Cited by 151Polymer crystallization and propertiesAdvanced Polymer Synthesis and CharacterizationPolymer composites and self-healing

Cleavable Comonomers for Chemically Recyclable Polystyrene: A General Approach to Vinyl Polymer Circularity

Kiel, Gavin R., Lundberg, David J., Prince, Elisabeth, Husted, Keith E. L., Johnson, Alayna M., Lensch, Valerie, Li, Sipei, Shieh, Peyton +1 more·2022·Journal of the American Chemical Society

Abstract

Many common polymers, especially vinyl polymers, are inherently difficult to chemically recycle and are environmentally persistent. The introduction of low levels of cleavable comonomer additives into existing vinyl polymerization processes could facilitate the production of chemically deconstructable and recyclable variants with otherwise equivalent properties. Here, we report thionolactones that serve as cleavable comonomer additives for the chemical deconstruction and recycling of vinyl polymers prepared through free radical polymerization, using polystyrene (PS) as a model example. Deconstructable PS of different molar masses (∼20-300 kDa) bearing varied amounts of statistically incorporated thioester backbone linkages (2.5-55 mol %) can be selectively depolymerized to yield well-defined thiol-terminated fragments (<10 kDa) that are suitable for oxidative repolymerization to generate recycled PS of nearly identical molar mass to the parent material, in good yields (80-95%). A theoretical model is provided to generalize this molar mass memory effect. Notably, the thermomechanical properties of deconstructable PS bearing 2.5 mol % of cleavable linkages and its recycled product are similar to those of virgin PS. The additives were also shown to be effective for deconstruction of a cross-linked styrenic copolymer and deconstruction and repolymerization of a polyacrylate, suggesting that cleavable comonomers may offer a general approach toward circularity of many vinyl (co)polymers.

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Crossref · 10.1021/jacs.2c05374

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Authors
Kiel, G. R., Lundberg, D. J., Prince, E., Husted, K. E. L., Johnson, A. M., Lensch, V., Li, S., Shieh, P., & Johnson, J. A.
Affiliations
Massachusetts Institute of Technology (US)
Corresponding author
Johnson, Jeremiah A.
Venue
Journal of the American Chemical Society
Published
2022-06-28
Volume
144
Issue
28
Pages
12979-12988
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W4283702232
Cited by
151
References
38
Citations by year
2026: 32 · 2025: 35 · 2024: 33 · 2023: 41 · 2022: 10
FWCI
9.55
Type
journal article
Language
en
Open access
closed
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
Funders
  • Massachusetts Institute of Technology
  • Arnold and Mabel Beckman Foundation
  • American Cancer Society
  • Natural Sciences and Engineering Research Council of Canada
  • National Science Foundation
Topics
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer composites and self-healing
Keywords
chemically recyclable polymers, polystyrene, thionolactones, thioester linkage, selective depolymerization, circular economy, vinyl polymers, polyacrylate, thermomechanical properties
MeSH terms
Molecular Weight, Polymers, Polystyrenes, Vinyl Compounds, Polymerization

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