INTAODUCTION AND HISTORY OF

POLYMERIC MATERIALS 111

1.7. CLASSIFICATION OF
Polymerisation processes or POLYMERISATION
reactions are classifiedPROCESSES
into two categories :
1.71. ADDITION OR CHAIN GROWTH
POLYMERISATION
Addition or chain growth polymerisation is the process of
formation of addition polymers from monomers
toame or different types, Without the loss of
the same formula as that of the monomer/s. small molecules. The repeating unit of the addition polymer nas
This polymerisation 1s also known as chain growth
additionof. monomers in a series of polymerisation because it is a chain reaction involving
reactions
ee steps: () Initiation (in) Propagation (üi) resulting in growth of chain. Addition polymerisation involves
Termination.
Depending on the nature of initiator, addition polvmerisation is further
() Free radical addition polymerisation (i) classified into three categories:
Às already explained that addition Cationic Polymerisation (ii) Anionic Polymerisation
polymerisation involves three steps as given below:
(i) Initiation : In this step, a reactive
attack of this reactive species on the monomer species (free radical, cation or anion) is generated followed by
forming another reactive intermediate/species.
(ii) Propagation : It involves a series of steps, each step
reactive intermediate resulting in formation of large polymer chaininvolving the attack of monomer on the
with reactive group at one end.
(iii) Termination: It involves deactivation of the end
resulting in formation of stable polymer. reactive group formed during propagation steP,
[Link]. Free Radical Addition or Chaln Growth
Polymerisation
As the name indicates, free radical addition polymerisation involves free
term chain growth' means a process involving a rapid and continuous addition of radical as initiator and the
the monomers to form a
long polymner chain.
Initiators used in free radical addition polymerisation :
Initiators used in free radical addition polymerisation are thermally unstable compounds and
intoproducts called free radicals as given below : decompose
Homolytic
R"iR Cleavage
’ 2R°

The following indicators are used in free radical addition polymerisation reactions:
(i) Peroxides :

Cçti---0-0--CçHs
70°C
Homolytic CçHi; O=
+ C=0
Benzoylperoxide (BPO) cleavage Phenylradical
Benzoyl radical

H-0-0-H 2 H-o
Homolytic cleavage
Hydrogen peroxide Hydroperoxide
radical

CH3 ÇH3
A
CH,
Homolysis CoHs- -Î
CH, CH; CH,
Cunyi peroxide
CH;-C=0 + CH,
Methyl
CoHs + CH-Ç=0
Phenyl
CoHs radical radical CH;
112 ÇH3
ÇH, CH3.
ÇHs 120C ’ 2 CH,- -Ï ’ 2 CH; + 2
CH-oo--CH, Homolysis Methyl
redical
CH,
H;
H H, tert-butoxide radical
ier-butylperoxide
(i) Aro compounds: CN
CN CN
40°C 2CH, -C: +N,
CH-CN=NC-CH, Homolysis
CH,
CH, CH, Lsobutyronitrileradical
Azobisisobutyronitrie
(AIBN)
H
H
H
C,H,-C+ N=NC CH, 2CH,C" +N,
CHs
C,Hs Diphenylmethyl radical
Azobis diphenyBmethane
:
(ü) Persulphate radicas
O==0
2 KO-S-0*
KO-$-o4o--OK orA

Potassium persulphateradical
Potassium persulphate

hv 2NH,0-S-0*
NH,0-5-o+0-3-oNH, orA

Ammoniumpersulphateradical
Ammonium persulphate
POLYMERISATION
MECHANISM OF FREE RADICAL of heator sunlight to produee
homolytically in presence
() Chain Initiation :The initiator decomposes
free radical/s
Aorhy
’ 2R*
R+R Homolysis
(CH, =CH)
further attacks the monomer
The radical R' thus formed is highly unstable and X
CH,ÇH R-CH,-ÇH
R
Initiator rnical
being coSumed X
X New radical genersted
INTRODUCTION AND
HISTORY OF POLYMERIC MATERIALS 1N3

X=-H,-Cl, -C=N, -CGls, - CH3, --0H, -C-NH, -C-Cl, -C-Hett.

