INTRODUCTION

Polymers are the high molecular mass compounds obtained by joining of repeating
structural units in a regular fashion. The simple reactive molecules from which the
repeating
units are derived are called manomers. The use of polymers in the manufacture
structural
of
toys, synthetic clothing materials, packaging bags, automobile tyres, plastic buckets, cups
etc. has completely revolutionised the
and
The
saucers daily life as well as industrial scenario.
giant molecules like DNA, chlorophyll, proteins, carbohydrates etc. are regarded as
macromolecules.
it does not
Chlorophyll is a macromolecule but is not regarded as a polymer because
contain a repeating unit. But
polythene, bakelite, PVC etc. are polymers as well
as macromolecules. Due to their grant size, polymers or macromolecules have a number of
chracteristic properties such as elasticity, high tensile strength, ability to fom fibres which
differentiate them from similar molecules having smaller molecular sizes. For example
Polythene is fomed from ethene (monomer) and Nylon 6, 6 from (i) hexamethylene diamine
and adipic acid (two monomers).
nCH2 =CH Polymerisationn -CH, -CH29 CH -CH2 t
Ethene Repeating unit Polythene polymer
(Linear polymer)
Polymerisation
nNH, (CH2), NH2 + nHOOC(CH,),COOH
Hexamethylene diamine (Monomer) Adipic acid (Monomer)

H H O O

-N -

(CH2) -

N -
C -

(CH2)4 - C >
Nylon-6, 6 (Copolymer)
(Condensation polymer)
(Step growth polynmer)
Nvlon-6, 6is (i) copolymers becausei s tormed trom two monomers. (i) Condensation
r due to the condensation of two different molecules with the removal of water
because poiymer growth is step by
iii) Step growth polymer sten
 LD FMODERN
Classification of Polymers together to form three dimensional net work structe MISTRY-XI
1. Classification based on origin. Polymers may be example, the reaction between phenol and formaldehuor
the presence of base results in the formation of a
divided into categories based on their origin.
cross-linked, three dimensional Bakelite highly
resin. Becaus
(a) Natural polymers. These are the complex the presence of cross-links, of
these polymers are also
compounds of high molecular mass obtained from natural as cross-linked polymers. Other examples are T know
sources. Examples are proteins, starch, cellulose, Nucleic acids, formaldehyde polymer, Melamine-formaldehyde polymerrea-
gums, resin, silk, wool, rubber etc.
Starch is a widely distributed substance
throughout the
plant kingdom. Its repeating unit is a-D-glucose. Cellulose is
ZeRosS LINK
a major
constituent of coton and its repeating unit is B-D-
glucose. Proteins are the basic units of life and are polymers ICROSS LINK
of a large number of different amino acids condensed in a
BRANCHED CHAIN
particular sequence. Nucleic acids are the biopolymers STRUCTURE
controlling heredity and are present in the cells of living
organisms. The well known nucleic acids are DNA and RNA. Note. (Polymers having long chains have high
Natural rubber is a gummy material obtained from rubber molecular mass and high degree of
trees and is polymer of 2-methyl-1,3-butadiene (Isoprene).
a
polymerisation. It makes the polymer tough
and heat resistant.
(b) Synthetic Polymers. These are man made ( A cross linked polymer is
polymers. There is an endless variety of such polymers. Some
unable to pack
itself in a compact manner. Such
have low densities. Such
polymers
important examples are PVC, Teflon, Nylon, Bakelite, polymers are
synthetic rubber etc. Synthetic polymers are made into sheets, strong, tough (due to strong covalent bonds)
brittle and do not melt.
films, threads, filaments, fibres etc. They can be designed to
withstand very high temperature. 3. Classification based on the mode of
merisation. Such
poly-
(c)
Semisynthetic polymers. These are made by
modes.
polymerisation mainly occurs by two
modifying the properties of natural polymers. Some important
examples are nitro-cellulose, cellulose acetate etc. Gun cotton (a) Addition Polymers. These are formed by the
which is cellulose nitrate is used in addition or combination of small molecules,
making explosives. containing double
Vulcanised rubber has much improved
properties and is used
or
triple bonds without the elimination of simple molecules
in making tyres. such as water. Addition
polymers have the same empinical
2. Classification based formula as their monomers.
upon structure. On the
basis of structures, polymers have been classified into three Homopolymers. Addition polymers formed by the
categories. polymerisation of a single monomeric species are called
(i) Linear polymers. The monomers are linked to
homopolymers. Polythene, PVC, Teflon are homopolymers.
form long straight chains of polymer molecules which are Copolymers. Polymers formed from two different
closely packed. Due to close packing of chains, the linear species (monomers) are called copolymers. BSR (butadiene
polymers have high melting points, high tensile strength styrene)
yrene) is copolymer.
1s copolymer
and high densities. Some of the common examples are
Nylon, Polyester, High density polythene etc.
nCH= CH- CH =CH, +C,H,CH = CH2
Buta-1, 3-diene Styrene
(ii) Branched chain polymers. In the formation of
branched chain polymers, the monomers are linked Polymerisation CH,- CH =CH
in such a manner so as to form branched chain
together Na CH,-CH - CH,,
alongwith the
linear main chains.
Due to branching, these polymer molecules do not
CH
Polybutadiene styrene (Copolymer)
pack (Addition polymer) Buna-S-Rubber
well. As a result, these have lower melting
points, densities (b) Condensation Polymers. These are
and tensile (pulling) strength than that of linear obtained Dy
polymers. condensation reaction of molecules
Some of the common examples of such having more than one
polymers are low functional group, resulting in the
density polythene, amylopectin, starch, glycogen etc. molecules such as H,0,
elimination or removal of simpie
(iii) Three dimensional network polymers. In NH3, CH OH etc. For exampie
Decron-a polyester is produced
by successive condensation
ethylene glycol molecules and terephthalic acid or its metnyo
these polymers, first of all a linear chain polymers with three
or more reactive sites is formed. These linear chains then link ester molecules
 801
P O L Y M E R S

