Polymers

JEE Syllabus
General introduction and classification of polymers, general methods of
polymerization - addition and condensation, copolymerization; Natural
CHAPTER
7
and synthetic rubber and vulcanization; some important polymers with
emphasis on their monomers and uses - polythene, nylon, polyester and
bakelite.

A polymer is a large but single chain-like molecule in which the repeating THIS CHAPTER
units derived from small molecules called monomers are held together. The INCLUDES
process by whi ch m onom ers t ran sf orm i nt o a pol ym er i s cal l ed
polymerization.  Classification of
Polymers
CLASSIFICATION OF POLYMERS
 Based on source
1. Classification based on source of availability. of availability
Natural Polymers : Natural polymers include starch, cellulose and natural
rubber. Starches are polymers of glucose. Cellulose is also a polymer of  Based on
glucose. It is made by plants from glucose produced during photo- molecular forces
synthesis. Similarly, protein is obtained as a result of polymerization of
amino-acids.  Based on mode of
polymerisation
Natural rubber is a polymer consisting of repeated units of the
hydrocarbons 2-methyl-1, 3-butadiene (isoprene).
 General Methods of
Polymerisation
CH2 C CH CH2
nCH2 C CH Polymeriza tion
CH2    
CH3 n  Addition
CH3 Natural rubber polymerisation
Isoprene
 Condensation
Synthetic polymers: Synthetic polymers are man-made polymers. e.g., polymerisation
Polyethene, Polystyrene, PVC, Bakelite, Nylon and Dacron.
 Commercially
(a) Neoprene rubber : Neoprene rubber is prepared from chloroprene Important Polymers
monomer. Chloroprene is prepared from acetylene
 Synthetic pol ym ers
CH2 Cl2
2HC  CH   CH2  CH  C  CH and their applications
NH4 Cl Vinylacety lene

Cl Cl
Polymerisation
nCH2 CH C CH2 (1, 4-Addition)
CH2 CH C CH2
n
Neoprene rubber

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(b) Styrene Butadine Rubber (SBR) : Styrene-Butadiene Rubber is a copolymer made up of styrene and
1, 3-butadiene.

Polymerisation CH CH2 CH2 CH CH CH2

(1, 4-addition)
n CH CH2 + nCH2 CH CH CH2
1, 3-Butadiene (SBR) n
Styrene

2. Classification based on molecular forces :

(a) Elastomers : In elastomers, the polymer chains are held together by the weakest intermolecular
forces. e.g., Vulcanized rubber.
(b) Fibres : The polymers which are used for making fibre possess high tensile strength and high
modulus. This can be attributed to the strong intermolecular forces like hydrogen bonding for
example, polyamides (e.g., nylon-66).
(c) Thermoplastics : The intermolecular forces of attraction in thermoplastic polymers are intermediary
to those of elastomers and fibres. As a result, these can be easily moulded by heating. In
thermoplastic polymers there is no cross-linking between chains. e.g., Polyethylene, Polystyrene, etc.
(d) Thermosetting : These polymers are normally made from relatively low molecular mass semi-fluid
polymers which when heated in a mould become infusible and form an insoluble hard mass. This
happens due to extensive cross-linking between different polymer chains. e.g., Bakelite.
3. Classification based on mode of polymerisation :
(a) Homopolymer and copolymer : Polymers made by polymerisation of a single monomeric species
are known as homopolymer.

nCH2 CH2 —
( CH2 — CH2)n—
(polyethene)

Polymers made by more than one type of monomers are known as co-polymers.

nCH2 CH CH CH2 + nC6H5 CH CH2 ( CH2 CH CH CH2 CH CH2 )n

buta-1, 3-diene styrene
Styrenebutadiene rubber C6H5

(b) Addition and condensation polymers : Polymers formed due to addition between monomer
molecules possessing multiple bonds through -bond without removal of any species are called
addition polymers.
e.g., Polyethylene, styrenebutadiene rubber are addition polymers.
Polymers formed by condensation between monomeric units with elimination of small molecules such
as water, NH3 or alcohol etc. are called condensation polymers.

GENERAL METHODS OF POLYMERISATION

Addition polymerisation :
The mode of polymerisation can take place through formation of either radical or anionic or cationic species. This
process is called chain growth polymerisation, because it takes place through stages leading to increase of chain
length and each stage produces reactive intermediate for use in the next stage of the growth of the chain.
1. Radical addition polmerisation : It is initiated by a source of radical and terminated by another radical.
2. Cationic addition polymerisation : Such type of polymers are initiated by any acid and terminated by
any base. Presence of electron-donating group in the monomeric unit increases the ease of cationic addition
polymerisation.

