18

Polymers
Polymers and Polymerisation Methods of Polymerisation
I t may be defined as a compound whose molecules are Addition or chain growth polymerisation
made up of a large number of repcating units. It may
be expressed as (M), where M is a monomer and n is
Apolymer formed by direct addition ofrepeated monomers
the number of repeating units, also known as Degree of
without the elimination of by product molecules is called
addition polymer and the phenomenon is known as
polymerisation.
The process by which the monomers are converted into addition polymerisation.
nCH=CH2 +CH2 - CH2
polymers is called polymerisation.
Ethene Polyethene
Classification of polymers Mechanism of chain growth polymerisation: It
O n the basis ofsource/origin involves a series of reactions, each of which consumes
Natural polymers: Substances ofnaturalorigin and a reactant particle and produces a similar one. These
are mainly found in plants and animals, e.g., starch, reactive particles may be free radicals or cations or
cellulose, proteins, etc. anions to which monomers get added by a chain. Itis
Synthetic polymers : Man made polymers are called an important reaction of all kinds of compounds
having
synthetic polymers. They are long chain organic C=C bond.
molecules containing thousands ofnmonomer units e.g., Chain growth polymerisation follows two basic
nylon, PVC, bakelite, polyethylene, etc. mechanisms:
O n the basis of monomer units Free-radical mechanism: This type of polymerisation
Homopolymers : They are formed by addition of
is initiated by organic peroxide or other reagents which
identical repeating units (monomers). decompose to give free radicals.
A-A-A-A4-A-A
Following steps are involved :
Polymers formed from one kind of monomers are
Chain initiation: R-CO-0+0-co- R
called homopolymers e.g, polythene.
nCH=CH2 +CH2-CH2 RCOO
unstable
R+CO%
Ethylene Polythene
Copolymers: They are formed by addition of two Chain propagation:
or more different monomeric units.
A-B-A-B-A-B-A-B
k+HCH R-CH2-H2
Polymers formed from more than
monomer units are called copolymers or mixed
one kind of RCHCH+H,¥H, RCH,CH,CH,CH
Chain termination:
polymers, e.g., nylon-6,6 is a polymer of two types 2R(CHCH2,CH2CH2-
of monomers: hexamethylenediamine and adipic R(CHCH),CH2CH,CH,CH2(CH,CH;),R
acid. lonic mechanism:
nHN(CH26NH2 + nHOOC(CH2)4COOH (a) Cationic mechanism: It normally occurs in the acidic
Hexamethylene diamine Adipic acid medium in the presence of protonic acids or Lewis acids.
HSO4H +HSOg
+HN-(CH2)6-NHCO-(CH2)4-CO
Nylon-6,6 or BF+H20H"+BF(OH)
Polymers 233
C h a i ni n i t i a t i o n :
CH=CH2
HCHCH CH,H,
Chain p r o p a g a t i o n :

nCH=CH-CH=CH+u
1,3-Butadiene
Styrene
CH+CH2CH2 CH,CH,CH,CH,
CHCHCH2CH2 + n(CH2=CH,) CH2-CH= CH-CH2 -ÇH-CH2
>CH,CH2(CH2CH2),CH,CH2
Chain termination:

Butadiene-styrene copolymer
CHCH(CH2CH2),CH CH2
HHSO Some Important Polymers
CHCH2CH,CH2),CH =CH2+ H,SO
Polymer Polythene
nerisation or acid catalysed mechanism is For
ationic Polyolefins are obtained from unsaturated hydrocarbons.
with vinyl monomers containing electron
effective only example, polythene, polypropylene, polystyrene.
releasing groups.
hl Anionic mechanism: It occurs in alkenes having
nCH,= CH, -POY +CH,-CH,
in them and it is carried out in
electron withdrawing groups
polythene

of a suitable base.
presence Polyamide (Nylon-6,
Chaininitiation: known
The polymers containing an amide linkage are

FCH=tH B-CH2-H2 as polyamides, e.g.. nylon-6, 6.

