniform cell formation. ƒExtensive
rupture before the foam is stabilized may lead to foam collapse. Cooling of closed cell foam
before stabilization may lead to shrinkage, because of the reduced pressure in cells. The foaming
of polymeric materials can be carried out by mechanical, chemical, or physical methods.4 Some
of the most commonly used methods are; ¾Thermal decomposition of a chemical blowing agent,
generating either nitrogen or carbon dioxide or both, by application of heat or as a result of the
exothermic reaction during polymerization. Chemical blowing agents are either inorganic
materials such as carbonates, bicarbonates, borohydrides, etc., or organic materials such as,
hydrazides, azides, and nitroso compounds, etc. Copyright IIT Kharagpur Chapter 1 4
¾Mechanical whipping (frothing) of gases into a fluid polymer system (melt, solution, or
suspension), then it hardens either by catalytic action or heat or both, thus entrapping the gas
bubbles in the polymeric matrix. ¾Volatilization of low−boiling liquids (fluorocarbons or
methylene chloride) within the polymer mass as a result of the exothermic reaction or by
application of heat. ¾Chemical blowing action via in-situ reaction during polymerization. (In
this in-situ reaction water reacts with isocyanate to form carbon dioxide which is responsible for
polyurethane foam formation). ¾Expansion of dissolved gas in a polymer mass upon reduction
of pressure in the system. ¾Incorporation of tiny beads or microspheres into a polymer mass.

Application of Polymeric Foams

Applications of polymeric foams depend on the nature of polymer and their types. For example,
the main applications of flexible foams are for cushioning, packaging, automotive safety,
footwear, etc.

6. Reinforcement

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 11/20

Fibre-reinforced plastic (FRP) (also called fibre-reinforced polymer, or fiber-reinforced
plastic) is a composite material made of a polymer matrix reinforced with fibres. The fibres are
usually glass (in fibreglass), carbon, aramid, or basalt. Rarely, other fibres such as paper, wood,
or asbestos have been used. The polymer is usually an epoxy, vinylester,
or polyester thermosetting plastic, though phenol formaldehyde resins are still in use.
FRPs are commonly used in the aerospace, automotive, marine, and construction industries.
They are commonly found in ballistic armor as well.

Process definition
A polymer is generally manufactured by step-growth polymerization or addition polymerization.
When combined with various agents to enhance or in any way alter the material properties of
polymers the result is referred to as a plastic. Composite plastics refer to those types of plastics
that result from bonding two or more homogeneous materials with different material properties
to derive a final product with certain desired material and mechanical properties. Fibre-
reinforced plastics are a category of composite plastics that specifically use fibre materials to
mechanically enhance the strength and elasticity of plastics.
The original plastic material without fibre reinforcement is known as the matrix or binding agent.
The matrix is a tough but relatively weak plastic that is reinforced by stronger stiffer reinforcing
filaments or fibres. The extent that strength and elasticity are enhanced in a fibre-reinforced
plastic depends on the mechanical properties of both the fibre and matrix, their volume relative
to one another, and the fibre length and orientation within the matrix.[1] Reinforcement of the
matrix occurs by definition when the FRP material exhibits increased strength or elasticity
relative to the strength and elasticity of the matrix alone.

Reinforcing Fibre is manufactured in both two-dimensional and three-dimensional orientations:

1. Two-dimensional fibreglass-reinforced polymer is characterized by a laminated structure
in which the fibers are only aligned along the plane in x-direction, and y-direction of the
material. This means that no fibers are aligned in the through-thickness or the z-
direction, this lack of alignment in the through thickness can create a disadvantage in
cost and processing. Costs and labor increase because conventional processing
techniques used to fabricate composites, such as wet hand lay-up, autoclave and resin
transfer molding, require a high amount of skilled labor to cut, stack and consolidate into
a preformed component.
2. Three-dimensional fiberglass-reinforced polymer composites are materials with three-
dimensional fiber structures that incorporate fibers in the x-direction, y-direction and z-
direction. The development of three-dimensional orientations arose from industry's need
to reduce fabrication costs, to increase through-thickness mechanical properties, and to
improve impact damage tolerance; all were problems associated with two-dimensional
fibre-reinforced polymers.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 12/20

Material requirements
A thermoset polymer matrix material, or engineering grade thermoplastic polymer matrix
material, must meet certain requirements in order to first be suitable for FRPs and ensure a
successful reinforcement of itself. The matrix must be able to properly saturate, and preferably
bond chemically with the fibre reinforcement for maximum adhesion within a suitable curing
period. The matrix must also completely envelop the fibres to protect them from cuts and notches
that would reduce their strength, and to transfer forces to the fibres. The fibres must also be kept
separate from each other so that if failure occurs it is localized as much as possible, and if failure
occurs the matrix must also debond from the fibre for similar reasons. Finally the matrix should
be of a plastic that remains chemically and physically stable during and after the reinforcement
and moulding processes. To be suitable as reinforcement material, fibre additives must increase
the tensile strength and modulus of elasticity of the matrix and meet the following conditions;
fibres must exceed critical fibre content; the strength and rigidity of fibres itself must exceed the
strength and rigidity of the matrix alone; and there must be optimum bonding between fibres and
matrix
Glass fibre
"Fibreglass reinforced plastics" or FRPs (commonly referred to simply as fibreglass) use textile
grade glass fibres. These textile fibres are different from other forms of glass fibres used to
deliberately trap air, for insulating applications (see glass wool). Textile glass fibres begin as
varying combinations of SiO2, Al2O3, B2O3, CaO, or MgO in powder form. These mixtures are
then heated through direct melting to temperatures around 1300 degrees Celsius, after which dies
are used to extrude filaments of glass fibre in diameter ranging from 9 to 17 µm. These filaments
are then wound into larger threads and spun onto bobbins for transportation and further
processing. Glass fibre is by far the most popular means to reinforce plastic and thus enjoys a
wealth of production processes, some of which are applicable to aramid and carbon fibres as well
owing to their shared fibrous qualities.
Roving is a process where filaments are spun into larger diameter threads. These threads are then
commonly used for woven reinforcing glass fabrics and mats, and in spray applications.
Fibre fabrics are web-form fabric reinforcing material that has both warp and weft directions.
Fibre mats are web-form non-woven mats of glass fibres. Mats are manufactured in cut
dimensions with chopped fibres, or in continuous mats using continuous fibres. Chopped fibre
glass is used in processes where lengths of glass threads are cut between 3 and 26 mm, threads
are then used in plastics most commonly intended for moulding processes. Glass fibre short
strands are short 0.2–0.3 mm strands of glass fibres that are used to reinforce thermoplastics
most commonly for injection moulding.
Carbon fibre
Carbon fibres are created when polyacrylonitrile fibres (PAN), Pitch resins, or Rayon are
carbonized (through oxidation and thermal pyrolysis) at high temperatures. Through further
processes of graphitizing or stretching the fibres strength or elasticity can be enhanced
respectively. Carbon fibres are manufactured in diameters analogous to glass fibres with
diameters ranging from 4 to 17 µm. These fibres wound into larger threads for transportation and
further production processes. Further production processes include weaving or braiding into
carbon fabrics, cloths and mats analogous to those described for glass that can then be used in
actual reinforcements.
Aramid fibre
Aramid fibres are most commonly known as Kevlar, Nomex and Technora. Aramids are
generally prepared by the reaction between an amine group and a carboxylic acid halide group
(aramid);[1] commonly this occurs when an aromatic polyamide is spun from a liquid

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 13/20

concentration of sulphuric acid into a crystallized fibre. Fibres are then spun into larger threads
in order to weave into large ropes or woven fabrics (Aramid). Aramid fibres are manufactured
with varying grades to based on varying qualities for strength and rigidity, so that the material
can be somewhat tailored to specific design needs concerns, such as cutting the tough material
during manufacture.
Advantages and limitations
FRP allows the alignment of the glass fibres of thermoplastics to suit specific design programs.
Specifying the orientation of reinforcing fibres can increase the strength and resistance to
deformation of the polymer. Glass reinforced polymers are strongest and most resistive to
deforming forces when the polymers fibres are parallel to the force being exerted, and are
weakest when the fibres are perpendicular. Thus this ability is at once both an advantage or a
limitation depending on the context of use. Weak spots of perpendicular fibres can be used for
natural hinges and connections, but can also lead to material failure when production processes
fail to properly orient the fibres parallel to expected forces. When forces are exerted
perpendicular to the orientation of fibres the strength and elasticity of the polymer is less than the
matrix alone. In cast resin components made of glass reinforced polymers such as UP and EP,
the orientation of fibres can be oriented in two-dimensional and three-dimensional weaves. This
means that when forces are possibly perpendicular to one orientation, they are parallel to another
orientation; this eliminates the potential for weak spots in the polymer.

7. Fiber Spinning

Fiber spinning is used to make synthetic fibers for use in many industries. There are three main
types of fiber spinning methods: melt, solution, and reaction spinning. In fiber spinning a liquid
polymer is extruded through small holes in a spinneret to form thin filaments, as shown below.
Upon leaving the spinneret the filaments solidify. After solidification, filaments can be combined
to make threads and/or drawn to change the filaments' properties.

The processes governing the three types of fiber spinning differ mainly in the way the polymer is
liquefied and solidified.

Melt Spinning
General Information
Melt spinning is the most widely used form of fiber spinning. In melt spinning either molten
polymer is used or polymer pellets are melted down. Once the filaments are extruded they are
cooled in a fluid medium such as air, gas, or even water.
Equipment Design
In melt spinning, as shown below , the molten or melted polymer is pushed vertically downwards
through the spinneret. When the filaments emerge from the spinneret they are cooled by a gas,

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 14/20

usually air, which flows either perpendicularly across, cocurrently , or countercurrently to the
filaments.

The filaments can then be brought together and/or twisted together to form a thread. Before
winding the thread on the bobbin, it is often treated with water or a wetting agent and then a
lubricant . Later, the wound thread may be dyed and drawn on other machines.
Spinneret design , such as those shown below, is dependent on the type of spinning and desired
cross sectional shape of the filament. The cross sectional shape determines different features the
filament will exhibit, such as how it will reflect light, the ability to insulate, and how easily it
shows dirt.

Spin plates and spinnerets may have as many as 80,000 bores spaced less than one millimeter
apart. Some spinnerets have superfine capillaries 50 micrometers in diameter. These tiny bores
and capillaries are very sensitive to impurities and corrosion; this is one reason why spinnerets
are often made of high-grade steel or other metals that can be easily cleaned.
Usage Examples
Some common fibers produced using melt spinning are: polypropylene, polyester, and nylon
which is shown below and to the right. Nylon was the world's first synthetic fiber discovered and
was initially used for tooth brush bristles before being used to produce women's stockings during
the 1940's.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 15/20

Advantages and Disadvantages
 Ablility to run at high line speeds.
 Requires no solvent that must be recovered later.
 Necessary high temperatures may damage some polymers.
Solution Spinning
Solution spinning is used when the desired polymer does not form a stable melt. These polymers
are dissolved in a solution to liquefy them rather than melting them. The two main types of
solution spinning are dry and wet spinning.
Dry Spinning
In dry spinning the polymer is dissolved in a volatile solvent. Once dissolved, the polymer
solution is extruded through the spinneret which is in an enclosed drying tower. The solution
goes through a drying process in this tower, where the solvent is evaporated.

Equipment Design
The spinning solution is often filtered many times to remove foreign materials that might cause
thread defects or clogging in the machine . The solution is extruded into the drying tower
through which hot air or other gases pass. The concentration of the polymer increases as the
solvent evaporates, leaving a solid polymer filament behind. The s olvent is later recovered from
the gas by condensation or absorption and is then recycled.
Solvent selection is very important, and is based on boiling point, latent heat of vaporization,
thermal stability, toxicity, and inertness. Non-polar solvents are often preferred because of their
low boiling points and heats of vaporization. However, non-polar solvents are prone to build-ups
of electrostatic charge, which can be very dangerous.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 16/20

Advantages and Disadvantages
 Better than melt spinning for temperature-sensitive polymers.
 Faster production rates than melt and wet spinning.
 Solvent recovery is costly.
Wet Spinning
In wet spinning the polymer is dissolved in a non-volatile solvent. The spinneret is located in a
coagulating bath that causes the fiber to precipitate out.

Equipment Design
The liquid in the coagulating bath is chosen so that the solvent is readily soluble in the liquid but
the polymer is not. This will cause the polymer to precipitate out and form the desired solid
filaments.The solvent can later be recovered by treating the wastewater in the bath.
The drag on the filament by the viscous liquid in the coagulating bath significantly reduces the
production speed of the process. This makes wet spinning a slower process than melt or dry
spinning.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 17/20

Advantages and Disadvantages
 Better than melt and dry spinning for temperature sensitive polymers.
 Lower production rates than melt or dry spinning due to viscous drag.
 Solvent recovery is costly.
Usage Examples
The synthetic fibers produced by solution spinning are made into threads which are woven into
fabric for everything from clothes and carpets to airbags and windsails. In addition, sterilized
synthetic fibers are used in the medical industry as sutures, dressings, and operating room drapes,
face masks, caps and overshoes. Many synthetic fibers can be cut into tiny pieces called flock .
Flock is used to make velvet or suede-like materials or added to plastics or papers for a
decorative finish.

Reference book
R1: M.S Bhatnagar,2004, “ A text book of polymers”. Ist Edition, S.Chand & Company.

POSSIBLE QUESTIONS

Multiple Choice Questions (Each Carry 1 Mark)

1. Which one of the following is obtained from acetaldehyde and hydrogen cyanide.
a. Acrylonitrile monomer b. Polyamide c. Polyester d. Polyethylene terephthalte
2. Wet spinning technique is commercially used to produce filament yarn of
a. Polypropylene b. Polyester c. Nylon 66 d. Acrylic
3. Too high resistivity leads to the development of static?
a. Mechanical charges b. Positive charges c. Negative charges d. Electrical
charges
4. Which properties of fibers are quite complex and have been subject of much
experimental work?
a. Physical b. Mechanical c. Chemical d. Thermal

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 18/20

5. In which spinning, the polymer solution is forced through a spinneret?
a. Melt spinning b. Dry spinning c. Wet spinning d. Spinning
6. Birefringence of filament yarn is related to its
Density b. Filament denier c. Orientation d. Crystallinity
7. In melt spinning the temperature used for melting is about ?
29K b. 30K c. 31K d. 32K
8. Which one of the following is the most important fibers produced commercially?
Nylons b. Wood c. Cotton d. Silk
9. In which spinning, the polymer is melted by heating and then passed through a spinneret
via
Melt spinning b. Dry spinning c. Wet spinning d. Spinning
10. Which one of the following is used for self-lubricating gears and bearings?
Nylons b. Wood c. Cotton d. Silk
11. Crease resist finishing of cotton fabric does not lead to
Reduction in tensile strength b. Increase in dimensional stability
c. Increase in moisture regain d. Increase in bending length
12. Which property causes the fabric to cling unpleasantly and to be difficult to clean?
a. Mechanical b. Electrical c. Chemical d. Thermal
13. In general, which is a difficult dye?
a. Polyamide b. Polyester c. Hydrophobic fiber d. Acrylic fibre
14. In which spinning, Polymer solutions are converted into fibers by diluting a highly
concentrated polymer solution in a coagulating bath?
a. Melt spinning b. Dry spinning c. Wet spinning d. Spinning
15. Which is soluble only in specific solvents?
a. Fibres b. Polymers c. Nylon d. Hydrophobic fibres
16. The PBNA is the standard
a. anti-oxidant b. anti-toxin c. anti-malarial d. anti-poisionus
17. Which one of the following is used as the staining anti-oxidant
a. DPPD b. PBNA c. TCS d. TMS
18. TCS is the example of the
a. Standard anti-oxidant b. non standard anti-oxidant c. staining anti-oxidant
d. non-staining anti oxidant
19. The rayon also known as
a. nylon b. orelon c. viscose d. resin
20. The rayon polymers belongs to the
a. silicon polymers b. epoxy polymers c. organic polymer d. rubber

6 Marks (Each Carry 6 Marks)

1. What is calendaring technique? explain it briefly?

2. Write a note on moulding techniques?
3. What are the thermoforming techniques?
4. How to produce the hollow and film products of polymers under casting technique?
5. Write a note on foaming techniques?
6. Write a note on reinforcing?
7. What is the compounding technique of polymer and fiber?
8. Write a note on injection and blow moulding?
9. What is moulding? Explain extrusion moulding in the preparation of polymers?

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 19/20

10. How to prepare the fiber by spinning method?

Compulsory Questions (Each Carry 10 Marks)

1. Give an account of fiber spinning technique?

2. Briefly explain the reinforcing technique?
3. What is moulding? Explain the four types of moulding?

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 20/20

KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

Questions Opt-1 Opt-2 Opt-3 Opt-4 Answers

The fibre that contains

1 Polyester Wool Nylon Kevlar Wool
nitrogen and sulfur is ?

It is the class of a hair like

2 materials that are continues Fibre Rubber Wood Glass Fibre
filaments.

Polyacrylonitrile (PAN), also Polyvinyl Polyethylene

3 Cyanide Polyester Polyvinyl cyanide
known as ? cyanide terephthalte

Which one of the following

Acrylonitrile Polyethylene Acrylonitrile
4 is produced by Polyamide Polyester
monomer terephthalte monomer
ammonidation of propylene.
Which one of the following
is obtained from Acrylonitrile Polyethylene Acrylonitrile
5 Polyamide Polyester
acetaldehyde and hydrogen monomer terephthalte monomer
cyanide.
Wet spinning technique is
6 commercially used to Polypropylene Polyester Nylon 66 Acrylic Acrylic
produce filament yarn of

Too high resistivity leads to Mechanical

7 Positive charges Negative charges Electrical charges Electrical charges
the development of static ? charges

Which properties of fibres

8 Physical Mechanical Chemical Thermal Mechanical
are quite complex and have
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

been subject of much

experimental work?

