Chromium Complexes Supported by Salen-Type Ligands for the Synthesis of Polyesters, Polycarbonates, and Their Copolymers through Chemoselective Catalysis

Int J Mol Sci. 2023 Apr 21;24(8):7642. doi: 10.3390/ijms24087642.

Abstract

Salen, Salan, and Salalen chromium (III) chloride complexes have been investigated as catalysts for the ring-opening copolymerization reactions of cyclohexene oxide (CHO) with CO2 and of phthalic anhydride (PA) with limonene oxide (LO) or cyclohexene oxide (CHO). In the production of polycarbonates, the more flexible skeleton of salalen and salan ancillary ligands favors high activity. Differently, in the copolymerization of phthalic anhydride with the epoxides, the salen complex showed the best performance. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures from mixtures of CO2, cyclohexene oxide, and phthalic anhydride with all complexes. In addition, all chromium complexes were revealed to be very active in the chemical depolymerization of polycyclohexene carbonate producing cyclohexene oxide with high selectivity, thus offering the opportunity to close the loop on the life of these materials.

Keywords: CO2 fixation; block copolymers; chromium (III) catalysts; depolymerization; polycarbonates; polyesters.

MeSH terms

  • Carbon Dioxide / chemistry
  • Carbonates
  • Catalysis
  • Chromium / chemistry
  • Ligands
  • Organometallic Compounds* / chemistry
  • Phthalic Anhydrides*
  • Polyesters
  • Polymers / chemistry

Substances

  • cyclohexene oxide
  • polycarbonate
  • disalicylaldehyde ethylenediamine
  • phthalic anhydride
  • Phthalic Anhydrides
  • Polyesters
  • Carbon Dioxide
  • Organometallic Compounds
  • Ligands
  • Polymers
  • Chromium
  • Carbonates

Grants and funding

The authors are grateful for the funding from the Università degli Studi di Salerno (FARB grants).