Cationic reactivation polymerization of vinyl monomers

The oationio polymerization of strong π‐donor monomers has been investigated, where initiation takes place with triphenylmethylium picrate and picric acid, respectively. In the case of p‐methoxystyrene the polymerization runs via aggregated species, where monomer and picric acid stabilizes the propagating intermediate state. The transfer‐suppressed polymerization oan be reactivated after monomer consumption. The mechanism of IBVE polymerization runs similar, however, by side reactions double bonds can be introduced into the polymer chains and chains can be terminated by water under formation of aldehyde groups. NVC polymerization proceeds via freely solvated ions, which results in relative broad MWD. The polymerization of NVC and p‐methoxystyrene initiated with cationogenes involving nucleophilic counterions, leads in the presence of AEROSIL to increased molecular weights and narrow distribution, in comparison with the polymerization under same conditions in solution.