Depending on the nature of - X,
posible: following vinyl monomers and their corresponding polymers are
Structure of monomer Name of Monomer Polymer Formed
- H CH, =CH, Ethylene Polyethylene
-Cl CH, =CH-CI Vinyl chloride Poly(vinyl chloride)
-CN CH, = CH-CN Acrylonitrile Poly(acryonitrile)
-CGHs CH, = CH-CHs Styrene Polystyrene
- CH3 CH, = CH-CH, Propene Polypropylene

-C-OH CH, = CH-COOH Acrylic acid Poly(acrylic acid)

-C-CI CH, =CH-COCI Acrylloylchloride Poly(acrylloyi chloride)

-C-NH, CH, = CH-CONH, Acrylamide Polyacrylamide

-C-H CH, = CH-CHO Acrylaldehyde Polyacrylaldehyde

(i) Propagation : Initiation is followed by propagation. In the propagation step, the radical generated
in the initiation step R-CH, -CH from the first monomer unit attacksthe double bondof afresh monomer
X

aOkecule esulting in the linking up of the second monomer unit to the first and the transfer of the radical site
from the first monomer to the second :

R-CH,-ÇH + CH, ÇH’R-CH,-ÇH-CH,-CH,- H

X X X X
lhis chain still has a raical site at the end carbon atom and can theretore attack yet another monomer
cCule with simultaneous transfer off the radical site to the fresh monomer.

R-CH,--CH-CH,- -CH + CH,CHRCH-ÇH--CH-ÇH-CH,-CH

X X X X
X X
and so on.
 1/14
This process continues and keeps on adding fresh monomers to the growing chain
Pradeep's Polymer Chenisty
transfer of radical site to the fresh monomer unit. The growing polymer with
-chain can be
OR
representedsimulas ta:neous
Rw CH-ÇH
X X
where 'n' is the number of monomer units added to the chain and wavy
line
made up of nnumber of monomers. denotes the polymer chain
Following four different types of additions are possible if -CH,- and
called head and tail respectively : -CH-X parts of a
monomer are
w ÇH-CH, + CH,= ÇH
LX
Head Head wwÇH--CH-CH-ÇH
Tail
X X X
Tail
Heat to head
wwCH-CH, + CH=
Head
CH2,
Head wÇH--CH,-ÇH-CH,
X X X
Tail Tail
+ Heat to tail
mwCH,--CH CH, CH wCH,-ÇH-CH;-CH
Head Head
LX X X X
Tail Tail Tail to Head
mCH,--CH + CH=CH
Head Head
wCH,-CH-CH-CH,
LX LX X X
Tail Tail
Tail to Tail
(iiü) Ternmination : Propagation step is followed by
units to the growing chain comes to an end and growthtermination in which any further addition of monomer
of polymer chain gets arrested. Termination can be
achieved by three processes as given below :
(a) Termination by coupling of growing radical chains :
In this process, the two growing chains
(macroradicals) come close and colloid with each other.

R+CH, -CH+ CH, -CH + CH-CH, CH-CH, +R

X X X X

Growing Macroradicals
J coupling
RfCH, -ÇH+ CH, -ÇH-ÇH-CH, fCH-CH; *
X X X
Jm |X Jny

Terminated polymer chain

(b) Termination by disproportionation : In this process, one Hydrogen from agrowing chainis
abstracted by the other growing
stabalised, while the chain. The
second macroradical firstdonates
which macroradical
H gets that
stabalised with lone electron gets
theHformation
acceptsbbythe of double bond.
N OF POLYMERICMATERIALS
1/15

H
H (H)
RfCH-ÇH+CH, X
Ist macro radical
Jn LfÇH-CHt
X H X

IInd macro radical

Jng
R

R+CHÇH+CH-H X
n X
+
CH=¢+ÇH-CH+R
X HX Jn
Terminated Polymers
(c)Termination by chain
transfer : This process involves the abstraction of a
some other atom from the initiator, Hydrogen atomn (H) or
impurities present in the system. monomer polymer or solvent or even from some other species including
or

RfCH-ÇH+CH,-CH X X
+
+ R+CH-ÇH+CH-ÇH, + R

X X
Termination by chain transfer differs from the first two
The products formed in the termination processes as explained below :
'deactivated' and termination caused by coupling or
disproportionation are dead' or
hence further propagation is possible. In chain
no
tansfer process besides one dead or
deactivated polymer, there is a simultaneous generation of a new free
polymer chain growth. radical (R) that can initiate a new
[Link]. lonic Polymerisation
In ionic polymerisation, ions (cations or anions) act as
nature of initiator (cation or anion), ionic polymerisationinitiator instead of free radicals. According to the
is of two types : (i) Cationic
(ii) Anionic polymerisation. polymerisation
[Link]. (0) Cationic Polymerisation
Cationic polymerisation can be reprsented by following scheme :
Y+ CH, =CH ’ Y-CH, -CH
X X

