Polymer Science and Engineering

References:
1. Polymer Science by V. R. Gowarikar, N. V. Viswanathan, Jayadev Sreedhar.
2. Polymer Science and Technology by Jewel R Fried.

Polymer:
A polymer (Greek poly-, "many" + -mer, "parts") is a large molecule, or macromolecule,
composed of many repeated subunits. a polymer is a long-chain molecule that is composed of a
large number of repeating units of identical structure. Because of their broad range of properties
both synthetic and natural polymers play an essential role 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
molecule compounds produces unique physical properties, including toughness and a tendency to
form glasses and semi-crystalline structures rather than crystals.

Monomer:
A monomer (mono-, "one" + -mer, "part") is a molecule that may bind chemically to other
molecules to form a polymer. The term "monomeric protein" may also be used to describe one of
the proteins making up a multi-protein complex.

Polymerization:
A process in which relatively small molecules, called monomers, combine chemically to produce
a very large chain like or network molecule, called polymer. The monomer molecules may be all
alike, or they may represent two, three, or more different compounds. Usually at least 100
monomer molecules must be combined to make a product that has certain unique physical
properties—such as elasticity, high tensile strength, or the ability to form fibres—that
differentiate polymers from substances composed of smaller and simpler molecules; often, many
thousands of monomer units are incorporated in a single molecule of a polymer.

Most generally the reaction may be represented as nM  M n

Where n is the degree of polymerization, usually n has high values.
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.

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.

Macromolecule:
Macromolecules are large molecules that are composed of smaller units. The four
major macromolecules are carbohydrates, lipids, nucleic acids, and proteins.

End group:
End groups are an important aspect of polymer synthesis and characterization. In polymer
chemistry, end groups are functionalities or constitutional units that are at the extremity of a
macromolecule. End groups are the terminal units that terminate polymer chain, where end
groups are specified they are shown outside the brackets.

e.g.: CH3 – CH2 – (CH2 – CH2)n – CH = CH2 End group.

Degree of Polymerization (D.P.)
The degree of polymerization, or DP, is usually defined as the number of monomeric units in
a macromolecule or polymer. For a homopolymer, there is only one type of monomeric unit and
the number-average degree of polymerization is given by,

,
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.

The importance of polymer science to study for textile engineering:

(1) Synthetic textile fibres are polymeric substance.

(2) Sizing materials used in preparatory stage before weaving process are polymer.
(3) Thickeners used in textile printing to control viscosity of print paste are polymers.
(4) Binders and fixers used in coloration with pigments are also polymers.
(5) Many of finishing agents such as easy care finish, soil release finish, antimicrobial
finish, etc. applied on textile materials are based on polymers.
(6) Polymers are also used as wet processing aids.
(7) Various biological polymers are used as enzymes in textile processing.
 Classification of polymer:
 Classification based on broad sense.
i) Biological polymer. e.g – D.N.A, R.N.A, Protein.
ii) Non- biological / Industrial polymer: e.g. fibre, plastic, rubber, adhesive materials,
coating materials.

Classification of Industrial Polymers:

1. On the basis of origin / source
(i) Natural: Those polymers are obtained from natural source such as plants and animals.
e.g cotton, silk, wool, rubber, Cellulose rayon.
(ii) Synthetic: These polymers are processed in laboratories and synthesized from low
molecular weight compound. e.g. Polyethylene, Poly vinyl chloride, PVA, etc.

2. On the basis of chemical nature of the polymer:

(i) Inorganic: These polymers usually contain no carbon atom in their chain backbone. e.g.
Glass, Silicon, Rubber etc
(ii) Organic: A polymer whose backbone is generally made of carbon atom. e. g. poly ethylene,
PVC, Nylon.

3. On the basis of behavior towards heat:

i) Thermoplastic: Those polymers that can be heat-softened in order to process into
a desired form are called thermoplastics..
 These polymers are softened when they heated and hardened when they cooled.
 These polymers do not have any cross bond.
 These polymers can easily convert into any shape by heating.
Ex: Polyethylene, Polystyrene, Teflone, PVC etc.

ii) Thermosetting: Theses polymers are made by low molecular mass semi fluid substance.
 These polymers can‘t be converted in other shape by heating.
 On heating, they become hard and in-fusible because these polymers have cross
bond.
Ex: Bakelite, Melamine formaldehyde, Resin etc.

