C H 3 2 2 : P O LY M E R E N G I N E E R I N G

COURSE OUTLINE
• INTRODUCTION
Monomers, polymers, classification of polymers
 POLYMER CHEMISTRY
Polymerization methods: addition and condensation; their kinetics, copolymerization, monomer reactivity
ratios and its significance, kinetics, different copolymers, random, alternating, azeotropic copolymerization,
block and graft copolymers, techniques for copolymerization-bulk, solution, suspension, emulsion
 POLYMER CHARACTERIZATION
Concept of average molecular weight, determination of number average, weight average, viscosity
average and Z-average molecular weights, Fractional precipitation, Fractional Elution, Gel Permeation
Chromatography (GPC), membrane osmometry, dilute solution viscosity method, ultracentrifugation,
analysis of polymers using IR, XRD, thermal (DSC, DMTA, TGA), microscopic (optical and electronic)
techniques
 POLYMER BLANDS AND COMPOSITES
Difference between blends and composites, their significance, choice of polymers for blending, FRP,
particulate, long and short fibre reinforced composites, Nanocomposites.

 POLYMER TECHNOLOGY
Polymer compounding, need and significance of polymer compounding, different compounding ingredients for
polymer, crosslinking and vulcanization.

 POLYMER PROCESSING
Compression molding, transfer molding, injection molding, blow molding, reaction injection molding, extrusion,
pultrusion, calendaring, rotational molding, thermoforming, rubber processing in two-roll mill, internal mixer.

 POLYMER DEGRADATION
Definition, Types of degradation, some new research on polymer degradation.

 POLYMER SYNTHESIS AND PROPERTIES

Commodity and general-purpose thermoplastics and thermosetting polymers: PE, PP, PS, PVC, PF, MF, UF,
Epoxy, Unsaturated polyester etc.
 COURSE OUTCOMES (COS)

CO1: Estimate the basic concept of monomer, polymer and repeating units with properties
CO2: Classify different polymerization reactions and their mechanisms/kinetics
CO3: Analyse and improve skills in thermal and mechanical properties of polymers

CO4: Describe the viscoelastic behaviour of polymers with respect to their chemical structures and
molecular weights
CO5: Demonstrate an ability to predict how the molecular weight will affect properties.
CO6: Analyze polymerization data and predict the conversion and molecular weight
INTRODUCTION
P O LY M E R
 The term polymer stems from the Greek roots poly (many) and meros (part). The word thus means
“many parts” and designates a molecule made up by the repetition of some simpler unit called a
mer. Polymers contain thousands to millions of atoms in a molecule that is large; they are also called
macromolecules. Polymers are prepared by joining a large number of small molecules called
monomers.

 The structure of polystyrene, for example-

Which depicts the mer or repeating unit of the molecule within parentheses with a subscript, such as n,
to represent the number of repeating units in the polymer molecule.
 The value of n usually ranges from a few hundred to several thousand, depending on
the molecular weight of the polymer. The polymer molecular weight may extend, on the higher
side, to several millions. Often the term high polymer is also used to emphasize that the polymer
under consideration is of very high molecular weight.
 MONOMER
 Monomers are generally simple organic molecules from which the polymer molecule is made. The
structure of the repeating unit of a polymer is essentially that or closely related to that of the
monomer molecule(s). The formula of the polystyrene repeating unit (II) is thus seen to
be essentially the same as that of the monomer styrene CH2 = CH-C6H5.

Repeating Unit
 The repeating unit of a linear polymer is a small portion of the macromolecule such that
linking together these units one after another gives rise to the formula of the whole molecule. A
repeating unit may be a single component such as (II) for the polymer (I), or it may consist of the
residues of several components, as in poly(ethylene terephthalate), which has the structure :
 Though it has been stated above that structures of repeating units are essentially those of the
monomers from which the polymers are made, this is not always the case. Considering, for
example, poly(vinyl alcohol) :

 The obvious precursor monomer for this polymer is vinyl alcohol, CH2=CH-OH, which is an unstable
tautomer of acetaldehyde and does not exist. Poly(vinyl alcohol) is instead made by alcoholysis of
poly(vinyl acetate),

 Which, in turn, is synthesized by polymerization of the monomer vinyl acetate, CH2=CHOOCCH3.

 END GROUPS
 In none of the above examples of the structural representation of polymers have the end groups been
shown. This is partly because the exact nature of the end groups of polymer molecules is often not
known and partly because end groups constitute an insignificant fraction of the mass of high molecular
weight polymer and so usually have negligible effect on polymer properties of major interest.