Chain propagation: heat
HOOC (CH,),COOH + nH,N(CH,)NH; condensation
B-CH2-CH2+ H2=H2 B-CH,CH,CH,H2 Hexamethylene
Adipic acid nH,O
diamine
B-CH2-CH2-CH2-CH2 n(CH2 CH2) t =

B-CH2 f CH2-CH2» CH2-CH + CO(CH,),CONH(CH,),NH

Nylon-6, 6
Chain termination:
B-CH2 CH2- CH2, CH2 -CH2 + H Polyester
Polyesters are polymers formed from a dicarboxylic
CH (CH CH), CH, CHs
acid and a diol.
Condensation or step growth polymerisation
A polymer formed by the condensation of two or more
T h e main example of polyester is terylene or dacron
than two monomers with the elimination of simple molecules which is a copolymer of benzene-1,4-dicarboxylic acid
nke water, ammonia, alcohol, etc. is called condensation and ethane-1,2-diol.
POulymer and the phenomenon is known as condensation

polymerisation, e.g., terylene. OH

O=o HO-CH2
OH
CH-OH
nHOCH,CH,OH + nHOOC- -coOH
Ethylene glycol Terephthalic acid

Dacron
o-CH-CH0
toCH,CHo-
Terylene Uses

Copolymerisation
Apolymerisation r
ymerisation reaction in which a mixture of more than
.Fabrics woven or knitted from polyester thread or yarn
are used extensively in apparel and home furnishings.
one to form
onomeric species are allowed to polymerise Industrial polyester fibers, yarns and ropes are usedin
both chain-
ymer. Copolymers
owth and step-g
growth polymerisation
can be prepared by
e.g., butadiene-
car tire reinforcements, fabrics for conveyor belts, safety

Styrene copolymer. belts etc.

234 WtG Chapterwise WB JEE EXPLORER
Bakelite Vulcanization: Vulcanization is a
process in which natural
rubber is treated with 3-5% sulphur. It
Bakelite is thermosetting phenol-formaldehyde resin formed introduces sulphur
by the condensation ofphenol and formaldehyde
in presence bridges between polymer chains thereby increasing tensile
its
of either acid or base catalyst. strength, elasticity and resistance to abrasion. The
vulcanized rubber depends
rigidity of
any upon the extent of
Step-I OH OH sulphur
CH,OH cross-linking. The process of vulcanization was
developed
HCHO [O by Charles Goodyear in 1839

OH OH
CH,OH Biodegradable Polymers
CHOH HOH,CY
4 Biodegradable polymers the
polymers which are
are

degraded by micro-organisms within a suitable period so

CHOH CH,OH that biodegradable polymers and their degraded
Step-11: OH OH products
do not cause any serious effects on the environment.
HOH HOCH CHOH
nO T
nO In biological systems, biopolymers degrade mainly by
enzymatic hydrolysis and to some extent by oxidation
OH OH
T CH CH, Therefore, in view of the disposal problems of polymer waste
and for developing polymers for other safe uses in human
Novolac system, attempts have been made to develop biodegradable

Step-1ll:9 OOH synthetic polymers. These synthetic polymers mostly have

functional groups which are normally present in biopolymers
+nHCHO
and lipids.
Novolac The common examples of biodegradable polymers are
OH OH
OH polyhydroxy butyrate (PHB), polyhydroxy butyrate-co
wwHC CHJ CH CHw B-hydroxyvalerate (PHBV), polyglycolic acid (PGA)
nylon-2-nylon-6, etc.