which a r e soluble in many

fibres. These are linear polymers
to lack of
cross-
nHO-CH2-CH20H nHO- on heating due
organic solvents. They soften be
rigid on cooling. Thus, they
can
Glycol links and become hard or
heat-softening,
Terephthalic acid moulded to any shape.The process of
often as desired.
moulding and cooling can be repeated
as

PolymerisaiOn fo-CH2-CH2-0-- They hardlyaffect the property of the plastic.

Some typical
Cellulose
thermoplastics are Polythene, Polystyrene,
Poly(ethylene terephthalate) acetate, Nitrocellulose, PVC etc.
(used
in polyester
fibers) three-
(iv) Thermosetting plastics. These
are
(Copolymer) (Polyester)
Similarly, Nylon is a condensation polymer (also dimensional polymers which are insoluble in any kind of

coDolymer) obtained by condensation of 1,6-hexamethylene solvent. These are normally prepared from relatively low
diamine and adipic acid molecules. It is a polymide. molecular semi-fluid polymers which become infusible (or
4. Classification based on The
Molecular forces. permanently hard) and insoluble hard mass on heating.
Polymers are macromolecules in which the intermolecular formation of infusible hard mass is due to extensive cross-

forces of attraction like van der Waals forces and linking between different chains to give a three
polymer
of much hydrogen dimensional net work solid. This means the thermostatic
honds are significance. Many of their applications
are the outcome of their unique mechanical properties such plastics can be heated once before their formation, after
as tensile strength, elasticity, toughness etc. which in turn is which heating again results in chemical decomposition.
related to the magnitude of these intermolecular forces. The Hence they cannot be reworked. Some typical thermosetting
magnitude of these forces depends upon the size of the plastic are Bakelite (phenol-formaldehyde). Melamine
Dolymer and the number of functional groups along the formaldehyde, Urea-formaldehyde, Silicones etc. The
polymer chain.Evidently longer the polymer chain, greater magnitude of intermolecular forces has the order
the magnitude of intermolecular forces. Fibres> Thermosetting> Thermoplastics > Elastomers
Depending upon the magnitude of intermolecular forces, 5. Classification based on growth polymerisation.
polymers have been classified into the following four Both addition and condensation polymers are also called chain
categories: growth polymers and step growth polymers. The type off
i) Elastomers ii) Fibres polymerisation depends upon the mechanism they undergo
for their formation.
(ii) Thermoplastics (iv) Thermosetting plastics
(i) Elastomers. In elastomers, there exist weakest Types of Polymerisation reactions:
intermolecular forces between the polymer chains or the 1. Addition polymerisation or Chain growth
chains have irregular shape. Due to weak intermolecular polymerisation. In this type, the molecules of the () same
forces, the elastomers can be easily stretched. They also monomer (say ethene for polythene) or (ii) of differnet
regain their original position when the stretching force is monomers (say butadiene and styrene for butadiene-styrene
removed. This can be achieved by introducing a few cross rubber) add together on a large scale to form a polymer. The
inbetween the chain as in case of vulcanized rubber. monomers are unsaturated compounds like alkenes, alkadienes
links and their derivatives. This type of
