Issue 29, 2022

Chain end-group selectivity using an organometallic Al(iii)/K(i) ring-opening copolymerization catalyst delivers high molar mass, monodisperse polyesters

Abstract

Polyesters are important plastics, elastomers and fibres; efficient and selective polymerizations making predictable, high molar mass polymers are required. Here, a new type of catalyst for the ring-opening polymerization (ROCOP) of epoxides and anhydrides combines unusually high chain end-group selectivity, fast rates, and good molar mass control. The organometallic heterodinuclear Al(III)/K(I) complex, applied with a diol, is tolerant to a range of epoxides/phthalic anhydride and produces only α,ω-hydroxyl telechelic polyesters with molar masses from 6–91 kg mol−1, in all cases with monomodal distributions. As proof of its potential, high molar mass poly(vinyl cyclohexene oxide-alt-phthalic anhydride) (91 kg mol−1) shows 5× greater flexural strain at break (εb = 3.7%) and 9× higher maximum flexural stress (σf = 72.3 MPa) than the previously accessed medium molar mass samples (24 kg mol−1). It is also enchains phthalic anhydride, vinyl cyclohexene oxide and ε-decalactone, via switchable catalysis, to make high molar mass triblock polyesters (81 kg mol−1, Đ = 1.04). This selective catalyst should be used in the future to qualify the properties of these ROCOP polyesters and to tune (multi)block polymer structures.

Graphical abstract: Chain end-group selectivity using an organometallic Al(iii)/K(i) ring-opening copolymerization catalyst delivers high molar mass, monodisperse polyesters

Supplementary files

Article information

Article type
Edge Article
Submitted
17 may 2022
Accepted
10 iyn 2022
First published
13 iyl 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 8543-8549

Chain end-group selectivity using an organometallic Al(III)/K(I) ring-opening copolymerization catalyst delivers high molar mass, monodisperse polyesters

W. T. Diment and C. K. Williams, Chem. Sci., 2022, 13, 8543 DOI: 10.1039/D2SC02752F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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