Abstract: Two solid vinyl ether terminated aliphatic urethanes, named PUE1 and PUE2, were synthesized and characterized. PUE1 is a crystalline compound with a melting point of 101 ℃; PUE2 is a prepolymer with glass transition temperatures of 30.8 and 17.2 ℃. Both compounds undergo rapid thermal polymerization in the presence of diphenyliodonium hexafluorophosphate(PI810) at different temperatures. The thermal polymerization temperatures for these systems are much lower than the thermal decomposition temperature of neat PI810. The initiation mechanism is presumably based on the electron transfer from electron-rich vinyl ether to electron-dificient diphenyliodonium salt, forming an intermediate charge transfer complex, which can undergo rapid electron transfer or decompose to give radical-cationic vinyl ether or protonic acid, both of which are responsible for the initiation of vinyl ether cationic polymerization.

Key words: Urethane vinyl ether, Diphenyliodonium hexafluorophosphate, Thermal polymerization, Cationic polymerization