Synthesis of end-functionalized poly(methyl methacrylate) by ruthenium-catalyzed living radical polymerization with functionalized initiators

dA series of functionalized 2-bromoisobutyrates and 2-chloro-2-phenylacetates led to alpha-end-functionalized poly(methyl methacrylate)s in Ru(II)-catalyzed living radical polymerization; the terminal functions included amine, hydroxyl, and amide. These initiators were effective in the presence of additives such as Al(Oi-Pr)(3) and n-Bu3N. The chlorophenylacetate initiators especially coupled with the amine additive gave polymers with well-controlled molecular weights (M-w/M-n = 1.2-1.3) and high end functionality (F-n similar to 1.0). (C) 2002 Wiley Periodicals, Inc.