The tenacity at break of

typical fibres ranges from Synthetic Natural Rayons Carbon fibres Rayons
9
about 1 g/denier for ?
Which one of the following
is the least satisfactory
10 Silk Cotton Glass Wood Silk
fibres from the standpoint
of weather ability?
Natural fibers are consisting Nonlinear
11 Linear polymers Copolymers Chain polymers Linear polymers
of ? polymers

The fibre that dissolves in

12 59% (w/w) sulfuric acid Nylon Viscose Cotton Silk Viscose
solution is

Polyacrylonitrile is soluble in Dimethylforma Dimethylformamid

13 Methanol Water Acetone
which solvent? mide (DMF) e (DMF)

In which spinning, the

14 polymer solution is forced Melt spinning Dry spinning Wet spinning Spinning Dry spinning
through a spinneret?
In which spinning, the
polymer is melted by
15 Melt spinning Dry spinning Wet spinning Spinning Melt spinning
heating and then passed
through a spinneret via
Birefringence of filament
16 Density Filament denier Orientation Crystallinity Orientation
yarn is related to its
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

In melt spinning the

17 temperature used for 29K 30K 31K 32K 30K
melting is about ?
Which one of the following
18 is the most important fibers Nylons Wood Cotton Silk Nylons
produced commercially?
Which one of the following
19 is used for self-lubricating Nylons Wood Cotton Silk Nylons
gears and bearings?

Why does nylon make such Intramolecular Low Molecular High Molecular Intermolecular
20 Intermolecular forces
good fibers? forces weight weight forces

During bleaching of cotton

Sodium
21 with H2O2, the stabilizer Sodium silicate Acetic acid Sodium carbonate Sodium silicate
hydroxide
used is ?
The highest washing
fastness in a dyed cotton Van derWaal's
22 Ionic Hydrogen Covalent Covalent
fabric would be obtained if force
the dye-fibre bond is
The melt index, is generally
23 used to characterize which Electrical Chemical Mechanical Melting Melting
properties of polymers?
Crease resist finishing of Increase in
Reduction in Increase in moisture Increase in Increase in
24 cotton fabric does not lead dimensional
tensile strength regain bending length moisture regain
to stability
Which property cause the
25 fabric to cling unpleasantly Mechanical Electrical Chemical Thermal Electrical
and to be difficult to clean?
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

In general, which is difficult

26 Polyamide Polyester Hydrophobic fibre Acrylic fibre Hydrophobic fibre
to dye ?
In which spinning, Polymer
solutions are converted into
fibers by diluting a highly
27 Melt spinning Dry spinning Wet spinning Spinning Wet spinning
concentrated polymer
solution in a coagulating
bath?
Which is soluble only in Hydrophobic
28 Fibres Polymers Nylon Polymers
specific solvents? fibres
Cellulose acetate,
polyacrylonitrile, and
29 Melt spinning Dry spinning Wet spinning Spinning Dry spinning
polyurethane are spun by
this technique?

30 Nylon ends in? Building Ropes Chair Watch Ropes

Which one of the following

31 Terylene Nylon 6 Cotton Watch Nylon 6
is a polyamide?

Synthetic fibers are Nonlinear

32 Linear polymers Copolymers Chain polymers Linear polymers
consisting of ? polymers

The alkyd resins are

condensation polymers
33 Glycol Phenol Acetaldehyde Benzaldehyde Phenol
obtained from dibasic acids
and
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

Polyester Polyamide
34 Nylon threads are made of Polyvinyl chloride Acrylic polymer Polyamide polymer
polymer polymer

35 Acrylic resins are Brown colour Colourless Gold colour White colour Colourless

Which one of the following

36 can be polymerised to Ethylene Ethyl amide Ethyl ketone Ethyl acetate Ethylene
polythene

37 Hydrolysis of cellulose gives D-glucose L- glucose D-fructose L-fructose D-glucose

38 Orlon is a polymer of Polyamide Polyester Hydrophobic fibre Acrylic fibre Acrylic fibre

Condensation product of
39 Nylon 6 Cotton Nylon 6,10 Nylon 66 Nylon 6
caprolactum is

condensation condensation
40 Nylon is a example of copolymer coordination polymer chain polymer
polymer polymer

Diphenyl Diphenyl
Diphenyl phospho Diphenyl phospho Diphenyl
41 The DPPD is the phenylene phenylene
diamine diamine phenylene diamine
diamine diamide
phenyl ρ
phenylα phenyl β naphthyl phenyl γ naphthyl phenyl β naphthyl
42 PBNA is the naphthalene
naphthyl amine amine amine amine
amide
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

43 The PBNA is the standard anti-oxidant anti-toxin anti-malarial anti-poisionus anti-oxidant

Which one of the following

44 is used as the staining anti- DPPD PBNA TCS TMS PBNA
oxidant

Standard anti- non standard non-staining anti non-staining anti

45 TCS is the example of the staining anti-oxidant
oxidant anti-oxidant oxidant oxidant

46 The rayon also known as nylon orelon viscose resin viscose

The rayon polymers belongs

47 silicon polymers epoxy polymers organic polymer rubber silicon polymers
to the

Which one of the following

urea- phenol-
48 should give the strength to polysulphides polychloroprene urea-formaldehyde
formaldehyde formaldehyde
the paper

Which one of the following urea- phenol- phenol-

49 polysulphides polychloroprene
is used as a core binders formaldehyde formaldehyde formaldehyde

Which one of the following urea- phenol-

50 polysulphides polychloroprene polysulphides
is used as fuel material formaldehyde formaldehyde

which one of the following is

urea- phenol-
51 used to coating the wires polysulphides polychloroprene polychloroprene
formaldehyde formaldehyde
and cables
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: IV (POLYMER PROCESSING) BATCH-2017-2019

Which one of the following

is used as the insulation urea- phenol-
52 polybutadiene polysulphides polybutadiene
material in electrical formaldehyde formaldehyde
industry
Which one of the following
urea- phenol- polyvinyl polyvinyl
53 is consider as life saving polybutadiene
formaldehyde formaldehyde pyrrolidine pyrrolidine
substance
Which one of the following
54 is used in the paints and polybutadiene polysulphides polyvinyl pyrrolidine polyvinyl fluoride polyvinyl fluoride
surface coatings
Which one of the following
polyvinylidene polyvinylidene
55 is used to form the PVC polybutadiene polysulphides
chloride chloride
thermoplastic material

Which one of the following

56 PPG PVC PEG PABA PPG
is the liquid resins

57 PEG also known as alcowax carbowax hydrowax rubber carbowax

Which one of the following

is used as the surface
58 polyamines polyamides polyimides polyvinyls polyimides
coating in the supersonic
airgraft

Which one of the following

59 HDPE LDPE PPG PEG HDPE
is used to making the toys

Condensation
60 Nylon is not a ? Homo polymer Polyamide Caprolactum Homo polymer
polymer
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE:17CHP305A UNIT:V (PROPERTIES OF COMMERCIAL POLYMERS) BATCH: 2017-2019

UNIT – V
SYLLABUS

Polyethylene, polyvinyl chloride, polyamides, polyesters, phenolic resins, epoxy resins and
silicone polymers. Functional polymers, Fire retarding polymers and electrically conducting
polymers. Biomedical polymers – contact lens, dental polymers, artificial heart, kidney, skin and
blood cells.

Commercial Polymers
Synthetic polymers are human-made polymers. From the utility point of view they can be
classified into four main categories: thermoplastics, thermosets, elastomers and synthetic fibers.
They are found commonly in a variety of consumer products such as money, super glue, etc.
A wide variety of synthetic polymers are available with variations in main chain as well as side
chains. The back bones of common synthetic polymers such as polythene, polystyrene and poly
acrylates are made up of carbon-carbon bonds, whereas hetero chain polymers such as polyamides,
polyesters, polyurethanes, polysulfides and polycarbonates have other elements (e.g. oxygen,
sulfur, nitrogen) inserted along the backbone. Also silicon forms similar materials without the need
of carbon atoms, such as silicones through siloxane linkages; these compounds are thus said to be
inorganic polymers. Coordination polymers may contain a range of metals in the backbone, with
non-covalent bonding present.
Some familiar household synthetic polymers include: Nylons in textiles and fabrics, Teflon in non-
stick pans, Bakelite for electrical switches, polyvinyl chloride (PVC) in pipes, etc. The common
PET bottles are made of a synthetic polymer, polyethylene terephthalate. The plastic kits and
covers are mostly made of synthetic polymers like polythene and tires are manufactured from Buna
rubbers.[1] However, due to the environmental issues created by these synthetic polymers which
are mostly non-biodegradable and often synthesized from petroleum, alternatives like bioplastics
are also being considered. They are however expensive when compared to the synthetic polymers.
1. Polyethylene
Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(ethylene)) is the
most common plastic. The annual global production is around 80 million tonnes. Its primary use
is in packaging (plastic bags, plastic films, geomembranes, containers including bottles, etc.).
Many kinds of polyethylene are known, with most having the chemical formula (C2H4)n. PE is
usually a mixture of similar polymers of ethylene with various values of n.

Properties
The properties of polyethylene can be divided into mechanical, chemical, electrical, optical, and
thermal properties.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 1/26

Mechanical properties
Polyethylene is of low strength, hardness and rigidity, but has a high ductility and impact strength
as well as low friction. It shows strong creep under persistent force, which can be reduced by
addition of short fibers. It feels waxy when touched.
Thermal properties
The usefulness of polyethylene is limited by its melting point of 80 °C (176 °F) (HDPE, types of
low crystalline softens earlier). For common commercial grades of medium- and high-density
polyethylene the melting point is typically in the range 120 to 180 °C (248 to 356 °F). The melting
point for average, commercial, low-density polyethylene is typically 105 to 115 °C (221 to 239
°F). These temperatures vary strongly with the type of polyethylene.
Chemical properties
Polyethylene consists of nonpolar, saturated, high molecular weight hydrocarbons. Therefore, its
chemical behavior is similar to paraffin. The individual macromolecules are not covalently linked.
Because of their symmetric molecular structure, they tend to crystallize; overall polyethylene is
partially crystalline. Higher crystallinity increases density and mechanical and chemical stability.
Most LDPE, MDPE, and HDPE grades have excellent chemical resistance, meaning they are not
attacked by strong acids or strong bases, and are resistant to gentle oxidants and reducing agents.
Crystalline samples do not dissolve at room temperature. Polyethylene (other than cross-linked
polyethylene) usually can be dissolved at elevated temperatures in aromatic hydrocarbons such as
toluene or xylene, or in chlorinated solvents such as trichloroethane or trichlorobenzene.
Polyethylene absorbs almost no water. The gas and water vapor permeability (only polar gases) is
lower than for most plastics; oxygen, carbon dioxide and flavorings on the other hand can pass it
easily.
PE can become brittle when exposed to sunlight, carbon black is usually used as a UV stabilizer.
Polyethylene burns slowly with a blue flame having a yellow tip and gives off an odour of paraffin
(similar to candle flame). The material continues burning on removal of the flame source and
produces a drip.
Polyethylene cannot be imprinted or stuck together without pretreatment.
Electrical properties
Polyethylene is a good electrical insulator. It offers good tracking resistance; however, it becomes
easily electrostatically charged (which can be reduced by additions of graphite, carbon black or
antistatic agents).
Optical properties
Depending on thermal history and film thickness PE can vary between almost clear (transparent),
milky-opaque (translucent) or opaque. LDPE thereby owns the greatest, LLDPE slightly less and
HDPE the least transparency. Transparency is reduced by crystallites if they are larger than the
wavelength of visible light

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 2/26

High-density polyethylene (HDPE)

3
HDPE is defined by a density of greater or equal to 0.941 g/cm . HDPE has a low degree of
HDPE pipe installation in storm drain project in Mexico
branching. The mostly linear molecules pack together well, so intermolecular forces are stronger
than in highly branched polymers. HDPE can be produced by chromium/silica catalysts,
ZieglerNatta catalysts or metallocene catalysts; by choosing catalysts and reaction conditions, the
small amount of branching that does occur can be controlled. These catalysts prefer the formation
of free radicals at the ends of the growing polyethylene molecules. They cause new ethylene
monomers to add to the ends of the molecules, rather than along the middle, causing the growth of
a linear chain.
HDPE has high tensile strength. It is used in products and packaging such as milk jugs, detergent
bottles, butter tubs, garbage containers, and water pipes. One-third of all toys are manufactured
from HDPE. In 2007, the global HDPE consumption reached a volume of more than 30 million
tons.
Low-density polyethylene (LDPE)
LDPE is defined by a density range of 0.910–0.940 g/cm3. LDPE has a high degree of short- and
long-chain branching, which means that the chains do not pack into the crystal structure as well.
It has, therefore, less strong intermolecular forces as the instantaneous-dipole induced-dipole
attraction is less. This results in a lower tensile strength and increased ductility. LDPE is created
by free-radical polymerization. The high degree of branching with long chains gives molten LDPE
unique and desirable flow properties. LDPE is used for both rigid containers and plastic film
applications such as plastic bags and film wrap. In 2013, the global LDPE market had a volume of
almost US$33 billion.
The radical polymerization process used to make LDPE does not include a catalyst that
"supervises" the radical sites on the growing PE chains. (In HDPE synthesis, the radical sites are
at the ends of the PE chains, because the catalyst stabilizes their formation at the ends.) Secondary
radicals (in the middle of a chain) are more stable than primary radicals (at the end of the chain),
and tertiary radicals (at a branch point) are more stable yet. Each time an ethylene monomer is
added, it creates a primary radical, but often these will rearrange to form more stable secondary or
tertiary radicals. Addition of ethylene monomers to the secondary or tertiary sites creates
branching.

Production
Production of LDPE by addition polymerization requires:

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 3/26

• temperature range of 100-300oC
• very high pressure 1500-3000 atmospheres
• oxygen or an organic peroxide such as dibutyl peroxide, benzoyl peroxide or diethyl peroxide
as initiator.
An initiator is a substance which is added in small quantities and is decomposed by light
or heat to produce a free radical (R.). A free radical is formed when a covalent bond is
broken and a bonding electron is left on each part of the broken molecule. Since the O-O
covalent bond is weak, free radicals are easily formed from oxygen or peroxides.
• benzene or chlorobenzene used as the solvent since both polymer (polythene) and monomer
(ethene) dissolve in these compounds at the temperature and pressure used. Water or other
liquids may be added to dissipate the heat of reaction as the polymerization reaction is highly
exothermic.

Production of HDPE
1. Production of HDPE by addition polymerization with a supported metal oxide catalyst
requires:
o temperature ~300oC
o 1 atmosphere pressure (101.3kPa)
o aluminium-based metal oxide catalyst (metallocene catalyst)

The catalyst can be used in a variety of operating modes including fixed-bed, moving-
bed, fluid-bed or slurry processes
o The ethene (ethylene) monomer is fed with a paraffin or cycloparaffin diluent
(diluting agent). After polymerization the polymer (polythene) is recovered by
cooling or by solvent evaporation.
2. Production of HDPE by coordination polymerization requires:
o temperature 50-75oC o slight pressure
o Coordination catalyst is prepared as a colloidal suspension by reacting an
aluminium alkyl and titanium chloride (TiCl4) in a solvent such as heptane
(C7H16).
o The polymer (polythene) forms as a powder or granules which are insoluble in the
reaction mixture. When the polymerization is completed, the catalyst is destroyed
by adding water or alcohol to the reaction mixture. The polymer (polythene) is then
filtered or centrifuged off, washed and dried.
2. Polyvinyl chloride

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 4/26

Polyvinyl chloride

Polyvinyl chloride (/ˌpɒlivaɪnəl ˈklɔːraɪd/), also known as poly vinyl or vinyl, commonly
abbreviated PVC, is the world's third-most widely produced synthetic plastic polymer, after
polyethylene and polypropylene.
PVC comes in two basic forms: rigid (sometimes abbreviated as RPVC) and flexible. The rigid
form of PVC is used in construction for pipe and in profile applications such as doors and windows.
It is also used for bottles, other non-food packaging, and cards (such as bank or membership cards).
It can be made softer and more flexible by the addition of plasticizers, the most widely used being
phthalates. In this form, it is also used in plumbing, electrical cable insulation, imitation leather,
signage, phonograph records, inflatable products, and many applications where it replaces rubber.
Pure polyvinyl chloride is a white, brittle solid. It is insoluble in alcohol but slightly soluble in
tetrahydrofuran.

Discovery
PVC was accidentally synthesized in 1872 by German chemist Eugen Baumann. The polymer
appeared as a white solid inside a flask of vinyl chloride that had been left exposed to sunlight. In
the early 20th century the Russian chemist Ivan Ostromislensky and Fritz Klatte of the German
chemical company Griesheim-Elektron both attempted to use PVC in commercial products, but
difficulties in processing the rigid, sometimes brittle polymer thwarted their efforts. Waldo Semon
and the B.F. Goodrich Company developed a method in 1926 to plasticize PVC by blending it
with various additives. The result was a more flexible and more easily processed material that soon
achieved widespread commercial use.

Production
Polyvinyl chloride is produced by polymerization of the vinyl chloride monomer (VCM), as shown.

