Polymers

Polymers
Polymers are very high molecular mass substances where each molecule is derived from very large
number of simple molecules joined together in a regular way. Polymers are formed by repeated
combination of simplest units called monomers and the process of formation of polymers from simple
molecule (monomers) is called polymerization.
nCH2=CH2 —CH2–CH2—
n
Ethene Polythene

Polymers can be classified in following ways :

(A) Classification based on type of monomer units :
(i) Homopolymers : Polymers in which repeating structural units are derived from only one type
of monomer units are called homopolymers.
Examples: Polyethylene, polyvinyl chloride (PVC), polyisoprene, neoprene (polychloroprene)
polyacrylonitrile (PAN), nylon-6, polybutadiene, teflon (polytetrafluoroethylene), cellulose,
starch, glycogen etc.
Cl
nCH2=CH–Cl —CH2–CH—
n
Vinyl chloride Polyvinyl chloride
(ii) Copolymers : Polymers in which repeating structural units are derived from two or more types
of monomer units are called copolymers.
Examples : Nylon-66, Terylene, Bakelite, Glyptal, Buna-S, Buna-N etc.
nH2N–(CH2)6–NH2 + nHOOC–(CH2)4–COOH —NH–(CH2)6–NH–CO–(CH2)4–CO—
n
Hexamethylene Adipic acid Nylon-6,6
diamine
Nylon - Polymers which have amide linkage.
(B) Classification based on source of origin :
(i) Natural polymers : These polymers are found in plants and animals.
Examples: Proteins, cellulose, starch, resins and rubber.

Cellulose n
(ii) Synthetic polymers : These polymers are prepared in the laboratory.
Examples : Polyethylene, Nylon-6,6, Dacron & Polyacrylonitrile (PAN).
CN
nCH2=CH–CN —CH2–CH—
n
Acrylonitrile Polyacrylonitrile
(iii) Semi-synthetic polymers : These polymers are found in plants and animals then modified in
the laboratory.
CH2OAc CH2OAc

OAc OAc

OAc OAc
n
Cellulose acetate
Examples : Cellulose acetate (rayon) & Cellulose nitrate.
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Polymers
(C) Classification based on structure of polymers :
(i) Linear polymers : These polymers consist of long and straight chains.

Examples : High density polythene, Polyvinyl chloride.

6-7 atm
nCH2=CH2 High density polythene
333-345 K
Ethene Ziegler-Natta Catalyst
** Ziegler Natta Catalyst : (C2H5)3Al + TiCl4
(ii) Branched chain polymers : These polymers contain linear having some branches.

Examples : Low density polythene.

1000-2000 atm
nCH2=CH2 Low density polythene
350-570 K
Ethene O2 or R2O2
(iii) Cross linked or Network polymers : These are usually formed from bi-functional and tri-
functional monomers and contain strong covalent bonds between various linear polymer chain.

Examples : Bakelite, Melamine.

+     
Polymerisa tion

Formaldehyde
Melamine
Melamine Formaldehyde polymer
(Melmac)
(D) Classification based on mode of Polymerisation :
(i) Addition polymers : The addition polymers are formed by the repeated addition of monomer
molecules possessing double or triple bond.
Examples : Polythene, Buna-S, Buna-N
Ph Ph
Polymerisation
nCH2=CH —CH2—CH—n
Styrene Polystyrene
(ii) Condensation polymers : The condensation polymers are formed by repeated condensation
reaction between two different bi-functional or tri-functional monomeric units. In these
polymerisation reactions, the elimination of small molecules such as water. alcohol, hydrogen
chloride. etc.
Examples : Nylon-6, 6, Terylene.