In comparison,thermosets are polymers whose individual chains have been chemically linked by covalent bonds during
polymerization or by subsequent chemical or thermal treatment during fabrication. Once formed, these cross-linked
networks resist heat softening, mechanical deformation, and solvent attack, but cannot be thermally processed. Such
properties make thermosets suitable materials for composites, coatings, and adhesive applications. Principal examples
of thermosets include epoxy,phenol–formaldehyde resins, and unsaturated polyesters that are used in the manufacture
of glass-reinforced composites such as Fiberglas.
4. On the basis of geometrical structure of polymer:
(i) Straight/Linear: Having no branching in the polymer backbone.
e.g. polyethylene
(ii) Branched: Having branching in the polymer backbone.
e.g. PVC, PVA,
(iii) Cross linked: Having cross-linked between and among polymer chain.
e.g.- Urea Formaldehyde, Melamine Formaldehyde

Fig. Schematic diagrams of linear, branched, and crosslinked polymers.

5. Based on form and use:

Fibre: A fiber or staple fiber is a unit of matter which is usually at least 100 times longer than its
thickness. e.g. – Polyester, Nylon, Acrylic, etc.

Elastomer:An elastomer is a polymer with viscoelasticity (having both viscosity and elasticity)
and very weak inter-molecular forces. When vulcanized (harden by treating it with sulphur at a
high temperature) into rubbery products exhibiting good strength and elongation, polymers are
used as elastomers. e.g. Rubber.
 Plastics: When a polymer is shaped into hard and tough utility articles by the application of heat
and pressure it is used as a plastic. e.g. PVC, Polyethene.

6. Based on monomer present:

(i) Homopolymer: When the unit are all the same and are joined linearly (a linear polymer), the
polymer is a homo-polymer and it‘s structure may be represented as [M] n where M is the repeat
unit and n is the no of repeat units or degree of polymerization (D.P).

n H2C CH
H2C CH
Polymerisation

Styrene n
Polystyrene

(ii)Copolymer:Polymers with two different repeating units in their chains are called copolymers.
When there are three chemically different repeating units, the resulting polymer is termed a
terpolymer. Commercially, the most important copolymers are derived from vinyl monomers
such as styrene, ethylene, acrylonitrile, and vinyl chloride.. Example-PVC

n CH2=CH2 + n CH2=CH-Cl (-CH2-CH2-CH2-CH-)n

Ethylene Vinyl Chloride
Cl
Poly Vinyl Chloride
Under special circumstances, it is possible to prepare copolymers that contain a long
block of one monomer (A) followed by a block of the other monomer (B). These are
called AB-block copolymers.

ABA-triblock copolymers have a central B block joined by A blocks at both ends.

A commercially important ABA-triblock copolymer is polystyrene-block-
polybutadiene-block-polystyrene or SBS, a thermoplastic elastomer.

In addition to these copolymer structures, graft copolymers can be prepared

by polymerizing a monomer in the presence of a fully formed polymer of another
monomer. Graft copolymers are important as elastomers (e.g., SBR) and high-
impact polymers (e.g., high-impact polystyrene and acrylontrile−butadiene−styrene
or ABS resin).
7. Based on the mechanism of Polymerisation:
(i) Chain Polymerisation: e.g. Polyetylene
(ii) Step or condensation Ploymerisation

8. Based on resident of side chain present:

Isotactic — All the substituent groups, R, on the polymer lie above (or below) the plane of the
main chain.
Syndiotactic — Substituent groups lie alternately above and below the plane.

Atactic — Random sequence of position of substituent occurs along the chain.

