10

POLYMERS
Chapter 10

Polymers

1. Introduction The polymers made by addition polymerisation from two different

monomers are known as copolymers.
A polymer may be defined as a high molecular weight compound
For example: Buna- S, Buna- N
formed by the combination of a large number of one or more
types of small molecular weight compounds.
The small unit(s) of which polymer is made is (are) known as
monomer.
The polymerisation may be defined as a chemical combination of
a number of similar or different molecules to form a single large
molecule.

2. Classification of Polymers
2.1 Based on Source
2.1.1 Natural Polymers
2.2.2 Condensation Polymers
These are of natural origin or these are found in plants and
animals. Natural polymers also called as biopolymers. Condensation polymers are formed by the combination of
monomers with the elimination of simple molecules such as water
For Example: Proteins (Polymers of amino acids), Polysaccharides
or alcohol. This process is called condensation polymerisation.
(Polymers of monosaccharides), rubber (Polymers of isoprene)
Proteins, starch, cellulose etc. are the example of natural
silk, wool, starch, cellulose, enzymes, natural rubber, haemoglobin
condensation polymers.
etc.
Two main synthetic polymers of condensation types are
2.1.2 Synthetic Polymers polyesters (Terylene or dacron) and polyamides (Nylon-6, 6).
These are artificial polymers. For example: Polythene, nylon, PVC, For example:
bakelite, dacron etc.
2.1.3 Semi-Synthetic Polymers
Natural polymers modified according to human needs. For
Example: Nitro cellulose, cellulose acetate, cellulose xanthate, etc.

2.2 Based on mode of Polymerisation

2.2.1 Addition Polymers
These are the polymers formed by the repeated addition of
monomer molecules having double or triple bonds without
elimination of any thing.
The Addition polymer formed by polymerisation of single
monomeric species are known as homopolymers.
For example: Polythene

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POLYMERS 197

2.3 Based on Structure 2.4 Based on Molecular Forces

2.3.1 Linear Polymers 2.4.1 Elastomers
These consist of extremely long chains of atoms and are also These are the polymers having very weak intermolecular forces
called one dimensional polymers. For Example: Polyethylene, PVC, of attraction between polymer chains. Elastomers posseses elastic
Nylon, Polyester. character. A few cross links are introduced in between the chain
which help the polymer to regain its original shape after the force
is released as in case of vulcanised rubber.
For Example: Buna-S, Neoprene etc.

Fig. 10.4 : Elastomer : Neoprene

2.4.2 Fibres
Fig. 10.1 : Linear Polymer These are the polymers which have bit strong intermolecular
2.3.2 Branched Chain Polymers forces such as hydrogen bonding. For Example: Nylon - 6, 6,
Nylon-6, 10, Terylene etc.
These polymers contain linear chains having some branches,
Nylon - 6, 6 is obtained by condensation polymerisation of
For Example: low density polythene.
hexamethylene diamine (six carbon) and adipic acid (a dibasic
acid having six carbon).

Fig. 10.2 : Branched Chain Polymer

Fig. 10.5 : Fibre : Nylon - 6, 6
2.3.3 Three-Dimensional Polymers
Nylon-6, 10 is obtained by condensation polymerisation of
Those polymers in which chains are cross linked to give a three hexamethylene diamine (6C) and sebacic acid (10C).
dimensional network are called three dimensional polymers. For
Terylene (Dacron, teron, cronar, mylar) is a polyester fibre made
Example: Bakelite.
by the esterification of terephthalic acid with ethylene glycol.
2.4.3 Thermoplastics
A thermoplastic polymer is one which softens on heating and
becomes hard on cooling. PVC, Polyethylene, polypropylene,
polystyrene are the example of thermoplastics.

Fig. 10.3 : Three Dimensional Polymer

Fig.10.6 : Thermoplastic Polymer: PVC (Poly vinyl chloride)

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198 POLYMERS

2.4.4 Thermosetting Polymers or Resin Chain propagating step

A thermosetting polymer becomes hard on heating. Bakelite,
aniline aldehyde resin, urea formaldehyde polymer are its
examples.

