ISOMERIZATION OF SILYL KETENE ACETALS - MODELS FOR THE PROPAGATING CHAIN END IN GROUP TRANSFER POLYMERIZATION

The rate of E/Z isomerization for the propagating end in group transfer polymerization (GTP) of methyl methacrylate (MMA) is comparable to the rate of propagation for bifluoride catalysis, in contrast to bibenzoate catalysis where propagation is faster. Methyl 2,2,4-trimethyl-5-methoxy-5-(trimethylsiloxy)pent-4-enoate, 4 (the product of the initiation step in the GTP of MMA), was used as the model of the GTP living end. The rate of monomer addition to 4 was independent of the starting E/Z isomer ratio. The observation of random tacticity in the polymers prepared via anionically catalyzed GTP can be adequately explained by comparable rates of E/Z isomerization and propagation or in the case of bibenzoate catalysis, by the assumption that E and Z propagating ends react with similar stereochemistry. Silyl ketene acetal 2 (a model of the polyacrylate propagating end) underwent HgI2 catalyzed E/Z isomerization at a rate comparable to the polymerization of ethyl acrylate.