 Difference between Thermoplastic and Thermosetting polymer:

Fig. Structure of thermoplastic polymer

Fig. Structure of thermosetting polymer

 Thermoplastic Thermosetting
Thermoplastic polymers get soften and melt on Thermosetting polymers don‘t soften on
heating. heating but rather become hard.
Thermoplastic polymers can be reshaped. Thermosetting polymers can‘t be reshaped.
Thermoplastics polymers are less brittle and Thermosetting polymers are brittle and
soluble in organic solvents. insoluble in organic solvents.
These are formed by addition polymerization. These are formed by condensation
polymerization.
These have usually linear structure. Ex. These have three dimensional cross-linked
Polyethylene, PVC, Teflon. structures. Ex. Urea formaldehyde.
Degree of Polymerisation:
The size of a polymer molecule depends on the no of repeating units it contains and this no
represents the ―Degree of Polymerisation‖. For example, if there are 1000 repeat units in a
polymer molecule, the degree of polymerization (DP) is 1000.
DP provides another way of expressing the molecular weight as follows,
M=Dp.m

Where, M=The molecular weight of the polymer.

Dp= Degree of polymerization.
m=The molecular weight of the monomer or the repeat unit.

The ‘number average ‘and ‘weight average’ degree of polymerization:

Both DP and molecular weight are related to the molecular size. As a result, like the molecular
weight, DP can also be averaged over the size of the sample.

The ‗number average ‗and ‗weight average‘ degree of polymerization can be defined in a manner
similar to that in which Mn , Mw are defined –

Mn=(Dp )n .m
Mw =(Dp )w .m

*The molecular weight (M.W.) of a molecule is the sum of the weights of all the atoms which make up
the molecule.

Problem: Compute the number-average degree of polymerization for polypropylene, given that
the number-average molecular weight is 1,000,000 g/mol.
Mathematical expression for Mn & Mw :
In computing the molecular weight of a polymer we can also use either the number fraction or
the weight fraction of the molecules present in the polymer to get either the number-average
molecular weight(expressed as Mn ) or the weight-average molecular weight((expressed as Mw )
Let us consider a polymer sample having n molecules.

1. Expression for Mn :
Total number of molecules given by, n= n1 + n2 +n3 ----- ni = ni
Number of molecules in fraction 1 = n1
n  n1
Number fraction of fraction 1 = 1 
n  ni
n1 nM
Molecular weight contribution by fraction 1 =  M1  1 1
 ni  ni
Similarly, molecular weight contribution by other fraction will be as follows:
n 2 M2 n3M 3 nM
,  i i
 ni  ni  ni
nM nM nM
Number average molecular weight = n1 M1  2 2  3 3       i i
 n i  ni  ni  ni
=
n M
i i

n i
 MUSTAFIJUR RAHMAN 11
MSc in TEXTILE ENGINEERING, THE UNIVERSITY OF MANCHESTER, UK

2. Expression for(i) MW :
Total weight of polymer, W=W1+W2+W3+ ---------- +Wi
= n1M1 +n2M2 + n3 M3 +------ +niMi
= ni Mi
Weight of fraction 1 = n1M1 = W1
nM nM
Weight fraction of fraction 1 = 1 1  1 1
W  ni Mi
n1M1
Molecular weight contribution by fraction 1 =  M1
 ni Mi
2
nM1 1
=
 ni Mi
Similarly, molecular weight contribution by other fraction will be as follows:
nM2 nM 2 nM 2
2 2 , 3 3  i i
 ni M i  ni Mi  ni Mi
nM2 n M2 nM 2
nM 2
Weight average molecular weight = 1 1
 2 2
 3 3
 i i

n M i i n M n M
i i i i n M i i

= n M 2
i i

n Mi i

 Mw
Polydispersity:

Polydispersity is the characteristic of most macromolecules. It is a very important parameter which gives
an idea of lowest and highest molecular weight as well as the distribution pattern of the intermediate
molecular weight species. It is based on the concept by different polymerisation techniques show different
polydisperdities. e.g. Most of the polymer substance.
 MUSTAFIJUR RAHMAN 12
MSc in TEXTILE ENGINEERING, THE UNIVERSITY OF MANCHESTER, UK

Monodispersity:

If the weight average molecular weight is equal to the number average molecular weight, the polymer is
perfectly homogenous. Each molecule has the same molecular weight is called mondispersity of the
system. e.g. H2O and Alcohol.