Fig. 10.7 : Thermosetting Polymer: Bakelite

Fig. 10.9 : Chain propagating step
3. Types of Polymerisation Chain terminating step
For termination of the long chain, these free radicals can combine
Reactions in different ways to form polythene. One mode of termination of
3.1 Chain Growth Polymerisation chain is shown as under:
These polymers are formed by the successive addition of
monomer units to the growing chain having a reactive
intermediate (Free radical, carbocation or carbanion). However,
the free radical governed addition or chain growth polymerisation
is the most common mode. Chain growth polymerisation is an
important reaction of alkenes and conjugated dienes.
Polythene, polypropylene, teflon, PVC, polystyrene are some
examples of chain growth polymers.
Free Radical Mechanism of Polythene Polythene
The process starts with the addition of phenyl free radical formed
by the peroxide to the ethene double bond thus generating a new Fig. 10.10 : Chain terminating step
and larger free radical. This step is called chain initiating step. As 3.2 Step Growth Polymerization
this radical reacts with another molecule of ethene, another bigger
sized radical is formed. The repetition of this sequence with new These polymers are formed through a series of independent steps.
and bigger radicals carries the reaction forward and the step is Each step involves the condensation between two monomers
termed as chain propagating step. Ultimately, at some stage the leading to the formation of high molecular mass condensation
product radical thus formed reacts with another radical to form polymer. by the loss of some simple molecules like water e.g.
the polymerised product. This step is called the chain terminating
step. Nylon, terylene, bakelite etc.
The sequence of steps involved in the formation of polythene
are depicted as follows:
Chain initiation steps of Polythene

Benzoyl peroxide

Phenyl radical Fig. 10.11 : Step Growth Polymerization in terylene

 
C 6 H 5  CH 2  CH 2  C 6 H 5 – CH 2 – C H 2
Fig. 10.8 : Chain initiation steps

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POLYMERS 199

4. Polymers and their Properties

Table 10. 1: Polymers : Monomers, Type, Characteristics & Uses
[Link]. Monomer Polymer Type of Polymers Characteristics & Uses
(i) CH2= CH2(Ethylene) Low density Addition polymer Chemically inert & tough;
High pressure (1000-2000 atm) ; Polythene(LDP) used in making toys and
temperature (350 K -570 K); flexible pipes
O2/peroxide (catalyst)
(ii) CH2= CH2(Ethylene) High density Addition polymer Chemically inert & more tough;
Pressure (6-7 atm) ; Polythene (HDP) used in making buckets,
temperature (333 K -343 K); dustbins etc.
TiCl4+ (C2H5)3 Al
(Ziegler-Natta catalyst)
(iii) CH2= CH — CN Polyacrylonitrile (PAN) Addition Used as a substitute for wool
(Acrylonitrile) or Orlon homopolymer
(iv) CH2=CHOCOCH3 Poly vinyl acetate Addition Used in latex paints &
(Vinyl acetate) homopolymer as an adhesive
(v) CF2 = CF2 Teflon Chain growth Chemically inert; used in
(Tetrafluoro ethylene) (PTFE) homopolymer Non-stick cookwares,making
oil seals and gaskets
(vi) Ethylene Glycol + dimethyl Terylene or Dacron Copolymer, Crease resistant ; used in blending
terephthalate (Polyester) step growth with cotton and wool, also used in
safety helmets
(vii) Methyl methacrylate Poly methyl meth Addition Hard & scratch resistant; used in
acrylate (PMMA) homepolymer biomaterial applications like lenses,
(Plexiglass) also in dental implants
(viii) Melamine+formaldehyde Melamine Copolymer, Used in making
(Thermosetting polymer) step growth unbreakable crockery
(ix) Hexamethylene Nylon - 6, 10 Copolymer, step Resistant to alkalies & most
diamine + sebacic acid (Polyamide) growth linear organic solvents; used
for paint brushes, tooth brushes
& moulded plastic items
(x) 6-Aminohexanoic acid Nylon - 6 Homopolymer, Used in manufacture of tyre cords,
(Caprolactum) (Polyamide) step growth linear fabrics & ropes
(xi) Hexamethylene Nylon - 6, 6 Copolymer, Used in making sheets, bristles for
diamine + adipic acid (Polyamide) step growth linear brushes & in textile industries
(xii) Acrylonitrile+Vinyl chloride Dynel Addition Copolymer Good resistance &
high tensile strength ; used for
making synthetic hair wigs
(xiii) Phenol+formaldehyde Novalac, Copolymer, Used in making combs electrical
Bakelite (Cross linked step growth switches and handles of various
polymer of formaldehyde utensils.
& Novalac)

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5. Copolymerisation 5.2 Synthetic Rubber

Copolymerisation is a polymerisation reaction in which a mixture Synthetic rubber is any vulcanisable rubber like polymer, which
of more than one monomeric species is allowed to polymerise has the tendency to get stretched to twice its length.
and form a copolymer. The copolymer can be made not only by For Example: Nitrile Rubber is a synthetic rubber produced by
chain growth polymerisation but by step growth polymerisation the polymerization of acrylonitrile with butadiene.
also.
5.2.1 Preparation of Synthetic Rubber
For Example: Butadiene - styrene Copolymer is quite tough and
(i) Neoprene:
is a good substitute for natural rubber. It is used for the
Neoprene or polychloroprene is formed by the free radical
manufacture of autotyres, floortiles, footwear components, cable
insulation, etc. polymerisation of chloroprene.

