Cationic polymerization

Initiation and Propagation

The mechanism of cationic polymerization is a kind of
repetitive alkylation reaction

Electron donating groups are needed as the R groups

because these can stabilize the propagating species by
resonance. Examples:
Example:

Propagation is usually very fast. Therefore, cationic vinyl polymerizations must often
be run at low temperatures. Unfortunately, cooling large reactors is difficult and
expensive. Also, the reaction can be inhibited by water if present in more than trace
amounts, so careful drying of ingredients is necessary (another expense).
Cationic intiators:

Proton acids with unreactive counterions

Lewis acid and other reactive compd.

Chain Transfer Reactions
Cationic vinyl polymerization is plagued by numerous side reactions, most of which lead to
chain transfer. It is difficult to achieve high MW because each initiator can give rise to many
separate chains because of chain transfer. These side reactions can be minimized but not
eliminated by running the reaction at low temperature. Here are a few examples:
examples of commercial cationic polymers
Cationic Polymerization

the alkene monomer

reacts with an electrophile
The carbocation intermediates formed during
polymerization can undergo rearrangement
Monomers that are best able to undergo cationic
polymerization are those with electron-donating
substituents