The cross-links also prevent the chains from slipping over polymerisation leads to :
one another. As a result, they do not have plastic flow. increase in chain length or chain growth. The combination of
monomers take place through free radical mechanism.
Elastomers are rubber or rubber like elastic polymers. They
are intermediate in character between amorphous and Mechanism. Alkenes and their derivatives polymerise
in the presence of benzoyl
crystalline polymers. The most important example of peroxide, acetyl peroxide etc. These
elastomer is rubber. peroxides generate free radicals by exposing to light or by
(ii) Fibres. These polymers have the strongest heating. The free radical formed then adds to alkene double
bond and generates a new free radical. It
ntermolecular forces of attraction and therefore have high is called chain
intermolecular initiating effect.
iatingeffect.
ensile strength and elasticity. The strong which i) Chain initiating step:
Orces also result in close packing of chains these imparts
polymers
ne polymer crystalline nature. As a result, inter-molecular
ha
Sharp melting points.
These strong
66 (polyamide) C6H5 6Yo-C-CaHsgnt
R
orces are due to hydrogen bonding in Nylon, (polyester) and
Dpole-dipole interactions in Terylene
Polyacrylonitrile. thermosplastics, the 2CgHsC-0 2CgHs CO2
(ii) Thermoplastics. In
inter forces are
elastomers and
inbetween those of C6H+CH2=CH2-
Monomer CsHs-CH2-H2
Free radical
 -XII
Polyolefins. These
1. arethe polymers
derived from
unsaturated hydrocarbons. Some important
polyethene, polypropene and polystyrene. examples are
() Polythene. It is obtained by the
ethene. polymerisation of
These days, different types of
two
polythenes
produced which differ widely in their properties. are

These are
() Low density polythene () High density
(a) Low polythene
density polythene (LDP). It is
manufactured by heating ethylene to 473 K under a
of 1500-2000 atmospheres and in pressure
presence of traces of
oxygen (0.03-0.1%).
nCH=CH, 473 K, O2(-CH2 -CH2 )n
Ethene 1500-2000 atm
Polythene
This polymerisation occurs through a free radical
echanism initiated by oxygen. Polythene produced by this
process has a molecular mass around 20,000 and has
branched chain structure. Since branched chain molecules
do not
pack well, this type of polythene has low density
(0.92g cm*) and low melting point (384 K). That is why
polythene produced by this method is called low density
polythene.
Properties. It is transparent, has moderate tensile
strength and high toughness. It is chemically inert, slightly
flexible and a poor conductor of electricity.
Uses. It is used. () as a packing material (in the form
of thin films, bags, etc.)
(ii) for insulating wires and cables
(iii) in the manufacture of pipes, toys, bottles, etc.
(b) High density polythene (HDP). It is
manufactured by heating ethylene at about 333-343 Kunder
a pressure of 6-7 atm in presence of a catalyst such as
triethyl aluminium and titanium tetrachloride (Zeigler-Natta
catalyst).
nCH2 =
CH,
333-343 K, 6-7 atm (-CH2-CH2)n
Zeigler-Natta catalyst Polythene
Properties. Polythene produced by this process
mainly consists of linear chains. Therefore, the molecules
pack well and hence this type of polythene has high density
(0.97 g cm"). It is inert but harder, tougher and has greater
tensile strength than low density polythene.
Uses. It is used in the manufacture of containers

