Stereospecific Polymerization and Copolymerization of Stereoregular PMMA Macromonomers

It is one of the most effective methods for the structural control of comblike polymer and graft polymer to utilize macromonomers. In fact, many papers have been published on utilization of macromonomers for the preparation of comblike polymers and graft polymers with controlled structures1–17). However, few investigations have been reported on the preparation of comblike polymer and graft polymer with high stereoregularity. We have reported the preparation of isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate) (РММА) macromonomers with styrene end group, polymerizations of which give comblike polymers with stereoregular PMMA branches6–11). We have also reported the stereospecific anionic polymerization of polyisobutylene macromonomer having methacryloyl end-func-tion, which afforded comblike polymers with stereoregular main chainI2) The reason why methacryloyl group was selected as a polymerizable function in this case is that the stereoregularity of polymethacrylate can be controlled in a wide range by selecting a proper initiator and polymerization conditions18,19).