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3. Anionic addition polymerisation : Such type of polymerisation is initiated by a base and terminated by
any acid.
Presence of electron-withdrawing group in the monomeric unit increases the ease of anionic addition
polymerisation.

COMMERCIALLY IMPORTANT POLYMERS

(1) Polyamides
(i) Nylon-66 - from adipic acid and hexamethylene diamine

HOOC (CH2)4 COOH + NH2 (CH2)6 NH2

O O

( NH (CH2)6 NH C (CH2)4 C)n

amide group
Nylon 66

(ii) Nylon-6 - from Caprolactam

O H
O
(C (CH2 5 N )n
NH Nylon 6

(2) Formaldehyde resins

(i) Phenol formaldehyde resins (Bakelite) - from phenol and formaldehyde

OH OH OH
H H + CH2OH
+ C=O +
H OH–
CH2OH

OH OH OH
H2C CH2 CH2

(linear polymer)

H
C O Strong heating
H
OH OH OH OH
CH2 CH2 CH2 CH2

CH2 CH2

H2C CH2 CH2 CH2

OH OH OH
n
Bakelite (cross linked polymer)

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(ii) Melamine formaldehyde resin - from melamine and formaldehyde.

H2N N NH2
HN N NH – CH2
H
+ C O n
N N H N N
NH2
NH

SYNTHETIC POLYMERS AND THEIR APPLICATIONS

Addition Polymers

Polymer Monomer Application

Polyethylene Ethene  CH2 = CH2 Packing material carry bags, insulation for
electrical wires and cables... etc.
Polypropylene Propene  CH3 – CH = CH2 Packing of textiles and foods, linears for bags,
heat shrinkage wraps, carpet fibres... etc.
Polystyrene or Styrene  C6H5 – CH = CH2 Plastic toys, house hold wares radio and
Styron television bodies
Neoprene Chloroprene CH2 = C – CH = CH2 shoe heels, stoppers, printing rollers
Cl
Buna-s Styrene  CH = CH2, Butadiene  Manufacture of tyres, rubber sole, water proof
CH2=CH–CH=CH2 shoes

Polyacrylates Methyl methacrylate Lenses, light covers, light shades, air craft
CH3 windows... etc.
CH2 = C – COOCH3
Polyethyl CH2 = CH – COOC2H5 Latex paints adhesives
acrylate
Polyacrylonitrile Acrylonitrile  CH2 = CH – CN For making clothes, carpets, blankets... etc.
(PAN)(orlon)
Polyvinyl Vinyl chloride  CH2 = CH – Cl Good electrical insulator, hose pipes, rain
chloride (PVC) coats, hand bags... etc.
Polytetrafluoro Tetrafluoro ethylene  CF2 = CF2 For nonstick utensils coating etc.
ethylene (PTFE)
(Teflon)

Condensation Polymers

Polymer Monomer Application

Terylene (i) Ethylene glycol– For wash and wear fabric tyre cords, seat
or dacron HO – CH2 – CH2 – OH belts and sails
(ii) Terephthalic acid –

HOOC COOH

Glyptal or (i) Ethylene glycol – Paints and Lacquers

Alkyd resin HO – CH2 – CH2 – OH
COOH
(ii) Phthalic acid –
COOH

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Nylon 6, 6 Adipic acid – Textile fabrics

HOOC –(CH2)4–COOH
Hexamethylenediamine –
H2N –(CH2)6 – NH2

Nylon 6, 10 H2N(CH2)6NH2 Textile fabrics, carpets, bristles for brushes

Hexamethylene diamine
Sebacic acid –
HOOC – (CH2)8 COOH
H
Nylon 6 O Mountainering ropes, tyre cords fabrics
N
Caprolactum –

OH
Bakelite Phenol Formaldehyde, HCHO As binding glue for wood varnishes, lacquers

Melamine Melamine and Formaldehyde Non-breakable

Formaldehyde NH2
resin N N
and HCHO
NH2 N NH2

Urea (i) Urea NH2 — C — NH2 Buttons, bottle caps, surgical items
formaldehyde
resin (ii) Formaldehyde HCHO

Biodegradable Polymer

Name Monomer Uses

OH
(i) Poly- -hydroxy (a) CH3 – CH – CH2COOH As packaging
butyrate-Co- 3- hydroxybutanoic acid orthopaedic devices
hydroxy valerate and in controlled
OH drug release.
[PHBV].
(b) CH3 – CH2 – CH – CH2COOH
3-hydroxypentanoic acid



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