nHO–CH2–CH2–OH + nHOOC COOH —O–CH2–CH2–O–CO CO—

n

Glycol Terephthalic acid Terylene or Dacron

Polyester – Polymers which have ester linkage.
(E) Calssification based upon molecular force :
(i) Elastomers : These are rubber like solids with elastic properties. In these elastomeric
polymers, the polymer chains are held together by the weakest intermolecular forces.
Examples: Buna-S, Buna-N, Neoprene, etc.
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Polymers
(ii) Fibres : Fibres are the thread forming solids which possess high tensile strength and high
modulus. Polymers in which the intermolecular forces of attraction are the strongest are called
fibers. These forces are either due to H-bonding or dipole-dipole interactions. In case of nylon
(polyamides), the intermolecular forces are due to H-bonding while in polyesters (terylene,
dacron etc.) and polyacrylonitrile (orlon, acrylin etc.) Dipole-dipole interactions between the
polar carbonyl (C = O) groups and, between carbonyl and cyano (– C  N) groups respectively.
Examples: Polyamides (Nylon 6,6), polyesters (terylene), etc
(iii) Thermoplastics : These are the linear or slightly branched long chain molecules capable of
repeatedly softening on heating and hardening on cooling. These polymers possess
intermolecular forces of attraction intermediate between elastomers and fibres.
Examples : Polythene, polystyrene, polyvinyls, etc.
(iv) Thermosetting polymers : These polymers are cross linked or heavily branched molecules,
which on heating undergo extensive cross linking in moulds and again become infusible. These
cannot be reused.
Examples : Bakelite, urea-formaldehyde resins, etc.
(F) Classification based on Mechanism of polymerisation:
(i) Chain growth polymerisation : Additional polymers are chain growth polymers. Chain growth
polymerisation takes place by-
(a) Free radical mechanism : A variety of alkenes, dienes and their derivatives are
polymerised in the presence of a free radical generating initiator (catalyst) like benzoyl
peroxide, acetyl peroxide, tert-butyl peroxide, etc.
Chain initiation steps
O O O
C6H5–C–O–O–C–C6H5 2C6H5–C–O 2C6H5
Benzoyl peroxide Phenyl radical
C6H5 + CH2=CH2 C6H5–CH2–CH2
Chain propagating step
C6H5–CH2–CH2 + CH2=CH2 C6H5–CH2–CH2 –CH2–CH2
C6H5–CH2–CH2 –CH2–CH2 + CH2=CH2 C6H5 ( CH2–CH2 )n CH2–CH2
Chain terminating step
C6H5 ( CH2–CH2 )n CH2–CH2 + C6H5 ( CH2–CH2 )n CH2–CH2
C6H5 ( CH2–CH2 )n CH2–CH2–CH2–CH2 ( CH2–CH2 ) C6H5 n
Examples : CH2=CH2, CH2=CH–CH3, CH2=CH–CH=CH2, etc.
(b) Cationic mechanism : Alkenes having electron releasing group are polymerised by
cationic mechanism.
Examples : CH2=CH–O–CH3
(c) Anionic mechanism : Alkenes having electron withdrawing group are polymerised by
cationic mechanism.
Examples : CH2=CH–CN
(ii) Step growth polymerisation : Condensation polymers are step growth polymer. This
polymerisation progresses through step by step.
Examples : Nylon, bakelite, dacron, etc.

Examples of polymers :
(1) Polyethylene :
Polymerisation
nCH2=CH2 —CH2—CH2—n
Ethylene Polyethylene
Low density polythene is used in the insulation of electricity carrying wires and manufacture of squeeze
bottles, toys and flexible pipes.
High density polythene is used for manufacturing buckets, dustbins, bottles, pipes, etc.

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Polymers
(2) Polypropylene :
CH3 CH3
Polymerisation
nCH2=CH —CH2—CH—n
Propylene Polypropylene
Polypropylene is used for manufacture of ropes, toys, pipes, fibres, etc.

(3) Polyvinyl Chloride (PVC) :

Cl Cl
Polymerisation
nCH2=CH —CH2—CH—n
Vinyl chloride PVC
PVC is used in the manufacturing of rain coats, hand bags, vinyl flooring, water pipes, imitation leather,
floor covering and gramophone records.
(4) Polystyrene :
Ph Ph
Polymerisation
nCH2–CH —CH2—CH—n
Styrene Polystyrene
Polystyrene is used as insulator, wrapping material, manufacture of toys, radio and television cabinets.
(5) Polyacrylonitrile :
CN CN
Polymerisation
nCH2=CH —CH2—CH—n
Acrylonitrilc Polyacrylonitrile

Polyacrylonitrile is used as a substitute for wool in making commercial fibres as orlon or acrilan.
(6) Polyvinylacetate :
 