5.1 Natural Rubber

Natural rubber is cis 1, 4-polyisoprene. It is a linear 1,4-polymer
of isoprene. It is manufactured from rubber latex which is a
colloidal suspension of rubber in water.

Fig. 10.12 : Natural Rubber

5.1.1 Vulcanisation of Rubber:
Natural rubber becomes soft at high temperature (>335 K) and
brittle at low temperatures (<283 K) and shows high water
Fig. 10.14 : Preparation of Synthetic Rubber : Neoprene
absorption capacity.
(ii) Buna – N
To improve upon these physical properties, a process of
Buna –N is obtained by the copolymerisation of 1, 3 – buta diene
vulcanisation is carried out. This process consists of heating a
and acrylonitrile in the presence of a peroxide catalyst.
mixture of raw rubber with sulphur and an appropriate additive at
a temperature range between 373 K to 415 K. On vulcanisation,
sulphur forms cross links at the reactive sites of double bonds
and thus the rubber gets stiffened. 5% of sulphur is used as
cross linking agent in manufacture of rubber tyre.

Fig. 10.13 : Vulcanisation of Rubber

Fig. 10.15 : Preparation of Synthetic Rubber : Buna - N

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POLYMERS 201

6. Molecular Mass of Polymers 8. Biodegradable Polymers

There are two types of average molecular masses of polymers: Due to general awareness and concern for the problems created
by the polymeric solid wastes, various new biodegradable
 
(i) Number average molecular mass M n is given by synthetic polymers have been developed. These polymers
contain functional groups similar to the functional groups present
N1M1  N 2 M 2  N3 M3  .........  Ni Mi in biopolymers. Some biodegradable polymers are discussed
Mn  
N1  N 2  N3  ........  Ni below
(i) Poly  - hydroxybuyrate-co-- hydroxyvalerate (PHBV): It
Where N1 number of molecules having molecular mass M1 and so
is obtained by copolymerisation of 3-Hydroxybutanoic acid
on. It is measured by osmotic pressure measurement.
and 3-Hydroxypentanoic acid. It is used in controlled release

 
(ii) Mass- average molecular mass Mw is given by
of drugs, in speciality packaging and in orthopedic devices.

N1M12  N 2 M22  N3 M33  .........  Ni Mi2

Mw  
N1M1  N 2 M 2  N3 M3  ........  Ni Mi 3-Hydroxybutanoic acid 3-Hydroxypentanoic acid

It is determined by ultra centrifugation or sedimentation.

7. Polydispersity Index
PHBV
It is the ratio of mass average molecular mass M w to the number Fig. 10.16 : Biodegradable Polymer : PHBV

average molecular mass M n (ii) Nylon 2-Nylon 6: It is obtained by copolymerisation of amino

caproic acid and glycine, It is an alternating polyamide
Mw copolymer. It is used as a thread and also used in making
PDI  strings of musical instruments.
Mn
When PDI = 1 or nearly 1, we have monodisperse system in
which all molecules have identical molecular mass. Natural Amino Caproic Acid
Glycine
polymers are monodisperse and synthetic polymers are
polydisperse i.e. PDI > 1 for such polymers

Nylon - 2 - nylon - 6

Fig. 10.17 : Biodegradable Polymer : Nylon - 2 - nylon - 6

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9. Polymers of Commercial Importance

Table 10. 2: Polymers of Commercial Importance

Name of Polymer Monomer Structure

Polypropene Propene

Polystyrene Styrene

Polyvinyl chloride (PVC) Vinyl chloride

Urea-formaldehyle Resin (a) Urea (b) Formaldehyde

Glyptal (a) Ethylene glycol (b) Phthalic acid

Bakelite (a) Phenol (b) Formaldehyde

9.1 Uses of Commercialy Important

Polymers
(i) Polypropene-It is used to manufacture of ropes, toys, pipes, (iv) Urea-formaldehy’s Resin- It is used for making unbreakable
fibres, etc cups and laminatec sheets.
(ii) Polystyrene- It is used to as insulator, wrapping materail, (v) Glyptal- It is used to manufacture of paints and lacquers.
manufacture of toys, radio and television cabinets. (vi) Bakelite- It is used for making combs, electrical switches,
(iii) Polyvinyl chloride (PVC)- It is used to manufacture of rain handles of utensils and computer discs.
coats, hand bags, vinyl flooring, water pipes.

