Group transfer polymerization of methyl methacrylate and methyl acrylate in tetrahydrofuran with tris(piperidino)sulfonium bifluoride as catalyst

Abstract

AbstractGroup transfer polymerization of methyl methacrylate and methyl acrylate with (1‐methoxy‐2‐methyl‐1‐propenyloxy)trimethylsilane and (1‐methoxy‐1‐propenyloxy)trimethylsilane as initiators, respectively, and tris(piperidino)sulfonium bifluoride as catalyst in tetrahydrofuran as solvent was investigated. While the former system nearly behaves like a living system, in the latter system side reactions between the active centres and the catalyst are of greater importance and limit monomer conversion in some cases. The character of the side reactions could be revealed by NMR and GC/MS measurements. Number‐average molecular weights and polydispersities, as determined by gel permeation chromatography, show that tailoring of polymers with definite chain lengths and relatively narrow molecular weight distributions is only possible in the methyl methacrylate system. Reaction rates were proven to be very high, even at very low catalyst concentrations. Therefore, with respect to isothermicity in an industrial reactor, tris(piperidino)‐sulfonium bifluoride seems to be too active as catalyst in group transfer polymerization.