IONIC POLYMERISATION

• Addition polymerisation
• Growing chain bears –ve or +ve charge

Anionic Polymerisation

Cationic Polymerisation

• Both need different INITIATOR system & REACTION CONDITION

• Zwitterionic Polymerisation

ANIONIC POLYMERISATION
• Growing chain bears –ve charge

• Initiation started by species that undergo NUCLEOPHILIC ADDITION to monomer

X = e- withdrawing substituent
(stabilise the C depends on X)

THE MONOMERS

• Generally contain electron e- withdrawing

substituent group

• Stability of the carbonian (C¯) produced in the initiation reaction is stabilised by the presence of e-
withdrawing substituent

• Example:
• Order of reactivity of the monomer structure :

• Methyl substibution on ⍺-carbon decrease the reactivity:

 MECHANISM

[2] PROPAGATION
[3] TERMINATION
• usually NONE (polymer ends REPEL with each other).
• If starting reagents are all pure, and if the polymerisation reactor is purged off all O2
and traces of water; propagation will proceed or till all monomer is consumed.

• Anionic polymerisation is called as “living” polymerisation

TERMINATION for The Chain That Wouldn’t Die

• The “living polymer” can then be quenched /terminated in various ways : -

(Deliberately) addition of electrophile, such as H2O, CH3OH, CO2 followed by H+

LIVING POLYMERS
• Apply to anionic polymerisation that are not terminated
• Capability of continuing chain growth if more same monomers are added, or 2nd
monomers are added.
• Initiator that yield “living” polymer easily is those with RADICAL ANION.
• Example sodium metal, or sodium in napthalene.
 THE MECHANISM (example1)

[1] Initiation
STEP 1 : an electron is transferred from sodium to monomer to generate a radical
anion

STEP 2 : Dimerisation of the radical anion to form dianion (uses 2 mol of radical
anions)

[2] Propagation
•Occur at both ends by insertion
of MORE monomer molecules.
•The growing chain proceed at
both ends

[3] Termination
•None
•If need to stop, deliberately ADD reagent in termination slide
 THE MECHANISM (example2)

INITIATION
electron is transferred from sodium to naphthalene to generate a sodium
naphthalene then 1st monomer attack

STEP 2

Dimerisation of the radical anion to form dianion (2 mol of radical anions)

Propagation (SAME as example 1)

•Occur at both ends by insertion of
MORE monomer molecules.
•The growing chain proceed at both ends

Termination (SAME as example 1)

•None
•If need to stop, deliberately ADD
reagent in termination slide
GOOD for COPOLYMERISATION
• Different monomer is added into anionic chain which is remain “alive” (“living”
growing chain) = COPOLYMER

• 1st monomer, A & 2nd monomer B added & a growing copolymer might be represented
as :

• Resulting in Block copolymer is formed

restriction
•If monomer C have more powerful e- withdrawing substituent than monomer B &
monomer B > monomer A
(refer slides MONOMERS in Anionic intro)

• Example 1
An active chain made up of methyl metharylate units (B) will continued growth in the
presence of acrylonitrile (C) . But NOT in the presence of styrene (A)

• Acrylonitrile = most e- withdrawing

• Example 2
If Na or Na in naphthalene is used, then copolymer of B-A-B (triblock) can be prepared