Problem: Calculate the end group content (weight fraction) of polystyrene of molecular weight
150,000, assuming that phenyl (C6H5-) groups constitute both the end groups of an average polymer
molecule.
 D E G R E E O F P O LY M E R I Z AT I O N

 The number of repeating units that constitute a polymer molecule.

 The abbreviation DP is used for the degree of polymerization.
 The subscript n used on the parentheses in the foregoing structural formulas for polymers represents
this DP. The relation between degree of polymerization and molecular weight M of the same
macromolecule is given by -

Where Mo is the formula weight of the repeating unit.

 H O M O P O LY M E R
 If a macromolecule is made from only one species of monomer, the product is
a homopolymer, referred to simply as a polymer.
 The word homopolymer often is used more broadly to describe polymers whose
structure can be represented by repetition of a single type of repeating unit
containing one or more species. Thus, a hypothetical polymer -[-AB-]n-- made
from A and B species is also a homopolymer, e.g., poly(ethylene terephthalate) (III)
Polyethene –(– CH2 – CH2 –)–n is an example of homopolymer.
 C O P O LY M E R

 A copolymer is a polymer derived from more than one species of monomer. The copolymer with a
relatively random distribution of the different mers or repeating units in its structure is commonly
referred to as a random copolymer.
 Representing two different mers by A and B, a random copolymer can be depicted as-

 There are three other copolymer structures : alternating, block, and graft copolymer structures
 In the alternating copolymer, the two mers alternate in a regular fashion along the polymer chain :

 A block copolymer is a linear polymer with one or more long uninterrupted sequences of each mer in
the chain :

 Block copolymers may have a different number of blocks in the molecule. Thus, AxBy,
AxByAx, AxByAxBy, (AxBy)n are referred to as AB diblock, ABA triblock, ABAB tetrablock, and
AB multiblock copolymers, respectively. Since there is a distribution of block lengths and number
of blocks along the copolymer chain, x and y as well as n represent average values.
 A graft copolymer, on the other hand, is a branched copolymer with a backbone of one type of mer
and one or more side chains of another mer :

 Copolymerization, which, in its objective, may be compared to alloying in metallurgy, is very useful for
synthesizing polymer with the required combination of properties
Copolymer arrangements : (a) Two different types of mers (denoted by open and filled circles) are
randomly placed. (b) The mers are alternately arranged. (c) A block copolymer. (d) A graft copolymer.
 A polymer formed from more than one kind of monomer units is called copolymer
or mixed polymer.

 For example, Buna-S rubber which is formed from 1, 3-butadiene (CH2 = CH –

CH = CH2) and styrene (C6 H5 CH = CH2) is an example of copolymer.
 P O LY M E R I Z AT I O N A N D F U N C T I O N A L I T Y

 Polymerization may occur only if the monomers involved in the reaction have the proper
functionalities.
 Functionality is a very useful concept in polymer science
 The functionality of a molecule is the number of sites it has for bonding to other molecules
under the given conditions of the polymerization reaction (Rudin, 1982). Thus, a bifunctional
monomer, i.e., a monomer with functionality 2, can link to two other molecules under suitable
conditions.
 Styrene, C6H5CH=CH2, for example, has functionality 2 because of the presence of a
carbon-carbon double bond.
 The minimum functionality required for polymerization is 2.
 P O LY F U N C T I O N A L M O N O M E R
 A polyfunctional monomer is one that can react with more than two molecules under the conditions
of the polymerization reaction.
 Divinyl benzene (VIII) is tetrafunctional in reactions involving additions across carbon-carbon double
bonds, while glycerol (IX) is trifunctional and pentaerythritol, C(CH2OH)4, is tetrafunctional in
polyesterification reactions.

 Functionality in polymerization is, however, defined only for a given reaction (Rudin, 1982). Thus, a
glycol, HOROH, has a functionality of 2 in esterification or ether-forming reactions, but its
functionality is zero in amidation reactions.
Problem: What is the functionality of the following monomers in reactions with styrene, C6H5CH=CH2

In reaction with styrene, the functionalities of the

monomers are :

(a) 2 (one reactive carbon-carbon double bond)

(b) 0 (-OH groups do not take part in addition

reactions)

(c) 2 (one reactive carbon-carbon double bond; –OH

group nonreactive)

(d) 4 (two reactive carbon-carbon double bonds)

(e) 2 (one reactive carbon-carbon double bond)