About 80% of production involves suspension polymerization. Emulsion polymerization accounts

for about 12%, and bulk polymerization accounts for 8%. Suspension polymerization affords
particles with average diameters of 100–180 μm, whereas emulsion polymerization gives much
smaller particles of average size around 0.2 μm. VCM and water are introduced into the reactor
along with a polymerization initiator and other additives. The contents of the reaction vessel are
pressurized and continually mixed to maintain the suspension and ensure a uniform particle size
of the PVC resin. The reaction is exothermic and thus requires cooling. As the volume is reduced

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 5/26

during the reaction (PVC is denser than VCM), water is continually added to the mixture to
maintain the suspension.
The polymerization of VCM is started by compounds called initiators that are mixed into the
droplets. These compounds break down to start the radical chain reaction. Typical initiators include
dioctanoyl peroxide and dicetyl peroxydicarbonate, both of which have fragile O-O bonds. Some
initiators start the reaction rapidly but decay quickly, and other initiators have the opposite effect.
A combination of two different initiators is often used to give a uniform rate of polymerization.
After the polymer has grown by about 10 times, the short polymer precipitates inside the droplet
of VCM, and polymerization continues with the precipitated, solvent-swollen particles. The weight
average molecular weights of commercial polymers range from 100,000 to 200,000, and the
number average molecular weights range from 45,000 to 64,000.
Once the reaction has run its course, the resulting PVC slurry is degassed and stripped to remove
excess VCM, which is recycled. The polymer is then passed through a centrifuge to remove water.
The slurry is further dried in a hot air bed, and the resulting powder is sieved before storage or
pelletization. Normally, the resulting PVC has a VCM content of less than 1 part per million. Other
production processes, such as micro-suspension polymerization and emulsion polymerization,
produce PVC with smaller particle sizes (10 μm vs. 120–150 μm for suspension PVC) with slightly
different properties and with somewhat different sets of applications.
Properties
PVC is a thermoplastic polymer. Its properties are usually categorized based on rigid and flexible
PVCs.

Mechanical
PVC has high hardness and mechanical properties. The mechanical properties enhance with the
molecular weight increasing but decrease with the temperature increasing. The mechanical
properties of rigid PVC (uPVC) are very good; the elastic modulus can reach 1500-3,000 MPa.
The soft PVC (flexible PVC) elastic is 1.5–15 MPa.
Thermal and fire
The heat stability of raw PVC is very poor, so the addition of a heat stabilizer during the process
is necessary in order to ensure the product's properties. PVC starts to decompose when the
temperature reaches 140 °C (284 °F), with melting temperature starting around 160 °C (320 °F).
The linear expansion coefficient of rigid PVC is small and has good flame retardancy, the Limiting
oxygen index (LOI) being up to 45 or more. The LOI is the minimum concentration of oxygen,
expressed as a percentage, that will support combustion of a polymer and noting that air has 20%
content of oxygen.
Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 6/26
Electrical
PVC is a polymer with good insulation properties, but because of its higher polar nature the
electrical insulating property is inferior to non polar polymers such as polyethylene and
polypropylene.
Since the dielectric constant, dielectric loss tangent value, and volume resistivity are high, the
corona resistance is not very good, and it is generally suitable for medium or low voltage and low
frequency insulation materials.
Chemical
PVC is chemically resistant to acids, salts, bases, fats, and alcohols; therefore, it is used in sewerage
piping. It is also resistant to some solvents, mainly uPVC. Plasticized PVC, also known as PVC-
P, is in some cases less resistant to solvents. For example, PVC is resistant to fuel and some paint
thinners. Some solvents may only swell it or deform it but not dissolve it, but some of them, like
tetrahydrofuran or acetone, may damage it.

Applications

PVC is used extensively in sewage pipe due to its low cost, chemical resistance and ease of
jointing Pipes
Roughly half of the world's polyvinyl chloride resin manufactured annually is used for producing
pipes for municipal and industrial applications. In the water distribution market, it accounts for
66% of the market in the U.S., and in sanitary sewer pipe applications, it accounts for 75%. Buried
PVC pipes in both water and sanitary sewer applications that are 4 inches (100 mm) in diameter
and larger are typically joined by means of a gasket-sealed joint. The most common type of gasket
utilized in North America is a metal reinforced elastomer, commonly referred to as a Rieber sealing
system. Its light weight, low cost, and low maintenance make it attractive. However, it must be
carefully installed and bedded to ensure longitudinal cracking and overbelling does not occur.
Additionally, PVC pipes can be fused together using various solvent cements, or heat-fused (butt-
fusion process, similar to joining HDPE pipe), creating permanent joints that are virtually
impervious to leakage.
In February 2007 the California Building Standards Code was updated to approve the use of
chlorinated polyvinyl chloride (CPVC) pipe for use in residential water supply piping systems.
CPVC has been a nationally accepted material in the U.S. since 1982; California, however, has
permitted only limited use since 2001. The Department of Housing and Community Development
prepared and certified an environmental impact statement resulting in a recommendation that the
commission adopt and approve the use of CPVC. The commission's vote was unanimous, and
CPVC has been placed in the 2007 California Plumbing Code.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 7/26

Electric cables
PVC is commonly used as the insulation on electrical cables; PVC used for this purpose needs to
be plasticized. Flexible PVC coated wire and cable for electrical use has traditionally been
stabilised with lead, but these are being replaced with calcium-based systems.
In a fire, PVC-coated wires can form hydrogen chloride fumes; the chlorine serves to scavenge
free radicals and is the source of the material's fire retardance. While hydrogen chloride fumes can
also pose a health hazard in their own right, it dissolves in moisture and breaks down onto surfaces,
particularly in areas where the air is cool enough to breathe, and is not available for inhalation.
Frequently in applications where smoke is a major hazard (notably in tunnels and communal
areas), PVC-free cable insulation is preferred, such as low smoke zero halogen (LSZH) insulation.
Construction
"A modern Tudorbethan" house with uPVC gutters and downspouts, fascia, decorative imitation
"half-timbering", windows, and doors
PVC is a common, strong but lightweight plastic used in construction. It is made softer and more
flexible by the addition of plasticizers. If no plasticizers are added, it is known as uPVC
(unplasticized polyvinyl chloride) or rigid PVC.
uPVC is extensively used in the building industry as a low-maintenance material, particularly in
Ireland, the United Kingdom, in the United States and Canada. In the U.S. and Canada it is known
as vinyl or vinyl siding. The material comes in a range of colors and finishes, including a photo-
effect wood finish, and is used as a substitute for painted wood, mostly for window frames and
sills when installing insulated glazing in new buildings, or to replace older single-glazed windows.
Other uses include fascia, and siding or weatherboarding. This material has almost entirely
replaced the use of cast iron for plumbing and drainage, being used for waste pipes, drainpipes,
gutters and downspouts. uPVC is known as having strong resistance against chemicals, sunlight,
and oxidation from water.

Double glazed units

Signs
Polyvinyl chloride is formed in flat sheets in a variety of thicknesses and colors. As flat sheets,
PVC is often expanded to create voids in the interior of the material, providing additional thickness
without additional weight and minimal extra cost (see Closed-cell PVC foamboard). Sheets are cut
using saws and rotary cutting equipment. Plasticized PVC is also used to produce thin, colored, or
clear, adhesive-backed films referred to simply as vinyl. These films are typically cut on a
computer-controlled plotter (see Vinyl cutter) or printed in a wide-format printer. These sheets and
films are used to produce a wide variety of commercial signage products, including car body
stripes and stickers. Clothing and furniture

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 8/26

Black PVC trousers
PVC has become widely used in clothing, to either create a leather-like material or at times
simply for the effect of PVC. PVC clothing is common in Goth, Punk, clothing fetish and
alternative fashions. PVC is less expensive than rubber, leather, and latex which it is used to
simulate.
PVC fabric is water-resistant, so it is used in coats, skiing equipment, shoes, jackets, aprons, and
bags.
Healthcare
The two main application areas for single-use medically approved PVC compounds are flexible
containers and tubing: containers used for blood and blood components, for urine collection or for
ostomy products and tubing used for blood taking and blood giving sets, catheters, heart-lung
bypass sets, hemodialysis sets etc. In Europe the consumption of PVC for medical devices is
approximately 85,000 tons each year. Almost one third of plastic-based medical devices are made
from PVC. The reasons for using flexible PVC in these applications for over 50 years are numerous
and based on cost effectiveness linked to transparency, light weight, softness, tear strength, kink
resistance, suitability for sterilization and biocompatibility.
Flooring
Flexible PVC flooring is inexpensive and used in a variety of buildings covering the home,
hospitals, offices, schools, etc. Complex and 3Ddesigns are possible, which are then protected by
a clear wear layer. A middle vinyl foam layer also gives a comfortable and safe feel. The smooth,
tough surface of the upper wear layer prevents the buildup of dirt, which prevents microbes from
breeding in areas that need to be kept sterile, such as hospitals and clinics.
Wire rope
PVC coating placed onto wire rope and aircraft cable is used for general purpose applications. The
coating process consists of a jacketing application via pressurized extrusion. The benefits of PVC
coating on wire rope are for not only aesthetics, but for ergonomics, abrasion protection and
visibility. It is found in a variety of industries and environments both indoor and out. Other
applications

The handles of the Victorinox Swiss Army knives are made of PVC.
PVC has been used for a host of consumer products. One of its earliest mass-market consumer
applications was vinyl record production. More recent examples include wallcovering,

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 9/26

greenhouses, home playgrounds, foam and other toys, custom truck toppers (tarpaulins), ceiling
tiles and other kinds of interior cladding.
PVC piping is cheaper than metals used in musical instrument making; it is therefore a common
alternative when making instruments, often for leisure or for rarer instruments such as the
contrabass flute. 3. Polyamide
A polyamide is a macromolecule with repeating units linked by amide bonds.
Polyamides occur both naturally and artificially. Examples of naturally occurring polyamides are
proteins, such as wool and silk. Artificially made polyamides can be made through stepgrowth
polymerization or solid-phase synthesis yielding materials such as nylons, aramids, and sodium
poly(aspartate). Synthetic polyamides are commonly used in textiles, automotive applications,
carpets and sportswear due to their high durability and strength. The transportation manufacturing
industry is the major consumer, accounting for 35% of polyamide (PA) consumption.

Classification
Polymers of amino acids are known as polypeptides or proteins.
According to the composition of their main chain, synthetic polyamides are classified as follows:
Polyamide family Main chain Examples of polyamides Examples of
commercial products
Aliphatic Aliphatic Nylon PA 6 and PA 66 Zytel from DuPont,
polyamides Technyl from Solvay,
Rilsan and Rilsamid from
Arkema, Radipol from
Radici Group
Polyphthalamides Semi- PA 6T Trogamid T
aromatic = hexamethylenediamine + from Evonik Industries ,
terephthal ic acid Amodel from Solvay
Aramids = aromatic Aromatic Paraphenylenediamine + Kevlar and Nomex from
polyamides terephthalic acid DuPont, Teijinconex,
Twaron and Technora from
Teijin, Kermel from
Kermel.

All polyamides are made by the formation of an amide function to link two molecules of monomer
together. The monomers can be amides themselves (usually in the form of a cyclic lactam such as
caprolactam), α,ω-amino acids or a stoichiometric mixture of a diamine and a diacid. Both these
kinds of precursors give a homopolymer. Polyamides are easily copolymerized, and thus many
mixtures of monomers are possible which can in turn lead to many copolymers. Additionally many
nylon polymers are miscible with one another allowing the creation of blends.

Polymerization
Production of polymers requires the repeated joining of two groups to form an amide linkage. In
this case this specifically involves amide bonds, and the two groups involved are an amine group,
and a terminal carbonyl component of a functional group. These react to produce a carbon-nitrogen
bond, creating a singular amide linkage. This process involves the elimination of other atoms

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 10/26

previously part of the functional groups. The carbonyl-component may be part of either a
carboxylic acid group or the more reactive acyl halide derivative. The amine group and the
carboxylic acid group can be on the same monomer, or the polymer can be constituted of two
different bifunctional monomers, one with two amine groups, the other with two carboxylic acid
or acid chloride groups.
The condensation reaction is used to synthetically produce nylon polymers in industry. Nylons
must specifically include an straight chain (aliphatic) monomer. The amide link is produced from
an amine group (alternatively known as an amino group), and a carboxylic acid group. The
hydroxyl from the carboxylic acid combines with a hydrogen from the amine, and gives rise to
water, the elimination byproduct that is the namesake of the reaction.
As an example of condensation reactions, consider that in living organisms, Amino acids are
condensed with one another by an enzyme to form amide linkages (known as peptides). The
resulting polyamides are known as proteins or polypeptides. In the diagram below, consider the
amino-acids as single aliphatic monomers reacting with identical molecules to form a polyamide,
focusing on solely the amine and acid groups. Ignore the substituent R groups – under the
assumption the difference between the R groups are negligible:

The reaction of two amino acids. Many of these reactions produce long chain proteins
For fully aromatic polyamides or 'aramids' e.g. Kevlar, the more reactive acyl chloride is used as
a monomer. The polymerization reaction with the amine group eliminates hydrogen chloride. The
acid chloride route can be used as a laboratory synthesis to avoid heating and obtain an almost
instantaneous reaction. The aromatic moiety itself does not participate in elimination reaction, but
it does increase the rigidity and strength of the resulting material which leads to Kevlar's renowned
strength.
In the diagram below, Aramid is made from two different monomers which continuously alternate
to form the polymer. Aramid is an aromatic polyamide:

The reaction of 1,4-phenyl-diamine (para-phenylenediamine) and terephthaloyl chloride to produce

Aramid
Polyamides can also be synthesized from dinitriles using acid catalysis via an application of the

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 11/26

Ritter reaction. This method is applicable for preparation of nylon 1,6 from adiponitrile,
formaldehyde and water. Additionally, polyamides can be synthesized from glycols and dinitriles
using this method as well.

Synthesis of Nylon 1,6 from adiponitrile, formaldehyde, and water using sulfuric acid as a catalyst

Example: Nylon 66
Nylon 66

Nylon 66 (nylon 6-6, nylon 6/6 or nylon 6,6) is a type of polyamide or nylon. There are many
types of nylon: the two most common for textile and plastics industries are nylon 6 and nylon 66.
Nylon 66 is made of two monomers each containing 6 carbon
[1]
atoms, hexamethylenediamine and adipic acid, which give nylon 66 its name.

Synthesis and manufacturing

Hexamethylenediamine (top) and adipic acid (bottom), monomers used for polycondensation of
Nylon 66.
Nylon 66 is synthesized by polycondensation of hexamethylenediamine and adipic acid.
Equivalent amounts of hexamethylenediamine and adipic acid are combined with water in a
reactor. This is crystallized to make nylon salt, an ammonium/carboxylate mixture. The nylon salt
goes into a reaction vessel where polymerization process takes place either in batches or
continuously. n HOOC-(CH2)4-COOH + n H2N-(CH2)6-NH2 → [-OC-( CH2)4-CO-NH-(CH2)6-
NH-]n + (2n-1) H2O
Removing water drives the reaction toward polymerization through the formation of amide bonds
from the acid and amine functions. Thus molten nylon 66 is formed. It can either be extruded and
granulated at this point or directly spun into fibers by extrusion through a spinneret (a small metal
plate with fine holes) and cooling to form filaments.

Applications
In 2011 worldwide production was 2 million tons. At that time fibers consumed just over half of
production and engineering resins the rest. It is not used in films due to its inability to be oriented.
Fiber markets represented 55% of the 2010 demand with engineering thermoplastics being the
remainder.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 12/26

Nylon 66 is frequently used when high mechanical strength, rigidity, good stability under heat
and/or chemical resistance are required It is used in fibers for textiles and carpets and molded parts.
For textiles, fibers are sold under various brands, for example Nilit brands or the Cordura brand
for luggage, but it is also used in airbags, apparel, and for carpet fibres under the Ultron brand.
Nylon 66 lends itself well to make 3D structural objects, mostly by injection molding finding broad
use in auto application under the hood such as radiator end tanks, rocker covers, air intake
manifolds, oil pans and numerous other structural parts such as ball bearing cages, electro-
insulating elements, pipes, profiles, various machine parts, zip ties, conveyor belts, hoses, polymer
framed weapons, and the outer layer of turnout blankets.[clarification needed] Nylon 66 is also a popular
guitar nut material.
Nylon 66, especially glass fibre grades can be effectively fire retarded with halogen free products.
Phosphorus-based flame retardant systems are used in these fire-safe polymers and are based on
aluminium diethyl phosphinate and synergists. They are designed to meet UL 94flammability tests
as well as Glow Wire Ignition Tests (GWIT), Glow Wire Flammability Test (GWFI) and
Comparative Tracking Index (CTI). Main applications are in the electrical and electronics (E&E)
industry.
The Remington Nylon 66 was a .22 rifle manufactured by Remington Arms from 1959 to 1989. It
had a stock made from nylon 66.
3. Polyester

Polyester is a category of polymers that contain the ester functional group in their main chain. As
a specific material, it most commonly refers to a type called polyethylene terephthalate (PET).
Polyesters include naturally occurring chemicals, such as in the cutin of plant cuticles, as well as
synthetics through step-growth polymerization such as polybutyrate. Natural polyesters and a few
synthetic ones are biodegradable, but most synthetic polyesters are not. The material is used
extensively in clothing.
Depending on the chemical structure, polyester can be a thermoplastic or thermoset. There are also
polyester resins cured by hardeners; however, the most common polyesters are thermoplastics.
Fabrics woven or knitted from polyester thread or yarn are used extensively in apparel and home
furnishings, from shirts and pants to jackets and hats, bed sheets, blankets, upholstered furniture
and computer mouse mats. Industrial polyester fibers, yarns and ropes are used in car tire
reinforcements, fabrics for conveyor belts, safety belts, coated fabrics and plastic reinforcements
with high-energy absorption. Polyester fiber is used as cushioning and insulating material in
pillows, comforters and upholstery padding. Polyester fabrics are highly stain-resistant—in fact,
the only class of dyes which can be used to alter the color of polyester fabric are what are known
as disperse dyes.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 13/26

Polyester fibers are sometimes spun together with natural fibers to produce a cloth with blended
properties. Cotton-polyester blends (polycotton) can be strong, wrinkle and tear-resistant, and
reduce shrinking. Synthetic fibers in polyester also create materials with water, wind and
environmental resistance compared to plant-derived fibers. Disadvantages of cotton and polyester
blends include being less breathable than cotton and trapping more moisture while sticking to the
skin. They are also less fire resistant and can melt when ignited.
Polyester blends have been renamed so as to suggest their similarity or even superiority to natural
fibers (for example, China silk, which is a term in the textiles industry for a 100% polyester fiber
woven to resemble the sheen and durability of insect-derived silk).
Polyesters are also used to make bottles, films, tarpaulin, canoes, liquid crystal displays,
holograms, filters, dielectric film for capacitors, film insulation for wire and insulating tapes.
Polyesters are widely used as a finish on high-quality wood products such as guitars, pianos and
vehicle/yacht interiors. Thixotropic properties of spray-applicable polyesters make them ideal for
use on open-grain timbers, as they can quickly fill wood grain, with a high-build film thickness
per coat. Cured polyesters can be sanded and polished to a highgloss, durable finish.
Liquid crystalline polyesters are among the first industrially used liquid crystal polymers. They are
used for their mechanical properties and heat-resistance. These traits are also important in their
application as an abradable seal in jet engines.

