Living carbocationic polymerization. 55. Living polymerization of indene

The cationic polymerization of indene (In) has been investigated using the 2-chloro-2,4,4-trimethylpentane(TMPCl)/TiCl sub(4) initiating system and a methyl chloride-methylcyclohexane solvent mixture at - 80 degree C. According to kinetic studies, initiation is slow relative to propagation. The quantitative treatment of slow initiation in living carbocationic polymerization applied to this system led to the conclusion that this polymerization is living and the rate-determining step is cationation. Functionally analysis by a chloride-selective electrode indicates that the end groups of polyindene (PIn) are secondary chlorines. The electron donors, N,N-dimethylacetamide (DMA) and hexamethylphosphoramide (HMPA), do not affect the polymerizations.