PoLMERS 535

CLASSIFICATION
OF POLYME

13
of the followingypes:
are
These
hasis of their occurrence in naure polymers have been classified into two types:

Natural polymer and (i) Synthetic polymer.

(O
polymers. The polymers which occur in nature are called natural polymers, for
(0 Natural
celluloSe, starch, natural rubber etc.
example, protein,
(n Symthetic polymers 1he poiymers whrch have been prepared in the laboratory by synthetic
tes are called synthetic polymers. These are also known as made polymers for example,
bakelite, rubber, PVC, polyethene etc.
ol monomerie unit it is of five types.
1 On the basis
lomopolymers: These are the polymers obtained by the polymerisation of only one type of

cgoner. For example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene
S, polyisoprene (PIP), poly acrylonitrile (PAN), polyvinyl acetate (PVA), polymethyl methacrylate
PMMA), nylon 6, polybutadiene (PBD), Tetlon, cellulose, starch, glycogen etc.
Copolymers: These are the polymers obtained by the polymerisation of two or more monomers.
Ftexample, nylon 66, nylon 6l1, bakelite, urea formaldehyde, melamine formaldehyde, styrene
hutadiene rubber, polyesterS, epoxy resins, alkyl resins etc.

Heterochain polymers: These polymers contain two different atoms in the main chain, one of
which is usually carbon atom. For example, nylon 6, nylon 610, nylon 611, urea formaldehyde, melamine
formaldehyde etc. All have nitrogen as the other atom along with the carbon atoms in the main chain.
Similarly, polyesters, epoxy resins, alkyl resins, cellulose, starch ete. contain oxygen as the other atom
iong with the carbon atoms in the main chain. Similarly, polyesters, epoxy resins, alkyl resins, cellulose,
sarch etc. contain the other atom
oxygen as along with the carbon atoms in the main chain.
Graft polymers: These the
are special type of copolymers in which the main chain is made up
o One
type of monomer (A) and side chain by another type of monomer (B). Thus branched chain
opolymers are also known as graft
polymers 1.e.,
A AAA-A-A A-A-A-A-

Block are another special type of copolymers in which the main chain is made
Pof both
a stcon
t ers: These
monomers, A and B. These polymers have a long chain of homopolymer ofA joined
0CK OI the
homopolymer of the second monomer B.

AA-A B-B-B-B-A-A-A-AAB B - B - B
 CHEMISTRY
536 A TEXTBoOK OF ENGINEERING
The block polymers may turther have random arrangement
chain to fom random
block copolymers, i.e.,
nomers A
and Bin
-A-A BA-A-AAB BB B-B-A-BA n the moon
or in a regular altemating tashion (ailernating copolymers) i.e., B-A-A B-B-A the

-A -B-A B-A -B-A-B-A-B -A-B-

3. On the basis of polymeric structure, it is of three types:
() Linear, (i) Branched chain and
(ii)flinked
0 Linear polbymer. When monomeric units are combined in alinear Cross-linked
-A-A A
Linear Homopolymer
-A-B-A-B
Linear Copolymer
(Homochain Polymer) (Heterochain Polymer)
() Branched polymer. When monomeric units are ined together in a
"branched polymer'. branched wayay itis
t called
. AB A BA B-A

Branched Copolymer

where A= Bifunctional monomer and B =

Trifunctional monomer
(iin Cross-linked polymers. When monomeric units are Joined together ina
it is called 'cross-linked polymer. cross-chain fashion

A-A
AA AA AA A-B A B A B-A
* AA-A
A

A-B-A-BA-B-A
Cross-linked homopolymer Cross-linked copolymer
where A= Trifunctional monomeric unit where A = Bifunctional monomeric unit
and B=Trifunctional monomeric unit
4. On the basis of monomeric unit in the backbone of polymer, it is clasified into two
ypes
() Organic polymer and (ii) Inorganie polymer.
Organic polymer. If the backbone (man chain) of polymer is made
called organic polymer.
ofonly carbon atom,

