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Synthesis of well-defined star-branched polymers by stepwise iterative methodology using living anionic polymerization
Authors:Tomoya Higashihara  Mayumi HayashiAkira Hirao
Affiliation:a Division of Polymer Chemistry, Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, H-120, 2-12-1 O-okayama, Meguro-Ku, Tokyo 152-8552, Japan
b Division of Soft Materials Chemistry, Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, H-127, 2-12-1 O-okayama, Meguro-Ku, Tokyo 152-8552, Japan
Abstract:This article reviews the synthesis of regular and asymmetric star-branched polymers with well-defined structures by methodologies using living anionic polymerization, especially focusing on the synthetic approaches accessible for precisely controlled architectures of star-branched polymers concerning molecular weight, molecular weight distribution, arm number, and composition. The reason for selecting living anionic polymerization from many living/controlled polymerization systems so far developed is that this living polymerization system is still the best to meet the strict requirements for the precise structures of star-branched polymers. Furthermore, we herein mainly introduce a novel and quite versatile stepwise iterative methodology recently developed by our group for the successive synthesis of many-armed and multi-compositional asymmetric star-branched polymers. The methodology basically involves only two sets of the reaction conditions for the entire iterative synthetic sequence. The reaction sequence can be, in principle, limitlessly iterated to introduce a definite number of the same or different polymer segments at each stage of the iteration. As a result, a wide variety of many-armed and multi-compositional asymmetric star-branched polymers can be synthesized.
Keywords:NCA  N-Carboxyanhydrides  PA  Polyacetylene  DVB  Divinylbenzene  RLi  Alkyllithium  PS  Polystyrene  PI  Polyisoprene  PB  Polybutadiene  MMA  Methyl methacrylate  EO  Ethylene oxide  PMMA  Poly(methyl methacrylate)  PEO  Poly(ethylene oxide)  PSLi  Polystyryllithium  PS-SiCl2  Chain-end-SiCl2-functionalized PS  PBLi  Polybutadienyllithium  PILi  Polyisoprenyllithium  PI-SiCl2  Chain-end-SiCl2-functionalized PI  PI-SiCl-PS  In-chain-SiCl-functionalized diblock copolymer of PI and PS  DPE  1  1-Diphenylethylene  PDMS  Poly(dimethylsiloxane)  tBMA  tert-Butyl methacrylate  PtBMA  Poly(tert-butyl methacrylate)  PαMSLi  Poly(α-methylstyryl)lithium  2VP  2-Vinylpyridine  P2VP  Poly(2-vinylpyridine)  PEE  Poly(ethylethylene)  PFPO  Poly(perfluoropropylene oxide)  PIB  Polyisobutylene  PMEVE  Poly(methyl vinyl ether)  PIB-Fu  Chain-end-2-furan-functionalized PIB  BnX  Benzyl halide  BnBr  Benzyl bromide  BnCl  Benzyl chloride  ATRP  Atom transfer radical polymerization  NMP  Nitroxy-mediated polymerization  RAFT  Reversible addition-fragmentation chain transfer  PCL  Poly(?-caprolactone)  PTHF  Poly(tetrahydrofuran)  SMP  3-tert-Butyldimethylsilyloxymethylphenyl  PMSLi  Poly(4-methylstyryl)lithium  PMSiSLi  Poly(4-trimethylsilylstyryl)lithium  PMOSLi  Poly(4-methoxystyryl)lithium  PBMSiOSLi  Poly(3-tert-butyldimethylsilyloxystyryl)lithium  Bd  1  3-Butadiene  PS-(Bd)n  Chain-end-(Bd)n-functionalized (PS)s  Anh  Anhydride  PS(BnBr)n  Chain-end-(BnBr)n-functionalized PS  PVS  Phenyl vinyl sulfoxide  MPVS  4-Methylphenyl vinyl sulfoxide  PMPVS  Poly(4-methylphenyl vinyl sulfoxide)
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