POLYMERS

The word ‘polymer’ is coined from Greek words. ‘Poly’ means many and ‘mer’ means unit or part. Polymer is a
gaint molecule. It is also called complex molecule.

Polymer is a very large molecule having molecular mass in the order of 103 to 107u. Polymer is also referred to as
macromolecule which is formed by repeating structural units, on a large scale, joined by covalent bonds.
The smallest unit that repeatedly combines to form the polymer is termed as monomer. The process of formation of
polymer from respective monomers is called polymerisation.

Common examples of polymers are plastics, rubbers, foams, fibres, proteins, nucleic acids, etc.
Classification of polymers:
(I) Based on source
(A) Natural polymers
Polymers found in plants and animals are called natural polymers.
Starch, cellulose, proteins, rubber, etc., are examples of natural polymers.
(B) Synthetic polymers
Man made polymers are called synthetic polymers.
Plastics like polythene, neoprene rubber, gyptal, synthetic fibres like terylene, nylon6,
nylon 6,6 etc., are examples of synthetic polymers.
(C) Semi-synthetic polymers.
Cellulose derivatives like rayon, cellulose nitrate, etc., are examples of semi–synthetic
polymers. Rayons are used in packages, wrappings and photofilms. They are also called artificial
silks. Pyroxylin, viscose rayon, acetate rayon and cuprammonium rayon are familiar semi-synthetic
polymers.
(II) Based on the structure
Polymers are classified into three types based on the structure.
(A) Linear polymers
Linear polymers consist long and unbranched chains.
High density polythene, polyvinyl chloride, etc., are examples of linear polymers.

(B) Branched chain polymers

Polymers like low density polythene have linear chains having branches. These are
called branched chain polymers.
 (C) Cross linked or Network polymers
Polymers having cross links are called network polymers.
They are usually formed from bifunctional or poly–functional monomers. They contain covalent
bonds between long chains.
Bakelite, melamine, phenol–formaldehyde resin, etc., are examples of network polymers.
Structures of these three types of polymers are shown in Fig

(III) Classification based on mode of polymerisation

Based on mode of polymerisation, polymers are classified into two types, as addition polymers and
condensation polymers.
(A) Addition polymers
Addition polymers are formed by the repeated addition of monomer molecules possessing
multiple bonds.
Formation of polythene from ethylene, PVC from vinyl chloride, polypropene from propylene, etc.,
are examples of addition polymerisation.
 Condensation polymers

Condensation polymers are formed by the repeated condensation of monomer molecules possessing
bifunctional or polyfunctional groups. Elimination of small molecules such as water, hydrogen chloride, alcohol, etc., take
place during condensation.
Homopolymers
Polymerisation of a single monomeric species is known as homopolymerisation
Polythene, polystyrene, isoprene rubber, etc., are homopolymers
Coplymers
Polymerisation of two or more different monomeric species is known as
copolymerisation.
Bakelite, terylene, buna–S rubber, etc., are copolymers.
Classification based on molecular forces
Polymers are also classified based on molecular forces. The mechanical properties
like elasticity, tensile strength, hardness, toughness, etc., are governed by intermolecular forces like
van der Waals forces, dipolar forces and hydrogen bonds present in the polymer. These molecular
forces bind polymer chains.
1. Elastomers
Rubber like solids with elastic properties are called elastomers. Polymer chains are
held together in elastomers by weakest intermolecular forces. These weak binding forces permit the
polymer to be stretched.
Natural rubber, neoprene rubber, buna–S rubber, buna–N rubber, etc., are elastomers.
2. fibres
Thread forming solids with high tensile strength and high modules are called fibres.
Polymer chains are held together in fibres by stronger hydrogen bond forces and thus impart
crystalline nature.
Polyesters like terylene and polyamides like nylon 6,6 are examples of fibres.
3. Thermoplastic polymers
Thermoplastic polymers possess intermolecular attraction forces intermediate between
elastomers and fibres. These are linear or slightly branched long chain molecules capable of
repeatedly softening on heating and hardening on cooling.
Polythene and polyvinyls are common thermoplastics.
4. Thermosetting polymers
Thermosetting polymers are heavily branched or cross linked polymers. On heating
they under go extensive cross linking and become infusible. They cannot be reused.
Bakelite and polysiloxanes are common thermosetting polymers.
Polymers are also classified based on polarity and mechanism of polymerisation. Different
classifications of polymers are summarised in Table
Different classifications of polymers

