Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis

Macromol Rapid Commun. 2014 Feb;35(4):484-91. doi: 10.1002/marc.201300809. Epub 2013 Dec 13.

Abstract

Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment.

Keywords: biodegradable; block copolymer; kinetics (polym.); living polymerization; nitroxide-mediated polymerization (NMP).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylonitrile / chemistry
  • Ethylenes / chemistry
  • Ketones / chemistry
  • Magnetic Resonance Spectroscopy
  • Methacrylates / chemistry
  • Methylmethacrylate / chemistry
  • Nitrogen Oxides / chemistry*
  • Phosphorus / chemistry
  • Polymerization
  • Polymers / chemical synthesis
  • Polymers / chemistry*

Substances

  • Ethylenes
  • Ketones
  • Methacrylates
  • Nitrogen Oxides
  • Polymers
  • Methylmethacrylate
  • Phosphorus
  • nitroxyl
  • ketene
  • Acrylonitrile