Issue 22, 2022

Metallocene catalysts for the ring-opening co-polymerisation of epoxides and cyclic anhydrides

Abstract

The ring-opening co-polymerisation (ROCOP) of epoxides and cyclic anhydrides is a versatile route to new polyesters. The vast number of monomers that are readily available means that an effectively limitless number of unique polymeric materials can be prepared using a common synthetic route, thereby paving the way to polymers that are more recyclable and could be used in applications that currently lie exclusively within the remit of polyolefins. Metallocene complexes [Cp2MCl2] (M = Ti, Zr, Hf, Cp = η5-C5H5) are known to be excellent pre-catalysts for olefin polymerisation and yet have not been reported for ROCOP, despite their supreme pedigree in the polymerisation realm. Herein, we report the first application of [Cp2MCl2] as catalysts for the ROCOP of epoxides and anhydrides and show that they are effective catalysts for this reaction. The catalytic performances are good with standard epoxides such as cyclohexene oxide but are excellent with more challenging sterically demanding limonene oxide, and this therefore represents a highly effective catalyst system for the preparation of bio-derived recyclable polymers.

Graphical abstract: Metallocene catalysts for the ring-opening co-polymerisation of epoxides and cyclic anhydrides

Supplementary files

Article information

Article type
Paper
Submitted
17 Mar 2022
Accepted
13 May 2022
First published
16 May 2022
This article is Open Access
Creative Commons BY license

Polym. Chem., 2022,13, 3315-3324

Metallocene catalysts for the ring-opening co-polymerisation of epoxides and cyclic anhydrides

M. S. Shaw, M. R. Bates, M. D. Jones and B. D. Ward, Polym. Chem., 2022, 13, 3315 DOI: 10.1039/D2PY00335J

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