Ring-Opening Metathesis Copolymerization of Cyclopentene Above and Below Its Equilibrium Monomer Concentration

Michael Torre, William D. Mulhearn, Richard A. Register

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Cyclopentene (C) and norbornene (N) may both be enchained by ring-opening metathesis polymerization (ROMP). N homopolymerizes to essential completion, but C has a significant equilibrium monomer concentration, [C]eq = 1.17 m at 30 °C. While C cannot homopolymerize below [C]eq, it can still be enchained in copolymerizations with N. A terminal kinetic model, where one monomer shows depropagation competitive with propagation, well represents experimental data for the “living” ROMP copolymerization of C and N with a Mo-based “Schrock-type” initiator, covering a broad range of monomer feed ratios, both above and below [C]eq. Incorporating a penultimate unit effect on C depropagation increases the model's accuracy when both the monomers are dilute. Below [C]eq, polymerization halts when all N is consumed; above [C]eq, a C homopolymer block forms once all N is consumed. As polycyclopentene may be hydrogenated to linear polyethylene, such copolymerizations offer a facile route to polyethylene-containing block copolymers from a single charge of mixed-monomer feed.

Original languageEnglish (US)
Article number1800030
JournalMacromolecular Chemistry and Physics
Volume219
Issue number9
DOIs
StatePublished - May 2018

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Keywords

  • block copolymers
  • copolymerization
  • living polymerization
  • polymer kinetics
  • ring-opening metathesis polymerization (ROMP)

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