Index of polydispersity:
The ratio of weight average molecular weight to number average molecular weight is called
index / degree of polydispersity.
For all synthetic polymer, the ration is higher than 1.
If , Mw = Weight average molecular-weight.
Mn = Number average molecular weight.
Mw
Then, index of polydispersity =
Mn
Mw
Incase of, monodispersed system, =1
Mn
Mw
Polydispersity , >1
Mn
Different methods of determination of molecular weight:
The molecular weight (M.W.) of a molecule is the sum of the weights of all the atoms which
make up the molecule.
Example:
R-[CH2 -CH2 ]500  R; M .W.  14, 000
R-[CH2 -CH2 ]550  R; M .W.  15, 400
R-[CH2 -CH2 ]600  R; M .W .  16,800
 MUSTAFIJUR RAHMAN 13
MSc in TEXTILE ENGINEERING, THE UNIVERSITY OF MANCHESTER, UK

Problem:
No.of each (n) Weight of each(m) Total weight
Orions 2 10 W1=20

Bringals 4 20 W2=80
Cabages 3 100 W3=300
Cauliflower 3 250 W4=750

 n  12i W  1150
i

Calculate (I) Mn (ii) MW (III) Index of polydispersity.

2 4 3 3
(I) Mn = 12 10  12 20  12100  12 250
 95.833

20 80 300 750
(II) MW  1150
10   20 
1150
100 
1150
 250
1150
 190.693
MW 190.693
(III) Index of polydispersity:  

 1.98(say)
 polymerization Mechanism
Classification of Polymerization:
1) Chain / Addition polymerization
i) Free Radical Polymerization
ii) Ionic Polymerization
(a) Anionic
(b) Cationic
iii) Co-ordination Polymerization

2) Step / Condensation Polymerization

i) Poly addition
ii) Amidation
iii) Ester interchange
iv) Ring opening
Chain / Addition polymerization
 Chain polymerization is a polymerization technique where unsaturated monomer
molecules add onto the active site on a growing polymer chain one at a time.
 Formation of polymer via chain reaction.

n CH2=CH2 -CH2-CH2-CH2-CH2-CH2-
Monomer Polymer
Key factors of chain-growth polymerization
 Monomers
 Initiator( to break π-bond)

Characteristics of chain-growth polymerization

 Only growth reaction adds repeating units one at a time to the chain
 Monomer concentration decreases steadily throughout the raction
 High molecular weight polymer is formed at once; polymer molecular weight changes
little throughout the reaction.
 Long reaction times give high yields but affect molecular weight little.
 An initiator is required to start the reaction.
 Different mechanisms operate at different stages of the reaction.
Types of Chain growth polymerization
1. Free radical polymerization.
2. Ionic polymerization.
 Anionic polymerization.
 Cationic polymerization.
3. Group transfer polymerization.
4. Coordination polymerization.

Monomers capable of undergoing chain polymerization

The monomers which have reactive double bond show the chain polymerization. These
monomers a four types as follows:
i. Vinyl compounds (CH2 = CHX):
e.g. Vinyl chloride (CH2 = CHCl)
Acrylic acid (CH2 = CHCOOH)
Acrylonitrile (CH2 = CHCN)
Acrylamide (CH2 = CHCONH2)
ii. Allyl compounds (CH2 = CHCH2X):
e.g. Allyl acetate (CH2 = CHCH2OCOCH3)
Allyl alcohol (CH2 = CHCH2OH)
Allyl chloride (CH2 = CHCH2Cl)
iii. Olefines compound (CH2 = CHR):
e.g. Ethylene (CH2 = CH2)
Propylene (CH2 = CHCH3)
Isobutylene [CH2 = C(CH3)2]
iv. Di-enes compounds (CH2 = CR –CH = CH2):
e.g. 1, 3 – Butadiens (CH2 = CH – CH = CH2)
Chloroprene (CH2 = CH – CCl= CH2)
Isoprene (CH2 = CCH3 – CH = CH2)
Free Radical Polymerization
Monomer for free radical polymerization
 Most Alkenes

Initiator for free radical polymerization

 Initiators are sometimes called ―Catalysts‖
 The initiation of the polymer chain growth is brought about by the free radicals produced
by the decomposition of compounds called initiators. Initiators are thermally unstable
compounds and decomposed into products called free radicals. The decomposition of the
initiators to form free radicals can reduce by heat energy e.g.
If R-R is an initiator and the pair of electron forming between the two R can be
represented by dot.
energy
R-R or R:R 2Ro
heat/ light/ catalyst
(initiator) (free radical)
  Requirements for an initiator
 A source of free radials
 Radicals must be produced at an acceptable rate at convenient temperatures
 Have the required solubility behavior.
 Transfer their activity to monomers efficiently.
 Be amenable to analysis, preparation, and purification.