OCOCH3  OCOCH3 
|  | 
Polymerisa tion CH  CH n
nCH2  CH   2

Vinylacetate Polyvinylacetate

(7) Teflon (PTFE) :

F F
Polymerisation
nCF2=CF2 —C—C—
Tetrafluoroethylene F F n

Teflon
Teflon is used in making oil seals, valves and gaskets and it is also used for non-stick surface coated
utensils. Because of its low chemical reactivity, excellent toughness, electrical and heat resistance,
teflon is used as insulation for electrical items.
(8) Polymethylmethacrylate :
CH3OOC
COOCH3

Polymerisation CH2 – C —
—
nCH2=C–CH3 n
Methylmethacrylate
CH3

Polymethylmethacrylate

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Polymers
(9) Rubbers :
(a) Natural Rubber : Rubber is a natural polymer and possesses elastic properties. It is also
termed as elastomer and has a variety of uses. It is manufactured from rubber latex which is a
colloidal dispersion of rubber in water. This latex is obtained from the bark of rubber tree and is
found in India, Srilanka, Indonesia, Malaysia and South America. Natural rubber is a linear
polymer of isoprene (2-methyl-1,3-butadiene) and is also called as cis-1, 4-polyisoprene.
Natural Ruber is isotactic polymer (polymers which have same configuration at all
stereocentre).

* Gutta parcha, has isoprene unit in trans-form (dentist used it in the filling of teeth).
Vulcanization : .Raw rubber does not posses the characteristic of the rubber with which we are
familar. In order to give it strength & elasticity it is vulcanised. In the vulcanization process, raw
rubber is mixed with small amount of sulphur and heated. Use of external sulpher increases the
cross-linking and toughness.1-3 % S is used in rubber bands and 5% S is used in tyre rubber.
CH3
CH2–C–CH–CH2
S S
CH2–C–CH–CH2
CH3

(b) Synthetic Rubber : Synthetic rubber is rubber like polymers, which is capable of getting
stretched to twice its length. However, it returns to its original shape and size as soon as the
external stretching force is released. Thus, synthetic rubbers are either homopolymers of 1,3-
butadiene derivatives or copolymers of 1, 3-butadiene or its derivatives with another
unsaturated monomers.
(i) Cis-polybutadiene :

n CH2 CH CH CH2
By n
butadiene (1, 4 adition) cis-polybutadiene

(ii) Neoprene :

n CH2 C CH CH 2

Cl Cl Cl Cl n
Chloroprene
Neoprene

Neoprene has superior resistance to vegetable and mineral oils. It is used for manufacturing
conveyor belts, gaskets and hoses.
(iii) Buna-N :
CN
|
nCH2  CH – CH  CH2  nCH2  CH Copoly merisation

1, 3  Butadiene Acry lonitrile

Buna-N is resistant to the acetion of petrol, lubricating oil and organic solvents. It is used in
making oil seals, tank lining etc.
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Polymers
(iv) Buna-S : It is obtained by the polymerization of butadiene and styrene in the
ratio of 3 : 1 in the presence of sodium. It is also known as styrene butadinene
rubber (SBR).
Na
nCH2  CH – CH  CH2 + CH  CH 2 
| Heat
Butadiene
C6H5
Styrene
Buna-S is used for the manufacture of autotyres, floortiles, footwear components, cable
insulation, etc.
(10) Polyamides :
(a) Nylon-6 :

Nylon-6 is used for the manufacture of tyre cords, fabrics and ropes.
(b) Nylon-6,6 :
HOOC–(CH2)4–COOH
HN2–(CH2)6–NH2 –[NH2–(CH2)6–NH–C–(CH2)4–C–]n–
Adipic acid
Hexamethylene O O
Diamine Nylon 6, 6

Nylon-6, 6 is used in making sheets, bristles for brushes and in textile industry.
(c) Nylon-6,10 :
HN 2–(CH 2)6–NH 2 + HOOC(CH2)8COOH –– NH –(CH 2)6–NH –C –(CH 2)8–C– –
Hexamethylene Sebacic acid O O n
Diamine
Nylon 6, 10
(11) Polyesters :
(a) Dacron :

nHO–CH2–CH2–OH + nHOOC COOH —O–CH2–CH2–O–CO CO—

n
Glycol Terephthalic acid Terylene or Dacron
Dacron fibre (terylene) is crease resistant and is used in blending with cotton and wool fibres
and also as glass reinforcing materials in safety helmets, etc.
(b) Glyptal :

nHO–CH2–CH2–OH + nHOOC COOH —O–CH2–CH2–O–CO CO—

n
Glycol

Phthalic acid Glyptal

Glyptal is used as manufacture of paints and lacquers.
(12) Melamine formaldehyde Resin :

+     
Polymerisa tion

Formaldehyde
Melamine
Melamine Formaldehyde polymer
(Melmac)
Melamine formaldehyde resin is used in the manufacture of unbreakable crockery.

