Polymers from sugars and isothiocyanates: ring-opening copolymerization of a D-xylose anhydrosugar oxetane

Ella F. Clark, Gabriele Kociok-Köhn, Matthew G. Davidson, Antoine Buchard

Research output: Contribution to journalArticlepeer-review

3 Citations (SciVal)

Abstract

A d-xylose 3,5-anyhydrosugar (d-Ox) has been applied in the ring-opening copolymerisation (ROCOP) with isothiocyanates to form alternating AB-type copolymers with imidothiocarbonate linkages (M n ≥ 34 900 g mol −1). Catalysed by an Al(iii)-based aminotrisphenolate complex, ROCOP proceeds with high selectivity with four aromatic isothiocyanates, including di-isothiocyanates used for crosslinking, to form thermally robust polymers (T d,5% >228 °C) with a range of high glass-transition temperatures (76-134 °C). Kinetic studies show a reaction order of two with respect to the binary catalytic system, and a first order with respect to d-Ox. When using an Al(iii) porphyrin complex as catalyst, the reactivity can be tailored to form exclusively a non-polymerisable cyclic thionocarbamate byproduct. The topology, thermal and physical properties of the polymer could be altered by adding a difunctional isothiocyanate crosslinker. The synthesis of di and triblock copolymers was possible by using difunctional (macro)initiators and by exploiting the living character of the ROCOP process, which allowed chain-extension by the ring-opening polymerisation (ROP) of lactide. The polymers readily degrade under acidic and basic conditions. Photodegradation without additives is also possible with an 85% decrease in molar mass in one week. The potential of the imidothiocarbonate linkages for metal capture has been investigated, and good affinity for Cu 2+ ions is seen.

Original languageEnglish
Pages (from-to)2838-2847
Number of pages10
JournalPolymer Chemistry
Volume14
Issue number23
Early online date22 May 2023
DOIs
Publication statusPublished - 22 May 2023

Bibliographical note

The authors thank the Royal Society (UF/160021 and URF\R\221027: fellowship to A. B., RGF\R1\180036 studentship to E. F. C.) for research funding.

Electronic supplementary information (ESI) available: Experimental procedures; catalyst screening data; spectroscopic and crystallographic data for C1; SEC traces, spectroscopic (NMR,MALDI-ToFMS) and thermal (TGA,DSC) data for the polymers; degradation and metal coordination data. CCDC2253111. For ESI and crystallographic data in CIF or other electronic format see DOI:https:// doi.org/10.1039/d3py00443k

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