• cationic polymerization;
  • Lewis acid;
  • chain-end functionality;
  • poly(vinyl ether)s


N-Methyleneamines, formed by treating 1,3,5-trimethylhexahydro-1,3,5-triazines with Lewis acids, have been shown to be capable initiators in the cationic polymerization of tert-butyl vinyl ether, yielding polymers with amine functionality at the chain ends. Previous work was limited to titanium(IV) chloride (TiCl4) as the Lewis acid in dichloromethane solvent at 0 °C (with resulting polymers possessing relatively broad polydispersity index (PDI) values near 2), while this contribution details the effect of reaction parameters on the polymeric products; specifically, the role of temperature, solvent, Lewis acid and additives. Ultimately, performing the polymerization at −78 °C in dichloromethane with TiCl4 as the Lewis acid and tetra-n-butylammonium chloride (nBu4NCl) as the additive afforded the best control over the system, with polymers formed possessing low PDI values (<1.2). Dramatic changes in number-average molecular weight and PDI were observed in polymers formed by initiating systems of Lewis acid-induced N-methyleneamines, with temperature, solvent, Lewis acid and additives all playing a role. By varying single parameters, optimization of the system was achieved. Copyright © 2009 Society of Chemical Industry