Cleavable Comonomers for Chemically Recyclable Polystyrene: A General Approach to Vinyl Polymer Circularity
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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The rROP approach requires delicate design of the cyclic monomer to achieve high reactivity and to control the ratio of ring-opened and cyclic structures.
“However, the rROP approach requires delicate design of the cyclic monomer to achieve high reactivity and to control the ratio of ring-opened and cyclic structures.”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [28]
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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.
- ORCID
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- 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
- Licence
- 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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