Mechanism of free radical polymerization

 Initiation:
A free radical contains a lone (unpaired) electron. A lone electron is like a prospective bachelor,
always looking for another lone electron to couple with and get stabilized. At first the free-
radical attacks the double bond in the monomer molecules and resulting in the following
chemical change-

 Propagation:
In the propagation step, the radical site at the first monomer unit attacks the double bond of a
fresh monomer molecule and produces a new active free radical which can attack a fresh
monomer molecule. This results in the linking up of the second monomer unit to the first and the
transfer of the radical site from the first monomer unit to the second, by the unpaired electron
transfer process.
This process involving a continuing attack on fresh monomer molecule which in turn keep
successively adding to the growing chain one after another. The picture is as follows:

R CH2 CH + CH2 CH R CH2 CH CH2 CH

X X X X
R CH2 CH CH2 CH + CH2 CH R CH2 CH CH2 CH CH2 CH
X X X X X X

The structure of growing chain can be represented by

R CH2 CH CH2 CH R CH2 CH

n
X X X
 Termination :
After propagation comes termination. It is the last step of free radical polymerisation. It is also
called dead of the polymerisation. It depends on time, temperature and pressure etc. Termination
occurs two reactions as follows:
(I) Termination by coupling:
In this case, the two growing chains unite by the coupling of the lone electron present in each
chain to from an electron pair and thus nullify their reactiveness. This kind termination is known
as termination by coupling.
R CH2 CH CH2 CH + R CH2 CH CH2 CH
X n1 X X n2 X

R CH2 CH CH2 CH CH CH2 CH CH2 R

X n1 X X X n2
(II) Termination by disproportionation:
In this case, one H atom from one growing chain is abstracted by the other growing chain for
getting stabilized. In this process two polymer molecules are formed. One is saturated and other
is unsaturated.
R CH2 CH CH2 CH + R CH2 CH CH2 CH
X n1 X X n2 X

R CH2 CH CH2 CH2 + R CH2 CH CH CH

X n1 X X n2 X

Comparison of termination by coupling and disproportionation

Coupling Disproportionation
1. Produce one polymer chain. 1. Produce two polymer chains.
2. One polymer chain contains single ―head- 2.One polymer chain contains double bond and
to-head‖ linkage. another contains only single bond.
3. A polymer chain contains tow initiator 3.Each polymer chain contains one initiator
fragments ( R) per molecule. fragments (R).
4. Higher average MW. 4.Lower average MW.
Retarder: The materials which slow down the chain growth Polymerization is
called retarder. It also decreases molecular weight of the polymer e.g,
Dinitrobenzene.

Chain Transfer Agent: The compound with which the chain transfer reaction
takes place is called C.T.A.
If the C.T.A. is present in large quantity, the polymers produced have very low D.
P. Such polymers are called Telomer and the C.T.A. assumes the name of Telogen.
e.g.CCl4,, CBr4, H2 gas etc

Characteristic of Ionic Chain Polymerization

 Ionic polymerization is limited because the ions are usually unstable and
require stabilization and lower temperature for polymerization to proceed.
 The ionic polymerization proceeds with very high rates and is very sensitive
to the presence of small amounts of impurities.
 Cationic and anionic polymerizations have very similar characteristics. Both
depend on the formation and propagation of ionic species.
 Solvents of very high polarity cannot be used. The highly polar hydroxylic
solvents(water, alcohol) react and destroy most ionic initiators. Ionic
polymerization, thus require solvent of low or moderate polarity such as
CH3Cl, CH2Cl2 and pentane.
 Ionic polymerizations are characterized by a wide variety of modes of
initiation and termination.

