Arenesulfonyl iodides: The third universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates and styrenes

Abstract

Abstract The metal‐catalyzed living radical polymerization of methyl methacrylate and styrene initiated with freshly prepared p ‐toluenesulfonyl iodide (TsI) and catalyzed with CuX/2,2′‐bipyridine (bpy), where X is Cl, Br, or I, and various self‐regulated copper‐based catalytic systems, such as copper/bpy, copper(I) oxide/bpy, copper(I) sulfide/bpy, copper(I) selenide/bpy, and copper(I) telluride/bpy, is reported. The exchange of CI into CBr and CCl takes place when the living radical polymerization of methyl methacrylate is catalyzed by copper(I) bromide/bpy and copper(I) chloride/bpy, respectively. Therefore, the use of the TsI initiator facilitates the synthesis, starting from a single initiator, of poly(methyl methacrylate) containing CI, CBr, and CCl chain ends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3920–3931, 2005