Intrinsically Re-curable Photopolymers Containing Dynamic Thiol-Michael Bonds

J Am Chem Soc. 2022 Jul 6;144(26):11729-11735. doi: 10.1021/jacs.2c03525. Epub 2022 Jun 24.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes
  • Polymers* / chemistry
  • Sulfhydryl Compounds* / chemistry
  • Sulfides

Substances

  • Alkenes
  • Polymers
  • Sulfhydryl Compounds
  • Sulfides