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Lec 10: Carbanion, Carbcation and

Free Radical

Ionic Addition Polymerisation

Many ionic polymerisation proceed at much higher rates than free-radical

polymerisation, because the concentration of actively propagating chains is
very much higher.
A propagating ionic active centre is accompanied by a counter-ion
Termination cant occur (anionic polymerization) by reaction between two
ionic active sites because they are of similar charge

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Anionic Polymerisation

Monomers can be polymerised anionically if there is an excess of one electron

at the active site i.e. a negative charge.
The active site may be a carbanion or an oxanion (formed during an anionic
ring-opening polymerization).
Initiators:

Grignard reagent (R-X-Mg), organometallic

compounds, alkali metals, metal amides.

Termination does not occur in anionic

polymerisation (except protic solvents), as alkali

counterions do not combine with carbanionic
active sites.

Such polymers which permanently retain their active centres and continue to
grow until the monomer is available are called living polymers.

Anionic Polymerisation

The initiator in anionic polymerization may be any compound providing a

strong nucleophile (Grignard reagents and other organometallic
compounds). Initiation involves the addition of the initiator to the double
bond of the monomer.
If a solvent that is able to release a proton is used, it can react with the
active site. Ammonia is an

example of such a protic

solvent and the reaction results in

the formation of a negatively
charged NH2 ion, which can
initiate the polymerization of a
new chain. In other words, we
have chain transfer to the solvent.

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Anionic Polymerisation:
Applications

Can you make polystyrene chain by anionic

polymerisation using K-NH2 initiator ?
Initiation involves the dissociation of K-NH2 followed by addition of amide
ions to styrene.

KNH 2 K NH 2
CH CHPh

NH 2 CH 2 CHPh H 2 NCH 2 CH K Ph 2

Anionic Polymerisation:
Styrene in liquid ammonia
K-NH2 K+ + NH2-

No living polymer of polystyrene in this case as the chain is

transferred to ammonia.

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Anionic Polymerisation:
Triblock copolymer

Anionic Monomers

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Cationic Polymerisation

Cationic polymerizations involve an active site/centre where there is a

positive charge (deficit of one electron, hence electrophile).
Initiators

Protonic acids (H2SO4, HClO4), or Lewis acids (BF3, SnCl4, AlCl3) with
cocatalyst, such as water or organic chloride (R-Cl)
BF3 H 2O H ( BF3OH )
AlCl3 RCl R ( AlCl 4 )

HCl cant be used, why?

Termination can occur either by unimolecular rearrangement of the ion pair,

(anion-cation recombination) or through chain transfer to the monomer.
Many side reactions can also occur; with trace amounts of water.

Cationic Polymerisation:
Lewis Acid initiator

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Cationic Polymerisation:
Applications

Butyl Rubber by copolymerization of isobutylene with small quantities of

isoprene at low temperatures (-90C) using AlCl3 initiator and
Chlomomethane.

Coordination Polymerisation

Some polymerisation reactions involve complexes formed between a

transition metal and the -electrons of the monomer.
Reaction/addition of monomer is similar to anionic polymerizations
These types of polymerizations usually lead to linear and stereoregular
chains (isotactic) and use catalysts, also called Ziegler-Natta catalysts
Ziegler-Natta catalysts generally consist of a metallo-organic nature
involving a metal (from groups I-Ill) such as triethyl aluminium, and a
transition metal compound (from groups IV-VIII), such as titanium
tetrachloride.
The degree of stereo-regularity depends on the nature of the catalyst, the
nature of the monomer, temperature, the nature of the solvent.

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Coordination Polymerisation:
Ziegler-Natta catalyst

The metal organic compound acts as a weak anionic initiator, first forming a
complex. The transition metal ion (Ti) is connected to the end of the growing
chain and simultaneously coordinates the incoming monomer at a vacant
orbital site.

Coordination Polymerisation:
Ziegler-Natta catalyst

Ethylene, in the presence of a combination of an organo-aluminum and a

zirconium compound, at relatively low pressure, produced polyethylene.
The gas ethylene could be polymerized at 100, 20, or 5 atmospheres and
finally even at atmospheric pressure very rapidly in the presence of certain,
easily prepared, catalysts to give a high molecular weight plastic.