Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs.

Chemoselective, living/controlled polymerizations of allyl methacrylate (AMA) and vinyl methacrylate (VMA) with/without methyl methacrylate (MMA) by using the phosphonium ylide/organoaluminum based Lewis pairs (LPs) have been realized. The P-ylide-2/AlMe(BHT)₂ (P-ylide-2 = Ph₃P=CHMe and BHT = 2,6-iBu₂-4-MeC₆H₂O) was demonstrated to be superior by which homopolymers PAMAs (M_n=27.6–111.5 kg/mol and Đ=1.14–1.25) and PVMAs (M_n=28.4–78.4 kg/mol and Đ=1.12–1.18) and block copolymers PMMA-b-PAMA, PAMA-b-PVMA, PAMA-b-PMMA, PMMA-b-PAMA-b-PMMA, PAMA-b-PMMA-b-PAMA, and PAMA-b-PVMA-b-PAMA were synthesized. In the polymerizations, all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups. The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical "thiol-ene" reaction using PhCH₂SH. The thiolether side group-containing polymers PAMA-SCH₂Ph and PAMA-SCH₂Ph-b-PMMA-b-PAMA-SCH₂Ph were thus prepared. [ABSTRACT FROM AUTHOR]