Group transfer polymerization of methyl acrylate in tetrahydrofuran with tetrabutylammonium fluoride trihydrate and tetrabutylammonium cyanide as catalysts

Abstract

AbstractGroup transfer polymerization (GTP) of methyl acrylate (MA) with 1‐methoxy‐1‐propenyloxytrimethylsilane (MTP) as initiator and tetrabutylammonium fluoride trihydrate and tetrabutylammonium cyanide as catalysts in tetrahydrofuran was investigated. Tetrabutylammonium fluoride trihydrate turned out to be absolutely unsuited as GTP catalyst, since its crystal water destroys the initiator and the active centres. Furthermore, in side reactions between the initiator and the catalyst, the concentrations of both are diminished. Tetrabutylammonium cyanide is a powerful catalyst of GTP of MA, leading to complete conversion of the monomer, but initiates an anionic polymerization of MA too, which, however, is of minor importance in the main part of the reaction. Reaction rates may easily be controlled by the catalyst concentration. Number‐average molecular weights are dependent on initiator concentration. They are lower as well as higher than those expected for a really living system, pointing to a rather complicated overall reaction.