B. Anionic polymerization:
In this polymerization, the initiating species is negatively charged (Carbonion) and
the growing polymer chain will have also negative charge at the end.
C: A→C+……A-(Carbonion)
Catalysts/Initiators:
(I) Alkyl metal or aryl metal. e.g. Butyl lithium. sodium napthalene, ethyl
sodium etc.
 (II) Alkali metal amides e.g. Sodium amide (NaNH2), potassium amide
(KNH2).
(III) Metal alkoxide.
(IV) Grignard reagents e.g.

Monomers
Monomers having electro-negative constituents respond to anionic polymerisation:
(I) Vinyl chloride (CH2 = CH - Cl)
(II) Vinyl cyanide (CH2 = CH - CN)
CH2 CH

(III) Styrene
(IV) -Methyl styrene
(V) H2C=CH-CH=CH2

C. Cationic polymerization:
The polymerization in where the initiation is done by a ‗proton‘ and the
propagation is carried out by a ‗carbonium ion‘ is called cationic polymerization. A
catalyst and a co-catalyst are used in polymerization. These together generate a
carbonium ion which initiates the polymerization.
Catalysts:
Acidic compounds are used as catalysts such as H2SO4, CH3COOH etc.
Co-catalysts:
Water is most commonly used co-catalyst. e.g. CH3OH.
Cationic polymerization can be expressed by three steps are as follows:
 Initiation:
Lewis acid such as BF3 in presence of small amount of water or methanol form
hydrates which exists as ion pairs.
F F
F B + H O H F B OH H
F F
Counter Ion
+
The H now attacks the pi electron of the monomer starts the chain growth through
the carbonium ion and the anion [F3BOH]- faces the growing chain ends.

F3BOH H + CH2 CH CH3 CH F3BOH

X X
1st monomer
 Propagation:
The propagation reaction involves further adding up of monomer units and
simultaneously transter of the charge to the newly addede monomer units.

CH3 CH2 F3BOH + CH2 CH CH3 CH CH2 CH2 F3BOH

X X X X
2nd monomer

CH3 CH CH2 CH2 F3BOH + CH2 CH

X X X
3rd monomer

CH3 CH CH2 CH CH2 CH2 F3BOH

X X X

 Termination:
(I) Donation of proton pairs:
Donation of a proton to the counter – ion resulting in the formation of a double
bond at the end of the growing polymer molecule and the resultant arrest of the
chain growth.
 CH3 CH CH2 CH F3BOH

X X
(Growing polymer chain)

CH3 CH CH2 CH + F3BOH

X X

(Dead polymer molecule)

(II) Termination by coupling:

Formation of a covalent bond between the carbonium - ion and the counter - ion
when the termination occurs by simple ‗coupling‘.

CH3 CH CH2 CH F3BOH

X OH
X

CH3 CH CH2 CH + BF3

X X
Step polymerization:
Step polymerization is a process in which the polymer build up proceeds through a
reaction between functional groups of monomer. The reaction takes place in a step
wise manner and the polymer build up is therefore slow. Step polymerization is
mostly accompanied by the elimination of small molecules like NH3, H2O, HCl
etc.

Example:
(I) Formation of Polyester-

n HO CH2 CH2 OH + n HOOC COOH

Ethylene glycol Terepthililc acid

O O
H O CH2 CH2 O C C OH + (2n-1)H2O

Polyethelyne glycol terepthilic

n

(II) Formation of Nylon 6:6-

n H2N (CH2)6 NH2 + n HOOC (CH2)4 COOH
Hexa methylene diamine Adipic acid
O O
H HN (CH2)6 NH C (CH2)4 C OH + (2n-1)H2O
Hexa methylene adipamide
n

Condition / salient feature of step polymerization:

(I) Monomers should have two reactive functional groups for polymerization
to proceed.
(II) Polymerization proceeds by step wise reaction between reactive
functional groups.
(III) Only one type of reaction between two functional groups is involved in
polymer formation.
 (IV) One small molecule is eliminated for every reaction between two
functional groups and hence it is active and not dead as in chain
polymerization.
(V) The product (polymer) contains both the reactive functional groups at its
chain ends.

Types of step polymerization reaction:

(I) Condensation or Poly Addition type:
Condensation polymerization is brought about by monomers containing two or
more reactive functional groups condensing with each other.
e.g. Formation of polyester & formation of nylon 6:6
There are two types of condensation polymerization -
 A-B type:
When a monomer contains two different types of by functional group of monomer
called A-B type condensation polymerization. The reaction is depicted as follows:
A B B A.B A + by product

e.g.

