Syntheses and adhesion properties of novel syndiotactic block copolymers of alkyl (meth)acrylate with methacrylic acid and its analogues

Abstract

Block copolymerizations of (1) methyl methacrylate (MMA) with butyl acrylate (BuA), (2) trimethylsilyl methacrylate (TMSMA) with MMA, and (3) TMSMA with BuA were carried out using an organosamarium complex, SmMe(C 5Me 5) 2(THF), as an initiator. All copolymerizations proceeded quantitatively in a short period and the resulting polymers exhibit a high molecular weight ( M n>200 000) with narrow molecular weight distributions ( M w/ M n<1.5). The resulting poly(TMSMA) block in the copolymers was hydrolyzed with aq. HCl solution to afford the corresponding poly(methacrylic acid) block. The viscoelastic and adhesive properties of these block copolymers proved to be very useful, especially in the high temperature range, compared with those obtained using conventional radical initiators.