Polyethylene-g-poly(cyclohexene oxide) by Mechanistic Transformation from ROMP to Visible Light-Induced Free Radical Promoted Cationic Polymerization

Ciftci M., KORK S., XU G., BUCHMEISER M. R., Yagci Y.

MACROMOLECULES, vol.48, no.6, pp.1658-1663, 2015 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 48 Issue: 6
  • Publication Date: 2015
  • Doi Number: 10.1021/acs.macromol.5b00086
  • Journal Name: MACROMOLECULES
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1658-1663
  • Istanbul Technical University Affiliated: No

Abstract

A novel polymerization mechanism transformation strategy, combining ring-opening metathesis polymerization (ROMP) and visible light induced cationic polymerization, is successfully applied for the synthesis of polyethylene-graft-poly(cyclohexene oxide) (PE-g-PCHO). First, cis-cyclooctene (COE) was polymerized via ROMP in the presence of a chain transfer agent and quantitatively hydrobrominated to give bromo functional polyethylene (PE-Br). Subsequent irradiation of PE-Br in the visible range using dimanganese decacarbonyl (Mn-2(CO)(10)) and diphenyl iodonium hexafluorophosphate (Ph2I+PF6) as radical generator and oxidant, respectively, initiated cationic polymerization of cyclohexene oxide (CHO) resulting in the formation of PE-g-PCHO. The effect of irradiation time and Mn-2(CO)(10) concentration on the grafting density and efficiency was evaluated. Both the precursor polymers and the corresponding graft copolymers were characterized by H-1 NMR and Fourier transform infrared (FT-IR) spectroscopy, gel-permeation chromatography (GPC), and differential scanning calorimetric (DSC) analyses.