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Cationic Polymerisation

The document discusses cationic polymerization. Cationic polymerization uses cationic initiators like strong protonic acids or Lewis acids. The growing chain end bears a positive charge. Suitable monomers contain electron-donating substituents that can stabilize carbocation intermediates formed during polymerization. Examples include isobutylene and styrene. Factors like solvent, steric hindrance, and stability of carbocation intermediates determine whether a monomer can undergo cationic polymerization. The general mechanism involves initiation by generation of proton ions from the acid initiator, propagation through addition of monomers to the carbocation, and termination through reactions like chain transfer or proton abstraction.

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Nazratul Najwa
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169 views

Cationic Polymerisation

The document discusses cationic polymerization. Cationic polymerization uses cationic initiators like strong protonic acids or Lewis acids. The growing chain end bears a positive charge. Suitable monomers contain electron-donating substituents that can stabilize carbocation intermediates formed during polymerization. Examples include isobutylene and styrene. Factors like solvent, steric hindrance, and stability of carbocation intermediates determine whether a monomer can undergo cationic polymerization. The general mechanism involves initiation by generation of proton ions from the acid initiator, propagation through addition of monomers to the carbocation, and termination through reactions like chain transfer or proton abstraction.

Uploaded by

Nazratul Najwa
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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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,

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