Synthesis
Synthesis of polyesters is generally achieved by a polycondensation reaction. See "condensation
reactions in polymer chemistry". The general equation for the reaction of a diol with a diacid is :

(n+1) R(OH)2 + n R´(COOH)2 → HO[ROOCR´COO]nROH + 2n H2O

Azeotrope esterification
In this classical method, an alcohol and a carboxylic acid react to form a carboxylic ester. To
assemble a polymer, the water formed by the reaction must be continually removed by azeotrope
distillation.
Alcoholic transesterification

Transesterification: An alcohol-terminated oligomer and an ester-terminated oligomer

condense to form an ester linkage, with loss of an alcohol. R and R' are the two oligomer
chains, R'' is a sacrificial unit such as a methyl group (methanol is the byproduct of the
esterification reaction).

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 14/26

Acylation (HCl method)
The acid begins as an acid chloride, and thus the polycondensation proceeds with emission of
hydrochloric acid (HCl) instead of water. This method can be carried out in solution or as an
enamel.
Silyl method
In this variant of the HCl method, the carboxylic acid chloride is converted with the trimethyl
silyl ether of the alcohol component and production of trimethyl silyl chloride is obtained
Acetate method (esterification) Silyl acetate method Ring-opening polymerization
Aliphatic polyesters can be assembled from lactones under very mild conditions, catalyzed
anionically, cationically or metallorganically. A number of catalytic methods for the
copolymerization of epoxides with cyclic anhydrides have also recently been shown to provide a
wide array of functionalized polyesters, both saturated and unsaturated.
Cross-linking
Unsaturated polyesters are thermosetting resins. They are generally copolymers prepared by
polymerizing one or more diol with saturated and unsaturated dicarboxylic acids (maleic acid,
fumaric acid...) or their anhydrides. The double bond of unsaturated polyesters reacts with a vinyl
monomer, usually styrene, resulting in a 3-D cross-linked structure. This structure acts as a
thermoset. The exothermic cross-linking reaction is initiated through a catalyst, usually an organic
peroxide such as methyl ethyl ketone peroxide or benzoyl peroxide.

Example: Poly(ethylene terephthalate)

A polyester is a polymer (a chain of repeating units) where the individual units are held together
by ester linkages.

The diagram shows a very small bit of the polymer chain and looks pretty complicated. But it isn't
very difficult to work out - and that's the best thing to do: work it out, not try to remember it. You
will see how to do that in a moment.
The usual name of this common polyester is poly(ethylene terephthalate). The everyday name
depends on whether it is being used as a fibre or as a material for making things like bottles for
soft drinks.
When it is being used as a fibre to make clothes, it is often just called polyester. It may sometimes
be known by a brand name like Terylene.
When it is being used to make bottles, for example, it is usually called PET.
Making polyesters as an example of condensation polymerisation
In condensation polymerisation, when the monomers join together a small molecule gets lost.
That's different from addition polymerisation which produces polymers like poly(ethene) - in that
case, nothing is lost when the monomers join together. A polyester is made by a reaction involving
an acid with two -COOH groups, and an alcohol with two -OH groups.
In the common polyester drawn above:
The acid is benzene-1,4-dicarboxylic acid (old name: terephthalic acid). The alcohol is ethane-1,2-
diol (old name: ethylene glycol).

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 15/26

Now imagine lining these up alternately and making esters with each acid group and each alcohol
group, losing a molecule of water every time an ester linkage is made.

That would produce the chain shown above (although this time written without separating out the
carbon-oxygen double bond - write it whichever way you like).

Hydrolysis of polyesters
Simple esters are easily hydrolysed by reaction with dilute acids or alkalis.
Polyesters are attacked readily by alkalis, but much more slowly by dilute acids. Hydrolysis by
water alone is so slow as to be completely unimportant. (You wouldn't expect your polyester fleece
to fall to pieces if you went out in the rain!)
If you spill dilute alkali on a fabric made from polyester, the ester linkages are broken. Ethane1,2-
diol is formed together with the salt of the carboxylic acid.
Because you produce small molecules rather than the original polymer, the fibres are destroyed,
and you end up with a hole!
For example, if you react the polyester with sodium hydroxide solution:

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 16/26

5. Phenol formaldehyde resin

Phenol formaldehyde resins (PF) or phenolic resins are synthetic polymers obtained by the
reaction of phenol or substituted phenol with formaldehyde. Used as the basis for Bakelite, PFs
were the first commercial synthetic resins (plastics). They have been widely used for the
production of molded products including billiard balls, laboratory countertops, and as coatings and
adhesives. They were at one time the primary material used for the production of circuit boards
but have been largely replaced with epoxy resins and fiberglass cloth, as with fireresistant FR-4
circuit board materials.
There are two main production methods. One reacts phenol and formaldehyde directly to produce
a thermosetting network polymer, while the other restricts the formaldehyde to produce a
prepolymer known as novolac which can be moulded and then cured with the addition of more
formaldehyde and heat. There are many variations in both production and input materials that are
used to produce a wide variety of resins for special purposes.

Formation and structure

Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that
can be either acid- or base-catalysed. Since formaldehyde exists predominantly in solution as a
dynamic equilibrium of methylene glycol oligomers, the concentration of the reactive form of
formaldehyde depends on temperature and pH.
Phenol reacts with formaldehyde at the ortho and para sites (sites 2, 4 and 6) allowing up to 3 units
of formaldehyde to attach to the ring. The initial reaction in all cases involves the formation of a
hydroxymethyl phenol:
HOC6H5 + CH2O → HOC6H4CH2OH
The hydroxymethyl group is capable of reacting with either another free ortho or para site, or with
another hydroxymethyl group. The first reaction gives a methylene bridge, and the second forms
an ether bridge:
HOC6H4CH2OH + HOC6H5 → (HOC6H4)2CH2 + H2O
2 HOC6H4CH2OH → (HOC6H4CH2)2O + H2O
The diphenol (HOC6H4)2CH2 (sometimes called a "dimer") is called bisphenol F, which is an
important monomer in the production of epoxy resins. Bisphenol-F can further link generating tri-
and tetra-and higher phenol oligomers. Novolacs

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 17/26

Novolac
Novolacs are phenol-formaldehyde resins with a formaldeh yde to phenol molar ratio of less than
one. The polymerization is brought to completion using acid-catalysis such as oxalic acid,
hydrochloric acid or sulfonate acids. The phenol units are mainly linked by methylene and/or ether
groups. Novolacs are commonly used as photoresists. See also photolithography. The molecular
weights are in the low thousands, corresponding to about 10–20 phenol units.
Hexamethylenetetramine or "hexamine" is a hardener added to crosslink novolac. At a temperature
>90 °C, it forms methylene and dimethylene amino bridges.

Applications
Phenolic resins are found in a myriad of industrial products. Phenolic laminates are made by
impregnating one or more layers of a base material such as paper, fiberglass or cotton with phenolic
resin and laminating the resin-saturated base material under heat and pressure. The resin fully
polymerizes (cures) during this process forming the thermoset polymer matrix. The base material
choice depends on the intended application of the finished product. Paper phenolics are used in
manufacturing electrical components such as punch-through boards, in household laminates, and
in paper composite panels. Glass phenolics are particularly well suited for use in the high speed
bearing market. Phenolic micro-balloons are used for density control. Snooker balls as well as
balls from many table-based ball games are also made from phenol formaldehyde resin. The
binding agent in normal (organic) brake pads, brake shoes and clutch disks are phenolic resin.
Synthetic resin bonded paper, made from phenolic resin and paper, is used to make countertops.
Phenolic resins are also used for making exterior plywood commonly known as WBP (Weather &
boil proof) Plywood because phenolic resins have no melting point but only a decomposing point
in the temperature zone of 220 °C (428 °F) and above.
Phenolic resin is used as a binder in loudspeaker driver suspension components which are made of
cloth.
Billiard balls are made from solid Phenolic resin.
Sometimes people select phenolic resin parts because their coefficient of thermal expansion closely
matches that of the aluminium used for other parts of a system, as in early computer systems and
Duramold.
6. Epoxy
This article is about the thermoset plastic materials. For the chemical group, see epoxide.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 18/26

A syringe of "5-minute" epoxy glue, containing separate compartments for the epoxy resin and the
hardener.

Structure of the highly reactive epoxide group present in all epoxy resins.

Epoxy is either any of the basic components or the cured end products of epoxy resins, as well as
a colloquial name for the epoxidefunctional group.[1] Epoxy resins, also known as polyepoxides,
are a class of reactive prepolymers and polymers which contain epoxide groups. Epoxy resins may
be reacted (cross-linked) either with themselves through catalytic homopolymerisation, or with a
wide range of co-reactants including polyfunctional amines, acids (and acid anhydrides), phenols,
alcohols and thiols. These co-reactants are often referred to as hardeners or curatives, and the cross-
linking reaction is commonly referred to as curing. Reaction of polyepoxides with themselves or
with polyfunctional hardeners forms a thermosetting polymer, often with high mechanical
properties, temperature and chemical resistance. Epoxy has a wide range of applications, including
metal coatings, use in electronics / electrical components/LED, high tension electrical insulators,
paint brush manufacturing, fiberreinforced plastic materials and structural adhesives.

Epoxy resin

Structure of a cured epoxy glue. The triamine hardener is shown in red, the resin in black. The
resin's epoxide groups have reacted with the hardener and are not present anymore. The material

Epoxy resins are low molecular weight pre-polymers or higher molecular weight polymers which
is highly crosslinkedand contains many OH groups, which confer adhesive properties.
normally contain at least two epoxide groups. The epoxide group is also sometimes referred to as
a glycidyl or oxirane group.
A wide range of epoxy resins are produced industrially. The raw materials for epoxy resin
production are today largely petroleum derived, although some plant derived sources are now
becoming commercially available (e.g. plant derived glycerol used to make epichlorohydrin).
Epoxy resins are polymeric or semi-polymeric materials, and as such rarely exist as pure
substances, since variable chain length results from the polymerisation reaction used to produce
them. High purity grades can be produced for certain applications, e.g. using a distillation
purification process. One downside of high purity liquid grades is their tendency to form crystalline
solids due to their highly regular structure, which require melting to enable processing.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 19/26

An important criterion for epoxy resins is the epoxide content. This is commonly expressed as the
epoxy equivalent weight, which is the number of epoxide equivalents in 1 kg of resin (Eq./kg),
or as the equivalent weight, which is the weight in grammes of resin containing 1 mole equivalent
of epoxide (g/mol). One measure may be simply converted to another:
Equivalent weight (g/mol) = 1000 / epoxide number (Eq./kg)
The equivalent weight or epoxide number is used to calculate the amount of co-reactant (hardener)
to use when curing epoxy resins. Epoxies are typically cured with stoichiometric or near-
stoichiometric quantities of curative to achieve maximum physical properties.
As with other classes of thermoset polymer materials, blending different grades of epoxy resin, as
well as use of additives, plasticizers or fillers is common to achieve the desired processing or final
properties, or to reduce cost. Use of blending, additives and fillers is often referred to as
formulating.

Examples: Bisphenol A epoxy resin

Important epoxy resins are produced from combining epichlorohydrin and bisphenol A to give
bisphenol A diglycidyl ethers.

Structure of bisphenol-A diglycidyl ether epoxy resin: n denotes the number of polymerized
subunits and is typically in the range from 0 to 25
Increasing the ratio of bisphenol A to epichlorohydrin during manufacture produces higher
molecular weight linear polyethers with glycidyl end groups, which are semi-solid to hard
crystalline materials at room temperature depending on the molecular weight achieved. As the
molecular weight of the resin increases, the epoxide content reduces and the material behaves more
and more like a thermoplastic. Very high molecular weight polycondensates (ca. 30 000 – 70 000
g/mol) form a class known as phenoxy resins and contain virtually no epoxide groups (since the
terminal epoxy groups are insignificant compared to the total size of the molecule). These resins
do however contain hydroxyl groups throughout the backbone, which may also undergo other
cross-linking reactions, e.g. with aminoplasts, phenoplasts and isocyanates.
Bisphenol F epoxy resin
Bisphenol F may also undergo epoxidation in a similar fashion to bisphenol A. Compared to
DGEBA, bisphenol F epoxy resins have lower viscosity and a higher mean epoxy content per
gramme, which (once cured) gives them increased chemical resistance.

Applications
The applications for epoxy-based materials are extensive and include coatings, adhesives and
composite materials such as those using carbon fiber and fiberglass reinforcements (although
polyester, vinyl ester, and other thermosetting resins are also used for glass-reinforced plastic).
The chemistry of epoxies and the range of commercially available variations allows cure polymers
to be produced with a very broad range of properties. In general, epoxies are known for their
excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties and
very good electrical insulating properties. Many properties of epoxies can be modified (for

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 20/26

example silver-filled epoxies with good electrical conductivity are available, although epoxies are
typically electrically insulating). Variations offering high thermal insulation, or thermal
conductivity combined with high electrical resistance for electronics applications, are available. [6]
Paints and coatings
Two part epoxy coatings were developed for heavy duty service on metal substrates and use less
energy than heat-cured powder coatings. These systems provide a tough, protective coating with
excellent hardness. Some epoxy coatings are formulated as an emulsion in water, and can be
cleaned up without solvents. Epoxy coatings are often used in industrial and automotive
applications since they are more heat resistant than latex-based and alkyd-based paints. Epoxy
paints tend to deteriorate, known as "chalking out", due to UV exposure.[7]
Polyester epoxies are used as powder coatings for washers, driers and other "white goods". Fusion
Bonded Epoxy Powder Coatings (FBE) are extensively used for corrosion protection of steel pipes
and fittings used in the oil and gas industry, potable water transmission pipelines (steel), and
concrete reinforcing rebar. Epoxy coatings are also widely used as primers to improve the adhesion
of automotive and marine paints especially on metal surfaces where corrosion (rusting) resistance
is important. Metal cans and containers are often coated with epoxy to prevent rusting, especially
for foods like tomatoes that are acidic. Epoxy resins are also used for decorative flooring
applications such as terrazzo flooring, chip flooring, and colored aggregate flooring. Epoxies were
modified in a variety of ways, Reacted with fatty acids derived from oils to yield epoxy esters,
which were cured the same way as alkyds .
Adhesives

Epoxy adhesives are a major part of the class of adhesives called "structural adhesives" or
"engineering adhesives" (that includes polyurethane, acrylic, cyanoacrylate, and other
chemistries.) These high-performance adhesives are used in the construction of aircraft,
automobiles, bicycles, boats, golf clubs, skis, snowboards, and other applications where high
strength bonds are required. Epoxy adhesives can be developed to suit almost any application.
They can be used as adhesives for wood, metal, glass, stone, and some plastics. They can be made
flexible or rigid, transparent or opaque/colored, fast setting or slow setting. Epoxy adhesives are
better in heat and chemical resistance than other common adhesives. Some epoxies are cured by
exposure to ultraviolet light. Such epoxies are commonly used in optics, fiber optics, and
optoelectronics. Industrial tooling and composites
Epoxy systems are used in industrial tooling applications to produce molds, master models,
laminates, castings, fixtures, and other industrial production aids. This "plastic tooling" replaces

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 21/26

metal, wood and other traditional materials, and generally improves the efficiency and either
lowers the overall cost or shortens the lead-time for many industrial processes. Epoxies are also
used in producing fiber-reinforced or composite parts. They are more expensive than polyester
resins and vinyl ester resins, but usually produce stronger and more temperatureresistant thermoset
polymer matrix composite parts.
Electrical systems and electronics

An epoxy encapsulated hybrid circuit on a printed circuit board.

