Versatile Synthesis of Multiarm and Miktoarm Star Polymers with a Branched Core by Combination of Menschutkin Reaction and Controlled Polymerization
作者：Meijing Zhang, Huanhuan Liu, Wei Shao, Chunnuan Ye, and Youliang Zhao*
關鍵字：Star Polymers, Menschutkin Reaction.
論文來源：期刊
具體來源：Macromolecules
發(fā)表時間：2012年
http://pubs.acs.org/doi/abs/10.1021/ma301973v?prevSearch=meijing%2Bzhang&searchHistoryKey
Menschutkin reaction and controlled polymerization were combined to construct three types of star polymers with a branched core. Branched PVD was synthesized by reversible addition−fragmentation chain transfer (RAFT) copolymerization and used as a core reagent to synthesize multiarm and miktoarm stars with poly(ε-caprolactone) (PCL), polystyrene, poly(methyl methacrylate), poly(tert-butyl acrylate), and poly(N-isopropylacrylamide) segments. E?ects of reaction time, feed ratio, and arm length on coupling reaction between PVD and bromide-functionalized polymer were investigated, and a variety of Am-type stars (m ≈ 7.0−35.1) were obtained. Meanwhile, AmBn stars (m ≈ 9.0, n ≈ 6.1−11.3) were achieved by successive Menschutkin reactions, and AmCo stars (m ≈ 8.8−9.0, o ≈ 5.0) were generated by tandem quaternization and RAFT processes. Molecular weights of various stars usually agreed well with the theoretical values, and their polydispersity indices were in the range of 1.06−1.24. The arm number, chain length, and chemical composition of star polymers could be roughly adjusted by control over reaction conditions and utilization of alternative methods, revealing the generality and versatility of these approaches. These ion-bearing stars were liable to exhibit solubility di?erent from normal covalently bonded polymers, and the chain relaxation and melting behaviors of polymer segments were strongly dependent on the macromolecular architecture.