Radical Ring Opening Polymerization of Cyclic Ketene Acetals Derived From d-Glucal

Craig Hardy; Martin E. Levere; Gabriele Kociok-Köhn; Antoine Buchard

doi:10.1021/acsmacrolett.3c00397

Radical Ring Opening Polymerization of Cyclic Ketene Acetals Derived From d-Glucal

Craig Hardy, Martin E. Levere, Gabriele Kociok-Köhn, Antoine Buchard

Department of Chemistry/Dynamic Reaction Monitoring Facility/Institute for Sustainability, University of Bath, UK

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

4 Citations (SciVal)

Abstract

A cyclic ketene acetal (CKA) derived from d-glucal was synthesized, and its polymerization using free radicals has been investigated. NMR analysis of the resulting polymers revealed the formation of polyacetal-polyester copolymers, with up to 78% of ester linkages formed by radical ring-opening polymerization (rROP). Conversely, the polymerization of the monomer-saturated analogue only produced acetal linkages, demonstrating that the alkene functionality within the d-glucal pyranose ring is essential to promote ring-opening and ester formation, likely via the stabilization of an allyl radical. The thermal properties of the polymers were linked to the ratio of the ester and acetal linkages. Copolymerization with methyl methacrylate (MMA) afforded statistically PMMA-rich copolymers (66-98%) with linkages prone to hydrolytic degradation and decreased glass-transition temperatures. The retention of the pseudoglucal alkene function offers opportunities to functionalize further these bioderived (co)polymers.

Original language	English
Pages (from-to)	1443-1449
Number of pages	7
Journal	ACS Macro Letters
Volume	12
Issue number	11
Early online date	12 Oct 2023
DOIs	https://doi.org/10.1021/acsmacrolett.3c00397
Publication status	Published - 21 Nov 2023

Bibliographical note

Funding: The Royal Society: (UF\160021 and URF\R\221027, fellowship to A.B.; RGF\EA\201023; RGF\EA\180028, studentship to C.H.).

Funding

We thank the Royal Society (UF\160021, fellowship to A.B.; RGF\EA\201023; RGF\EA\180028, studentship to C.H.) for research funding. Analytical facilities were provided through the Material and Chemical Characterization Facility (MC2) at the University of Bath. We also thank Dr. Catherine Lyall for facilitating the acquisition of the quantitative NMR spectroscopic data. We thank the Royal Society (UF\160021, fellowship to A.B.; RGF\EA\201023; RGF\EA\180028, studentship to C.H.) for research funding. Analytical facilities were provided through the Material and Chemical Characterization Facility (MC) at the University of Bath. We also thank Dr. Catherine Lyall for facilitating the acquisition of the quantitative NMR spectroscopic data. 2

Funders	Funder number
Royal Society	RGF\EA\201023, UF\160021, RGF\EA\180028
University of Bath

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title = "Radical Ring Opening Polymerization of Cyclic Ketene Acetals Derived From d-Glucal",

abstract = "A cyclic ketene acetal (CKA) derived from d-glucal was synthesized, and its polymerization using free radicals has been investigated. NMR analysis of the resulting polymers revealed the formation of polyacetal-polyester copolymers, with up to 78% of ester linkages formed by radical ring-opening polymerization (rROP). Conversely, the polymerization of the monomer-saturated analogue only produced acetal linkages, demonstrating that the alkene functionality within the d-glucal pyranose ring is essential to promote ring-opening and ester formation, likely via the stabilization of an allyl radical. The thermal properties of the polymers were linked to the ratio of the ester and acetal linkages. Copolymerization with methyl methacrylate (MMA) afforded statistically PMMA-rich copolymers (66-98%) with linkages prone to hydrolytic degradation and decreased glass-transition temperatures. The retention of the pseudoglucal alkene function offers opportunities to functionalize further these bioderived (co)polymers.",

author = "Craig Hardy and Levere, {Martin E.} and Gabriele Kociok-K{\"o}hn and Antoine Buchard",

note = "Funding: The Royal Society: (UF\160021 and URF\R\221027, fellowship to A.B.; RGF\EA\201023; RGF\EA\180028, studentship to C.H.).",

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N2 - A cyclic ketene acetal (CKA) derived from d-glucal was synthesized, and its polymerization using free radicals has been investigated. NMR analysis of the resulting polymers revealed the formation of polyacetal-polyester copolymers, with up to 78% of ester linkages formed by radical ring-opening polymerization (rROP). Conversely, the polymerization of the monomer-saturated analogue only produced acetal linkages, demonstrating that the alkene functionality within the d-glucal pyranose ring is essential to promote ring-opening and ester formation, likely via the stabilization of an allyl radical. The thermal properties of the polymers were linked to the ratio of the ester and acetal linkages. Copolymerization with methyl methacrylate (MMA) afforded statistically PMMA-rich copolymers (66-98%) with linkages prone to hydrolytic degradation and decreased glass-transition temperatures. The retention of the pseudoglucal alkene function offers opportunities to functionalize further these bioderived (co)polymers.

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Radical Ring Opening Polymerization of Cyclic Ketene Acetals Derived From d-Glucal

Abstract

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