CH CH CH Poly-B-hydroxybutyrate-co-B-hydroxyvalerate
PHBV) It is copolymer of 3-hydroxybutanoic acid
and 3-hydroxypentanoic acid, in which the monomer
wwH.C CH CH CHww units are joined by ester linkages.
OH OH OH
Polyglycolic acid (PGA) : Polyglycolic acid (PGA) is
Bakelite
obtained by the chain polymerisation of cyclic dimer of
Uses
glycolic acid, HO- CH,COOH.
Bakelite has a low electrical conductivity and high heat
resistance so it can be used in manufacturing of electrical
switches and machine, parts of electrical systems. n HO CH COOHHea 0CH2 C
These are extensively used as adhesive and binding Glycolic acid Polyglycolic acid (PGA)
agents. Nylon-2-Nylon-6 : It is a polyamide copolymer of
glycine (NH2-CH2-COOH) and aminocaproic acid
Rubber
(NH2-(CH2)s-COOH). It is also a biodegradable
Natural rubber: Natural rubber is a poly cis-isoprene. It is
prepared from latex (obtained from rubber trec by coagulations
nHN-CH2-COOH+nHN-(CH2)s-C0OH
Aminocaproic acid
with acetic acid). It is soft and tacky material. Gutta-percha, Glycine
on the other hand, is HN-CH-C-HN-(CH)-C
trans-polyisoprene. It is a hard and horny
material.
CH3 Nylon-2-nylon-6
nCH=C-CH=CHolymerisation Biodegradable polymers are used mainly for medical goods
1soprene Such as surgical sutures, tissue in growth materials or to

CH3 controlled drug release devices, plasma substitutes ec

These are also finding use in agriculture materials (sucha
+CH-CCH-CH2t
Natural rubber films, seed coatings) fast food wrappers, personal hygien
(Polyisoprene) products etc.
Polymers

235

WB JEE WORKOUT
C A T E
a v 1:
G O R
Single Option Correct Type (1 Mark)
CH3
obtained by condensation polynnerization is (b)
Poly
(a) Polythene (b) Tetlon HC
(e)
Phenol - formaldehyde COOCH "
(d) Nitrile ubber.

Which of the followingfibres is made up

of polyamides? CH2 CH
(c)
(a) Dacron (b) Orlon
(c) Nylon (d) Rayon COOC2Hs n
Which one of the following can be used as a monomer fCH2-CH
reaction? (d)
in a polymerization CI
(a) CHCH2CI (b) CH3CH2OH
(c) CH (d) CaH 12. The biodegradable polymer among the following is
The monomer unit of polyvinyl chloride has the (a) nylon-6 (b) nylon-6-nylon-6,6
(c) nylon-2-nylon-6 (d) nylon-6-nylon-6, 10
formula
13. Super glue or crazy glue isS
(a) CH3CH2CI (b) CHCH2
(c) CHClCHCI (d) CH2-CHCI (a) Poly methyl methacrylate
(b) Poly ethyl acrylate
The process involving heating of rubber with sulphur
(c) Poly methyl alpha-cyanoacrylate
is called (d) Poly ethyl methacrylate.
(a) galvanisation (b) vulcanization 14. Which of the following is a polymer?
(c) bessemerisation (d) sulphonation. (a) Carnauba wax (b) Carbowax
(C) Beeswax (d) Paraffin wax
6. Teflon and neoprene are

(b) condensation polymers 15. The catalyst used for olefin polymerization is
(a) copolymers
(d) monomers. (a) Ziegler-Natta catalyst (b) Wilkinson catalyst
(c) homopolymers Merrifield resin.
7. Caprolactam polymerises to give (c) Raney nickel catalyst (d)
16. The monomer used to produce orlon is
(a) terylene (b) teflon
(a) CH2=CHF (b) CH2 =CCl2
c) glyptal (d) nylon-6. (c) CH2 =CHCI (d) CH2=CH-CN
CH3 17. Which one of the following is an example of co-

&. Monomer of -CH2t is polymer?

(a) Buna-S (b) Teflon
CH3 (c) PVC (d) Polypropylene
sets contains only addition
a) 2-methylpropene (6) styrene 18. Which of the following
(d) ethene. polymers?
C) propylene
in step growth
(a) Polyethylene, polypropylene, terylene
acrilan
Polymer formation from monomers (b) Polyethylene, PVC,
polymerisation starts by Buna-S, nylon, polybutadiene
(c)
(a) condensation reaction between monomers (d) Bakelite, PVC, polyethylene
(6) coordination reaction between monomers 19. Co-polymer is
to monomer jons by (a) nylon-6 (b) nylon-6,6
Conversion of monomer (d) polyethylene.
(c) PMMA
protons
(d) hydrolysis of monomers. 20. Bakelite is polymer of
a