Basis for classification Nature of polymers Common examples of polymers

Structure of polymers Linear polymer Polythene, PVC.
Branched polymer Low density polythene.
Network polymer Bakelite, Melamine.
Mechanism of Addition polymers Neoprene rubber, PVC.
polymerisation Condensation polymers Terylene, Nylon 6,6, Bakelite.
Number of types of Homopolymer Polythene, Neoprene rubber.
monomers used Copolymer Buna-S rubber, Bakelite,
Nylon 6,6.
Molecular forces Elastomers Buna rubber, Neoprene rubber.
Fibres Polyesters, Polyamides.
Thermoplastics Polystyrene, Polyvinyls.
Thermosetting Bakelite, Urea-HCHO resin.

Polarity Cationic polymerisation Polystryrene, Polyvinyl ether,

Polyisobutene.
Anionic polymerisation Buna rubber, Polyisoprene,
Polyacrylonitrile.
 Polymerisation process
Depending upon the mechanism, polymerisation reactions are broadly classified
into two types : Condensation or step growth polymerisation and addition or chain growth
polymerisation.
Condensation polymerisation
It takes place between molecules having polyfunctional groups. A condensation polymer is
defined as a polymer in which the polymer unit contains fewer atoms than the number of atoms in all
the monomer units from which the polymer is formed. The condensation occurs between molecules
having polyfunctional groups and leads to the formation of high molecular mass polymer. The
polymerisation reactions may result in the loss of some simple molecules like water, hydrogen
halide, etc.
The product of each step is again a polyfunctional group and the sequence of condensation goes
on. Since, each step produces a distinct functionalised species and is independent of other, this
process is also called step growth polymerisation.
Polyesters, polyamides, bakelite, melamine formaldehyde resin, etc., are important examples of
step growth polymers.
Polyesters
Polyesters are the polycondensation products of diols and dicarboxylic acids.
Terylene, also called dacron, is the best known example of polyester. It is a copolymer. It is
manufactured by heating a mixture of terephthalic acid and ethylene glycol at 450K in the presence
of zinc acetate – antimony trioxide catalyst.
Dacron, also called terylene or PET, is water resistant and is used in blending with cotton and
wool fibres. It is also used in safety belts and helmets.

Polyamides
Polyamides are polycondensation products of diamines and dicarboxylic acids.
They are important examples of synthetic fibres and are termed as nylons.
Nylon 6,6 is prepared by the condensation of adipic acid with hexamethylene diamine under high
pressure and at high temperature. It is a copolymer.
nHOOC–(CH2)4–COOH + nH2N–(CH2)6–NH2

Nylon 6,6 is used in textile industry and in making tyre cords, ropes, sheets, bristles for brushes,
etc.
Nylon 6 is a condensation homopolymer. It is also called perlon L. It is obtained by heating
caprolactum with water at 540K. It is used for the manufacture of fabrics, ropes and tyre cords.

Addition polymerisation
It is the process in which the molecules of same or different monomers add together on a large
scale to form polymer. The monomers are unsaturated compounds like alkenes, alkadienes and their
derivatives. They are also called vinyl polymers. The mode of polymerisation leading to an increase
in chain length or chain growth can take place through the formation of either ionic species or free
radials.
Ionic polymerisation
It is of two types based on the nature of ions used for the chain initiation. If a positive ion is
used, the process is called cationic polymerisation. If a negative ion is used, the process is called
anionic polymerisation.
Cationic polymerisation : Formation of a polyvinyl compound from its monomer is a simple
example in which cation is a chain initiator. Lewis acids like BF3, AlCl3, FeBr3, SnCl2, etc., are
common chain initiators. Three steps are involved in cationic polymerisation.
Step 1 : Chain initiation

Step 2 : Chain propagation

Step 3 : Chain termination

eg : polystyrene, polyvinylethers, polyisobutene, etc.

Anionic polymerisation :
Formation of a vinyl compound can also be initiated by typical initiators like potassium amide,
butyl lithium, etc. Anionic polymerisation involves two steps. A most striking aspect of anionic
polymerisation is that the chain termination is absent.
Step 1 : Chain initiation

Step 2 : Chain propagation

Another example of anionic polymerisation is involving Lewis base, NHas catalyst.

eg : Buna type synthetic rubbers, polyacrylonitrile, polyisoprene, etc.