Y-CH, -CH CH, =CH ’Y-CH, -CH -CH, -CH

X X X X
(a) Initiators used in cationic polymerisation : In cationic
AOrS are Lewis acids, such as BF3, AICl4, BCl3, SnCl4 etc. Thepolymerisation, the most commonly used
advantage of such an initiator is that, it
does not have
accompanying nucleophile that could act as chain terminator.
an
In case of protonic acids like HCI, H,SO and HCI04, the accompanying
nucleophile CI, SO0; and
respectively would terminate the growing polymeric chain.
 (b) Monomers used in catlonic polymerlsation :
Pradeep's Polymer Chemistry
CH, CH CH, =C-CH, C,H, -CH=CH, CH, = CH
CH, Styrene
CH,
Propylene Isobutylene OCOCH,
Vinylacetate
MECHANISM OF CATIONIC POLYMERISATION :
Like free radical addition polymerisation, cationic
() Initiation (ii) Propagation (iüi) Termination.
polymerisation also involves three steps :
() Chain Initlation :

BF + CH,CH ’ BF3-CH,-CH
Initiator
X X
Monomer
The -electron pair of unsaturated monomer is attracted by the
of -ve charge on BF, part and +ve charge an Lewis acid (BF) resulting in generation
double bonded carbon atom of monomer. In this process, a
signna bond is formed between Lewis acid (or H*, if initiator is
protonic acid) and monomer unit and
polymerisation gets initiated with the simultaneous formation of carbocation.
(ii) Chain propagation : In propagation step, further addition of
simultaneous transfer of monomer unis takes place with the
charge
to the newly added monomer unit.

BF-CH,-ÇH +
CH2 CH ’ BF:CH,-CH-CH-CH
X X X
With the addition of each monomer unit, the chain keeps on growing and the
T-electron pairs of the
monomer units are transferred in a direction opposite to the growth of chain and C* ion keeps on moving in
thedirection of the chain growth.

BE} -CH, -CH-CH, -CH + CH, =CH ’ BE -CH, -CH-CH, -CH1-CH, -CH
X X X X X -X
and so on....

Ingeneral, the growing polymer chain with 'n' number of monomers can be represented as :
o
BE CH, -CH CH, -ÇH
X n X

(ii) Termination :Cationic polymerisation can be terminated in following three types :

(a) Termination by proton (H) loss:
-H®
BFf-CH-ÇH CHCH BE;CHÇH CH=ÇH
H X X
Terminated polymer
INIHOL
Terminatlon by MATERIALS 1N7
(b) nucleophlle Nucleophile can be added from outside or if protonic acid is
:
used as
the
jnitiator, accompanying nucleophle (SO% of H,SO4, CI of HCI etc.) can termination.
H
cause
H
BR +CH,-CH + CH, + Nuf
X X
BE, 4 CH, -CH CH, -C- Nu
X X

Terminated polymer
(c) Termination by chain transfer :Termination can take place by chain transfer
monomer. with solvent or with
X
X

tcH ÇHT + CH,FCH

BE;f-CH-ÇH-CH=CHX + CHy
X (H H X
X H
Monomer Monomer cation

[Link].( ) Anlonic Polymerlsation : Living Polymers

Asthe name indicates, anionic polymerisation is initiated by
nucleophile and can be represented as :
nCH,=CHX
Nu+CH, =CH ’ Nu -CH, -CH Nuf CH, -CH \CH, -CHe
X X X n X

Initiators used in Anionic Polymerisation :

Alkenes can not be easily attacked by nucleophiles because they themselves are electron rich and tend
to repel the nucleophile (which are also electron rich). Therefore nucleophile must be strong. Following
Mcleophiles can be used us initiators in anionic polymerisation :

Sodium amide NaNH

Butyl lithium n-C,H, Li
+

Alkali metal hydroxides NaOH, KOH etc.