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POLYMERS 203

Summary
Polymers : Monomers, Type, Characteristics & Uses
[Link]. Monomer Polymer Type of Polymers Characteristics & Uses
(i) CH2= CH2(Ethylene) Low density Addition polymer Chemically inert & tough;
High pressure (1000-2000 atm) ; Polythene(LDP) used in making toys and
temperature (350 K -570 K); flexible pipes
O2/peroxide (catalyst)
(ii) CH2= CH2(Ethylene) High density Addition polymer Chemically inert & more tough;
Pressure (6-7 atm) ; Polythene (HDP) used in making buckets,
temperature (333 K -343 K); dustbins etc.
TiCl4+ (C2H5)3 Al
(Ziegler-Natta catalyst)
(iii) CH2= CH — CN Polyacrylonitrile (PAN) Addition Used as a substitute for wool
(Acrylonitrile) or Orlon homopolymer
(iv) CH2=CHOCOCH3 Poly vinyl acetate Addition Used in latex paints &
(Vinyl acetate) homopolymer as an adhesive
(v) CF2 = CF2 Teflon Chain growth Chemically inert; used in
(Tetrafluoro ethylene) (PTFE) homopolymer Non-stick cookwares,making
oil seals and gaskets
(vi) Ethylene Glycol + dimethyl Terylene or Dacron Copolymer, Crease resistant ; used in blending
terephthalate (Polyester) step growth with cotton and wool, also used in
safety helmets
(vii) Methyl methacrylate Poly methyl meth Addition Hard & scratch resistant; used in
acrylate (PMMA) homepolymer biomaterial applications like lenses,
(Plexiglass) also in dental implants
(viii) Melamine+formaldehyde Melamine Copolymer, Used in making
(Thermosetting polymer) step growth unbreakable crockery
(ix) Hexamethylene Nylon - 6, 10 Copolymer, step Resistant to alkalies & most
diamine + sebacic acid (Polyamide) growth linear organic solvents; used
for paint brushes, tooth brushes
& moulded plastic items
(x) 6-Aminohexanoic acid Nylon - 6 Homopolymer, Used in manufacture of tyre cords,
(Caprolactum) (Polyamide) step growth linear fabrics & ropes
(xi) Hexamethylene Nylon - 6, 6 Copolymer, Used in making sheets, bristles for
diamine + adipic acid (Polyamide) step growth linear brushes & in textile industries
(xii) Acrylonitrile+Vinyl chloride Dynel Addition Copolymer Good resistance &
high tensile strength ; used for
making synthetic hair wigs
(xiii) Phenol+formaldehyde Novalac, Copolymer, Used in making combs electrical
Bakelite (Cross linked step growth switches and handles of various
polymer of formaldehyde utensils.
& Novalac)

Polymers
204 POLYMERS

Solved Examples
Example-1 Example-7
Classify the following as addition and condensation Write short note on elastomer.
polymers: Terylene, Bakelite, Polyvinyl chloride, Polythene
Sol. Elastomers are polymers that are having a viscosity as well
Sol. Addition polymers: Polyvinyl chloride, Polythene as elasticity and therefore are known as viscoelasticity.
Condensation polymers: Terylene, bakelite. The molecules of elastomers held together by weak
Example-2 intermolecular forces. They inherit the unique property of
regaining original shape and size after being stretched to a
Arrange the following increasing order of their
intermolecular forces. great extent.

(i) Nylon 6, 6, Buna-S, Polythene Example-8

(ii) Nylon 6, Neoprene, Polyvinyl chloride Distinguish between the terms homopolymer and
copolymer and give an example of each.
Sol. On the basis of intermolecular forces, polymers are classified
as elestomers, fibres and plastics. The increasing order of Sol. Polymers whose repeating structural units are derived from
only one type of monomer units are called homopolymers,
intermolecular forces is: Elastomer < Plactic < fibre.
e.g., PVC polyethene, PAN, teflon, polystyrene, nylon-6
Thus, we have etc.
(i) Buna-S < Polythen < Nylon 6, 6 Polymers whose repeating structural units are derived from
(ii) Neoprene < Polyvinyl chloride < Nylon 6. two or more types of monomer molecules are copolymers,
e.g., Buna-S, Buna-N, nylon-66, polyester, bakelite.
Example-3
Example-9
Define the term polymerisation?
Write the names and structures of monomer of
Sol. It is a process of formation of a high molecular mass polymer Polypropylene.
from one or more monomers by linking together large
Sol. Propylene (CH3CH = CH2)
number of repeating structural units through covalent
bonds. Example-10
Example-4 Why are rubbers called elastomers?
Is (–NH – CHR – CO)n a hompolymer or copolymer? Sol. They change their shape on applying force and regain their
Sol. It is a homopolymer because the repeating structural unit original shape on removal of the applied force. Hence,
has only one type of monomer, i.e., NH2– CHR – COOH. rubbers are called elastomers.