+CH CH,) CH, CH>, fCH CH%

CH, C
Polyethene Polyvinylchloride (PVC)
Polypropene
 PonMERS 537
er If the backbone
of made of inorganic (other thanFor
polymer 1scalled carbon) atom
inorganic polymer. example,
gen, sulphur, etc., it 1s
etc.
glasses,
chalcogenised
zine, silicones,
e Ox
PoOposphazi

Polyphosphazine
Silicones

halide groups
where R-Cl, OCH. OC.H
or
- Alkyl
where R -As S-AsS -As---

S AS

As S As S AS ---

(Chalcogenised glasses)

the polymers are classified into three classes:

On the basis of tacticity
s
(ii) Syndiotactic and (ii) Atactic.
(0 Isotactic
(orientation) or characteristic monomer

Tacticity. Tacticity
is actually the geometrie arrangement
main chain (backbone) of thepolymers.
unit with respect to the are arranged on the same side
(0 Isotactic polymer 1f
the
characteristic groups (side groups)
It is obtained by co-ordination polymerization Ziegler
chain, it is called an isotactic polymer.
due to the presence of regularty of the chain
Natta catalyst). It is more crystalline and strong
structure.

CH3 CH CH CH
---CH CH-CH CH, CH CH CH CH
Isotactic polypropene

u) Syndiotactic polymer If the side groups (characteristic groups) are arranged in an alternate
then
Tashion, it is called the
astatic polymer.
syndiotactic polymer. It is also stronger and more crystalline

CH CH
-CH-CH CH CH CH-CH CH CH

CH, CH
Syndiotactic polypropene
G olmer. If the characteristic groups (side groups) are arranged in iregular fashion
domnes
elasticit chain, it is called atactic polymer. It has poor strength more
C y and around the mainis obtained by free radical polymerization process.
538 A TEXTmoOK or ENcINEERING CHEMISTRY

CH CH CH,
CH-CH-CH-CH CH CH, CH-Cl,
CH
Atactic polypropene
Syndiotactic and isotactic polymers are more crystalline than the alactiC polymer because n
Syndiotactie and isotactic polymers the characteristics groups are m eguiar orientation which
allow the adjacent chains to approach each other so that the attractive 1orce may be effective

0. On the basis of synthesis (Chemical combination) polymers are of two types:

0 Addition polymer and (i) Condensation polymer.

() Addition polymer. If the polymer is formed by the repeating of an exact multiple of the
original monomeric molecule it is called 'addition polymer and the process ot polymerization
1S known as 'addition polymerization'. Such polymerization always occurs through free or
carbocations or carbanions intermediates and favoured by heat, light, pressure or a catalyst

radicals.
For example,
1. nCH, = CH, fCH, CH,);
Ethene Polyethene
2. nCH, =CH-CI +CH CH};
Cl
Vinyl chloride Polyvinylchloride
(i) Condensation polymer. If the polymer is formed by the combination of two or more similar
or different molecules of monomeric units usually with the loss of simple molecules like

NH, H,O etc., it is called 'condensation polymer" and the process of polmerizations is
known as"condensation polymerizAtion'. The basic requirements is the presence of some
reactive functional groups like-OH, -COOH, etc., in the monomeric units.

For example,
n[H,N-(CH,)%-NH,]+ n[HOOC(CH,) COOH]
Hexamethylenediamine Adipic acid

2nH,0
o+HN-(CH,)-NH-CO-(CH,)-C0
Nylon 6:6

n HO-C-
OH+n HO (CH) OH 2nH,0
Terephthalic acid Ethylene glycol

0-(CH)h
Terylene (Dacron)

