Addition polymerization:

The process of repeated addition of monomers that possess

double or triple bonds to form polymers.
eg. Addition Polymerization of alkene (ethylene) to form
polythene

200 oC
1000 atm
Benzoyl peroxide
Monomer Polymer

Ethylene = Monomer Polythene = Polymer

Mechanism of Addition polymerization:

Takes place through the formation of intermediates:

• Free radical (Free radical addition polymerization)

• Cation or Carbonion (Cationic addition polymerization)

• Anion or Carbanion (Anionic addition polymerization)

Catalysts (organic peroxide or acids or bases) are used.

They undergo decomposition to form intermediates.
2
 Mechanism of Addition (contd.)
 Involves three steps:
 Chain Initiation: Generation of intermediate (free
radical, carbonium or carbanium ion) by catalyst
(organic peroxide or acids or bases). The generated
intermediate are transferred to the monomer molecule
to form new intermediate.
 Chain Propagation- The new intermediate is added to
other monomer molecule to form other new
intermediate and so on.
 Chain Termination: The polymer chain reaction can be
interrupted (ends) by combination two chain
intermediate or with (loss or gain of a proton).
 Mechanism of Free radial Addition
Polymerization
- Occurs through the formation of Free –Radical
- Catalyzed by organic peroxide or other reagent which
undergo decomposition to from free radical.
eg. Polymerization of ethylene to give polythene.

Polymerize

- Involves three steps-

 Chain initiation
 Chain propagation
 Chain termination
 1st step: Chain Initiation- Formation of free radical by
homolytic fission of peroxide (Benzoyl peroxide) as
catalyst.

2
Benzoyl peroxide Phenyl
This bond free radical
breaks

The free radical formed in above step adds to an alkene

molecule to form new free radical.
•n
. C6H5
C6H5 2

Phenyl New radical

free radical
2nd step: Chain Propagation: The new free radical adds to
another alkene and so on.

3rd step: Chain termination: The chain propogation is interrupted

by combination or dis-proportionation (with loss or gain of
proton) of two free radicals

(Redox reaction)

Saturated polymer Un-saturated polymer

In disproportionation H-atom of one radical center is
transferred to another radical center. This results in the
formation of two polymers : one saturated and another
unsaturated

The reaction in which one reactant gets oxidized and the same
reactant gets reduced is known as disproportionation
reaction.
The disproportionation reaction is also known as dismutation
reaction. The same element is oxidized and reduced in the
disproportionation reaction.

7
Ionic Mechanism of Addition Polymerization
Two ways:
1. Cationic Mechanism of Addition Polymerization
2. Anionic Mechanism of Addition Polymerization

Cationic Mechanism of Addition Polymerization: Occurs

via. formation of cation (carbonium ion or carbocation).
Catalyst
Monomer Polymer
Co-catalyst
 Catalyst :Lewis acid (BF3, AlCl3, H2SO4)
 Co-catalyst (H2O,Carbonic acid)
 Monomer: Contains electron donating group. eg CH3, C2H5
Electron donating groups in
Eg. CH2= CH (G = CH3)
monomer supports to form
G stable Carbonium ion.
G- electron donating group
 Stability of carbocation
3

Stability increases
Tertiary (3°) carbobcation > secondary (2°) carbobcation >
primary (1°) carbobcation > methyl carbocation

Propylene Isobutylene

Isobutylene form more substituted (stable) 3o carbocation than

ethyelene. Isobutylene is reactive towards cationic polymerization
(speeds up the polymerization). This lowers the activation energy for
the reaction and increases the rate of reaction.
 Cationic Addition polymerization:

Example: Polymerization of isobutylene

CH3
CH3

CH3
CH3
Poly-isobutylene
Isobutylene

Involves three steps.

• Chain initiation:
• Chain propagation
• Chain termination
 Cationic Mechanism of Addition Polymerization
 1st step: Chain initiation step – Proton is generated by
catalyst in presence of co-catalyst. Proton adds to carbon-
carbon double bond of alkene to form stable carbocation or
carbonium ion (cation).

BF3 + H2O [BF3-OH] - + H+

(Initiator)
G G
Carbocation
 Cationic Mechanism of Addition Polymerization (contd.)
 2nd step: Chain propagation step - Carbonium ion added to
other alkene molecule to form a new carbonium ion which
can similarly add to other alkene molecule and so on.

G G G G
New carbonium ion

G G
+ 2

G G G G G G
Carbonium ion New carbonium ion
Or

22
G G G G G G
Newcarbonium ion
 3rd step: Chain termination-The chain reaction can be
interrupted by combination with loss of a proton.

[BF3-OH] -

Removal of
G G G proton G G G
Polymer + BF3 +H2O

This type of polymerization is successful when EDG ( Electron

donating groups) such as methyl should be attached to monomer
since there occurs the formation of stable Carbonium ion.