Highly efficient access to well-defined linear polymers with substantial vinyl pendants via ATRP of divinyl monomers

Abstract

Reported herein is a highly efficient access to well-defined linear polymers with substantial vinyl pendants via activators generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) of dissymmetric divinyl monomers by side armed bisoxazoline (SaBOX)/copper catalysts. High conversions (>90%) of the divinyl monomers allyl methacrylate (AMA) and vinyl methacrylate (VMA) without gelation through ATRP were realized with a relatively high concentration ratio of monomer to initiator in feed ([M]₀/[I]₀ ≥ 100), yielding completely soluble homopolymers with relatively high molecular weights and narrow molecular weight distributions (M_n's = 1.49–3.69 × 10⁴, Đ's = 1.2–2.0). Besides, random MMA copolymers with different amounts of pendant vinyl groups (18–54 mol%) were conveniently obtained by employing AMA or VMA as the comonomer.