The interior of a pocket calculator. The dark lump of epoxy in the center covers the processor
chip

Epoxy resin formulations are important in the electronics industry, and are employed in motors,
generators, transformers, switchgear, bushings, and insulators. Epoxy resins are excellent
electrical insulators and protect electrical components from short circuiting, dust and moisture. In
the electronics industry epoxy resins are the primary resin used in overmolding integrated circuits,
transistors and hybrid circuits, and making printed circuit boards. The largest volume type of
circuit board—an "FR-4 board"—is a sandwich of layers of glass cloth bonded into a composite
by an epoxy resin. Epoxy resins are used to bond copper foil to circuit board substrates, and are a
component of the solder mask on many circuit boards.
Petroleum & petrochemical
Epoxies can be used to plug selective layers in a reservoir which are producing excessive brine.
The technique is named "water shut-off treatment".[2]
Consumer and marine applications
Epoxies are sold in hardware stores, typically as a pack containing separate resin and hardener,
which must be mixed immediately before use. They are also sold in boat shops as repair resins for
marine applications. Epoxies typically are not used in the outer layer of a boat because they
deteriorate by exposure to UV light. They are often used during boat repair and assembly, and then
over-coated with conventional or two-part polyurethane paint or marine-varnishes that provide UV
protection.
There are two main areas of marine use. Because of the better mechanical properties relative to the
more common polyester resins, epoxies are used for commercial manufacture of components
where a high strength/weight ratio is required. The second area is that their strength, gap filling
properties and excellent adhesion to many materials including timber have created a boom in
amateur building projects including aircraft and boats.
Epoxy materials tend to harden somewhat more gradually, while polyester materials tend to harden
quickly, particularly if a lot of catalyst is used.[9] The chemical reactions in both cases are

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 22/26

exothermic. Large quantities of mix will generate their own heat and greatly speed the reaction, so
it is usual to mix small amounts which can be used quickly.
As adhesives, epoxies bond in three ways: a) Mechanically, because the bonding surfaces are
roughened; b) By proximity, because the cured resins are physically so close to the bonding
surfaces that they are hard to separate; c) Ionically, because the epoxy resins form ionic bonds at
an atomic level with the bonding surfaces. This last is substantially the strongest of the three. By
contrast, polyester resins can only bond using the first two of these, which greatly reduces their
utility as adhesives and in marine repair.
Aerospace applications
In the aerospace industry, epoxy is used as a structural matrix material which is then reinforced by
fiber. Typical fiber reinforcements include glass, carbon, Kevlar, and boron. Epoxies are also used
as a structural glue. Materials like wood, and others that are 'low-tech' are glued with epoxy resin.
Biology
Water-soluble epoxies such as Durcupan are commonly used for embedding electron microscope
samples in plastic so they may be sectioned (sliced thin) with a microtomeand then imaged. Art
Epoxy resin, mixed with pigment, may be used as a painting medium, by pouring layers on top of
each other to form a complete picture.
Industry
These commodity epoxy manufacturers mentioned above typically do not sell epoxy resins in a
form usable to smaller end users, so there is another group of companies that purchase epoxy raw
materials from the major producers and then compounds (blends, modifies, or otherwise
customizes) epoxy systems from these raw materials. These companies are known as
"formulators". The majority of the epoxy systems sold are produced by these formulators and they
comprise over 60% of the dollar value of the epoxy market. There are hundreds of ways that these
formulators can modify epoxies—by adding mineral fillers (talc, silica, alumina, etc.), by adding
flexibilizers, viscosity reducers, colorants, thickeners, accelerators, adhesion promoters, etc. These
modifications are made to reduce costs, to improve performance, and to improve processing
convenience. As a result, a typical formulator sells dozens or even thousands of formulations—
each tailored to the requirements of a particular application or market.

7. Silicone

Silicone caulk can be used as a basic sealant against water and air penetration.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 23/26

Silicones, also known as polysiloxanes, are polymers that include any inert, synthetic compound
made up of repeating units of siloxane, which is a chain of alternating silicon atoms and oxygen
atoms, frequently combined with carbon and/or hydrogen. They are typically heatresistant and
rubber-like, and are used in sealants, adhesives, lubricants, medicine, cooking utensils, and thermal
and electrical insulation. Some common forms include silicone oil, silicone grease, silicone rubber,
silicone resin, and silicone caulk. Silicones are of three types: 1. straight chain silicones; 2. cyclic
silicones; 3. crosslinked silicones.

Synthesis
Most common are materials based on polydimethylsiloxane, which is derived by hydrolysis of
dimethyldichlorosilane. This dichloride reacts with water as follows:
n Si(CH3)2Cl2 + n H2O → [Si(CH3)2O]n + 2n HCl
The polymerization typically produces linear chains capped with Si-Cl or Si-OH (silanol) groups.
Under different conditions the polymer is a cyclic, not a chain.
For consumer applications such as caulks silyl acetates are used instead of silyl chlorides. The
hydrolysis of the acetates produce the less dangerous acetic acid (the acid found in vinegar) as the
reaction product of a much slower curing process. This chemistry is used in many consumer
applications, such as silicone caulk and adhesives.
Branches or cross-links in the polymer chain can be introduced by using organosilicone precursors
with fewer alkyl groups, such as methyltrichlorosilane and methyltrimethoxysilane. Ideally, each
molecule of such a compound becomes a branch point. This process can be used to produce hard
silicone resins. Similarly, precursors with three methyl groups can be used to limit molecular
weight, since each such molecule has only one reactive site and so forms the end of a siloxane
chain.
Combustion
When silicone is burned in air or oxygen, it forms solid silica (silicon dioxide)(SiO2) as a white
powder, char, and various gases. The readily dispersed powder is sometimes called silica fume.

Properties
Silicones exhibit many useful characteristics, including:[1]
• Low thermal conductivity
• Low chemical reactivity
• Low toxicity
• Thermal stability (constancy of properties over a wide temperature range of −100 to 250
°C).
• The ability to repel water and form watertight seals.
• Does not stick to many substrates, but adheres very well to others, e.g. glass.
• Does not support microbiological growth.
• Resistance to oxygen, ozone, and ultraviolet (UV) light. This property has led to
widespread use of silicones in the construction industry (e.g. coatings, fire protection,
glazing seals) and the automotive industry (external gaskets, external trim).
• Electrical insulation properties. Because silicone can be formulated to be electrically
insulative or conductive, it is suitable for a wide range of electrical applications.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 24/26

• High gas permeability: at room temperature (25 °C), the permeability of silicone rubber for
such gases as oxygen is approximately 400 times[citation needed] that of butyl rubber, making
silicone useful for medical applications in which increased aeration is desired. Conversely,
silicone rubbers cannot be used where gas-tight seals are necessary.
Uses
Silicones are used in many products. Ullmann's Encyclopedia of Industrial Chemistry lists the
following major categories of application: Electrical (e.g., insulation), electronics (e.g., coatings),
household (e.g., sealants for cooking apparatus), automobile (e.g., gaskets), aeroplane (e.g., seals),
office machines (e.g., keyboard pads), medicine/dentistry (e.g., teeth impression molds),
textiles/paper (e.g., coatings). For these applications, an estimated 400,000 tons of silicones were
produced in 1991. Specific examples, both large and small are presented below.
Automotive
In the automotive field, silicone grease is typically used as a lubricant for brake components since
it is stable at high temperatures, is not water-soluble, and is far less likely than other lubricants to
foul. It is also used as DOT 5 brake fluid.
Automotive spark plug wires are insulated by multiple layers of silicone to prevent sparks from
jumping to adjacent wires, causing misfires. Silicone tubing is sometimes used in automotive
intake systems (especially for engines with forced induction).
Sheet silicone is used to manufacture gaskets used in automotive engines, transmissions, and other
applications.
Automotive body manufacturing plants and paint shops avoid silicones, as they may cause "fish
eyes", small, circular craters in the finish.
Coatings
Silicone films can be applied to such silica-based substrates as glass to form a covalently bonded
hydrophobic coating.
Many fabrics can be coated or impregnated with silicone to form a strong, waterproof composite
such as silnylon.
Cookware

Soup ladle and pasta ladle made of silicone.

A silicone food steamer to be placed inside a pot of boiling water.
Ice cube trays made of silicone.
As a low-taint, non-toxic material, silicone can be used where contact with food is
required. Silicone is becoming an important product in the cookware industry,
particularly bakeware and kitchen utensils.
Silicone is used as an insulator in heat-resistant potholders and similar items; however, it
is more conductive of heat than similar less dense fiber-based products. Silicone oven mitts
are able to withstand temperatures up to 260 °C (500 °F), allowing reaching into boiling
water.
Molds for chocolate, ice, cookies, muffins and various other foods.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 25/26

Non-stick bakeware and reusable mats used on baking sheets.
Other products such as steamers, egg boilers or poachers, cookware lids, pot holders,
trivets, and kitchen mats.
Defoaming
Silicones are used as active compound in defoamers due to their low water solubility and good
spreading properties. Dry cleaning
Liquid silicone can be used as a dry cleaning solvent, providing an alternative to the traditional
chlorine-containing perchloroethylene (perc)solvent. Use of silicones in dry cleaning reduces the
environmental impact of a typically high-polluting industry.
Electronics
Electronic components are sometimes encased in silicone to increase stability against mechanical
and electrical shock, radiation and vibration, a process called "potting".
Silicones are used where durability and high performance are demanded of components under hard
conditions, such as in space (satellite technology). They are selected over polyurethane or epoxy
encapsulation when a wide operating temperature range is required (−65 to 315 °C). Silicones also
have the advantage of little exothermic heat rise during cure, low toxicity, good electrical
properties and high purity.
The use of silicones in electronics is not without problems, however. Silicones are relatively
expensive and can be attacked by solvents. Silicone easily migrates as either a liquid or vapor onto
other components.
Silicone contamination of electrical switch contacts can lead to failures by causing an increase in
contact resistance, often late in the life of the contact, well after any testing is completed. Use of
silicone-based spray products in electronic devices during maintenance or repairs can cause later
failures.
Firestops
Silicone foam has been used in North American buildings in an attempt to firestop openings within
fire-resistance-rated wall and floor assemblies to prevent the spread of flames and smoke from one
room to another. When properly installed, silicone-foam firestops can be fabricated for building
code compliance. Advantages include flexibility and high dielectric strength. Disadvantages
include combustibility (hard to extinguish) and significant smoke development. Silicone-foam
firestops have been the subject of controversy and press attention due to smoke development from
pyrolysis of combustible components within the foam, hydrogen gas escape, shrinkage, and
cracking. These problems have led to reportable events among licensees (operators of nuclear
power plants) of the Nuclear Regulatory Commission (NRC).
Silicone firestops are also used in aircraft.

Prepared by Dr. S. Manickasundaram, Assistant Professor, Dept. of Chemistry, KAHE 26/26

KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: V (PROPERTIES OF COMMERCIAL POLYMERS) BATCH-2017-2019

Questions Opt-1 Opt-2 Opt-3 Opt-4 Answers

Which is more flexible than

Low Density Low density Low Density
1 HDPE due to lower Polyethylene Polyamide
Polyethylene polyamide Polyethylene
crystallinity?

80-90% of all plasticizers

2 DOP DIOP PVC Colourants PVC
used with?

It must not exude from the Primary Secondary

3 Antioxidents Colourants Primary plasticizers
plastic material? plasticizers plasticizers

Limited compatibility with Primary Secondary Secondary

4 Antioxidents Colourants
the polymers are? plasticizers plasticizers plasticizers
Inhibiting the oxidation of
polymers is usually filled by
5 Antioxidants Flame retardants Colourants Mgo Antioxidants
a substance which itself is
readily oxidized.
In polymer industry 2-
6 hydroxybenzophones are Light stabilizers Antioxidants Polymer initiators Fillers Light stabilizers
used as
Any of a group of
substances that are used in
plastics or other materials to
7 Plasticizers Antioxidants Polymer initiators Fillers Plasticizers
impart viscosity, flexibility,
softness or other properties
to the finished product
KARPAGAM ACADEMY OF HIGHER EDUCATION
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It often added to
semicrystalline polymer to
8 Light stabilizers Colouarants Plasticizers Flame retardents Plasticizers
lower the value of Tg below
room temperature.
The basic requirement that
must be met by a plasticizer Compatibility Prevent oxidation Retard flame Impart a colour Compatibility
9
are

Porosity increased as Suddenly

10 Increased Decreased Never change Increased
plasticizers content? decreased
The substances which
weaken the intermolecular
11 Plasticizers Antioxidants Polymer initiators Fillers Plasticizers
forces between the polymer
chains and decrease Tg.
Which content did not have
12 a significant effect on the Light stabilizers Colouarants Plasticizers Flame retardents Plasticizers
rate of erosion?
Which type of compound is
Aluminum Halogen Phosphorous
13 not used as a flame Ferrocene Ferrocene
Hydroxide compounds compounds
retardant in polymers
Chemical compounds
capable of interfering with
14 the physical and chemical Plasticizers Antioxidants Polymer initiators Light stabilizer Light stabilizer
processes of UV light-
induced degradation .
which one of the following
polymers is the product of a Polytetrafluoroeth
15 Polypropylene Polyacetic acid PVC Polyacetic acid
condensation ene
polymerisation reaction?
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
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The phenol-formaldehyde
resins are formed by Addition Cationic Condensation Anionic Condensation
16
polymerisation of phenol polymerisation polymerisation polymerisation polymerisation polymerisation
and formaldehyde by
The addition of polyethylene
Electrolytic Dielectric Electric
17 glycol in dielectric property Ionic conductivity Ionic conductivity
conductivity conductivity conductivity
significantly improves?

White crystaline White crystaline

18 Melamine is Gas Colourless liquid Yellow liquid
solid solid

19 Plastics are ? Hydrocarbons Aldehyde Ester Amide Hydrocarbons

Which one is an inorganic

20 Barium sulfate Perylenes Pyrroles Arylamides Barium sulfate
pigment?

An allotrope An addition A polymer of An addition

An isomer of vinyl
21 Poly vinyl chloride is? polymer of vinyl product of vinyl hydrated vinyl product of vinyl
chloride
chloride chloride chloride chloride

Which one is more active Aluminum Antimony Halogen Antimony

22 Phosphorous
flame retardant? hydroxide oxychloride compounds oxychloride

The most useful material

Antimony Aluminum Halogen Antimony
23 imparting flame retardance Antimony trioxide
trioxide hydroxide compounds oxychloride
to plastics is?
Which one of the following
24 flame retardant forms a gas Calcium Phosphorous Ammonium Aluminium oxide Phosphorous
shield layer?
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: V (PROPERTIES OF COMMERCIAL POLYMERS) BATCH-2017-2019

Which one of the following

flame retardant breaks Aluminum Aluminum
25 Phosphorous Ammonium Aluminium oxide
down endothermic Hydroxide Hydroxide
reaction?
Melting Point of Low
26 Density Polyethylene (LDPE) ~115oC ~116 oC ~135oC ~148 oC ~135oC
is?

Which one is a synthetic

27 Cellulose Cotton Polyamide Fibers Polyamide
polymer?

Polymethyl methacrylate is
28 a colourless and transparent Plastic Rubber Cotton Nylon Plastic
?
Polymethyl methacrylate
29 can be prepared by using Nitric acid Acetic acid Sulphuric acid Hydrochloric acid Sulphuric acid
acetone cyanohydrin and

Silicones was commercially

30 1943 1930 1936 1947 1943
introduced in ?

Polyvinyl chloride was

31 commercially introduced in 1943 1930 1936 1947 1936
?
Polyvinyl acetate monomer
32 is prepared by the reaction Benzaldehyde Acetaldehyde Acetic acid Sodium acetate Acetaldehyde
of acetic anhydride with ?

Polyvinyl acetate is used for Polyvinyl Poly methyl

33 Polyvinyl alcohol Polyvinyl acetate Polyvinyl alcohol
the manufacture of ? chloride methacrylate
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Styrene(butadiene rubber)
34 was commercially 1943 1930 1936 1947 1930
introduced during the year

Polyvinyl acetate is insoluble

35 Alcohols Aromatic solvents Esters Water Water
in which solvent?

Polythene was first

36 1877 1853 1890 1898 1898
synthesied in ?

Polythene was first

37 German England India USA England c
produced in ?

Polyethylene was first

38 Pechmann Fawcett Karl ziegler Walter Pechmann
synthesized by ?

Which one of the compound

39 is used in the manufacture Vinyl chloride Ethylene glycol Vinyl alcohol Ethylene Ethylene glycol
of terylene ?
Which one of the following
40 is an example of Terylene PVC Vinyl alcohol Ethylene Terylene
condensation polymer?
The synthetic polymer
41 which resembles natural Cotton Nylon Chloroprene Neoprene Neoprene
rubber is ?
Which one is prepared by
the melt polycondensation
42 Polyamides Polyester Acrylic fibre Polyethylene Polyamides
between dicarboxylic acids
and diamides.
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Aliphatic polyamides are

43 Cotton Nylon Polyamide Polyester Nylon
generally known as ?

Which one of the following

44 is obtained from dibasic Cotton Nylon Polyamide Polyester Nylon
acids and diamides.
The ring opening
polymerization of
45 Single number Double number Triple number No number Single number
lactometated is represented
only by ?
It has good tensile strength
46 Polyamides Polyester Acrylic fibre Polyethylene Polyamides
and abrasion resistance

It is used as a plastic as well

47 Polyamides Polyester Acrylic fibre Polyethylene Polyamides
as a fibre

Which one is used in tires

48 Cotton Nylon Polyamide Polyester Nylon
and ropes?

Which is used in clothes,

49 Cotton Nylon Polyamide Polyester Nylon
belts and accessories?

It is prepared by
polycondesation reaction
50 Polyamides Polyester Acrylic fibre Polyethylene Polyester
between a dicarboxylic acid
and a diol.
Which polymers contains
51 ester groups in the main Polyamides Polyester Acrylic fibre Polyethylene Polyester
chain of the polymer itself.
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The molecular weight of 20000 to

52 10000 to 20000 10000 to 12000 1000 to 2000 20000 to 500000
cellulose varies between 500000

Condensation
53 polymerization is not used Polyester Nylon 6 Nylon 66 Polypropylene Polypropylene
to produce
Polyethylene terephthalte
(PETP) has a high melting
54 Aliphatic chain Aromatic ring Nitrogen bond CN bond Aromatic ring
point because of the
presence of ?
Which one of the following
55 is resistant to heat and Polyamides Polyester Acrylic fibre Polyethylene Polyester
moisture.

56 PETP melts at ? 275oC 266oC 267oC 265oC 265oC

Which one of the following

is used in the manufacturing
Polyethylene Polyethylene
57 of magnetic recording tapes, Polyester Acrylic fibre Polyethylene
terephthalte terephthalte
aluminished sheets for
certain special applications?

The polymer made from Polyacrylic Polyethylene

58 Polyethylene Polyester Polyacrylic fibres
acrylenitrile ? fibres terephthalte

Polymer which contains

59 between 35-65% of Orlon Modaerylics Acrilan Verel Modaerylics
acrylonitrile are known as?

