Synthesis of Poly(vinyl acetate) and Poly(vinyl alcohol) Containing Block Copolymers by Combination of Cobalt-Mediated Radical Polymerization and ATRP

Abstract

Poly(vinyl acetate) (PVAc) chains of a low polydispersity ( M w / M n ∼ 1.1−1.2) have been prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc). They have been end-capped by an activated bromide by addition of an α-bromoester or an α-bromoketone containing nitroxide and converted into effective macroinitiators for the atom transfer radical polymerization of styrene (Sty), ethyl acrylate, and methyl methacrylate. Because each block is formed by a controlled process, well-defined PVAc containing diblock copolymers are easily prepared. The PVAc- b -PS copolymers synthesized from α-bromoketone end-capped PVAc can be converted into well-defined poly(vinyl alcohol)- b -polystyrene amphiphiles by methanolysis of the poly(vinyl acetate) block. Self-association of an amphiphilic poly(vinyl alcohol)(3500)- b -polystyrene(16 600) in a (4/1) water/tetrahydrofuran mixture results in the formation of vesicles as observed by transmission electron microscopy.