Example-5 Example-11
In which classes, are the polymers classified on the basis Write the name and structure of one the common initiators
of molecular forces? used in free radical addition polymerisation.
Sol. Polymers are classfied into four classes on the basis of Sol.
molecular forces. These are elastomer, fibres, thermoplastic
polymers and thermoseting polymers. Benzoyl peroxide,
Example-6
Example-12
Explain the term copolymerisation and give two examples.
How is dacron obtained from ethylene glycol and
Sol. When two or more different monomers are allowed to terephthalic acid?
polymerise together the product formed is called a
Sol. Dacron is obtained by condensation polymerization of
copolymer, and the process in called copolymerisation.
ethylene glycol and terephthalic acid with the elimination
Example, Buna-S and Buna-N. Buna-S is a copolymer of 1, of water molecules. The reaction is carried out at 420 - 460 K
3-butadiene and styrene while Buna-N is a copolymer of 1, in presence of a catalyst consisting of a mixture of zinc
3-butadiene and acrylonitrile. acetate and antimony trioxide.
POLYMERS 205

Example-13 The monomeric repeating unit of nylon 6, 6 is derived

Discuss the main purpose of vulcanisation of rubber. from two monomers, hexamethylenediamine and adipic
acid and has the following structure:
Sol. To improve the properties, natural rubber is vulcanised by
heating it with about 5% sulphur at 373-415 K. The O O
vulcanized rubber thus obtained has excellent ealsticity || ||
over a large range of temperature, has low water absorption —NH —  CH 2 6 — NH — C—  CH 2  4 — C—
tendency and is resistant to the action of organic solvents
and oxidising agents. Example-17
Write the names and structures of the monomers of
Example-14
Neoprene
Write the names and structures of the monomers of natural
rubber. Cl
|
Sol. Neoprene: and Chloroprene or 2-
Sol. CH 2  C — CH  CH 2
The name of monomer of natural rubber is isoprene. chloro-1, 3-butadiene.

CH3
Example-18
 
 |  Identify the monomer
 H 2 C  C — CH  CH 2 
 
 

Example-15
t Write the names of the monomers of the following polymers:
Sol.
Monomers
(i)
HOOC —  CH 2 8 — COOH and H 2 N —  CH 2 6 — NH 2
Sebacicacid Hexamethylenediamine

Example-19
(ii) Write the monomers used for getting the following
polymers:
(i) Polyvinylchloride
(iii)
(ii) Teflon
Sol. Sol.
(i) Hexamethylene diamine NH2-(CH2)6NH2 and adipic acid
HOOC – (CH2)4 – COOH
(ii) Caprolactum
(i)
(iii) Tetrafluoroethene F2C = CF2
Example-16
What are the monomeric repeating units of Nylon-6 and
Nylon 6, 6?
(ii)
Sol. The monomeric repeating unit of nylon-6 is

O
||
—NH —  CH 2 5 — C—

which is derived from caprolactam.

206 POLYMERS

Example-20 Sol.
Explain the difference between Buna-N and Buna-S.
Sol. Both Buna-N and Buna-S are synthetic rubber and are co-
polymers in nature. They differ in their constituents.
Buna-N: Constituents are : buta-1, 3-diene and acrylonitrile.
Buna-S: Constituents are: buta-1, 3-diene, and styrene.
They condense in the presence of Na.
Example-21
What is a blodegradable polymer? Give an example of a
biodegradable aliphatic polyester.
Sol. Polymers which disintegrate by themselves over a period
of time due to environment degradation by bacteria, etc.,
are called biodegradable polymers. Example is PHBV, i.e.,
Poly--Hydroxybutyrate-co--Hydroxyvalerate. Example-24
How will you synthesise Polystyrene from benzene.
Sol.

Example-22
How will you synthesise
Polyvinyl chloride (PVC) from acetylene.
Sol.

Example-25
How will you synthesise Terylene from ethylene glycol and
terephthalic acid.
Sol.

Example-23
Describe how the following polymer is synthesised:
Bakelite