Metal Alkoxides RONa, ROK

Monomers used in Anionic Polymerisation :

due to electron rich nature of both the
Cxplained earlie, attack of nucleophile on alkene is not easy
cleophile alkene. The monomer alkenes usted for anionic polymerisation should contain an electron
and
density. Therefore X in CH, =ÇH must be some electron
wiwithhddrraawwiinngg substituent to decrease
group such as :
its electron
X
 1/18

-C=N Nitrite -C-OH Carboxylic acid

-CçHs Phenyl -C-0CH, Ester

Acid amide -C-CI Acid chloride

-C-NH,
Followingmonomers are generally used in Anionic Polymerisation :

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

Styrene
CN C1
Acrylonitrite Vinyl chloride

CH, =CH CH, =C-CH, CH, =CH

ooCH,
Methyl Acrylate
COOCH,
Methyl methacrylate
CONH,
Acrylamide

MECHANISM OF ANIONIC POLYMERISATION

Like free radical and cationic polymerisation, anionic polymerisation also involves initiation, propagation
and termination.
) Chain Initiation: In this step T-electron pair of the monomer is attacked by
pair of [Link] electrons of nucleophile are used to form asigma bond between nucleophile with lone
bonded carbon atom of the monomer, pushing the T-electron pair of the monomer to the
nucleophile and double
Le., to the end of the molecule. This results in the formation of a carbanion. next carbon atom

Nu + CH,=CH ’ Nu-CH,-CH
X X
(1)
(ü) Propagation : The carbanion () formed in the initiation step attacks the second
pushing its T-electron pair further away to the end and form a sigma bond monomer unit,
anionic polymerisation, movement of the electron pair takes place in the with the new monomer unit. In
case of cationic polymerisation movemnent of the direction of chain growth, while in
electron
direction of chain growth (explained earlier in cationic pair takes place in the direction opposite to the
polymerisation).
Nu-CH-ÇH +
"CH,CH + Nu--CH-ÇHCHCH
X X X X

Nu-CH-ÇH-CH,-ÇHCH,-ÇH
X X X
 the growing hand, [Link]) polymerisation
terephthalic
reactions witnwill propagauol
system free small
+Y° propagation because in
react otherand of
each
Nu-+CH,-CH-CH,-CHH the here loss (chain
transfer can to monomer. lossreactions. at
the (or nH0-CH-CH,-oH
+
theadded POLYMERS,because thegroups and terephthalate
that On (H*) addition
chain X chainconsumed,
impurities fresh polymer.
by hexamethylenediamine
is coupling
proton
polymerisation accompained
functional H
by case, monomer in H-N--(CH,)6
n glycol
Ethylene
adding by unlike
achieved methyl
all thatbeen LIVING the terminated or reactive
from disproportionation
hasmore by -
(CH)6-NH
+C-(CH,)4--NH-
X if
:
as and In
place. units slow
simply
anionic POLYMERISATION H of
represented be mixture.
Nu-+-CH,-CH’,CH,-CH
can chain. monomer
if called
loss
monomer
have is Polymerisation polymer
X continue proton
be polymerisation and Polymerisation-CH,0H
polymerisation not
take timefrom can
the are monomers acid
reaction all any by chain condensation Terylene
orDacron
be teminate will chains obtained or adipic
willifEven termination
by
can
the ye
chain
termination started polymer
polymerisation terminatedtwo + H,0 6,6
Nylon
monomers X Solvent non-terminated of Theand Polymers
CONDENSATION of (CH)4--OH
-
in
anionic H* to consumed,be be combination polymer
impurities (H) NH¡. manner a
can can undergo
the rapidly. molecules. is
+ POLYMERS' be Condensation polyester
n of
proton
Nu-fCH,-CH+CH,-CH polymerisationof
endcan or condensation terephthalate
Methyl
with Termination X beenand HClstepwise
with a Such not cationic
site involves grow
chain removed,
donate
active ROH, water
has do a
reaction
monomer months.'LIVING end radicalOR a chains
in Dacron,
glycol.
polymer be polymerisation
GROWTHpolymerisation
H,0,place a of
: not still and with-ve polymerisation whereof It loss
is
Termination
by X can carbanion
are
solventall
will or active Examples
molecule-generally
takes
6,6:by : and
ethylene
Dacron
growing or weeks of accompanied
polymerisation,
solvent (carbanion)
untill typechains STEP Nylon n
remains reaction
The ) the the growing after Thispolymer cationic This [Link].
() (ü)
If continue chain radical
1.72, acid)
h site even in
The is