Efficient polymerization and post-modification of N- substituted eight-membered cyclic carbonates containing allyl groups

Research output: Contribution to journalArticlepeer-review

Authors

  • Alexander Y. Yuen
  • Amaury Bossion
  • Antonio Veloso
  • David Mecerreyes
  • James L. Hedrick
  • Haritz Sardon

Colleges, School and Institutes

External organisations

  • University of the Basque Country
  • University of Bordeaux
  • Ikerbasque - Basque Foundation for Science
  • IBM Research - Almaden

Abstract

Aliphatic polycarbonates are promising materials in the biomedical field due to their low toxicity, biocompatibility, and biodegradability. A popular approach in obtaining these materials is through the organocatalyzed ring-opening polymerization (ROP) of cyclic carbonates. Functional polycarbonates can be obtained by (co)polymerizing allyl-functional cyclic monomers, which can be chemically modified via radical thiol-ene click reactions after the ROP process. To date, allyl-bearing 6-membered cyclic carbonates have been reported, however their polymerization kinetics are slow. In previous works, larger cyclic carbonates (e.g. N-substituted eight membered cyclic carbonates) have demonstrated superior reactivities over their smaller counterparts and hence, in this work, we investigated the preparation and ROP of two allyl bearing N-substituted eight membered cyclic carbonates. One of these monomers, with a pendent carbamate group, displayed substantially enhanced polymerization kinetics that allowed for efficient homopolymerizations and co-polymerizations with commercially available monomers (e.g. trimethylene carbonate, or TMC). Lastly, the polymers underwent almost quantitative post-polymerization modification via thiol-ene chemistry to yield different functionalized polycarbonates. We also demonstrated that the post-polymerization reaction could be used to form polycarbonate-based gels with multifunctional thiols.

Details

Original languageEnglish
Pages (from-to)2458-2467
Number of pages10
JournalPolymer Chemistry
Volume9
Issue number18
Early online date27 Mar 2018
Publication statusPublished - 14 May 2018