(buckets, tubes, etc). and for making housewares, pipes,

bottles, toys, etc.
ti) Polypropene. It is obtained by the polymerisation
and titanium
of propene in presence of triethyl aluminium
chloride.
nCH-CH =CH,
Al 5 ( - CH- CH, -)»
Propene TiCl4
CH Polypropene
 ) Teflon or
polytetrafluoroethylene (PTFE).
When tetrafluoroethylene is subjected to
polymerisation in
presence of acetyl peroxide, an addition polymer results.
F F
F
n CC Acetyl peroxide
F F (-C-C-)n
F F
Tetrafluoroethylene
Teflon
It is chemically inert substance. It is used as a
a

material resistant to heat. It is resistant to be attacked by

corrosive materials. It is used as non-stick coating on cooking
utensils and also as an insulator for making gaskets and
valves.
(ii) Polymonochlorotrifluoroethylene (PCTFE). It
is obtained from monochlorotrifluoroethylene.
CIFC=CF (-Cl FC- Ch -

Monochlorotrifluoroethylene Polymonochlorotrifluoroethylene
Its properties are similar to that of teflon. Due to the
presence of chlorine, it is however, less res1staui to heat and
to chemicals and its uses are also similar to that of teflon.
(ii) Polyvinyl chloride (PVC). When vinylchloride
polymerises in presence of organic peroxides, we get
polyvinyl chloride (PVC).
nCH, = CH Organic peroxide (-CH,- CH -),
high pressure
CI CI
Polyvinyl chloride
The monomer vinyl chloride is itself obtained by the
addition of HCl to acetylene in presence of Hg-t as catalyst
or dehydrochlorination of ethylene dichloride.
CH = CH + HCI Hg2+ CH, = CHCI

H CI

H C -

C -H 875-925, CH, = CHCI

Vinyl chloride
+ HCI

CI H
polymer
It is a hard horny material. It is thermoplastic
a
can be increased by
and can be moulded easily. Its plasticity
as n-butyl phthalate.
the addition of plasticizers such
 3. Formaldehyde resins. These polymers include
nolymers like bakelite and melamine polymers.
(i) Phenol-formaldehyde resins (Bakelite). Phenol
reacts with formaldehyde in presence of acid or dilute alkali as
catalyst. A resinous polymer known as phenol-formaldehyde
resin or bakelite results. The reaction involves the formation of
methylene(-CH-) bridges in ortho, para or both ortho and
para positions. As a result, either linear or crosslinked material
is obtained. The reaction is difficult to control because
condensation of ortho and para hydroxy methyl phenol leads to
the formation of polymerie products. The final product is a
dark, brittle and cross-linked product, called bakelite.
OH OH
OH

CH2OH
+ HCHO
OH
Formaldehyde
O
Phenol Phenol
CH2OH
 OH OH
OH

O
CH2OH -H20
Polymerisation
TOTOr
Phenol Linear polymer (Novolac)
Cross linking is also possible in the two isomeric benzyl
alcohols to give cross-linked polymer.
OH OH
CH2OH Polymerisation
O +
-H20

CH2OH
OH OH OH

TO*TOCH -CH2

CH2 CH2

-CH LcH2 L
OH OH OH
Cross-inked polymer-bakelite
Low degree of polymerisation leads to the formation of
soft bakelites which find use as binding glue for laminated
wooden plank and in varnishes and lacquers. High degree of
polymerisation leads to the formation of hard bakelites
which are used for making combs, phonograph records,
electrical goods, fountain pen barrels, formica table tops etc.
resins for
Sulphonated bakelites are used as ion exchange
bakelite is a thermo-
softening hard water. Cross-linked
setting bakelite.
When malamine
ii) Melamine-formaldehyde resin.
(2, 4, 6-triamino-1, 3, 5-triazine) and formaldehyde
is formed.
copolymerize, melamine polymer
It is used inmaking plastic crockery. The cups and
are very hard and do not
plates prepared from this polymer
break even on being dropped.
N NHCH2OH
HaN- -NH2 H2N-
+ HCHO O
NH2 NH2

