Farmer, T. J. orcid.org/0000-0002-1039-7684, Macquarrie, D. J. orcid.org/0000-0003-2017-7076, Comerford, J. W. orcid.org/0000-0002-9977-5695 et al. (2 more authors) (2018) Insights into post-polymerisation modification of bio-based unsaturated itaconate and fumarate polyesters via aza-michael addition : Understanding the effects of CC isomerisation. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY. pp. 1935-1945. ISSN 0887-624X
Abstract
Development of renewable bio-based unsaturated polyesters is undergoing a renaissance, typified by the use of itaconate and fumarate monomers. The electron-deficient CC bond found on the corresponding polyesters allows convenient post-polymerisation modification to give a wide range of polymer properties; this is notably effective for the addition of nucleophilic pendants. However, preservation of unsaturated functionality is blighted by two undesirable side-reactions, branching/crosslinking and CC isomerisation. Herein, a tentative kinetic study of diethylamine addition to model itaconate and fumarate diesters highlights the significance of undesirable CC isomerisation. In particular, it shows that reversible isomerisation from itaconate to mesaconate (a poor Michael acceptor) is in direct competition with aza-Michael addition, where the amine Michael donor acts as an isomerisation catalyst. We postulate that undesired formation of mesaconate is responsible for the long reaction times previously reported for itaconate polyester post-polymerisation modification. This study illustrates the pressing need to overcome this issue of CC isomerisation to enhance post-polymerisation modification of bio-based unsaturated polyesters.
Metadata
Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018, The Authors. | ||||
Keywords: | Biopolymers, renewable polymers, functionalization of polymers, monomers, oligomers and telechelics, polycondensation, resins | ||||
Dates: |
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Institution: | The University of York | ||||
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) | ||||
Funding Information: |
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Depositing User: | Pure (York) | ||||
Date Deposited: | 29 May 2018 13:40 | ||||
Last Modified: | 01 Feb 2024 00:28 | ||||
Published Version: | https://doi.org/10.1002/pola.29079 | ||||
Status: | Published | ||||
Refereed: | Yes | ||||
Identification Number: | https://doi.org/10.1002/pola.29079 | ||||
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Filename: Farmer_et_al_2018_Journal_of_Polymer_Science_Part_A_3A_Polymer_Chemistry.pdf
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Licence: CC-BY 2.5