C L A S S I F I C AT I O N S O F P O LY M E R S
(a) Classification of Polymers on the Basis of Origin.
On the basis of origin, polymers are classified as :
1. Natural polymers
2. Synthetic polymers
1. Natural Polymers : The polymers obtained from nature (plants and animals) are
called natural polymers. Starch, cellulose, natural rubber, proteins, etc. are
some examples.
2. Synthetic Polymers : The polymers which are prepared in the laboratories are called
synthetic polymers. These are also called man-made polymers. Polyethene,
PVC, nylon, Teflon, bakelite, terylene, synthetic rubber, etc. are common examples.
(b) Classification of Polymers on the Basis of structure
On the basis of structure of polymers, these can be
classified as :
1. Linear polymers
2. Branched chain polymers
3. Cross-linked polymers.
1. Linear polymers : These are polymers in which
monomeric units are linked together to form linear chains.
These linear polymers are well packed (Fig. 33.1) and
therefore, have high densities, high tensile (pulling) strength
and high melting points. For example, polyethelene, nylons
and polyesters are examples of linear polymers.
2. Branched chain polymers : These are polymers in which the monomers are joined to
form long chain with side chains or branches of different lengths [Fig. 33.2].
These branched chains polymers are irregularly packed and therefore, they have lower
tensile strength and melting points than linear polymers. For example, low density
polyethene, glycogen, starch, etc.
3. Cross-linked polymers : These are polymers in which long polymer chains are
crosslinked together to from a three dimensional network. These polymers are hard,
rigid and brittle because of the network structure. (Fig. 33.3) bakelite, melamine
and formaldehyde resin are some examples of this type.
(c) Classification of Polymers on the Basis of Method of Polymerisation Chemistry and Industry
On the basis of method of polymerisation the polymers are classified as :
1. Addition polymer : A polymer formed by direct addition of repeated monomers without the
elimination of any small molecule is called addition polymer. In this type, the monomers are
unsaturated compounds and are generally derivatives of ethene. The addition polymers have
the same empirical formula as their monomers. Examples are polyethene, polypropylene and
polyvinyl chloride, etc.
2. Condensation polymer : A polymer formed by the condensation of two or more than two
monomers with the elimination of simple molecules like water, ammonia, hydrogen chloride,
alcohol, etc. is called condensation polymer. In this type, each monomer generally contains two
functional groups. For example, nylon – 66 is obtained by the condensation of two monomers;
hexa methylenediamine and adipic acid with the loss of water molecules.
(d) Classification of Polymers on the Basis of Molecular Forces
Depending upon the intermolecular forces between monomer molecules, the
polymers have been classified into four types.
1. Elastomers 2. Fibers 3. Thermoplastics 4. Thermosetting
1. Elastomers : In case of elastomers the polymer chains are held together by
weak van der waals forces. Due to weak forces, the polymers can be easily stretched
on applying small stress and they regain their original shape when the stress is
removed. This is due to the presence of few- ‘cross links’ between the chains, which
help the polymer to retract to its original position after the force is removed, as in
vulcanized rubber.
The most important example of elastomer is natural rubber.
2. Fibres : These are the polymers which have strong intermolecular forces between
the chains. These forces are either hydrogen bonds or dipole-dipole
interactions. Because of the strong forces, the chains are closely packed, giving them
high tensile strength and less elasticity. These polymers can be drawn into long, thin
and thread like fibres and therefore can be woven into fabrics. The common
examples are nylon- 66, dacron, silk, etc.
3. Thermoplastics : These are linear polymers with very few cross linkages or no
cross linkages at all. The polymeric chains are held by weak VANDERWAAL forces
and slide over one another. Due to lack of cross linkages these polymers soften on
heating and harden or become rigid on cooling. Thus they can be moulded to any
shape.
Polythene, PVC, polystyrene are addition type thermoplastics and Terylene, nylon are
condensation type thermoplastics.
Plasticizers : Certain plastics do not soften much on heating. These can be
easily softened by the addition of some organic compounds which are called
plasticizers.
For example, polyvinyl chloride (PVC) is very stiff and hard but is made soft by adding
di-n-butylphthalate (a plasticizer). Some other common plasticizers are
dialkyl phthalates and cresyl phthalate.
4. Thermosetting polymers : Usually thermosetting polymer can be heated only
once when it permanently sets into a solid which can not be remelted and remoulded.
Thermosetting polymers are produced from relatively low molecular mass semi
fluid polymers (called polymers) which on heating develop extensive cross-linking
by themselves or by adding some cross-linking agents and become infusible and
insoluble hard mass. The cross links hold the molecules in place so that heating does
not allow them to move freely. Therefore, a thermosetting plastic is cross linked and
is permanently rigid. The common example are bakelite, melamine, formaldehyde
resin, etc.
DISTINCTION BETWEEN THERMOPLASTIC AND
T H E R M O S E T T I N G P O LY M E R S
 REFERENCE

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