Amino Heptanoic Acid Nylon 7

 AA-BB type:
When a pair of bi-functional group / monomer as di-carboxylic acid / di-alcohol
etc. undergoes polymerization, then it is called AA-BB type condensation
polymerization. The reaction is depicted as follows:
AA-BB > A—(-A.B-)—B + By Product

Ethylene Glycol Adipic Acid Polyester

II. Amidation type:
R NH2
RCONH R RCONHR + RNH [Amide interchange]
Amide

III. Ester interchanges:

RCOOH + HOR RCOOR R OH

RCOOR + R OH

IV. Ring opening type:

Monomers having a ring structure can be opened and polymerised if conditions are
favorable; condensing of bifunctional low molecular weight compounds can give
cyclic or ring compounds having a strain-free configuration-
(CH2)n CO
NH +H OH H2N (CH2)n COOH
Caprolactum

H2N (CH2)n COOH + m (CH2)n CO

NH

Amide
H2N (CH2)n CONH (CH2)n COOH
interchange m
Extent of reaction
The extent of reaction ( ) is a method of quantifying how many "times" a reaction
has occurred. It has units of moles/time.
In physical chemistry, the extent of reaction is a quantity that measures the extent
in which the reaction proceeds. It is usually denoted by the Greek letter ξ. The
extent of a reaction has units of amount (moles). It was introduced by the Belgian
scientist Théophile de Donder.
Relation between D.P. and Extent of reaction:

Let us consider, C0=Concentration of the monomer initially present.

C=Concentration of the monomer at a time t
P=Extent of reaction.
Now we have,
C0  C
P
C0
C
 P  1
CO
C
  1 P
CO
C
  1  (I )
CO 1 P

Again , Let No=No. of monomers initially present.

N =No. of monomers at a time t
According to definition of D. P,
N0 CO
D.P.    (II )
N C
Compare(I ) & (II ),
1
D.P. 
1 P
This is the required relation.
 Differences between chain and step polymerisation:

Chain polymerization Step polymerization

1. Compounds containing reactive double 1. Monomers should have two reactive

bonds. i.c. Vinyl compounds, Allyl functional groups for polymerization to
compounds, olefins and Di-enes can proceed.
therefore undergo a chain polymerization
reaction.
2. The monomers are added by self addition. 2. Polymerization proceeds by step wise
reaction between reactive functional groups.
3. No by-product is formed in this 3. By product is formed
polymerization.

4. Chain polymerization consists of three 4. Only one type of reaction between two
major steps such as – initiation, functional groups is involved in polymer
propagation and termination. formation.

5. The polymer has the same elemental 5. The product (polymer) contains both the
composition as that of the monomer. reactive functional groups at its chain ends.
 Polymerization Techniques

Different polymerization techniques:

The method by which monomer is converted to polymer is called polymerization
method / polymerization technique.
The following three conditions must be considered for polymerization techniques:
(I) Polymerization process.
(II) Purification of raw materials.
(III) Reaction vessel.

I) Polymerization Process:
Chain / Addition polymerization and Step/Condensation polymerization

(II ) Purification of raw materials:

Monomer reagents (catalyst / initiators / other chemicals) that are used in
polymerization should be highly pure. We can purify the raw material of different
polymerization process by the following process
a. Solid raw material-
We can purify solid raw material by two ways. Such as-
(I) Re-crystallization.
(II) Re- precipitation.
b. Liquid raw material:
We can purify liquid raw material by two ways, such as-
(I) Distillation at atmosphere pressure.
(II) Distillation at under reduced pressure.
c. Gas raw material
We can purify gas raw material by absorption process. The gases are usually
purified by passing absorption tower containing suitable liquids and solids.