Polymers which contain 85%

60 Orlon Modaerylics Vinyl acetate Verel Orlon
or more acrylenitrile is?
KARPAGAM ACADEMY OF HIGHER EDUCATION
CLASS: II M.Sc CHEMISTRY COURSE NAME: POLYMER CHEMISTRY
COURSE CODE: 17CHP305A UNIT: V (PROPERTIES OF COMMERCIAL POLYMERS) BATCH-2017-2019
Reg. No……………..

KARPAGAM ACADEMY OF HIGHER EDUCATION

COIMBATORE-21
(For the candidates admitted from 2017 & onwards)
M.SC DEGREE EXAMINATION-2018
III SEMESTER
INTERNAL TEST – I
M.SC., CHEMISTRY
POLYMER CHEMISTRY

DATE: SUBJECT CODE: 17CHP305A

TIME: 2 HRS TOTAL: 50 MARKS

Section-A (20x1=20 marks)

Answer All The Questions

1. The azo(bis-isobutyro)nitrile (AIBN) is commonly used at?

a. 60-70 °C b. 50–70°C c. 80-90 °C d. 40-50 °C
2. Teflon is a polymer of the monomer or Teflon is obtained by the polymerization of?
a. Monofluroethene b. Difluroethene
c. Trifluroethene d. Tetrafluroethene
3. Which of the following is an example of condensation polymer?
a. PVC b. Polyamide c. Terylene d. Polyester
4. Two trimers react together to form
a. Trimer b. Hexamer c. Monomer d. Heptamer
5. Example for radical sources for the polymerization reactions?
a) Peroxides b. Epoxides c. Nitrenes d. Carbenes
6. Two or more monomers are combined to form
a. Co-ordination polymer b. Co-polymer c. Crystalline polymer
d. Homo polymer
7. The metal in the co-catalyst is come from
a. I to III b. III to IV c. IV and V d. IV-VIII
8. R-Ti-Cl4 is an
a. bi-metallic catalyst b. mono metallic catalyst
c. tri metallic catalyst d. alkyl catalyst
9. Monometallic mechanism proposed by
a. Natta b. Cossee c. Robert d. Wilson
10. The catalyst used for the Ziegler–Natta polymerizations?
a. TiCl3 with Al(C2H5)2Cl b. BCl3 with Al(C2H5)2Cl
c. TiCl3 with Fe(C2H5)2Cl d. TiF3 with Al(C2H5)2F
11. Which one is not a polymer?
a. Carbohydrates b. Proteins c. Carboxylic acid d. Nucleic acid
12. The Polyesterification of a diol and a diacid will illustrate the general kinetics of a type of
polymerization.
a. Step polymerization b. Ionic polymerization
c. Radical polymerization d. Self catalyzed polymerization
13. In free radical vinyl polymerization
a. The electrons in the pi bond split up b. The electrons in the sigma bond split up
c. Non bonding electrons are used d. Electrons from the functional group splits.
14. The alkyl resins are condensation polymers obtained from dibasic acids and
a. phenol b. formaldehyde c. Acetaldehyde d. Glycol
15. Which find extensive use as radical sources?
a. Peroxides b. Epoxides c. Nitrenes d. Carbenes
16. Which polymer is not a copolymer?
a. CCDDDCCDDDCCD b. AAAAAAAAAAA
c. BBBBBBBAAAAAAA d. CCCDDCCCDDCCC
17. The various initiators are used at different temperatures depending on their rates of
a. Reaction b. Decomposition c. Composition d. Entropy
18. In the monometallic mechanism monomer attacks the
a. Ti-Cl bond b. Al-R bond c. Ti-R bond d. Al-Cl bond
19. Which of the following is an example of condensation polymer?
a. PVC b. Polyamide c. Terylene d. Polyester
20. Polymers are?
a. Large molecule b. small molecule c. Small chain molecule d. large chain molecule

Section-B (3x 2 = 6 marks)

Answer All The Questions

21. What is degree of polymerization?

22. Write briefly about self-polycondensation.
23. How inhibitors play role in addition polymerization?
Section-C (3x 8 = 24 marks)
Answer All The Questions

24. a. Explain the mechanism of step-growth polymerization.

Or
b. Write a note on free radical addition polymerization.

25. a. What are the types of addition polymers? Explain each one of them.
Or
b. Write a note on i) Monomer ii) Repeat unit iii) Polymer.

26. a. What is Zieglar-Natta catalyst? Explain it briefly.

Or
b. Write notes on Co-ordination polymerization.
Reg. No…………….. [17CHP305A]

KARPAGAM ACADEMY OF HIGHER EDUCATION

COIMBATORE-21
(For the candidates admitted from 2017 & onwards)
M.SC DEGREE EXAMINATION-2018
III SEMESTER
INTERNAL TEST – I
M.SC., CHEMISTRY
POLYMER CHEMISTRY

DATE: SUBJECT CODE: 17CHP305A

TIME: 2 HRS TOTAL: 50 MARKS

Section-A (20x1=20)
Answer All The Questions

1. b. 50–70OC
2. d. Tetrafluroethene
3. c. Terylene
4. b. Hexamer
5. a. Peroxides
6. b. Co-polymer
7. d. IV-VIII
8. b. mono metallic catalyst
9. b. Cossee
10. a. TiCl3 with Al(C2H5)2Cl
11. c. Carboxylic acid
12. a. Step polymerization
13. a. The electrons in the pi bond split up
14. a. phenol
15. a. Peroxides
16. b. AAAAAAAAAAA
17. b. Decomposition
18. c. Ti-R bond
19. c. Terylene
20. d. large chain molecule
Section-B 3x 2 = 6
Answer All The Questions

21. What is degree of polymerization?

The degree of polymerization, or DP, is the number of monomeric units in

22. What is self polycondensation?

Self-Condensation polymerization
The monomer that are involved in condensation polymerization having different
functional group (like alcohol, amine, or carboxylic acid-groups).
Or same functional groups in the end of the same monomer. Instead of double bonds,
these monomers have functional groups.

23. What is the role of inhibitors in addition polymerization?

Inhibitors react with the radical site of a growing polymer chain to give a less reactive
radical. Benzoquinone is a typical inhibitor used in free radical polymerization reactions.

Section-C 3x 8 = 24
Answer All The Questions

24. a. Explain the mechanism of step-growth polymerization?

Stepwise polymerization

A number of different chemical reactions may be used to synthesize polymeric materials by

step polymerization. These include esteriﬁcation, amidation, the formation of urethanes,
aromatic substitution, and others. Polymerization usually proceeds by the reactions between
two different functional groups, for example, hydroxyl and carboxyl groups, or isocyanate
and hydroxyl groups. All step polymerizations fall into two groups depending on the type of
monomer(s) employed. The ﬁrst involves two different bifunctional and/or polyfunctional
monomers in which each monomer possesses only one type of functional group. (A
polyfunctional monomer is a monomer with more than one functional group per molecule. A
bifunctional monomeris one with two functional groups per molecule.) The second involves a
single monomer containing both types of functional groups. The synthesis of polyamides
illustrates both groups of polymerization reactions. Thus polyamides can be obtained from
the reaction of diamines with diacids.
nH2N-R-NH2 + nHO2C-R’-CO2H → -(-NH-R-NHCO-R’-CO-)-nOH + (2n-1)H2O
or from the reaction of amino acids with themselves:

nH2N-R-CO2H → H-(-NH-R-CO-)-nOH + (n-1)H2O

The two groups of reaction can be represented in a general manner by the equations
nA-A + nB-B → -(-A-AB-B-)-n

nA-B → -(-A-B-)-n

where A and B are the two different types of functional groups. The characteristics of these
two polymerization reactions are very similar. The successful synthesis of high polymers
(i.e., polymer of sufﬁciently high molecular weight to be useful from the practical viewpoint)
using any step polymerization reaction generally is more difﬁcult than the corresponding
small molecule reaction, since high polymers can be achieved only at very high conversions
(>98–99%). A conversion of 90%, which would be considered excellent for the synthesis of
ethyl acetate or methyl benzamide, is a disaster for the synthesis of the corresponding
polyester or polyamide. The need for very high conversions to synthesize high polymer
places several stringent requirements on any reaction to be used for polymerization—a
favorable equilibrium and the absence of cyclization and other side reactions. These stringent
requirements are met by a relatively small fraction of the reactions familiar to and used by
chemists to synthesize small molecules. An additional requirement for achieving high
molecular weights is the need for the A and B functional groups to be present at very close to
stoichiometric amounts.

Kinetics of Stepwise Polimerisation:

Consider the polyesterification of a diacid and a diol to illustrate the general form of the
kinetics of a typical step polymerization. Simple esterification is a well-known acidcatalyzed
reaction and polyesterification follows the same course [Otton and Ratton, 1988; Vancso-
Szmercsanyi and Makay-Bodi, 1969]. The reaction involves protonation of the carboxylic
acid,

(C-OH) + HA K2
K1
── (HO-C+ -OH(A-) 1
followed by reaction of the protonated specie with the alcohol to yield the ester
OH OH
C+-OH + ─( OH) K3
C OH 2
(A−) K4
O+H) (A-)
II
OH O
│ ║
C─OH K5
C-O + H2O + HA 3
│
O+H (A−)

In the above equations and are used to indicate all acid or alcohol species in the
reaction mixture (i.e., monomer, dimer, trimer, . . . , n-mer). Species I and II are shown in the
form of their associated ion pairs since polymerization often takes place in organic media of
low polarity. (A-) is the negative counter ion derived from the acid HA. Polyesterifications,
like many other step polymerizations, are equilibrium reactions. However, from the practical
viewpoint of obtaining high yields of high-molecular-weight product such polymerizations
are run in a manner so as to continuously shift the equilibrium in the direction of the polymer.
In the case of a polysterification this is easily accomplished by removal of the water that is a
by-product of the reaction species II (Eq. 3).
Under these conditions the kinetics of polymerization can be handled by considering
the reactions in Eqs. 2 and 3 to be irreversible.
The rate of a step polymerization is conveniently expressed in terms of the
concentrations of the reacting functional groups. Thus the polyesterification can be
experimentally followed by titrating for the unreacted carboxyl groups with a base. The rate
of polymerization Rp can then be expressed as the rate of disappearance of carboxyl groups
-d[COOH]/dt. For the usual polyesterification, the polymerization rate is synonomous with
the rate of formation of species II; that is, k4 is vanishingly small (since the reaction is run
under conditions that drive Eqs. 2 and 3 to the right), and k1, k2, and k5 are large compared to
k3. An expression for the reaction rate can be obtained following the general procedures for
handling a reaction scheme with the characteristics described [Moore and Pearson, 1981].
The rate of polymerization is given by

R= -d[COOH]/dt] = k3[C+ (OH)2][OH] 4

Where [COOH], [OH], and [C+ (OH)2] represent the concentrations of carboxyl, hydroxyl,
and protonated carboxyl (I) groups, respectively. The concentration terms are in units of
moles of the particular functional group per liter of solution. Equation 4 is inconvenient in
that the concentration of protonated carboxylic groups is not easily determined
experimentally. One can obtain a more convenient expression for Rp by substituting for C+
(OH)2 from the equilibrium expression

K =k1/k2 = [C+(OH)2] / [COOH][HA] 5

for the protonation reaction (Eq. 1). Combination of Eqs. 4 and 5 yields

-d[COOH]/dt = k3K[COOH][OH][HA] 6

Two quite different kinetic situations arise from Eq. 6 depending on the identity of
HA, that is, on whether a strong acid such as sulfuric acid or p-toluenesulfonic acid is added
as an external catalyst.

Or
b. Write a note on free radical addition polymerization?
Free-Radical polymerization
Initiation The initiation reaction produces free radicals. There are several ways to do this: •
Chemical initiation The decomposition of the initiator (e.g. AIBN) forms free radicals:

where f is the initiator efficiency, typically f = [0.5, 1]. Note that in order to ensure a
continuous production of radicals all over the process, 1/kd should be larger than the
characteristic time of the polymerization reaction. Examples of the decomposition
characteristic time, τd for some commercial initiators are:
Acetyl peroxide 2 h 80 ◦C
Cumyl peroxide 12 h 110 ◦C
t-Butyl hydroperoxide 45 h 150 ◦C
Since this is a first order process, τd = 1/kd.
• Thermal initiation: thermal decomposition of the monomer (e.g. styrene).
This represents a danger, for example during monomer transportation, since it may lead to
undesired polymerization of the monomer. For this reason, inhibitors (scavengers of radicals)
are usually added to the monomers before storage. This causes the occurrence of a non
reproducible induction period when such monomers are polymerized.
• Initiation by radiation
The decomposition of the initiator is caused by light or another source of radiation. Since this
method is quite expensive, it is only applied to polymerization systems operating at very low
temperatures.
Initiation
Initiation is the first step in cationic polymerization. During initiation, a carbenium ion is
generated from which the polymer chain is made. The counterion should be non-nucleophilic,
otherwise the reaction is terminated instantaneously. There are a variety of initiators available
for cationic polymerization, and some of them require a coinitiator to generate the needed
cationic species.[7]
Classical protonic acids
Strong protic acids can be used to form a cationic initiating species. High concentrations of
the acid are needed in order to produce sufficient quantities of the cationic species.
The counterion (A−) produced must be weakly nucleophilic so as to prevent early termination
due to combination with the protonated olefin. Common acids used are phosphoric, sulfuric,
fluro-, and triflic acids. Only low molecular weight polymers are formed with these initiators.
Lewis acids/Friedel-Crafts catalysts
Lewis acids are the most common compounds used for initiation of cationic polymerization.
The more popular Lewis acids are SnCl4, AlCl3, BF3, and TiCl4. Although these Lewis acids
alone are able to induce polymerization, the reaction occurs much faster with a suitable cation
source. The cation source can be water, alcohols, or even a carbocation donor such as
an ester or an anhydride. In these systems the Lewis acid is referred to as a coinitiator while
the cation source is the initiator. Upon reaction of the initiator with the coinitiator, an
intermediate complex is formed which then goes on to react with the monomer unit. The
counterion produced by the initiator-coinitiator complex is less nucleophilic than that of
the Brønsted acid A− counterion. Halogens, such as chlorine and bromine, can also initiate
cationic polymerization upon addition of the more active Lewis acids.[1]

Carbenium ion salts

Stable carbenium ions are used to initiate chain growth of only the most reactive olefins and
are known to give well defined structures. These initiators are most often used in kinetic
studies due to the ease of being able to measure the disappearance of the carbenium ion
absorbance. Common carbenium ions are trityl and tropylium cations.

Ionizing radiation
Ionizing radiation can form a radical-cation pair that can then react with a monomer to start
cationic polymerization. Control of the radical-cation pairs are difficult and often depend on
the monomer and reaction conditions. Formation of radical and anionic species are often
observed.

Propagation
Propagation proceeds via addition of monomer to the active species, i.e. the carbenium ion.
The monomer is added to the growing chain in a head-to-tail fashion; in the process, the
cationic end group is regenerated to allow for the next round of monomer addition.
Effect of temperature
The temperature of the reaction has an effect on the rate of propagation. The overall
activation energy for the polymerization (E) is based upon the activation energies for the
initiation (Ei), propagation (Ep), and termination (Et) steps:
E = Ei + Ep - Et

Generally, is larger than the sum of and , meaning the overall activation
energy is negative. When this is the case, a decrease in temperature leads to an increase in the
rate of propagation. The converse is true when the overall activation energy is positive.
Chain length is also affected by temperature. Low reaction temperatures, in the range of 170–
190 K, are preferred for producing longer chains. This comes as a result of the activation
energy for termination and other side reactions being larger than the activation energy for
propagation. As the temperature is raised, the energy barrier for the termination reaction is
overcome, causing shorter chains to be produced during the polymerization process.
Effect of solvent and counterion
The solvent and the counterion (the gegen ion) have a significant effect on the rate of
propagation. The counterion and the carbenium ion can have different associations according
to intimate ion pair theory; ranging from a covalent bond, tight ion pair (unseparated),
solvent-separated ion pair (partially separated), and free ions (completely dissociated).
〰〰RXcovalent 〰〰R+
X−
tight ion pair 〰〰R+
/X−
solvent-separated
ion pair 〰〰R+
+X−
free ions

The association is strongest as a covalent bond and weakest when the pair exists as free
ions.[6] In cationic polymerization, the ions tend to be in equilibrium between an ion pair
(either tight or solvent-separated) and free ions. The more polar the solvent used in the
reaction, the better the solvation and separation of the ions. Since free ions are more reactive
than ion pairs, the rate of propagation is faster in more polar solvents.
The size of the counterion is also a factor. A smaller counterion, with a higher charge density,
will have stronger electrostatic interactions with the carbenium ion than will a larger
counterion which has a lower charge density. Further, a smaller counterion is more easily
solvated by a polar solvent than a counterion with low charge density. The result is increased
propagation rate with increased solvating capability of the solvent.
Termination
Termination generally occurs via unimolecular rearrangement with the counterion. In this
process, an anionic fragment of the counterion combines with the propagating chain end. This
not only inactivates the growing chain, but it also terminates the kinetic chain by reducing the
concentration of the initiator-coinitiator complex.

Chain transfer
Chain transfer can take place in two ways. One method of chain transfer is hydrogen
abstraction from the active chain end to the counterion. In this process, the growing chain is
terminated, but the initiator-coinitiator complex is regenerated to initiate more chains.

Chain transfer by hydrogen abstraction to the counterion

Chain transfer by hydrogen abstraction to the monomer

25. a. What are the types of addition polymers?

Polymers are long chain giant organic molecules are assembled from many smaller
molecules called monomers. Polymers consist of many repeating monomer units in long
chains. A polymer is analogous to a necklace made from many small beads (monomers).
Many monomers are alkenes or other molecules with double bonds which react
by addition to their unsaturated double bonds.

