Thiol-benzoxazine chemistry as a novel Thiol-X reaction for the synthesis of block copolymers

Musa A., Kışkan B., YAGCI Y.

POLYMER, vol.55, no.22, pp.5550-5556, 2014 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 55 Issue: 22
  • Publication Date: 2014
  • Doi Number: 10.1016/j.polymer.2014.06.076
  • Journal Name: POLYMER
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.5550-5556
  • Istanbul Technical University Affiliated: Yes


A novel synthetic procedure is reported for the preparation of block copolymers by means of successive 1,3-benzoxazine-thiol and Husigen type azide-alkyne coupling methodologies in one-pot and sequential synthesis. The applied 1,3-benzoxazine-thiol process based on catalytic opening of the lateral benzoxazine rings by thiols is proposed as a new thiol-X chemistry. Azide functional poly(methyl acrylate) (PMA-N-3), poly(ethylene glycol) (PEG-N-3) and thiol functional polystyrene (PS-SH) were prepared. The obtained PMA-N-3 or PEG-N-3, PS-SH and propargyl benzoxazine as a click-linker were reacted in sequential or one-pot two step manner to yield desired PS-b-PMA and PS-b-PEG block copolymer. The described thiol-benzoxazine chemistry offers a facile and efficient route to exploring the many possibilities in macromolecular synthesis. (C) 2014 Elsevier Ltd. All rights reserved.