Cationic Chain-Growth Polymerization

Polymerization of isobutylene (2-methylpropene) by traces of strong acids is an example of cationic polymerization. The polyisobutylene product is a soft rubbery solid, Tg = ^_70º C, which is used for inner tubes. This process is similar to radical polymerization, as demonstrated by the following equations. Chain growth ceases when the terminal carbocation combines with a nucleophile or loses a proton, giving a terminal alkene (as shown here).

Monomers bearing cation stabilizing groups, such as alkyl, phenyl or vinyl can be polymerized by cationic processes. These are normally initiated at low temperature in methylene chloride solution. Strong acids, such as HClO4 , or Lewis acids containing traces of water (as shown above) serve as initiating reagents. At low temperatures, chain transfer reactions are rare in such polymerizations, so the resulting polymers are cleanly linear (unbranched).