ANIONIC SYNTHESIS OF A “CLICKABLE” MIDDLE-CHAIN AZIDE-FUNCTIONALIZED POLYSTYRENE AND ITS APPLICATION IN SHAPE AMPHIPHILES

作     者：Kan Yue Jinlin He Chang Liu Mingjun Huang Xue-Hui Dong Kai Guo Peihong Ni Chrys Wesdemiotis Roderic P. Quirk Stephen Z. D. Cheng Wen-Bin Zhang 

作者机构：Department of Polymer ScienceCollege of Polymer Science and Polymer EngineeringThe University of Akron College of ChemistryChemical Engineeringand Materials ScienceJiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSoochow University Department of ChemistryThe University of Akron 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2013年第31卷第1期

页      面：71-82页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070305[理学-高分子化学与物理] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：Direct For Mathematical & Physical Scien Division Of Materials Research Funding Source: National Science Foundation 

主　　题：Living anionic polymerization Polyhedral oligomeric silsesquioxane (POSS) "Click" chemistry Generalfimctionalization methodology (GFM). 

摘      要：＂Click chemistry＂ is, by definition, a general functionalization methodology （GFM） and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis. This paper reports the synthesis of a ＂clickable＂ middle-chain azide-functionalized polystyrene （mPS-N3） by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane （POSS）. The mPS-N3 was synthesized by coupling living poly（styryl）lithium chains （PSLi） with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide. Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography. The raPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential ＂click＂ strategy. The copper（I）-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative （VPOSS-alkyne） ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain （mPS-VPOSS）. The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls, resulting in an amphiphilic shape amphiphile, mPS-DPOSS. This synthetic approach is highly efficient and modular. It demonstrates the ＂click＂ philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile ＂clickable＂ motif in polymer science for the precise synthesis of complex macromolecules.