benzaldehyde and phenol

Natural rubber is a
polymer(b)
of isoprene (a)
and phenol
(a) pyrene (b) formaldehyde and
benzyl aclohol
c) urea (d) ethylene. (c) formaldehyde
and phenol.
material. (d) acetaldehyde
ACrilan is a hard, horny and a high melting ? prepared by prolonged heating
Which structure 21. A synthetic polyamide
CCOllowing represents its of caprolactum is
FCH CH (a) nylon-6, 6 (b) nylon-6
a) (c) nylon-6,10
(d) glyptal.
CN
236 MtG Chapterwise WB JEE
EXPLORER
22. Which of the following is not a condensation (step (c) cross linked condensation product of phenol and
growth) polymer? formaldehyde
(a) Melamine-fomaldehyde resin (d) linear condensation product of urea and
(b) Bakelite formaldehyde.
(c) Polythene (d) Polyester 33. Natural rubber and gutta percha respectively are
-

23. In vulcanisation of rubber (a) cis polyisoprene and trans polyisoprene

(b) both are cis - polyisoprene
(a) sulphur reacts to fom a soft compound
(c) both are trans polyisoprene
b)sulphur cross-links are introduced (d) trans-polychloroprene and cis - polychloroprene
(c) sulphur forms a very thin protective layer over
nbber 34. Consider the following statements
(d) all statements are corect. () Tensile strength of vulcanised rubber is almost ten
24. Which of the following is a polyamide? times more than raw rubber.
(ii) Elasticity of raw rubber is very high.
(a) Nylon (b) Orlon (c) Teflon (d) Terylene
The correct statement is/are
25. Which of the following has ester linkage?
b) Bakelite (a) ) is true and (ii) is false.
(a) Nylon
(d) PVC
(b) (i) is false and (ii) is true.
()Terylene (c) both (i) and (1i) are true.
26. Which of the following is a biodegradable polymer? (d) both () and (ii) are false.
(a) Cellulose b) Polythene 35. Which one of the following pairs is not correctly
(c) Polyvinyl chloride (d) Nylon-6 matched?
27. Which of the following polymers can be used for (a) Terylene-condensation polymer of terephthalic
lubrication and as an insulator? acid and ethylene glycol.
(a) SBR b) PVC b) Teflon-thermally stable cross-linked polymer of
(c) PTFE (d) PAN phenol and formaldehyde.
28. The nylon salt (Hexamethylenediammonium adipate) (c) Perspex-homopolymer of methylmethacrylate.
1s (d) Synthetic rubber Buna-N-copolymer of butadiene
(a) NHCH:)»NH,OOC(CH),CO0 and acrylonitrile.
36. Which of the following is not correctly matched?
(b) NH(CH),NH,0OC(CH,)%C00
C) OOC(CH,%COO" NHs(CH2)4NH3 (a) Neoprene:fCH-=CH-CH2
(d) HNCH2),NH,00C(CH2)4CO0 Cl
29. What is the monomer of nylon-2-nylone-6? (b) Nylon-6,6
(a) Glycine and amino caproic acid
b) Amino caproic acid and adipic acid
(c) 3-Hydroxybutanoic acid and glycine
NH(CH2D6-NH-CO(CH2)4--0
(d) Ethylene glycol and adipic acid
30. Drugs which are to be released in a controlled manner (c) Terylene:oCH-CHOC-
in the body are enclosed in capsules made up of
(a) PGA (b) PCL CH3
(c) PHBV (d) none of these. (d) PMMA: +CH2-C-
CATEGORY 2:Single Option CorrectType (2 Marks)
COOCH3n
37.
31. Which compound/set of compounds is used in the During the polymerisation of caprolactum to
manufacture of Nylon -6,6? nylon-6 polymer, the temperature range is of about
(a) HOOCCH2),COOH+ H,N(CH2)NH2 (a) 533 K to 543 K (b) 473 K to 523 K
(b) CH3CH2 CCH3)=CH2 (c) 533 K to 573 K (d) 273 K to 373 K
(c) CH2CH2 38. The proportion of hexamethylenediamine and adip
acid used in the preparation of nylon-6,6 is
(d) HOOCKO-coOH +HOCH2-CH2OH (a) 1:2 (b) 1:1 (c) 2:1 (d) 2:3
32. Novolac is 39. Which of the
(a) linear condensation product of phenol and
following pairs is not correct?
(a) Viscose Synthetic fibre
formaldehyde (b) Polysaccharide - Artificial silk
(b) cross linked condensation product of urea and (c) Nylon-6,6 - Heteropolymer
formaldehyde (d) Nylon-6 - Perlon - L
P o l y m e r s
237
wOuld be the amount of polythene formed from b) Polyacetylene
40. Whatwou (a) Polypropylene
calcium carbide from the reactions given (d) Polyisoprene
20 kg
of (c) Polybutadiene
below? 45. Which of the following sets does contain only addition
CaC2 +2H20 >Ca(OH), + C,H,
homopolymers?
HC=CH+H2-Pd-Bas CH,=CH2 (a) Polythene, natural rubber, cellulose
nCH2=CH2- >+CH2-CH2
Polythene
(b) Starch, nylon, polyester
(c) Teflon, Buna-S, orlon
(b) 6 g (c)9kg (d) 64 kg
(a) 28 g (d) Neoprene, PVC, polythene
statements regarding
3:One or More than 0ne Option
CATEGORYCorrect 46. Which of the following
Type (2 Marks) thermoplastic are correct?
which are soluble in
(a) These are linear polymers
following are correct?
. Which of the many organic solvents.
be reclaimed.
Thermosetting polymers
can heating
the polymers which soften
on
(a) (6) These are
are insoluble in organic
(b)Thermosetting polymers and become rigid on cooling.
moulding and
(c) The process of heat softening,
solvents. -

