Synthesis of novel random and block copolymers of tert-butyldimethylsilyl methacrylate and methyl methacrylate by RAFT polymerization

Hydrophobic-hydrolysable copolymers consisting of methyl methacrylate (MMA) and tert-butyldimethylsilyl methacrylate (TBDMSMA) have been synthesized for the first time by Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization technique using cumyl dithiobenzoate (CDB) and cyanoisopropyl dithiobenzoate (CPDB) as chain transfer agents (CTAs). The monomer reactivity ratios for TBDMSMA (r1 = 1.40 ± 0.03) and MMA (r2 = 1.08 ± 0.03) have been determined using a non-linear least-squares fitting method. Well-defined random copolymers PMMA-co-PTBDMSMA have been prepared. Then, the versatility of the RAFT process to synthesize silylated block copolymers with controlled molecular weights and low polydispersities has been demonstrated using two strategies: the synthesis of PMMA-SC(S)Ph or PTBDMSMA-SC(S)Ph as macro-chain transfer agent (macro-CTA) for use in a two step method or an one-pot method which consists in the successive addition of the two monomers. Diblock copolymers with narrow molecular weight distributions (PDI < 1.2) were obtained from the one-pot method with number-average molecular weight values within the range 10,000-22,000 g mol−1.