(I) Polymerisation process:

Mainly Three types of polymerisation process. Such as –
a. Solid phase polymerization.
b. Gas phase polymerization.
 c. Liquid phase polymerization.
1. Bulk or mass polymerization.
2. Solution polymerization.
3. Suspension polymerization.
4. Emulsion polymerization.
5. Interfacial polymerization.
6. Melt polymerization.
7. Dispersion polymerization.
a. Solid phase polymerization:
 Solid phase polymerization is mostly restricted to chain polymerization.
 The polymer build up in this process is slow because molecular mobility in
the solid state is completely restricted.
 The thermal activation of the reaction is quite difficult.
 The photo or radiation activation technique is restricted.

b. Gas phase polymerization:

 It is known in the case of very few olefinic monomers.
 It has a very poor heat transfer.
 Two methods used in the gas phase polymerization are-
i) Spraying the catalyst into the gaseous monomer.
ii) Feeding the gaseous monomer into a fluidized bed made up of the catalyst
particles.
 In both (i) and (ii) cases the polymer is obtained as a free flowing powder.

Free radical polymerization can be accomplished in:

 Bulk
 Suspension
 Solution
 Emulsion Polymerization
 Ionic and other non radical polymerization are usually controlled to solution
techniques.
 Solid and gas-phase polymerization also possible for vinyl monomers.
 1. Bulk Polymerization:
Techniques: Liquid monmomer +Initiator+ C.T.A.→ Polymer.
Examples: Ethylene, styrene, methyl methacrylate.
Features:
 Simplest polymerization technique.
 The initiator or C.T.A is dissociated in the monomer. So, the whole system is a
homogeneous system.
 Heat transfer with the increase viscosity of monomer-polymer solution.
 In case of free radical polymerization, auto acceleration of polymerization rate has been
occurred.
Advantages:
 Simply, only the monomer and initiator are present in the reaction mixture.
 High molecular weight.
Disadvantages:
 Difficult to control the molecular weight.
 Requiring longer duration.
Solution polymerization:
In solution polymerization, the monomer, initiator, and resulting polymer are all soluble in the
solvent.
Techniques:
Monomer + Initiator + Solvent + Catalyst + C.T.A Polymer.
Features:
 Monomer dissolved in solvent. Formed polymer remains dissolved. Depending on the
concentration of monomer the solution does not increase in viscosity.
 Solution polymerisaiton allows efficient heat transfer.
 Require careful selection of solvent to avoid the limit of molecular weight.
 Difficult to remove solvent completely from the finished product.
Advantages:
 Suitable for producing low molecular weight products.
 Suitable for free radical cationic, anionic and co-ordination polymerization.
Disadvantages:
 Viscosity of the medium increases slowly.
 Requires longer duration.
Suspension Polymerization:
 Water insoluble monomers are dispersed in water.
 Initiator dissolved in monomer.
 Stabilization of polymer particles with emulsifiers such as poly vinyl alcohol or Sodium
Carboxy Methyl Cellulose.
 Small droplets dissolved in water.
 Polymer is formed in granular beads form, therefore isolated easily by filtration or spray
drying(spraying into a heated chamber), particles size 0.01-1 micron.
 Pore size can be controlled by adding combination of solvent and non-solvent.
 Viscosity does not change much.
 Efficient process and reaction is controllable.
 Not suitable of elastomers.

Figure : Suspension polymerization.

Applications: Ion-exchange resins, Polystyrene foam, PVC, Poly Vinyl Alcohol.
Emulsion Polymerization:
Techniques: Water insoluble monomer + Initiator (insoluble in monomer) + Water +
Polymer.
Example: Poly Vinyl Acetate (PVAC)

Figure: Schematic diagram of emulsion polymerization

Features:
 A micelle forming emulsifier is used.
 Initiator is water soluble.
 The formed latex particles are much smaller than suspension particles(0.5-2 µm).
 Polymer is formed within the micelles and not in the monomer droplets.
 Chain transfer agents are often required to control Degree of Polymerization.
Advantages:
 Suitable for producing very high molecular weight products.
 Suitable for free radical and poly condensation polymerization.
 Required shorter duration.
 Used for paints, adhesive and so on.
Disadvantages:
 The rate of polymerization is quite high.
Applications:
Large scale industrial application, particularly used for manufacturing water based paint or adhesives,
tacky polymers.
Definition of Micelle:
In aqueous solution, molecules having both polar or charged groups and non polar
regions (amphipathic molecules) form aggregates called micelles.