Introduction

The electrons in the double bond are used to bond two monomer molecules together. This is
represented by the red arrows moving from one molecule to the space between two
molecules where a new bond is to form. The formation of polyethylene from ethylene
(ethene) may be illustrated in the graphic on the left as follows. In the complete polymer, all
of the double bonds have been turned into single bonds. No atoms have been lost and you
can see that the monomers have just been joined in the process of addition. A simple
representation is -[A-A-A-A-A]-. Polyethylene is used in plastic bags, bottles, toys, and
electrical insulation.

• LDPE - Low Density Polyethylene: The first commercial polyethylene process used
peroxide catalysts at a temperature of 500 C and 1000 atmospheres of pressure.
This yields a transparent polymer with highly branched chains which do not pack
together well and is low in density. LDPE makes a flexible plastic. Today most LDPE
is used for blow-molding of films for packaging and trash bags and flexible snap-on
lids. LDPE is recyclable plastic #4.
• HDPE - High Density Polyethylene: An alternate method is to use Ziegler-Natta
aluminum titanium catalysts to make HDPE which has very little branching, allows
the strands to pack closely, and thus is high density. It is three times stronger than
LDPE and more opaque. About 45% of the HDPE is blow molded into milk and
disposable consumer bottles. HDPE is also used for crinkly plastic bags to pack
groceries at grocery stores. HDPE is recyclable plastic #2.

Other Addition Polymers

• PVC (polyvinyl chloride), which is found in plastic wrap, simulated leather, water
pipes, and garden hoses, is formed from vinyl chloride (H2C=CHCl). The reaction is
shown in the graphic on the left. Notice how every other carbon must have a chlorine
attached.
• Polypropylene: The reaction to make polypropylene (H2C=CHCH3) is illustrated in
the middle reaction of the graphic. Notice that the polymer bonds are always through
the carbons of the double bond. Carbon #3 already has saturated bonds and cannot
participate in any new bonds. A methyl group is on every other carbon.
• Polystyrene: The reaction is the same for polystrene where every other carbon has
a benzene ring attached. Polystyrene (PS) is recyclable plastic #6. In the following
illustrated example, many styrene monomers are polymerized into a long chain
polystyrene molecule. The squiggly lines indicate that the polystyrene molecule
extends further at both the left and right ends.

• Blowing fine gas bubbles into liquid polystyrene and letting it solidify
produces expanded polystyrene, called Styrofoam by the Dow Chemical Company.
• Polystyrene with DVB: Cross-linking between polymer chains can be introduced
into polystyrene by copolymerizing with p-divinylbenzene (DVB). DVB has vinyl
groups (-CH=CH2) at each end of its molecule, each of which can be polymerized into
a polymer chain like any other vinyl group on a styrene monomer.

Or
b. Write a note on i) Monomer ii) Repeat unit iii) Polymer?
Monomer
A monomer (/ˈmɒnəmər/ MON-ə-mər) (mono-, "one" + -mer, "part") is a molecule that, as a
unit, binds chemically or supramolecularly to other molecules to form
a supramolecularpolymer. Large numbers of monomer units combine to form polymers in a
process called polymerization. It is a small molecule of an organic substance. A double bond
exist between the individual molecule which is weak. Molecules of a small number of
monomer units (up to a few dozen) are called oligomers. The term "monomeric protein" may
also be used to describe one of the proteins making up a multiprotein complex.
Biopolymer groupings, and the types of monomers that create them:

• For lipids (Diglycerides, triglycerides)*, the monomers are glycerol and fatty acids.
• For proteins (Polypeptides), the monomers are amino acids.
Repeat unit
A repeat unit or repeating unit is a part of a polymer whose repetition would produce the
complete polymer chain (except for the end-groups) by linking the repeat units together
successively along the chain, like the beads of a necklace.

Polymer
The term "polymer" derives from the ancient Greek word πολύς (polus, meaning "many,
much") and μέρος (meros, meaning "parts"), and refers to a molecule whose structure is
composed of multiple repeating units, from which originates a characteristic of high relative
molecular mass and attendant properties.

22 a) What is Zieglar-Natta catalyst explain it briefly?

Ziegler–Natta catalysis and polymerization

Historical Development of Ziegler–Natta Initiators
Various mechanisms have been proposed to explain the stereoselectivity of Ziegler-
Natta initiators [Boor, 1979; Carrick, 1973; Corradini et al., 1989; Cossee, 1967; Ketley,
1967a,b; Tait and Watkins, 1989; Zambelli and Tosi, 1974]. Most mechanisms contain
considerable details that distinguish them from each other but usually cannot be verified. In
this section the mechanistic features of Ziegler–Natta polymerizations are considered with
emphasis on those features that hold for most initiator systems.
The major interest will be on the titanium–aluminum systems for isoselective
polymerization, more specifically, TiCl3 with Al(C2H 5)2Cl and TiCl4 with Al(C2H 5)3—
probably the most widely studied systems, and certainly the most important systems for
industrial polymerizations. Before proceeding with the mechanistic consideration it is useful
to review the evolution of the Ti-Al initiator system for industrial applications. The original
initiator used by Ziegler for ethylene polymerization was obtained in situ as a precipitate on
mixing the components TiCl4 and Al(C2H 5)3 in a hydrocarbon solvent. The mixture was
used directly for initiating polymerization. Natta, recognizing that the major product of the
reaction was b-TiCl3 (brown in color), explored various methods of preforming it outside the
polymerization system, for example, by reduction of TiCl4 with hydrogen, aluminum, and
various alkylaluminum compounds. The stereoselectivity of these early initiator systems was
low with isotactic indices of only 20–40% for polypropene. The isotactic index, a measure of
the isotactic content of a polymer, is the percentage of the sample insoluble in a hydrocarbon
solvent such as boiling n-heptane. This is not as informative a technique as high-resolution
NMR since insoluble molecules may contain some syndiotactic and atactic sequences and
soluble molecules may contain some isotactic sequences. It does, however, give a simple
measure of isotacticity that is usually within about 10% of the value obtained from NMR,
especially for highly isotactic samples.
There was a dramatic increase in stereoselectivity when the α-, δ-,or γ-crystalline
form of TiCl3 (all violet in color) was used directly. The early generations of industrial
processes used TiCl3 together with Al(C2H 5)3 and/or Al(C2H 5)2Cl. Over a two decade
period starting in the late 1950s, the isotactic indices for polypropene increased to the low 90
percentile range. The initiator activity was enhanced by various ball milling and heat
treatments of the initiator components before and after mixing. Ball milling involves
mechanical grinding and not only increases surface area but also facilitiates reactions
between the initiator components.
However, the activities were too low to allow the polymer products to be used
without purification (by treatment with base or acid) to remove the residual metals,
a process referred to as deashing. Also, optimization of the physical properties of the
product often required removal of the atactic fraction. The initiator systems were inefficient
with less than 1% of the Ti being active in polymerization. The later generations of initiators,
starting in the late 1970s, increased initiator efficiency and activity without sacrificing
stereoselectivity [Bohm, 2001; Busico and Cipullo, 2001; Cecchin et al., 2001; Chadwick,
2001; Chadwick et al., 2001; Chien et al., 1982; Hu and Chien, 1988]. The effective surface
area of the active component of the initiator system was increased by close to 2 orders of
magnitude by using MgCl2 as a solid support in which TiCl4 is finely dispersed.
Stereoselectivity was kept high and actually increased by the addition of electron-donor
additives.
A typical recipe for a present-day superactive or high-mileage initiator system involve
ball milling of MgCl2 (or the alkoxide) and TiCl4 followed by the addition of Al(C2H 5)3
with an electron donor (such as dialkyl phthalate and alkoxysilane) usually added in each step
of preparation. Activity is 50–200 kg polymer per gram of initiator system. Typically, the
initiator system is no more than 2–4% Ti, which makes the activity about 1500–6000 kg
polymer per gram of Ti. The high activity not only minimizes initiator and production costs
but also avoids the costly task of initiator removal from the polymer product (except possibly
for food- and medical-grade products). Isotactic indices for polypropene have been increased
to 98% or higher with (mmmm) pentad fractions up to 98% and higher. This not only
improves the product’s physical properties but also avoids the need to remove the a tactic
fraction.
Chemical Nature of Propagating Species
Some early polymerizations reported as Ziegler–Natta polymerizations were
conventional free-radical, cationic, or anionic polymerizations proceeding with low
stereoselectivity.Some Ziegler–Natta initiators contain components that are capable of
initiating conventional ionic polymerizations of certain monomers, such as anionic
polymerization of methacrylates by alkyllithium and cationic polymerization of vinyl ethers
by TiCl4. Most Ziegler–Natta components participate in a complex set of reactions involving
alkylation and reduction of the transition-metal component by the group I–III component as
shown below for TiCl4 + AlR3:
TiCl4 + AlR3 ───› TiCl3 R + AlR2 Cl

TiCl4 + AlR2Cl ───› TiCl3R + AlRCl2

TiCl3R + AlR3 ───› TiCl2 R2 + AlRCl2

TiCl3 R ───› TiCl3 + R•

TiCl3 + AlR3 ───› TiCl2 R + AlR2 Cl

R• ───› combination + disproportionation

Radicals produced in Eq. 8-31 are capable of initiating radical polymerizations with
some monomers, for example, vinyl chloride.The mechanism for the tereoselective
polymerization of a-olefins and other nonpolar alkenes is a p-complexation of monomer and
transition metal (utilizing the latter’s d-orbitals) followed by a four-center anionic
coordination insertion process in which monomer is inserted into a metal–carbon bond as
described in Fig. 8-10. Support for the initial p-complexation has come from ESR, NMR, and
IR studies [Burfield, 1984]. The insertion reaction has both cationic and anionic features.
There is a concerted nucleophilic attack by the incipient carbanion polymer chain end on the
a-carbon of the double bond together with an electrophilic attack by the cationic counterion
on the alkene p-electrons.The anionic character of the polymerization is consistent with the
polymerization rate decreasing in the order ethylene > propene > 1-butene [Bier, 1961; Boor,
1967].
The reverse order is expected for a polymerization involving the conversion of a
monomer into the corresponding carbocation. For addition of a carbanion to the monomers,
attack occurs at the a-carbon to form the less substituted (and more stable) carbanion. Further,
a-substituents sterically hinder the approach of a carbanion and/or counterion with the result
that reactivity decreases with increasing substituent size. Evidence for the anionic nature of
propagation also comes from studies in which labeled methanol is used to terminate chain
growth. The terminated polymer is radioactive when CH3 O3 H is used, while termination by
14
CH3 OH yields a nonradioactive polymer.

Or
a) Write notes on Co-ordination polymerization?

Coordination polymerization
Coordination polymerisation is a form of addition polymerization in which monomer adds
to a growing macromolecule through an organometallic active center. The development of
this polymerization technique started in the 1950s with heterogeneous Ziegler-Natta
catalysts based on titanium tetrachloride and an aluminium co-catalyst such
as methylaluminoxane. Coordination polymerization has a great impact on the physical
properties of vinyl polymers such as polyethylene and polypropylene compared to the same
polymers prepared by other techniques such as free-radical polymerization. The polymers
tend to be linear and not branched and have much higher molar mass. Coordination type
polymers are also stereoregular and can be isotactic or syndiotactic instead of just atactic.
This tacticity introduces crystallinity in otherwise amorphous polymers. From these
differences in polymerization type the distinction originates between low-density
polyethylene (LDPE), high-density polyethylene (HDPE) or even ultra-high-molecular-
weight polyethylene (UHMWPE).
Polymerizations catalysed by metallocenes occur via the Cossee-Arlman mechanism. The
active site is usually anionic but cationic coordination polymerization also exists.
In many applications Ziegler-Natta polymerization is succeeded by metallocene catalysis
polymerization. This method is based on homogeneous metallocene catalysts such as
the Kaminsky catalyst discovered in the 1970s. The 1990s brought forward a new range
of post-metallocene catalysts.
Typical monomers are nonpolar ethylene and propylene. The development of coordination
polymerization that enables copolymerization with polar monomers is more recent. Examples
of monomers that can be incorporated are methyl vinyl ketones methyl
acrylate and acrylonitrile.
Kinetics
A case of heterogeneous polymerization.
It is defined : H is the surface of the transition-metal compound,
AR is the metal alkyl,
M is the monomer,
MX is the polymer.
Adsorption of metal alkyl from solution to form the active site
K1 H AR
H + AR
Adsorption of M from solution
K2
H + M M H
Initiation
Ki
M H AR H A M R
Propagation
KP
M H A MX R H MX+1 R
Termination
(transfer)
Ktr
M H A MX R H A M R + MX
Termination
(monomer forms an inactive site)
K1
M H A MX R H A M + MXR

It is assumed that the process occurs in Langmuir isotherm condition and it is defined that
:
ƟA and ƟM are the fractions of the available surface covered by AR and M
respectively,
[C*] is the concentration of growing chains,
Then the overall rate can be determined.
K1 [AR] K2 [M]
A = M =
1 + K1 [AR] + K2 [M] 1 + K1 [AR] + K2 [M]

The overall rate :

d [M]
R = − = (kp + ktr ) M [C*]
dt
Assume that [C*] reaches steady state so that the initiation rate is similar to the
termination rate.
ki A M = kt [C*] M
The overall rate :
d [M] ( kp + ktr ) ki
K1 K2 [AR] [M]
R = − =
dt kt (1 + K1 [AR] + K2 [M] )2
Reg. No……………..

KARPAGAM ACADEMY OF HIGHER EDUCATION

COIMBATORE-21
(For the candidates admitted from 2017 & onwards)
M.SC DEGREE EXAMINATION-2018
III SEMESTER
INTERNAL TEST – II
M.SC., CHEMISTRY
POLYMER CHEMISTRY

DATE: SUBJECT CODE: 17CHP305A

TIME: 2 HRS TOTAL: 50 MARKS

Section-A (20x1=20 marks)

Answer All The Questions

1. The weight average molecular degree of polymerisation indicates as

a. Dp b. (Dp)w c. (Dp)n d. D
2. A simple chemical compounds which have same molecular weight to form
a. monodispersion b. bi dispersion c. poly dispersion d. polymer solution
3. A polymer contains different molecular weight compounds to form
a. monodispersion b. bi dispersion c. poly dispersion d. polymer solution
4. The symbol Mn represents the
a. Number-average molecular weight b. Weight average molecular weight
c. Viscosity average molecular weight d. Vapor pressure molecular weight
5. Wet spinning technique is commercially used to produce filament yarn of
a. Polypropylene b. Polyester c. Nylon 66 d. Acrylic
6. Which properties of fibers are quite complex and have been subject of much experimental
work?
a. Physical b. Mechanical c. Chemical d. Thermal
7. Crease resist finishing of cotton fabric does not lead to
a. Reduction in tensile strength b. Increase in dimensional stability
c. Increase in moisture regains d. Increase in bending length
8. Inhibiting the oxidation of polymers is usually filled by a substance which itself is readily
oxidized.
a. Antioxidants b. Flame retardants c. Colourants d. Mgo
9. Any of a group of substances that are used in plastics or other materials to impart viscosity,
flexibility, softness or other properties to the finished product
a. Plasticizers b. Antioxidants c. Polymer initiators d. Fillers
10. The symbol Mv represents the
a. Number-average molecular weight b. Weight average molecular weight
c. Viscosity average molecular weight d. Vapour pressure molecular weight
11. In polymer industry 2-hydroxybenzophones are used as
a. Light stabilizers b. Antioxidants c. Polymer initiators d. Fillers
12. In melt spinning the temperature used for melting is about?
a. 29K b. 30K c. 31K d. 32K
13. One of the following is the most important fibers produced commercially?
a. Nylons b. Wood c. Cotton d. Silk
14. Plastics are?
a. Hydrocarbons b. Aldehydes c. Ester d. Amide
15. The intrinsic viscosity is also known as
a. specific viscosity b. reduced viscosity
c. inherent viscosity d. Staudinger viscosity
16. The rpm maintained for minute in the sedimentation equilibrium method is
a. 30,000 b. 50,000 c. 15,000 d. 65,000
17. The error occurred in the viscometer due to the measurement of
a. level of solute b. density c. nature d. flow time
18. The phenomenon of depressing the freezing point of a liquid by the addition of solute is
known as
a. Cryoscopy b. Ebuliometry c. Osmometry d. Vapour phase Osmometry
19. Which one of the following spinning methods, the polymer is melted by heating and then
passed through a spinneret
a. Melt spinning b. Dry spinning c. Wet spinning d. Spinning
20. Any of a group of substances that are used in plastics or other materials to impart
viscosity, flexibility, softness or other properties to the finished product
a. Plasticizers b. Antioxidants c. Polymer initiators d. Fillers

Section-B (3x 2 = 6 marks)

Answer All The Questions

21. What is Fibre-Reinforced Plastics (FRP)?

22. Write briefly about glass transition temperature.
23. What is ‘compounding’ of the resin?

Section-C (3x 8 = 24 marks)

Answer All The Questions

23. a. How to calculate the molecular weight of the polymer based on the number average
method? Explain anyone of its experimental method.
Or
b. Give an account of viscosity methods.
24. a. What is calendaring technique? Explain it briefly.
Or
b. Write a note on injection moulding techniques.

26. a. Describe the compression moulding and Thermoforming techniques.

Or
b. Explain the ultracentrifugation techniques.
Reg. No……………..

