Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne "click" chemistry


Alkayal N., DURMAZ H. , Tunca Ü. , HADJICHRISTIDIS N.

POLYMER CHEMISTRY, vol.7, no.17, pp.2986-2991, 2016 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 7 Issue: 17
  • Publication Date: 2016
  • Doi Number: 10.1039/c6py00331a
  • Title of Journal : POLYMER CHEMISTRY
  • Page Numbers: pp.2986-2991

Abstract

Novel well-defined polyethylene-based graft terpolymers were synthesized via the "grafting onto" strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "click" chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(epsilon-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of epsilon-caprolactone using PE-OH as a macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) "click" linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (H-1 NMR) and differential scanning calorimetry (DSC).