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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.

SUBMITTER: Stubbs CJ

PROVIDER: S-EPMC9264357 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Intrinsically Re-curable Photopolymers Containing Dynamic Thiol-Michael Bonds.

Stubbs Connor J CJ Khalfa Anissa L AL Chiaradia Viviane V Worch Joshua C JC Dove Andrew P AP

Journal of the American Chemical Society 20220624 26

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 ...[more]

PMID: 35749449

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Project description:Step-growth thiol-Michael photopolymerizable resins, constituting an alternative chemistry to the current methacrylate-based chain-growth polymerizations, were developed and evaluated for use as dental restorative materials. The beneficial features inherent to anion-mediated thiol-Michael polymerizations were explored, such as rapid photocuring, low stress generation, ester content tunability, and improved mechanical performance in a moist environment. An ester-free tetrafunctional thiol and a ultraviolet-sensitive photobase generator were implemented to facilitate thiol-Michael photopolymerization. Thiol-Michael resins of varied ester content were fabricated under suitable light activation. Polymerization kinetics and shrinkage stress were determined with Fourier-transform infrared spectroscopy coupled with tensometery measurements. Thermomechanical properties of new materials were evaluated by dynamic mechanical analysis and in 3-point bending stress-strain experiments. Photopolymerization kinetics, polymerization shrinkage stress, glass transition temperature, flexural modulus, flexural toughness, and water sorption/solubility were compared between different thiol-Michael systems and the BisGMA/TEGDMA control. Furthermore, the mechanical performance of 2 thiol-Michael composites and a control composite were compared before and after extensive conditioning in water. All photobase-catalyzed thiol-Michael polymerization matrices achieved >90% conversion with a dramatic reduction in shrinkage stress as compared with the unfilled dimethacrylate control. One prototype of ester-free thiol-Michael formulations had significantly better water uptake properties than the BisGMA/TEGDMA control system. Although exhibiting relatively lower Young's modulus and glass transition temperatures, highly uniform thiol-Michael materials achieved much higher toughness than the BisGMA/TEGDMA control. Moreover, low-ester thiol-Michael composite systems show stable mechanical performance even after extensive water treatment. Although further resin/curing methodology optimization is required, the photopolymerized thiol-Michael prototype resins can now be recognized as promising candidates for implementation in composite dental restorative materials.

Dataset Information

Intrinsically Re-curable Photopolymers Containing Dynamic Thiol-Michael Bonds.

Publications

Intrinsically Re-curable Photopolymers Containing Dynamic Thiol-Michael Bonds.

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