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Polymers
(13) Phenol formaldehyde polymers :
Phenol formaldehyde polymers are the oldest synthetic polymers. These are obtained by the
condensation reaction of phenol with formaldehyde the presence of either an acid or a base catalyst.
(a) Novalac : It is linear polymer of formaldehyde & phenol.
OH OH OH OH
+ CH2OH CH2OH HOH2C CH2OH
H or
+ CH2O OH
+ +

CH2OH CH2OH
OH OH OH OH
CH2OH +
H H2C CH2 CH2 CH2
n

Novolac
Novalac is used in paints.
(b) Bakelite : It is cross linked polymer of formaldehyde & phenol.
OH OH OH
H2 C CH2 CH2 CH2

CH2 CH2 CH2

H2 C CH2 CH2 CH2

OH OH OH
Bakelite
Bakelite is used for making combs, phonograph records, electrical switches, handles of various
utensils & computer discs.
(14) Urea formaldehyde Resin :
H2N–C–NH2 + HCHO H2N–C–NH–CH2–OH
O O
nH2N–C–NH–CH2–OH —HN–C–NH–CH2—
O O n
Urea formaldehyde Resin is used for making unbreakable cups and laminated sheets.
(15) Biodegradable Polymers :
A large number of polymers are quite resistant to the environmental degradation processes and are
thus responsible for the accumulation of polymeric soild waste materials. These soild wastes cause
acute environmental problems and remain undegraded for quite a long time. In view of the general
awareness and concern for the problems created by the polymeric soild wastes, certain new
biodegradable synthetic polymers have been designed and developed. These polymers contain
functional groups similar to the functional groups present in biopolymers.
Aliphatic polyesters are one of the important classes of biodegradable poylmers. Some examples are
given below :
(a) Poly -hydroxybutyrate-co--hydroxy valerate (PHBV) : It is obtained by the
copolymerisation of 3-hydroxybutanoic acid and 3-hydroxypentanoic acid.
OH OH
| |
CH3  CH  CH2  COOH + CH3  CH2  CH  CH2  COOH 
(3  Hydroxybutanoic acid) (3  Hydroxypentanoic acid)

PHBV is used in speciality packaging, orthopaedic devices and in controlled release of drugs.
PHBV undergoes bacterial degradation in the environment.
(b) Nylon-2-nylon-6 : It is an alternating polyamide copolymer of glycine (H 2N–CH2–COOH) and
amino caproic acid (H2N(CH2)5COOH) and it is also biodegradable polymer.
nH2N–CH2–COOH + nH2N–(CH2)5–COOH —NH–CH2–CO–NH–(CH2)5–CO—
n

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Polymers
Some common addition polymers/chain growth polymer
S.
Name(s) Formula Monomer Uses
No.
Polyethylene CH2=CH2 Film wrap,
1. –(CH2-CH2)n–
(low density (LDPE)) (ethylene) Plastic Bags
Electrical
Polyethylene CH2=CH2
2. –(CH2-CH2)n– insulation bottles,
(high density (HDPE)) (ethylene)
toys
CH3 Manufacture of
Polypropylene CH2=CHCH3
3. CH CH2 ropes, toys,
(PP) different grades (propylene)
n
pipes, fibres etc.
Manufacture of
Cl rain coats, hand
CH2=CHCl
4. Poly vinyl chloride (PVC) CH CH2 bags, vinyl
(vinyl chloride)
n flooring, water
Pipes etc.
Cl
Poly vinylidene chloride C CH2 CH2=CCl2 Seat covers,
5.
(Saran A) n (vinylidene chloride) films & fibers
Cl
As insulator,
CH2 CH wrapping
n material,
Polystyrene CH2=CHC6H5
6. manufactures of
(Styron) (styrene)
toys, radio and
Television
cabinets
CN
Polyacrylonitrile CH2=CHCN Rugs, Blankets
7.
(PAN, Orlon, Acrilan) —CH–CH2—n (acrylonitrile) clothing