soften on heating and

(c)Thermosetting polymers cooling affects the properties
of thermoplastics.
harden on cooling irreversibly.
are cross linked polymers. (d) Nylon is an example of thermoplastics.
dThermosetting polymers addition homo-polymer?
statements are true about the 47. Which of the following are
. Which of the following (a) Teflon
(b) SBR
addition polymerization? (d) Natural rubber
occurs between molecules (c) PVC
(a) Addition polymerization
in
containing double or triple
bond. 48. Cross-linking is not present
(b) bakelite
in the presence of organic peroxides. (a) polythene
b) It takes place of (d) polyester
via ionic mechanism in the presence C) nylon-6
(c) It proceeds
organic peroxides. fibres of are made polyamides?
49. Which of the following
are addition polymers. (b) Natural silk
d) Polythene and polystyrene (a) Wool
following are biodegradable polymers? (d) Nylon
3. Which of the (c) Rayon
(a) Nylon-6, 6 (b) PHBV
following, chain transfer reagent(s) is/are
50. Among the
(d) Polychloroprene
c) Nylon-2-nylon-6
(a) carbon tetrachloride (b) benzoyl peroxide
exist in geometrical (d) carbon tetrabromide.
4. Which of the following polymers (c) benzoquinone
isomeric forms?

HINTS& SOLUTIONS
CN
L (e):Phenol-formaldehyde
CN -CH2-C-
2 (e): Nylon is a polyamide. 13. (c): CH2=cooCH3 CoOCH3
and dienes undergo
d):Only olefines (here C3H6) Methyl a-cyanoacrylate Super glue or crazy ghue
addition polymerization.
oxide.
4 d):CH=CHCI
Carbowax is a polymer of ethylene
14. (b) :
wax are esters of higher
and Bees
b): Vulcanization Whereas Carnuaba
wax

alcohols while paraffin wax is a

with higher
6.(e:Homopolymers fatty acids
containing 20 or m o r e C-atoms.
. (d): Nylon-6 mixture of hydrocarbons
catalyst IC>Hs)3Al
+ TiCL] is
Ziegler-Natta
15. (a):
CH3 polymerisation to prepare high density
used in linear
(a): CHa-C=CH, :2-Methylpropene polyethylene (HDPE).
. in step
a)
Polymer formation from monomers
Towth polymerisation or condensation polymerisation 16. (d) These
Buna-S is an example of co-polymer.
monomersS. 17. (a) :
than one
condensation reaction between are formed by polymerisation of more

(b): Natural rubber is a polymer of isopren polymers Buna-S is formed by

are called co-polymers.
. monomer

(a):AAcrilan or orlon is a polymer of

acrylonitrile.
polymerisation of buta-1,3-diene
and styrene.

