Quadruple click reactions for the synthesis of cysteine-functional heterograft brush copolymer


Candan O. A. , Kopan D., Durmaz H. , Hızal G. , Tunca Ü.

EUROPEAN POLYMER JOURNAL, vol.49, no.7, pp.1796-1802, 2013 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 49 Issue: 7
  • Publication Date: 2013
  • Doi Number: 10.1016/j.eurpolymj.2013.03.035
  • Title of Journal : EUROPEAN POLYMER JOURNAL
  • Page Numbers: pp.1796-1802

Abstract

The quadruple click reactions, thiol-ene, copper catalyzed azide-alkyne cycloaddition (CuAAC), Diels-Alder cycloaddition, and nitroxide radical coupling (NRC) reactions were successfully employed for the synthesis of cysteine-functional heterograft brush copolymer. An equimolar mixture of oxanorbornenyl-anthracene (ONB-anthracene), oxanorbomenyl-bromide (ONB-Br), and oxanorbomenyl tosylate (ONB-OTs) was polymerized via ring opening metathesis polymerization (ROMP) using the first generation Grubbs' catalyst in CH2Cl2 at room temperature to form poly(ONB-anthracene-co-ONB-Br-co-ONB-OTs)(10) copolymer as a main backbone. Next, this main backbone was first reacted with N-acetyl-L-cysteine methyl-ester via radical thiol-ene click reaction and then sequentially clicked with a furan protected maleimide-terminated poly(methyl methacrylate) (PMMA(20)-MI), and 2,2,6,6-tetramethyl-1-piperidinyloxy-terminated poly(ethylene glycol)(PEG(13)-TEMPO), alkyne-terminated poly(epsilon-caprolactone) (PCL28-alkyne) via Diels-Alder, and NRC/CuAAC reactions, respectively to yield a cysteine-functional poly(ONB-g-PMMA-co-ONB-g-PEG-co-ONB-g-PCL)(10) heterograft brush copolymer. (c) 2013 Elsevier Ltd. All rights reserved.