Non-stick
Polytetrafluoroethylene CF2=CF2 surfaces
8. –(CF2-CF2)n–
(PTFE, Teflon) (tetrafluoroethylene) electrical
insulation
Poly methyl methacrylate Lighting covers,
CH2=C(CH3)CO2CH3
9. (PMMA, Lucite, Plexiglas, –[CH2C(CH3)CO2CH3]n– signs
(methylmethacrylate)
perspex) skylights
Poly vinyl acetate CH2=CHOCOCH3 Latex paints,
10. –(CH2-CHOCOCH3)n–
(PVAc) (vinyl acetate) Adhesives
Requires
–[CH2-CH=C(CH3)-CH2]n– CH2=CH–C(CH3)=CH2
11. Natural Rubber vulcanization for
(cis) (isoprene)
practical use
Synthetic rubber,
CH2=CH-CCl=CH2 oil resistant seal,
12. Neoprene –[CH2-CH=CCl-CH2]n–
(chloroprene) gaskets, hoses &
conveyor belts
-[CH2-CH-CH2-CH=CH-CH2]- Tyres, floortiles,
SBR styrene butadiene H2C=CHC6H5 and
13. foot wear & cable
rubber (Buna-S) Ph H2C=CH-CH=CH2
insulation

-[CH2-CH-CH2-CH=CH-CH2]- Making oil seals,

H2C=CHCN and
14. Nitrile Rubber (Buna-N) tank lining and
CN H2C=CH-CH=CH2
hoses

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 Polymers
Some condensation polymers/step growth polymers
S.
Name(s) Formula Monomer Uses
No.
O O HO2C C6H4 CO2H
Polyester/Dacron/ O (Terephthalic acid)
1. Fabric, Tyrecord
Terylene/Mylar O HO–CH2CH2–OH
n Ethylene glycol
O O
O–CH2–CH2–O–C C HO2C–C6H4–CO2H
Glyptal or Alkyds Paints and
2. (Phthalic acid)
resin Lacquers
HO–CH2CH2–OH
n
Polyamide HO2C–(CH2)4–CO2H Parachutes
3. ~[CO(CH2)4CO–NH(CH2)6NH]n~
(Nylon 6,6) H2N–(CH2)6–NH2 & Clothing
O O HOOC–(CH2)8–COOH
4. Nylon 6,10
—C–(CH
( 2)6)–C–NH–(CH2)6–NH—
)n H2N–(CH2)6–NH2
Polyamide
5. Nylon 6, ~[CO(CH2)5NH]n~ O Rope & Tyrecord
Perlon-L NH Caprolactam
Electrical
O–H O–H Switch, combs,
CH2 Handle of
6. Bakelite CH2 PhOH + HCHO in (excess) Utensils,
n
computer
discs and
Bowling Balls
Making
Urea-formaldehyle H2N–CO–NH2 (Urea) unbreakable
7. (–NH–CO–NH–CH2–)n
resin HCHO (Formaldehyde) cups and
laminated sheets.
N H2N N NH2
HN HN–CH2–
Melamine +HCHO
N N N N (melamine) Unbreakabl
8. formaldehyde
e crockery
resin NH NH2
n (formaldehyde)
O O
Polyamide Para HO2C–C6H4–CO2H
9. Tyre
Kevlar N N Para H2N–C6H4–NH2
H H
n
O O
Meta HO2C–C6H4–CO2H
10. Polyamide Nomex N N
Meta H2N–C6H4–NH2
H H n
HOCH2CH2OH
CH3 H3C O
C Foams, Shoes,
Polyurethane O O N Automobile
11.
Spandex N N seats and
O–(CH2)2–O N components
H H C
n O
CH3 O
O C O–C (HO–C6H4–)2C(CH3)2 Bike helmet,
Polycarbonate
12. (Bisphenol A) goggles, bullet
Lexan CH3
n X2C=O (X = OCH3 or Cl) proof glass

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