Macromonomers of acrylates by group transfer polymerization

Bifunctional initiators for group transfer polymerization (GTP) were prepared, substituted by a vinyl, 2‐propyl, isoprenyl (2‐methylene‐3‐butenyl) or 4‐vinylphenyl group at the ketene acetal CC double bond. All initiators initiated GTP of methyl methacrylate in tetrahydrofuran with tris(piperdino)sulfonium bifluoride or tetrabutylammonium cyanide as catalysts to yield macromonomers with low polydispersities. It is recommended to perform GTP as the first step, since the silyl groups of the initiators give side reactions with active species of other polymerization systems. Macromonomers from isoprenyl ‐ or 4‐vinylphenyl‐substituted initiators could be radically copolymerized with styrene to yield graft copolymers. The copolymerization of acrylic macromonomers derived from the other two initiators has yet to be established.