Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Abstract Defined diblock and triblock copolymers composed of methyl methacrylate‐ co ‐glycidyl methacrylate block and 3‐{3,5,7,9,11,13,15‐hepta(2‐methylpropyl)‐pentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 ]‐octasiloxan‐1‐yl}propyl methacrylate block(s), i.e., P(MMA‐ co ‐GMA)‐ b ‐PiBuPOSSMA and PiBuPOSSMA‐ b ‐P(MMA‐ co ‐GMA)‐ b ‐PiBuPOSSMA, were synthesized by atom transfer radical polymerization (ATRP). First, monofunctional and bifunctional P(MMA‐ co ‐GMA) copolymers were synthesized by ATRP. Subsequently, these copolymers were successfully used as macroinitiators for ATRP of POSS‐containing methacrylate monomer. The process showed high initiation efficiency of macroinitiators and led to products with low dispersity. The synthesized block copolymers were characterized by size exclusion chromatography, 1 H‐NMR spectroscopy and their glass transition temperatures were determined by differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013