Addition and condensation polymerization are also termed as chain growth and step grou

polymerization.
 EMISTRY

540 A TeXTBOOK OF ENGINEERING CH 1sati

on
condensation

P O L Y M E R I S A T I O N
and (i)
polymerisation

14.5 MECHANISM OF types

(i)
addition

process of addition
two the
of t 1s molecular

Thepolymerisation
on process
process
is
15
Growth
Polymerization:

product
in
which
the
cular
polvmerieas grant
Chain of a
erisation. or f o r m a t i o n

P o l y m e r i z a t i o n

in
the m a t e r i a .

monomer.
The
resulting
starting ot t h e
Addition

different
monomer( s) as
that of the
integral
multple
the addition
of the similar or
or unit is
the
same

is an
to u n d e r g o
ar polymer
the presence
m o n o m e r ,

f repeating
ofthe For a in i1, 1.e,
l a

ofthe the
molecular
weight polymers. m u i i p i c i t y

is the
addition

often as
Very are
termed
the
m o n o m e r

thus
obtained

requirementpossessed
by
polymers
basic
the
polymerisation,

bond. For
example, -CH, CH),
double o r
triple
polyethene (polymer)
of nCH,=CH,

ethene (monomer)

C
C HC H
polyvinyl chloride (polymer)
nCH=CH-Cl
vinyl chloride ( m o n o m e r )

-CH CHOCOCH,),
polyvinyl acetate (polymer)
nCH=CHOcOCH,
vinyl acetate (monomer)

monomer
units to the
Chain Growth Polymers successive
addition of carbanion
which are
formed by the radical,
carbocation
or

polymers like free these

It is the type of
intermediate formation
intermediate
reactive
generated to the
chain through the polymerization.
According

growing is
called chan growth
and the process called initiators producing
are of the following
types:
Polymerizations
initiated by catalysts, (benzoylperoxide
polymerization. peroxides
(a) Free radical Generally organic
known as free
radicals polymerization.
For example,
polymerization of substituted
free radical are as free
radical
initiators.

acetylperoxide, etc.) are used

or
as
alkene takes place

Organic peroxiO CH CH
nCH,=CH
G
G
Monomer Polymer
where G - C l , - C N , C H s , - C O O C H , etec.

Mechanism. The mechanism

involves in the following steps
() Chain initiation

R R Homolytic fision 2R-O

Organic peroxide Organic peroxide free radical
 PoLMERS 541
Here R-O-or-CH

Homolytic ftission R + CO
Free radical attacks the reactant molecule and produces another (reactant) free radical.

omolyic s R-CH,-CH
or CH-CH

G G
2 free radical 1° free radical
(more stable) css stao
major product minor prodiuct

(i) Chain proportion. 1he generated free radicals attack another molecule of reactant (a and
propagates the process.

R-CH CH H,CH R CH-CH-CH-CH

G G

This step is repeated many times to form desired

a
long chain.
(i) Chain temination. This step may take place due to coupling or
reactions.
disproportionation or transfer
(a) Coupling. It involves collision between free radical chains between
chain and a catalyst radical.
or
growing free radical

)RACH, CH)CH, CH + CH CH,fCH CHR

G G
(free radical growing chain) (another free radical growing chain)

R-fCH CHCH, CH-CH CH,fCH-CH9;R

G G G

)
R--CHCHCHCH + R R-CH, CH,CH, CH-R
G G (1initiator
free radical)
(free radical growing chain)
- a-e
 POLYMERS 543
(a) Polymerization of propene
oles:
E r a m y p v e s

nCH,=CH CH, CH)

CH CH
Propene Polypropene

Polymerization of isobutylene
()

CH CH,
nCHy-CCH, HHO4CHC
CH
tylene Butyl rubber

in the following setps:

Mechanism. The mechanism involves
initiation step. Proton is formed in this step:
() Chain

H
+ BF H-BF, H[BF,OH]
H
Trifluorohydroxyboric acid

(i) Chain initiation step. The proton H" attracks on reactant molecule and forms stable cation.
Ths step 1S repeated and 1orms a long chain.

