Studies on the polymerization of methyl methacrylate using ylide as an initiator and degradative transfer agent

Abstract

The polymerization of methyl methacrylate (MMA) initiated by α‐picolinium‐p‐chlorophenacylide in CCl4 at 30, 35, and 40°C for four h was investigated dilatometrically. The orders of reaction with respect to the concentrations of ylide and MMA are 0.22 ± 0.01 and 1.0, respectively. The overall energy of activation and an average value of k p2/kt are 21.0 kJmol−1 and 0.37 ± 10−2, respectively. The results are explained in terms of radical mode of polymerization with initiator dependent transfer besides bimolecular termination.

Strained Azetidinium Ylides: New Reagents for Cyclopropanation

“…Attempts to isolate compound 45 were unsatisfactory, all resulting in impure material. Ylide-induced polymerizations of acrylate derivatives have been reported, but the factor governing this change of reactivity between the cyano- and ester-stabilized ylides is rather unclear. The deprotonation step is hardly in question, since the respective p K a values are virtually equal as extrapolated from cyano- or ester-substituted methylenetrimethylammonium salts 12 (p K a of 20.6 in DMSO for both ammoniums).…”