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Chinese Journal of Polymer Science

, Volume 31, Issue 1, pp 71–82 | Cite as

Anionic synthesis of a “clickable” middle-chain azidefunctionalized polystyrene and its application in shape amphiphiles

  • Kan Yue
  • Jinlin He
  • Chang Liu
  • Mingjun Huang
  • Xue-Hui Dong
  • Kai Guo
  • Peihong Ni
  • Chrys Wesdemiotis
  • Roderic P. Quirk
  • Stephen Z. D. ChengEmail author
  • Wen-Bin ZhangEmail author
Paper

Abstract

“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 mPS-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.

Keywords

Living anionic polymerization Polyhedral oligomeric silsesquioxane (POSS) “Click” chemistry General functionalization methodology (GFM) 

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Copyright information

© Chinese Chemical Society, Institute of Chemistry, Chinese Academy of Sciences and Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Kan Yue
    • 1
  • Jinlin He
    • 1
    • 2
  • Chang Liu
    • 1
  • Mingjun Huang
    • 1
  • Xue-Hui Dong
    • 1
  • Kai Guo
    • 1
  • Peihong Ni
    • 2
  • Chrys Wesdemiotis
    • 1
    • 3
  • Roderic P. Quirk
    • 1
  • Stephen Z. D. Cheng
    • 1
    Email author
  • Wen-Bin Zhang
    • 1
    Email author
  1. 1.Department of Polymer Science, College of Polymer Science and Polymer EngineeringThe University of AkronAkronUSA
  2. 2.College of Chemistry, Chemical Engineering, and Materials Science, Jiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSoochow UniversitySuzhouChina
  3. 3.Department of ChemistryThe University of AkronAkronUSA

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