SET-LRP of Methyl Methacrylate Initiated with Sulfonyl Halides

Single electron transfer-living radical polymerization (SET-LRP) represents a robust and versatile method for the rapid synthesis of macromolecules with defined architecture. The present article describes the polymerization of methyl methacrylate by SET-LRP in protic solvent mixtures. Herein, the polymerization process was catalyzed by a straightforward Cu(0)wire/Me-6-TREN catalyst while initiation was obtained by toluenesulfonyl chloride. All experiments were conducted at 50 degrees C and the living polymerization was demonstrated by kinetic evaluation of the SET-LRP. The process follows first order kinetic until all monomer is consumed which was typically achieved within 4 h. The molecular weight increased linearly with conversion and the molecular weight distributions were very narrow with M-w/M-n similar to 1.1. Detailed investigations of the polymer samples by MALDI-TOF confirmed that no termination took place and that the chain end functionality is retained throughout the polymerization process. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2236-2242, 2010