Free radical polymerisation

A variety of alkenes or dienes and their derivatives are polymerised in the presence of a free
radical generating initiator like benzoyl peroxide, acetyl peroxide, etc., acting as catalyst.
Polymerisation of ethylene to polythene on heating a mixture of ethylene and a small amount of
benzoyl peroxide is an example of free radical polymerisation.
The process starts with the addition of phenyl free radical formed from the peroxide to ethylene
double bond generating a new and larger free radical. This is called chain initiation. The repetition of
the reaction leads to the formation of bigger free radicals called chain propagation. Ultimately
product free radical reacts with another free radical to give the polymerised product called chain
termination.
In presence of a free radical generating initiator (catalyst) like benzoyl peroxide, acetyl
peroxide, tert-butyl peroxide, etc., a variety of alkenes or alkdiemes and their derivatives are
polymerised. The sequence of various steps may be depicted as follows :
Step 1 : Chain initiation

Step 2 : Chain propagation

 Step 3 : Chain termination
For termination of the long chain, these free radicals can combine in different ways to from
polythene. One of the possible modes of termination of chain is as shown below :

1.What is crosslinking in polymers ?

Solution Based on the structures, polymers are 3 types : Unbranched, branched and network polymers. Polymers
containing strong covalent bonds between various linear chains are called network polymers. Joining various
chains by covalent bonds is called cross linking and this leads to network structure like in bakelite and
malamine polymers.

2. Si(CH3)2Cl2 is hydrolysed. What type of polymer is formed ?

Solution Hydrolysis of Si(CH3)2Cl2 is given as Si(CH3)2Cl2Si (CH3)2(OH)2

The hydrolysis product undergoes condensation homopolymerisation. The product is an example of inorganic
polymer, called polysiloxane

3. Alternating copolymers are commonest copolymers. Comment.

Solution Alternating copolymers are usually produced when two monomers which differ in their reactive groups
undergo condensation. A dicarboxylic acid reacts with a diol and the chain is propagated to give a polyester
like polyethylene terephthalate (PET). PET also called dacron or terylene is an alternating copolymer.
Nylon 6,6 is another familiar condensation alternating copolymer.
Buna type rubbers, on the other hand, are addition alternating copolymers.
4A polymer is formed between ethylene dichloride and sodium disulphide. Discuss.
Solution Ethylene dichloride reacts with sodium disulphide to give a polymer called thiocol. This is a condensation
copolymer obtained by the elimination of sodium chloride.
n Cl–CH2–CH2–Cl + n Na–S–S–Na + 2n NaCl

5.How are the polymers classified based on heat treatment ?

Solution Based on heat treatment polymers are two types. They are thermoplastic polymers and thermosetting polymers.
Thermoplastic polymers are addition linear polymers. These soften and melt on heating. They can be
remoulded, recast and reshaped. eg : PVC, polystyrene, nylon, etc.
Thermosetting polymers are condensation cross linked polymers. These become more hard on heating. They
cannot be remoulded or reshaped, eg : Bakelite, terylene, urea - formaldehyde resin, etc.

6What are plastics and plasticisers ?

Solution Substances like polythene and polyvinyls are commonly called plastics. They are usually addition vinyl
polymers. They are familiar for their flexibility and softness.
Substances added to plastics to impart viscosity, flexibility and other properties to the finished products are
called plasticisers.
 NATURAL AND SYNTHETIC RUBBER
Rubber is a polymer which is capable of returning to its original length, shape or size, after
being stretched or deformed. It is a common example of elastomer. It is the oldest natural polymer
used by man kind. Rubber is chemically a polydiene.

