CATIONIC POLYMERISATION

• Growing active chain end bears +ve charge.

CATIONIC INITIATORS

[1] Strong Protonic Acid

[2] Lewis Acids & Their Complexes

Example STRONG
PROTONIC ACIDS
Example LEWIS ACIDS ~ need CO-
CATALYST (H2O or methanol) in equimolar
concentration or less

MONOMERS
• Contain e- supplying/donating
substituent groups
MONOMERS
• Good monomers for cationic polymer

CH2 CH R CH2 CH
Benzylic
R + carbocation

initiator
styrene

CH3 CH3
R + CH2 C R CH2 C 3° carbocation
CH3 CH3
initiator
isobutylene



• Monomers will be polymerized by cationic depends on the stability of the
carbanium ions / carbocation C+ formed.
• Example: Isobutene/isobutylene ;

• Isobutene will be polymerized by cationic and formed high molecular

weight.
• Example : PROPENE/propylene
• will also be polymerized but yield low molecular weight CH2 CH
• 2° carbocation formed is less stable than 3° CH3
• 2° carbocation is more reactive so termination reaction may occur early.

• e- donating group can stabilize C+ by resonance.

CH2 CH CH2 CH
OR OR
• e- donating susbtitution will increase the nucleophilicity of the monomer
Hence, easily bonding with initiator, H+

• STERIC HINDRANCE may stop monomer to cationic attack

• Example : Isobutene polymerized CH3
easily by cationic. CH2 C
CH3

• But diisobutene will proceed dimerisation only

 • SOLVENT is important in cationic polymerization
H
• Counter ion Y- separated by polar solvent
CH2 C Y

e- X
H2O or alcohol (separates +ve/-ve
charges so that monomer can attack)

• Resulting in increase in the rate of polymerization.

• Example: Styrene

(i) polymerised easily in HCl in polar solvent

(ii) in non-polar solvent = NO POLYMERISATION REACTION just ADDITION to ALKENE

GENERAL MECHANISM  Generation of H+

[1] INITIATION

 Addition of H+ to monomer

 Generation of H+
H2SO4 H + HSO4

Strong Acids HClO4 H + ClO4

HCl H + Cl

Lewis Acids BF3 + H2O F3BOH + H

BF3 + CH3OH F3BOCH3 + H
SnCl4 + H2O Cl4SnOH + H
[1] INITIATION

 Addition of H+ to monomer

• Initiation of a monomer molecule involve the addition of initiator ion pair across the
double bond.
• The proton will add to C that bears the greatest density & formed stable carbonium ion
/ C+

[2] PROPAGATION

[3] TERMINATION
(a) Donation H+ from terminal growing chain to a monomer molecule (Chain Transfer)

AND

(b) By loss of proton to the counter ion , Y- = HY

(c) By the reaction of a growing chain end with traces water (H2O) or other protonic
reagent

(d) Involving abstraction of hydride ion = chain transfer reaction

(e) By addition of basic reagent (B) like amines, ethers or sulfides.

Hence the polymer structure formed by cationic polymerization initiated by proton acids
are,