Intrinsically re-curable photopolymers containing dynamic thiol-Michael bonds

Connor Stubbs; Anissa Khalfa; Viviane Chiaradia; Josh Worch; Andrew Dove

doi:10.1021/jacs.2c03525

Intrinsically re-curable photopolymers containing dynamic thiol-Michael bonds

Connor Stubbs, Anissa Khalfa, Viviane Chiaradia, Josh Worch, Andrew Dove

Chemistry

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Abstract

The development of photopolymers that can be depolymerized and subsequently re-cured using the same light stimulus presents a significant technical challenge. A bio-sourced terpenoid structure, l-carvone, inspired the creation of a re-curable photopolymer in which the orthogonal reactivity of an irreversible thioether and a dynamic thiol-Michael bond enables both photopolymerization and thermally driven depolymerization of mechanically robust polymer networks. The di-alkene containing l-carvone was partially reacted with a multi-arm thiol to generate a non-crosslinked telechelic photopolymer. Upon further UV exposure, the photopolymer crosslinked into a mechanically robust network featuring reversible Michael bonds at junction points that could be activated to revert, or depolymerize, the network into a viscous telechelic photopolymer. The regenerated photopolymer displayed intrinsic re-curability over two recycles while maintaining the desirable thermomechanical properties of a conventional network: insolubility, resistance to stress relaxation, and structural integrity up to 170 °C. Our findings present an on-demand, re-curable photopolymer platform based on a sustainable feedstock.

Original language	English
Pages (from-to)	11729–11735
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	144
Issue number	26
Early online date	24 Jun 2022
DOIs	https://doi.org/10.1021/jacs.2c03525
Publication status	Published - 6 Jul 2022

Bibliographical note

Funding Information:
A.P.D., J.C.W., and C.J.S. acknowledge the funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program under the grant agreement no. 681559. A.K. acknowledges the funding from the University of Birmingham. V.C. acknowledges the funding from Unilever.

Keywords

photopolymer
l-carvone
Michael bonds
telechelic

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10.1021/jacs.2c03525Licence: Creative Commons: Attribution (CC BY)

StubbsC2022IntrinsicallyFinal published version, 2.71 MBLicence: Creative Commons: Attribution (CC BY)

H2020_ERC_STEREOPOL
Dove, A. (Principal Investigator)
European Commission
1/01/18 → 30/04/23
Project: EU

Cite this

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title = "Intrinsically re-curable photopolymers containing dynamic thiol-Michael bonds",

abstract = "The development of photopolymers that can be depolymerized and subsequently re-cured using the same light stimulus presents a significant technical challenge. A bio-sourced terpenoid structure, l-carvone, inspired the creation of a re-curable photopolymer in which the orthogonal reactivity of an irreversible thioether and a dynamic thiol-Michael bond enables both photopolymerization and thermally driven depolymerization of mechanically robust polymer networks. The di-alkene containing l-carvone was partially reacted with a multi-arm thiol to generate a non-crosslinked telechelic photopolymer. Upon further UV exposure, the photopolymer crosslinked into a mechanically robust network featuring reversible Michael bonds at junction points that could be activated to revert, or depolymerize, the network into a viscous telechelic photopolymer. The regenerated photopolymer displayed intrinsic re-curability over two recycles while maintaining the desirable thermomechanical properties of a conventional network: insolubility, resistance to stress relaxation, and structural integrity up to 170 °C. Our findings present an on-demand, re-curable photopolymer platform based on a sustainable feedstock.",

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N2 - The development of photopolymers that can be depolymerized and subsequently re-cured using the same light stimulus presents a significant technical challenge. A bio-sourced terpenoid structure, l-carvone, inspired the creation of a re-curable photopolymer in which the orthogonal reactivity of an irreversible thioether and a dynamic thiol-Michael bond enables both photopolymerization and thermally driven depolymerization of mechanically robust polymer networks. The di-alkene containing l-carvone was partially reacted with a multi-arm thiol to generate a non-crosslinked telechelic photopolymer. Upon further UV exposure, the photopolymer crosslinked into a mechanically robust network featuring reversible Michael bonds at junction points that could be activated to revert, or depolymerize, the network into a viscous telechelic photopolymer. The regenerated photopolymer displayed intrinsic re-curability over two recycles while maintaining the desirable thermomechanical properties of a conventional network: insolubility, resistance to stress relaxation, and structural integrity up to 170 °C. Our findings present an on-demand, re-curable photopolymer platform based on a sustainable feedstock.

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Intrinsically re-curable photopolymers containing dynamic thiol-Michael bonds

Abstract

Bibliographical note

Keywords

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Projects

H2020_ERC_STEREOPOL

Cite this