Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane

Thomas M. Mcguire; Ella F. Clark; Antoine Buchard

doi:10.1021/acs.macromol.1c00365

Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane

Thomas M. Mcguire
, Ella F. Clark
, Antoine Buchard

Research output: Contribution to journal › Article › peer-review

36 Citations (SciVal)

294 Downloads (Pure)

Abstract

A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit a broad range of glass-transition temperatures (Tg 60–145 °C). These polyesters are amenable to further postpolymerization functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addition experiments.

Original language	English
Pages (from-to)	5094-5105
Number of pages	12
Journal	Macromolecules
Volume	54
Issue number	11
Early online date	18 May 2021
DOIs	https://doi.org/10.1021/acs.macromol.1c00365
Publication status	Published - 8 Jun 2021

Funding

Analytical facilities were provided through the Material and Chemical Characterisation Facility (MC) at the University of Bath. The authors thank the University of Bath HPC for computing resources, and the UK EPSRC and the University of Bath (EP/N022793/1, DTP studentship for T.M.M.), as well as the Royal Society (RG/150538, UF/160021 fellowship to A.B., RGF\R1\180036 studentship to E.F.C.), for research funding. Prof. Charlotte K. Williams and Gregory S. Sulley are thanked for the provision of the dinuclear catalysts and for useful discussions when preparing the manuscript. 2

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

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10.1021/acs.macromol.1c00365

McGuire et al_manuscript_revision_ACCEPTED.PDF
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.1c00365
Accepted author manuscript, 1.37 MB

Catalysis as an Enabling Science for Sustainable Sugar-based Polymers
Buchard, A. (PI)
The Royal Society
1/03/20 → 30/09/25
Project: Research council
A functional xylose polymer platform for sustainable plastics and biomaterials
Buchard, A. (PI)
The Royal Society
1/10/18 → 30/09/25
Project: Research council
UR Fellowship - Sugar-based Polymers for a New Generation of Sustainable Materials
Buchard, A. (PI)
The Royal Society
1/10/17 → 30/09/22
Project: Research council

Cite this

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title = "Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane",

abstract = "A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100\% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit a broad range of glass-transition temperatures (Tg 60{\textendash}145 °C). These polyesters are amenable to further postpolymerization functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addition experiments.",

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N2 - A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit a broad range of glass-transition temperatures (Tg 60–145 °C). These polyesters are amenable to further postpolymerization functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addition experiments.

AB - A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit a broad range of glass-transition temperatures (Tg 60–145 °C). These polyesters are amenable to further postpolymerization functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addition experiments.

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Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane

Abstract

Funding

UN SDGs

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Projects

Catalysis as an Enabling Science for Sustainable Sugar-based Polymers

A functional xylose polymer platform for sustainable plastics and biomaterials

UR Fellowship - Sugar-based Polymers for a New Generation of Sustainable Materials

Cite this