Synthesis of graft copolymers. III. Polystyrene‐ g ‐poly(butyl acrylate)

Polystyrene (PS) chains functionalized with pendant 1,2‐bis(trimethylsilyloxy)tetraphenylethane (TPSE) groups are used as macroinitiators to initiate the polymerization of n ‐butyl acrylate (BuA) to synthesize PS‐ g ‐poly(BuA) (PS‐ g ‐PBuA) copolymers at 130°C. The TPSE groups are known to function as initers in the polymerization of several vinyl monomers. The homolytic decomposition of TPSE results in a diphenylmethyl (DPM) radical attached to the main chain and a free DPM radical. The former is responsible for the polymerization initiation and the latter momentarily stops the growth of the growing grafts by the formation of a dormant species. Unfortunately, side reactions like the combination between growing grafts take place and the polymerization can only be controlled in a limited range of conversion. The most appropriate conditions for the synthesis of PS‐ g ‐PBuA are reported to present their potential use as thermoplastic elastomers with relatively controlled structures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 19–26, 2002