Natural rubber: South Americans called rubber ‘caoutchoue’, meaning to weep. Joseph Priestley named the
solid material as rubber, because it is used to erase pencil marks.
Natural rubber is obtained from a variety of shaubs and vines called rubber trees. The plants
yield a milky suspension known as latex. Latex is an emulsion of negatively charged
polyhydrocarbon particles in an aqueous solution. It contains 30-40% rubber, which is coagulated
using acetic acid or formic acid. This crude rubber is refined by masticating and then compounding
by the addition of necessary agents.
The raw natural rubber is a soft and sticky mass. It is insoluble in aqueous solutions, but soluble
in petrol, benzene, carbon disulphide, etc. It has low tensile strength and breaks when too much
stretched.
The empirical formula of natural rubber is C5H8. It is a hydrocarbon as it burns in air finally to
give carbon dioxide and water. In the absence of air, heating rubber produces isoprene.
Isoprene is chemically 2–methyl–1,3–butdiene.
Ozonolysis experiments on natural rubber suggested that the isoprene units are joined head-to-
tail by 1,4–links. In the 1,4–link formation, the residual double bonds are rearranged between C 2 and
C3 of each isoprene unit. X-ray studies of Bunna established that rubber is composed of long chain
isoprene units arranged in the ‘cis’ form as shown in Fig 21.2. The ‘trans’form is called gutta percha.
The weight average molecular weight of rubber is in between 1,30,000 to
3,40,000. Natural rubber has no polar groups and hence the intermolecular forces are limited only to
van der Waals forces. Rubber has a coiled structure and it can be stretched like a spring.
Natural rubber (cis–1,4–polyisoprene)
Vulcanisation of rubber
Natural rubber is brittle at low temperature (< 283K) and becomes soft at high
temperature (>335K). It shows high capacity to water absorption, low elasticity and is readily
abrasive. It is non-resistant to attack by oxidising agents. These properties of rubber are not suitable
for its use as automobile tyres and tubes. Good year found that these physical properties of rubber
can be improved by adding sulphur to hot rubber. This process is called vulcanisation
Vulcanisation was originally performed by heating a mixture of raw rubber and sulphur at 373 -
415K. This process can be accelerated by adding catalysts like zinc oxide, zinc stearate, etc.
On vulcanisation, sulphur forms cross links at the respective sites of double bonds and thus
rubber gets stiffened. In the manufacture of tyre rubber, generally 5% of sulphur is used for
vulcanisation.
Vulcanisation is a very complex phenomenon. However it leads to develop cross links. The
possible structures of vulcanised rubber are shown below. Cross links may be formed at double
bonded carbon atoms or at the allylic –CH2– groups
Cross links formed by sulphur on vulcanisation

When the proportions of sulphur are increased, rubber can be hardened. If the amount of
sulphur is 40 - 45% used in vulcanisation, rubber sets to a non-elastic hard material known as
ebonite.
Due to cross links during vulcanisation, rubber gets stiff. The intermolecular moment of rubber
coils is prevented. Vulcanised rubber has excellent physical properties like elasticity, high resistance
to chemical oxidation, minimum tendency to absorb water and low solubility in organic solvents.

Synthetic rubber Any polymer which is capable of getting stretched almost to double the length and which is also
vulcanisable as in the case of natural rubber is called synthetic rubber. As soon as the external
stretching force is released, it returns to original size and shape.
Natural and synthetic rubber resumble in their properties. Both rubbers undergo vulcanisation.
However, there are some differences. The main differences between natural rubber and synthetic
rubber are listed in the following table
Differences between natural and synthetic rubbers
Property Natural rubber Synthetic rubber
Source of polymer Rubber trees Chemicals
Type of polymer Homopolymer Homopolymer or copolymer
Length of polymer chain Length is not uniform Length may be uniform
Fixing quality Generally low Generally high
Affinity to vat dyes Generally high affinity Generally low affinity
 Synthetic rubbers are two types. They may be homopolymers of derivatives of
1,3–butadiene. They may be copolymers of 1,3–butadiene with another unsaturated hydrocarbon
derivative.
Neoprene is homopolymer. It is an example of synthetic rubber and is called polychloroprene. It
is formed by the free radical polymerisation of 2-chloro-1,3-butadiene, in the presence of a peroxide
catalyst.
Neoprene has superior resistance to vegetable and mineral oils. It is used for the manufacture of
belts, gaskets and hoses.

Buna rubbers are copolymers. Buna-S rubber is obtained by the copolymerisation of 1,3-
butadiene and styrene. It is called styrene butadiene rubber (SBR) and is denoted as GRA. It is used
in making automobile tyres and foot-wear.

Buna-N rubber is obtained by the copolymerisation of 1,3-butadiene and acrylonitrile. It is

denoted as GRN. It is resistant to action of petrol, oil and organic solvents. It is used in making oil
seals, tank linings and hosepipes.
7. How is neoprene rubber obtained ?
Solution Neoprene rubber is synthetic polymer of 2-chloro-1,3- butadiene.
Heating the monomer in the presence of very small amount of oxygen brings about polymerisaiton and rubber
is obtained.

