Effect of type of catalyst on structure of poly(β‐vinyloxyethyl methacrylate)

Infrared analysis and glass transition temperature measurements on the polymers obtained from β‐vinyloxyethyl methacrylate with stannic chloride (cationic) and titanium tetrachloride–triisobutyl aluminum (Ziegler‐type) catalysts indicate that these polymers have essentially the same structure, comprising a polyvinyl ether backbone with pendant methacrylatoethyl groups. The polymer obtained with lithium–tributylamine (anionic) catalyst has a different structure involving a methacrylate backbone with vinyloxyethyl pendant groups. These data suggest that in the polymerization of this monomer with the Ziegler‐type catalyst the mechanism of polymerization is cationic. Polymerization with triethylboron gives a crosslinked material similar in structure to the peroxide‐catalyzed polymer.