MELAMINE Formal- RESIN

dehyde INTERMEDIATE

Polymerisation
-HN- -NH-CH2

NH

MELAMINE POLYMER
do hoth hevomethulene diomine and odinio ooid
RUBBERS MISTRY-XI
(a) Natural Rubber. It is a natural
manufactured from rubber latex obtained by makineymer
in the bark of rubber trees. It is a linea
ear 1,4-polym of
mer o
isions
isoprene (2-methy1-1,3-butadiene). The residual
bonds are located between C2 and C3 of isoprene units.double
cH2 CH2 CH2
cHCH-C CH3 H CH2
CH CH
In natural rubber, intermolecular attractions are r
van der Waal interactions. It has a coiled structure andmainly
can
be stretched like a spring.
It is a themoplastic and has 11000 to 20000 isn
units. It is soft, sticky and has low elasticity. Theree
cross links between the chains. It is not hard and touo no
becomes soft and sticky at high temperature. and
Vulcanisation. The elasticity, tensile and
abrasion can be increased by a process, called resistance t
The hardness and toughness of vulcanised rubber vulcanisation
depends
upon the amount of sulphur added. It consists of heatino
rubber with 3-5% sulphur when sulphur reacts
polymer molecules forming
with the
cross-linked a net bond.
Vulcanised rubber has the structure as shown.
cHa CH3
w
CH C =CH CH2 -CH2 - C CH CH2
=
CH2 -

CCH CH2

S S

w
CH-C CH CH2 CH2 -C =CH CH CH2 -C -CH CH2
CH3 CH3 CHs
The linking gives mechanical strength to the
cross
polymer. When the stretching force is removed, the chains
can straighten out.
The comprison of the main
properties of natural rubber
and valcanised rubber are given below:
Synthetic Rubbers. Following important are some
synthetic rubbers.
) Neoprene. It is a polymer of 2-chloro-1, 3-butadiene.
It resembles natural rubber in
its properties. Starting materia
for neoprene is
1s
chloroprene (2-Chloro-1, 3-butadiene) which
prepared as below
Natural Rubber
Vulcaused Rubber
1. It is soft and
sticky |It is hard and non-sticky
2.| It has low elasticity
|it has high elasticity
3. It can be used over a
It can be used over a wide
narrow range of
(283 to 433 K)
temperature range of temperature
It has low
elasticity. |lt has high tensile strength
5. It can be easily attacked bylIt is not attacked D
organic solvents. Common organic solvents
6. It has low wear
and tearIthas high wear and e
resistance.
7. it has large water resistance
capacity.
absorption|It has low water absorp
capacity.
 (ii) Buna-S-Rubber. It is also called
BSR i.e.
Butadiene-Styrene rubber
CH =CH2
nCH,=CH-CH=CH,+
1,3-Butadiene

Styrene
Na

Heat CH2-CH=CH-CH2-CH-CH2),
Buna-S-Rubber
Buna-S was the first synthetic rubber produced. Sodium
is used as a polymerising agent.
It has improved heat and abrasion resistance than that
of natural rubber. It is used in the manufacture of tyres, rubber
soles, water proof shoes etc.
(iii) Nitrile rubber (Buna-N). It is obtained by
copolymerisation of one part of acrylonitrile and two parts of
1,3-butadiene.
nCH=CH-CH=CH, tnCH,=CH
1,3-Butadiene
CN
Acrylonitrile

CH,-CH=CH-CH,-CH2-CH,

Buna-N CN
to heat treatment
and is
It is quite rigid, responds less
oil and
action of petrol, lubricating
gnly resistant to swelling
many other organic solvents.
tank linings.
oil seals, loses and fuel
It is used in making
obtained by the
These are
(v) Silicone rubbers. molecule
elimination of a
POymerisation of silane diol through dimethyl
from two hydroxyl
groups of the adjacent
er
silane diol