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Journal of Polymer Science Part A Polymer Chemistry1.pdf

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Journal of Polymer Science Part A Polymer Chemistry1

Preparation of Miktoarm Star-Block Copolymers PSn-b-PVAc4-n via Combination of ATRP and RAFT Polymerization YANSHENG QIU, WEI ZHANG, YUEFANG YAN, JIAN ZHU, ZHENGBIAO ZHANG, XIULIN ZHU Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China Received 16 June 2010; accepted 12 August 2010 DOI: 10.1002/pola.24317 Published online in Wiley Online Library (). ABSTRACT: Three tetrafunctional bromoxanthate agents (Xan- thate3-Br, Xanthate2-Br2, and Xanthate-Br3) were synthesized. Initiative atom transfer radical polymerizations (ATRP) of sty- rene (St) or reversible addition fragmentation chain transfer (RAFT) polymerizations of vinyl acetate (VAc) proceeded in a controlled manner in the presence of Xanthate3-Br, Xanthate2- Br2, or Xanthate-Br3, respectively. The miktoarm star-block copolymers containing polystyrene (PS) and poly(vinyl acetate) (PVAc) chains, PSn-b-PVAc4-n (n ? 1, 2, and 3), with controlled structures were successfully prepared by successive RAFT and ATRP chain-extension experiments using VAc and St as the second monomers, respectively. The architecture of the mik- toarm star-block copolymers PSn-b-PVAc4-n (n ? 1, 2, and 3) were characterized by gel permeation chromatography and 1H NMR spectra. Furthermore, the results of the cleavage of PS3- b-PVAc and PVAc2-b-PS2 confirmed the structures of the obtained miktoarm star-block copolymers. VC 2010 Wiley Period- icals, Inc. J Polym Sci Part A: Polym Chem 000: 000–000, 2010 KEYWORDS: atom transfer radical polymerization (ATRP); mikto- arm star polymer; radical polymerization; reversible addition fragmentation chain transfer (RAFT); vinyl acetate INTRODUCTION A star polymer is defined as a polymer that consists of multiple linear chains bonded to a junction point.1 Miktoarm star polymers refer to a star polymer, where at least one linear chain is chemically different from others.2 Miktoarm star polymers are