Next Generation of Zinc Bisguanidine Polymerization Catalysts towards Highly Crystalline, Biodegradable Polyesters

Angew Chem Int Ed Engl. 2020 Nov 23;59(48):21778-21784. doi: 10.1002/anie.202008473. Epub 2020 Oct 22.

Abstract

Polylactide and polycaprolactone are both biodegradable polymers produced through metal-catalyzed ring-opening polymerization. For a truly sustainable lifecycle of these polymers it is essential to replace the industrially used cytotoxic catalyst tin(II) bis(2-ethylhexanoate) [Sn(Oct)2 ] with non-toxic alternatives. Here, we report the fastest known robust catalyst in the polymerization of lactide and ϵ-caprolactone. This zinc guanidine catalyst can polymerize non-purified technical rac-lactide and ϵ-caprolactone in the melt at different [M]/[I] ratios with fast rate constants, high molar masses, and high yields in a short time, leading to colorless, transparent polymer. Moreover, we report that polylactide and polycaprolactone produced by zinc-guanidine complexes have favorably high crystallinities. In fact, the obtained polylactide shows a more robust degradation profile than its Sn(Oct)2 -catalysed equivalent due to a higher degree of crystallinity.

Keywords: bioplastic; crystallinity; polylactide; ring-opening polymerization; zinc.

MeSH terms

  • Coordination Complexes / chemical synthesis
  • Coordination Complexes / chemistry*
  • Guanidine / chemistry*
  • Molecular Structure
  • Polyesters / chemical synthesis*
  • Polyesters / chemistry
  • Polymerization
  • Zinc / chemistry*

Substances

  • Coordination Complexes
  • Polyesters
  • polycaprolactone
  • poly(lactide)
  • Zinc
  • Guanidine