KARPAGAM ACADEMY OF HIGHER EDUCATION

COIMBATORE-21
(For the candidates admitted from 2017 & onwards)
M.SC DEGREE EXAMINATION-2018
III SEMESTER
INTERNAL TEST – II
M.SC., CHEMISTRY
POLYMER CHEMISTRY

DATE: SUBJECT CODE: 17CHP305A

TIME: 2 HRS TOTAL: 50 MARKS

Section-A (20x1=20 marks)

Answer All The Questions

1. b. (Dp)w
2. a. monodispersion
3. c. poly dispersion
4. a. Number-average molecular weight
5. d. Acrylic
6. b. Mechanical
7. c. Increase in moisture regains
8. a. Antioxidants
9. a. Plasticizers
10. c. Viscosity average molecular weight
11. a. Light stabilizers
12. b. 30K
13. Nylons
14. a. Hydrocarbons
15. d. Staudinger viscosity
16. d. 65,000
17. d. flow time
18. a. Cryoscopy
19. a. Melt spinning
20. a. Plasticizers
Section-B (3x 2 = 6 marks)
Answer All The Questions

21. What is Fibre-Reinforced Plastics (FRP)?

Fibre-reinforced plastic (FRP) (also called fiber-reinforced polymer, or fiber-reinforced
plastic) is a composite material made of a polymer matrix reinforced with fibres. The
fibres are usually glass (in fibreglass), carbon (in carbon-fiber-reinforced polymer),
aramid, or basalt. Rarely, other fibres such as paper, wood, or asbestos have been used.
The polymer is usually an epoxy, vinylester, or polyester thermosetting plastic, though
phenol formaldehyde resins are still in use.
FRPs are commonly used in the aerospace, automotive, marine, and construction
industries. They are commonly found in ballistic armor as well.
22. Write briefly about glass transition temperature.
The glass–liquid transition or glass transition for short is the reversible transition
in amorphous materials (or in amorphous regions within semicrystalline materials) from a
hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is
increased. An amorphous solid that exhibits a glass transition is called a glass.
23. What is ‘compounding’ of the resin?
Compounded Resins
Compounded Resins are quite common in our industry. Sometimes the additive has
processing characteristics so similar to the basic resin that you can dry and process in
exactly the same manner as is indicated for the main ingredient.

Section-C (3x 8 = 24 marks)

Answer All The Questions

23. a. How to calculate the molecular weight of the polymer based on the number
average method. Explain anyone of its experimental method?

Concept of Average Molecular Weight

A specified polymer material is generally a mixture of molecules of identical or near –
identical chemical structure and composition, but differing in degree of polymerization
(DP) or molecular weight. The molecules produced by polymerization reaction have
chain lengths that are distributed according to a probability function that is governed by
the polymerization mechanism and by the condition prevailing during the process. A
concept of average molecular weight, therefore, assumes importance and very much
relevant. However, assignment of a numerical value to the molecular weight will be
dependent on the definition of a particular average. An average molecular weight, M
may in fact be generally expressed as

M = f1 M1 + f2 M2 + f3 M3 + ------ = Σ fi Mi (1)

Here, M1 , M2 , M3 etc. refer to molecular weights of different sizes of molecules and

the coefficients f1 , f2 , f3 etc. are fractions such that their summation Σ fi equals to
unity. The average molecular weight M may otherwise be expressed as

Σ Ni Mi a
M = (2)
Σ Ni Mi (a – 1)

where, Ni is the number of molecules, each of which is characterized by the molecular

weight Mi and the index ‘a’ may have any real value. Two very important average
molecular weight widely recognized and used are (i) number average molecular weight,
Mn and (ii) weight average molecular weight, Mw. Setting a = 1 in equation (2), one
obtains the expression for the number average molecular weight, Mn :
Σ Ni Mi
Mn = (3)
Σ Ni
Equation (3) can, in fact, be expressed as a simple summation series resembling equation
(1) where the fractional coefficients are actually the mole fractions of the respective
molecular species existing in the polymer system such that total weight W = Σ Ni Mi
and total number of molecules N = Σ Ni , Thus,

W Σ Ni Mi N1 N2 N3
Mn = = = M1 + M2 + M3 + ------
N Σ Ni N N N
= f1 M1 + f2 M2 + f3 M3 + ------- (4)
On the other hand, however, setting a = 2 in equation (2), one finds the expression for
weight average molecular weight, Mw , i.e.,
Σ Ni Mi 2
Mw = (5)
Σ Ni Mi
Equation (5) can also be rearranged and expressed as a summation series as given by
equation (1), but in this case, the fractional coefficients actually correspond to weight
fractions of different molecular species present. So, one may write :

Σ Ni Mi . Mi Σ wi Mi Σ wi Mi
Mw = = =
Σ Ni Mi Σ wi W

w1 w2 w3
= M1 + M2 + M3 + ------
W W W
= f1 M1 + f2 M2 + f3 M3 + ------- (6)
Here, w1 , w2 , w3 , etc. stand for weight of different molecular species having
molecular weight M1 , M2 , M3 etc. respectively and Σ wi = W gives the total weight
of all the molecules present.

The obvious consequences of above definitions imply that Mw ≥ Mn , i.e., Mw / Mn ≥

1; the equality, however, relates to a perfectly monodisperse polymer sample where all
the polymer molecules are of equal molecular weight, i.e. M1 = M2 = M3 = ----- = M.
So, for monodisperse systems, (Mw / Mn) = 1. Deviation from unity of the ratio Mw /
Mn , known as the distribution ratio is taken as a measure of polydispersity of the
polymer sample. The said ratio is also referred to as polydispersity index; a higher value
of the ratio means a greater polydispersity.

Evaluation of number average molecular weight is helpful for having a good

understanding of polymerization mechanism and relevant kinetics. Mn is useful in the
analysis of kinetic data and assessing or ascertaining effects of many side reactions such
as chain transfer, inhibition and retardation and also autoacceleration effects during vinyl
and related polymerizations. The number average molecular weight assumes prime
importance in the context of studies of solution properties that go by the name of
colligative properties viz., vapour pressure lowering, freezing point depression, boiling
point evaluation and osmometry. Polymer molecules of lower molecular weight or even
low molecular weight soluble impurities contribute equally and enjoy equal status with
polymer molecules of higher molecular weights in determining the colligative properties.

On the other hand, weight average molecular weight assumes importance in the context
of various bulk properties of polymers, particularly the rheological and resistance
properties. Softening/melting and hot deformation, melt – viscosity or melt – flow,
tensile and compressive strength, elastic modulus and elongation at break, toughness and
impact resistance and some other bulk properties of polymers are better appreciated on
the basis of weight average molecular weight, keeping in mind, however, the influence
of chemical nature of the repeat units, degree of branching and cross linking, thermal or
thermomechanical history of the polymer sample, etc.

Number Average Molecular Weight

Number average molecular weight can be evaluated using dilute solution of a polymer
making use of ebulliometric (boiling point elevation), cryoscopic (freezing point
depression) and osmometric (membrane osmometry) measurements.Direct
measurements of vapour pressure lowering of dilute polymer solution lack precision and
mostly produce uncertain results. Vapour – phase osmometry, however, allows indirect
exploitation of vapour pressure lowering of polymer solution at equilibrium as can be
related through the Clapeyron equation and in this method, one measures a temperature
difference that can be related to vapour pressure lowering. This difference in
temperature is comparable to or of the same order of magnitude as those observed in
cryoscopy and ebulliomtry. These methods require calibration with low molecular
weight standards and they may produce reliable results for polymer molecular weights <
30,000. The working equations for ebulliometric, cryoscopic and osmometric
measurements are as follows:

∆ Tb RT 2 1
lim = . (7)
c→o c ρ ∆ Hν M

∆ Tf RT 2 1
lim = . (8)
c→o c ρ ∆ Hf M
π RT
lim = (9)
c→o c M

where, ∆ Tb , ∆ Tf , and π are boiling point elevation, freezing point depression and
osmotic pressure, ρ is the density of the solvent, ∆ Hν and ∆ Hf are respectively the
latent heat of vaporization and of fusion of the solvent per gram, c is the polymer
(solute) concentration in g/cm3 and M is the solute molecular weight. Very low
observed temperature differences (of the order of 10-3 0C) for low finite concentrations
of a polymer of the molecular weight range of ≥ 20,000 and lack of development of
equipments for ebulliometric and cryoscopic measurements have turned them
unattractive and less useful. Vapour pressure lowering for low finite concentrations is
also very low (of the order of 10-3 mm Hg) for such polymers. The osmotic method is
in more wide use than other colligative techniques as because the osmotic response is of
a magnitude that is easily observable and measurable, even though success of this
method is contingent upon availability of prefect osmotic membranes.

Or
b. Give an account of viscosity methods?
Introduction
Viscosity of a polymer solution depends on concentration and size (i.e., molecular weight) of
the dissolved polymer. By measuring the solution viscosity we should be able to get an idea
about molecular weight. Viscosity techniques are very popular because they are
experimentally simple. They are, however less accurate and the determined molecular weight,
the viscosity average molecular weight, is less precise. For example, Mv depends on a
parameter which depends on the solvent used to measure the viscosity. Therefore the
measured molecular weight depends on the solvent used. Despite these drawbacks, viscosity
techniques are very valuable. This chapter discusses the theory and methods for determining
polymer molecular weight by measuring solution viscosity 6.2 Viscosity and Viscosity
Nomenclature Figure 6.1 shows a piece of a liquid moving at a strain rate ˙γ under an applied
shear stress of τ . The viscosity of the liquid is the ratio of the applied shear stress to the
resulting strain rate (or equivalently, the ratio of the shear stress required to move the solution
at a fixed strain rate to that strain rate). The shear strain in Fig. 6.1 is γ = du dy (6.1) where u
is displacement in the x direction. The strain rate is therefore γ˙ = d dt du dy = d dy du dt =
dvx dy (6.2) where vx is velocity in the x direction. The relations between viscosity (η), shear
stress (τ ), and shear rate ( ˙γ) are τ = ηγ˙ or ˙γ = τ η or η = τ γ˙ (6.3) 77 78
VISCOSITY
F τ = F A dγ dt γ = • γ Figure 6.1: A piece of a liquid moving at shear rate ˙γ under an applied
shear stress of τ . A Newtonian fluid is one in which the viscosity is independent of the shear
rate. In other words a plot of shear stress versus shear strain rate is linear with slope η. In
Newtonian fluids all the energy goes into sliding molecules by each other. In non-Newtonian
fluids, the shear stress/strain rate relation is not linear. Typically the viscosity drops at high
shear rates — a phenomenon known as shear thinning. Although the following development
will not discuss shear rate effects in detail, the possibility of experimental results being
affected by the shear rate of the measurement should be kept in mind. Plots of shear force vs.
shear rate for Newtonian and non-Newtonian fluids are given in Fig. 6.2. We let η0 be the
viscosity of the pure solvent and η be the viscosity of a solution using that solvent. Several
methods exist for characterizing the solution viscosity, or more specifically, the capacity of
the solute to increase the viscosity of the solution. That capacity is quantified by using one of
several different measures of solution viscosity. The most common solution viscosity terms
are: 1. Relative viscosity ηr = η η0 (6.4) 2. Specific viscosity ηsp = η − η0 η0 = ηr − 1 (6.5) 3.
Inherent Viscosity ηi = ln ηr c (6.6) 4. Intrinsic Viscosity [η] = lim c→0 ηsp c
VISCOSITY AND VISCOSITY NOMENCLATURE
Shear Force Non-Newtonian Newtonian Shear Rate Shear Force Figure 6.2: Schematic plots
of shear force vs. shear rate for Newtonian and non-Newtonian fluids. In these equations, η is
solution viscosity, η0 is viscosity of the pure solvent, and c is concentration. Relative
viscosity is self-explanatory. Specific viscosity expresses the incremental viscosity due to the
presence of the polymer in the solution. Normalizing ηsp to concentration gives ηsp/c which
expresses the capacity of a polymer to cause the solution viscosity to increase; i.e., the
incremental viscosity per unit concentration of polymer. As with other polymer solution
properties, the solutions used for viscosity measurements will be nonideal and therefore ηsp/c
will depend on c. As with osmotic pressure, it will probably be useful to extrapolate to zero
concentration. The extrapolated value of ηsp/c at zero concentration is known as the intrinsic
viscosity — [η]. [η] will be shown to be a unique function of molecular weight (for a given
polymer-solvent pair) and measurements of [η] can be used to measure molecular weight.
The remaining form for the viscosity is the inherent viscosity. Like ηsp, ln ηr is zero for pure
solvent and increases with increasing concentration, thus ln ηr also expresses the incremental
viscosity due to the presence of the polymer in the solution. Normalizing ln ηr to
concentration or ln ηr/c gives the inherent viscosity In the limit of zero concentration, ηi
extrapolates the same as ηsp/c and becomes equal to the intrinsic viscosity. This can be
proved by: lim c→0 ln ηr c = lim c→0 ln (1 + ηsp) c = lim c→0 ηsp c = [η] (6.8) We can thus
find [η] be extrapolating either ηsp/c or ηi to zero concentration. When c is not equal to zero
the specific viscosity and inherent viscosities will be different, even for an ideal solution. In
ideal solutions ηsp/c will be independent of concentration, but ni will depend on
concentration.

24. a. What is calendaring technique? Explain it briefly.

Plastics are mainly organic polymers of high molecular mass, but they sometimes contain
other substances as well. Plastics are usually synthetic, most commonly derived
from petrochemicals, but many are partially natural. Plastics are usually classified by
their chemical structure of the polymer's backbone and side chains. Some important groups in
these classifications are the acrylics, polyesters, silicones, polyurethanes, and halogenated
plastics. There are a variety of methods used to process plastic. Each method has its
advantages and disadvantages and are better suited for specific applications. There are
various plastic processing techniques.

Calendering

Calendering is a continuous process which works in much the same way as an old-fashioned
clothes mangle. For plastics, there are usually four heated rollers of different sizes rotating at
slightly different speeds. The material is fed into these rollers, heated and melted, then shaped
into a sheet or film. This is then cooled and rolled up. The sheets can be mono-oriented
during this process. The most commonly calendered material is PVC.

Or
b. Write a note on injection moulding techniques?

Injection molding
Injection molding is a manufacturing process for producing parts by injecting material into a
mold. The main method used for processing plastic is injection molding. With this process,
the plastic is placed into a hopper. The hopper then feeds the plastic into a heated injection
unit, where it is pushed through a long chamber with a reciprocating screw. Here, it is
softened to a fluid state. A nozzle is located at the end of the chamber. The fluid plastic is
forced through the nozzle into a cold, closed mold. The halves of the mold are held shut with
a system of clamps. When the plastic is cooled and solidified, the halves open and the
finished product is ejected from the press.

26. a. Explain the method of compression moulding and Thermoforming.

Compression molding

Compression molding is the most common process used with thermosetting materials and is
usually not used for thermoplastics. With this process, the material is squeezed into its desired
shape with the help of pressure and heat. Plastic molding powder and other materials are
added to the mix in order to create special qualities or to strengthen the final product. When
the mold is closed and heated, the material goes through a chemical change that causes it to
harden into its desired shape. The amount temperature, amount of pressure, and length of
time utilized during the process depends on the desired outcome.
Thermoforming
Thermoforming is a manufacturing process where a plastic sheet is heated to a pliable
forming temperature, formed to a specific part shape in a mold, and trimmed to create a
usable product. The sheet, or film when referring to thinner gauges and certain material types,
is heated in an oven to a high-enough temperature that it can be stretched into or onto a mold
and cooled to a finished shape. The second animation shows the twin sheet thermoforming
process whereby two individual components are fused together through the application of
tremendous pressure which forces two molds together, thereby fusing the materials together.

Or
b. Write a note on ultracentrifugation techniques?
Analytical ultracentrifugation (AUC) is a powerful method for the characterization of
polymers, biopolymers, polyelectrolytes, nanoparticles, dispersions, and other colloidal
systems. The method is able to determine the molar mass, the particle size, the particle
density and interaction parameters like virial coefficients and association constants.
Because AUC is also a fractionation method, the determination of the molar mass
distribution, the particle size distribution, and the particle density distribution is possible.

In an analytical ultracentrifuge, a sample being spun can be monitored in real time

through an optical detection system, using ultraviolet light absorption and/or interference
optical refractive index sensitive system. This allows the operator to observe the evolution
of the sample concentration versus the axis of rotation profile as a result of the applied
centrifugal field. With modern instrumentation, these observations are electronically
digitized and stored for further mathematical analysis. Two kinds of experiments are
commonly performed on these instruments: sedimentation velocity experiments and
sedimentation equilibrium experiments.
Sedimentation velocity experiments aim to interpret the entire time-course of
sedimentation, and report on the shape and molar mass of the dissolved macromolecules,
as well as their size-distribution. The size resolution of this method scales approximately
with the square of the particle radii, and by adjusting the rotor speed of the experiment
size-ranges from 100 Da to 10 GDa can be covered. Sedimentation velocity experiments
can also be used to study reversible chemical equilibria between macromolecular species,
by either monitoring the number and molar mass of macromolecular complexes, by
gaining information about the complex composition from multi-signal analysis exploiting
differences in each components spectroscopic signal, or by following the composition
dependence of the sedimentation rates of the macromolecular system, as described in
Gilbert-Jenkins theory.

Sedimentation equilibrium experiments are concerned only with the final steady-state of
the experiment, where sedimentation is balanced by diffusion opposing the concentration
gradients, resulting in a time-independent concentration profile. Sedimentation
equilibrium distributions in the centrifugal field are characterized by Boltzmann
distributions. This experiment is insensitive to the shape of the macromolecule, and
directly reports on the molar mass of the macromolecules and, for chemically reacting
mixtures, on chemical equilibrium constants.

The kinds of information that can be obtained from an analytical ultracentrifuge include
the gross shape of macromolecules, the conformational changes in macromolecules, and
size distributions of macromolecular samples. For macromolecules, such as proteins, that
exist in chemical equilibrium with different non-covalent complexes, the number and
subunit stoichiometry of the complexes and equilibrium constant constants can be
studied.

Analytical ultracentrifugation has recently seen a rise in use because of increased ease of
analysis with modern computers and the development of software, including a National
Institutes of Health supported software package, SedFit.

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