CH,
CH H +H [BF,OH]
[BF,OHJC-CH,
CH
CH

CH, CH

CH CBF,OH
- CH C-CH, C[BF,OHJ
CH, CH CH,
carbocation (most stable)

CH CH CHCH CH,
--CH-C [BF,OH] +nCH,=C CH-CCH-CCH CBF,OH]
CH CH,
CH CH,
CH CH
 544 A TeXTBOOK OF ENGINEERING CHEMISTRY
(ii) Chain termination step. It takes place by
the loss of hydrogen ion (H") from the c a
arbocation chan
CH
CHa CH CH
CH-C-CH- Yc CHBE,OHJ H,0 CH-CH CH=-CH.
CH, -BF,
CH CHd CH CHIn CH,
Polyisobutylene (Buryl nubber)
Note. Only alkene carrying electron releasing substinuents undergoes such polymerization
ene,
etc., do not show cations poljymerization.
vinyl
(c)Anionic addition polymerization. This type ot poiymerization is initiated by hae
ike a
alkali metal amides and Grignard reagents. Alkene
metals, alkyl metals (7-buty llithum), carrying elktrons
involves in anionic addition polymerization.
withdrawing substitutents generally
Examples:
(a) Polymerization of styrene

nCH=CH
MNH CH -CH

Styrene Polystyrene
(6) Polymerization of acrylonitrile

NaNH, in hq (CH, CH
nCH,CH
CN CN
Acrylonitrile Poly (acrylonitrile) (PAN) or Orlon

Mechanism. The mechanism involves the following steps:

() Chain initiation step. It involves in the formation of carbanion.

NANH, NH NA+ NH

NH+CHCH NH CH CH
CN CN
(2 carbanion)
(i) Chain propagation step. This carbanion attracks reactants to form another carbanion. Ihe
step 15 repeated to torm a long chain.

NH CH=CH + CH-CH NH, CHCH-CH CH

CN CN CN CN

Kepetnnon NH,CH-CHHCH CH
CN
CN CNJ
 PoLMERS 545

nit termination step. It takes place in the presence of H' or some Lewis acid. In the
( d s or H"
H the
the rea
reaction continues till the whole of monomer is polymerized.
a c h d s
or
of
sence

CH , NHCH-CH--CH CH, NH,

NH-CH, CHFCH CHHCH,
+

CN CN CN CN CN
Poly (acrylonitrile) (PAN) or Orlon
imto a nore and can be made to look like silk or wool. It has excellent
orlon (PAN) can be spun with
etc. It can be woven or knitted and be blended
e to sunlight, outdoor exposure, acid, can

i sIt. used in making Carpets, sweaters, bathing suits, etc.

sool two
m Condensation Folymerizaton
t 1s the process of the combination of
similar or difterent molecules usually with the loss of simple molecules like
raly/chemically
Tesulting in the tormation of a high molecular weight substance. The polymers
o NH., ROH, etc.,
For monomer, to undergo the condensation
ohtained are termed as condensation polymers.
a

some reactive
the monomers is the presence of
merisation, the basic requirement possessed by
cional groups like-O,-cO0H,NH, For example, etc.

N-(CH,)% NH, +nHOOC-(CH,)-COOH nt0

nH
hexamethy lene diamine adipic acid
NH-(CH)NH-CO CH,), CO
Nylon 60

-OH) + nH0 (CH) OH

-RH,O
nt0C -0-CH-0%
ethylene glycol
terylene or dacron
terephthalic acid

A polymer with a given structure can be prepared starting with different monomers either by
addition polymerisation or by condensation polymerisation processes. For example, nylon 6 can be

Papared either starting with caprolactum via addition polymerisation, ie,

H,
H,C NH -(CHNH
Nylon 6
H,C-CH,
Caprolactum
tng with 6-aminohexanoic acid via condensation polymerization, i.e.,

nHi,N{CH,)- -OH -NH (CH,),C - 0

-H,O
O-aminohexanoic acid nylon