8. What is the ozonolysis derivative of natural rubber ?

Solution Natural rubber is cis-polyisoprene. Ozonolysis of polyisoprene gives 4-oxopentanal. The double bonds cleave
during ozonolysis to give carbonyl groups.

9. Write the order of intermolecular forces in neoprene, nylon 6 and PVC.

Solution Increasing order of intermolecular forces is : neoprene < polyvinylchloride < nylon 6.
Neoprene rubber is cis–1,4–polychloroprene. It has very weak van der Waals forces.
Van der Waals forces are relatively stronger in polyvinylchloride, because of the presence of halogen atoms.
Nylon 6 is a polyamide and hence van der Waals forces are even stronger.

10. Why the natural rubber is elastic ?

Solution Intermolecular forces in rubber are weaker van der Waals forces. These forces are further weakened because of
all cis configurations about double bonds do not let the polymer chains come closer enough for an effective
attraction.
As a consequence the rubber molecule cannot be present as a straight chain and exists in coiled structure.
Hence natural rubber is elastic and can be stretched like a spring.
11. What are the differences between buna - S and buna - N rubbers ?
Solution Both buna - S and buna - N are synthetic rubbers.
Buna - S rubber is a copolymer of 1, 3 - butadiene and styrene.
Buna - N rubber is a copolymer of 1, 3 - butadiene and acrylonitrile.
There is a slight difference in the position of side chain in these rubbers.

BIOPOLYMERS AND BIODEGRADABLE POLYMERS

The living systems are constituted of many polymers. Carbohydrates, proteins, nucleic acids,
etc., are a few of such essential polymers for life.

Biodegradable Many polymers are quite resistant to the natural degradation process and are thus
polymers responsible for the accumulation of polymeric solid waste materials. The management of these solid
wastes created acute environmental problems. These polymeric wastes remain undergraded for quite
a long time.
In view of the problems created by the polymeric solid wastes and of the general awareness,
certain new biodegradable polymers have been designed, synthesised and developed. These
polymers have functional groups that are mostly present in biopolymers and lipids. They may
degrade quickly in living systems by enzymatic chemical reactions like oxidation or hydrolysis.
Aliphatic polyesters are one of the important classes of biodegradable polymers. The
condensation reaction between carboxylic acids and alcohols was utilised by Carothers to prepare
polyesters. Polyamides are also prepared in a similar way.
Poly -hydroxy butyrate-co-–hydroxy valerate is a biodegradable polymer and is known as
PHBV. This polymer undergoes bacterial degradation in the environment. It is obtained by
copolymerisation of 3-hydroxybutanoic acid and 3-hydroxypentanoic acid.

The physical properties of PHBV change according to the relative amounts of the two hydroxy
carboxylic acids used in the preparation. Excess amounts of hydroxy butanoic acid makes the
polymer tougher, while excess amounts of hydroxypentanoic acid makes the copolymer more
flexible.
PHBV is of immense utility in the field of medicine for making capsules. When the drug is put
in the capsule of PHBV, it is released only when the polymer is degraded. It is also used in speciality
packaging and in orthopaedic devices.
 Polyglycolic acid and polylactic acid are homopolymers of the polyester type. These polymers
are prepared by the condensation of the monomers 2–hydroxyethanoic acid and 2–hydroxypropanoic
acid respectively.

Polyglycolic acid

Polylactic acid

Both these polymers are biodegradable esters. Polyglycolic acid, also called dextron was the first
polymer used for biodegradable stitches. Now these polyesters are commercially used for post
operative sutures.
Nylon 2 – nylon 6 is an alternating polyamide. It is also a biodegradable polymer. It is obtained
by the copolymerisation of glycine and aminocaproic acid. Threads and fibres used as sutures are
prepared from it, as it is degraded by bacteria.
n H2N–CH2–COOH + n H2N(CH2)5COOH
[ NH–CH2–CO–NH–(CH2)5–CO ] n
12 Write the main differences between the structures of starch and cellulose.
Solution 100 to 3000 D– glucose units are joined by 1, 4 – glycoside linkages and also 1, 6 – cross links in starch.
300 to 2500 D– glucose units are joined by 1, 4–glycoside linkages in cellulose. Cellulose has packed
arrangement of chains. Hence, it is stiff and hard.

13 Suggest the structure of nylon 2–nylon 6.

Solution Nylon 2–nylon 6 is a biodegradable polymer. It is an alternating copolymer obtained by the condensation of
glycine and amino caproic acid. It is chemically a polyamide.