(e):Nylon-2-nylon-6
 wtG Chapterwise WB JEE EXPLORER
238
35. (b): Teflon s linear addition polymer
18. b) tetrafluoroethene.
of adipic acid and
19. (b): Nylon-6,6 is a co-polymer
36. (b):Nylon does not contain -CO0-group.
hexamethylenediamine.
20. (b) Nylon-6,6:tNH(CH2)6-NH-CO(CH)a-Co Jn
37. (a)
38. (b): In the preparation of Nylon-6,6, 1 mole
260-270°C
of
reacts with I mole of adipic ai
21. (b): +C-(CH)-NHt hexamethylenediamine
because hexamethylenediamine is a diacid base and adini
Nylon-6 acid is dibasic acid.
Caprolactum
22. (c): Polythene is an addition polymer. fibre.
39. (a): Viscose is a regenerated
forms cross-links 40 + 24 64
(b): During vulcanisation, sulphur 40. (c): Molecular weight of CaC2
=

23.
between different polymeric layers. 28 kg of ethene
64 kg of CaC2 give, 24 +4
24. (a): Nylons are polyamide
condensation polymers. 28 20 7x20 =8.75 kg
25. (c): Terylene is a polyester. 20kg of CaC2 will give 64 16 4
=9 kg polythene
26. (a): Cellulose is naturally occurring biodegradable
permanent changeon
polymer. 41. (b, c, d): Polymers that undergo Cross linking of
polymers.
27. () 28. (b) heating are called thermosetting or packing process.
the polymers is observed for curing
29. (a): Nylon-2-nylon-6 is a co-polymer of glycine
reactions (electrophilic or free
(HN-CH2-COOH) and amino caproic
acid 42. (a, b, d) : Addition
are common for the alkenes and alkynes which are
(HN H2)s- COOH). radical)
initiated by ions or free radical initiators (R2 O2).
it
30. (c): When a drug is enclosed in a capsule PHBV, of
in the body.
is released only when the polymer is degraded 43. (b, c)
and
31. (a): HOOC(CH2)4coOH +HN(CH2),NH2| 44. (b, e, d) : Polyisoprene, polyacetylene, show
polymer of polybutadiene contain a double bond hence, cis-trans
32. (a): Novolac is a linear condensation
isomerism.
phenol and formaldehyde.
OH OH 45. (d)
--- CHY CH2
CH -
46. (a, b, d) : Thermoplastic polymers (eg., nylon) can
be softened or plasticized repeatedly on application heat
of
without much change in properties.
Novolac 47. (a, c, d): Polythene, nylon-6 and polyester are chain
while gutta
33. (a): Natural rubber is cis-polyisoprene polymers whereas bakelite is cross
network polymer.
percha is trans-polyisoprene.
48. (a, c, d) 49. (a, b, d)
and after
34. (a): Natural rubber is soft and sticky 50. (a, d): Carbon tetrachloride and carbon tetrabromide
linked
vulcanisation its strength increases due to cross

units. act as chain transfer reagents in vinyl polymerisation.

formed between diferent monomer

8. yrs. WB JEE Previous Years Questions

2013-202004

(c)methyltrichlorosilaneand dimethyldichlorosilane
CATEGORY 1:Single Option Correct Type (1 Mark) (d) triethylchlorosilane and diethyldichlorosilane.
1. Silicone oil is obtained from the hydrolysis and (2013
polymerization of 2. Which one of the following is a condensation polymer
(a) trimethylchlorosilane and dimethyldichlorosilane (a) PVC b) Teflon
(2018
(b) trimethylchlorosilane and methyltrichlorosilane (c) Dacron (d) Polystyrene

HINTS &SOLUTIONS
1. (a) I2. (c): Dacron is a condensation polymer.