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Emulsion polymerization of allyl sulfide copolymers for enhanced molar mass

Polymer Journal (2025)Cite this article

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Abstract

Existing recycling approaches for vinyl-derived polymers, which constitute approximately 50% of global plastic production, rely heavily on energy-intensive incineration and pyrolysis, whereas laboratory-scale chemical recycling is material specific. To enable more universal chemical recyclability in vinyl polymers, ring-opening copolymerization with the cyclic comonomer 3,7-bis(methylene)-1,5-dithiacyclooctane (BMDTO) is an emerging solution that involves the integration of cleavable C–S bonds in the backbone. However, bulk free radical polymerization (FRP) with BMDTO limits the molar mass because of undesired radical transfer, prohibiting access to the desired mechanical properties. In this study, we employ emulsion polymerization to synthesize PS-BMDTO (PSB) copolymers with 1–7 mol% BMDTO. Compared with bulk FRP, size exclusion chromatography reveals that emulsion polymerization yields a greater molar mass (81 kg mol−1 vs. 17 kg mol−1) at 2.4 mol% BMDTO. The incorporation of BMDTO is observed by 1H nuclear magnetic resonance spectroscopy and further confirmed by a chain scission reaction with allyl dithiol. The molar mass of 3.9 mol% PSB decreases from 33 kg mol−1 to 10 kg mol−1, while the molar mass of PS without BMDTO remains unchanged. These results reveal that emulsion polymerization effectively prevents undesired radical transfer and extends radical lifetime, offering a suitable synthesis route for high-performance, recyclable vinyl copolymers.

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Acknowledgements

This work is supported by the Japan Science and Technology Agency (JST) PRESTO, Grant Number JPMJPR22N2, and is partially supported by the 3 M Non-Tenure Faculty Award. Michelle Gross thanks Grace Leone and Eva Morgenthaler at the University of Massachusetts Amherst for their insightful discussions.

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  1. These authors contributed equally: Michelle Gross, Autumn M. Mineo

Authors and Affiliations

  1. Department of Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, MA, USA

    Michelle Gross, Autumn M. Mineo & Reika Katsumata

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  1. Michelle Gross
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  2. Autumn M. Mineo
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  3. Reika Katsumata
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RK directed the research. AM conceived the idea, synthesis procedure, and interpretation. AM and MG performed the experiments. All the authors participated in writing the manuscript.

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Correspondence to Reika Katsumata.

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Gross, M., Mineo, A.M. & Katsumata, R. Emulsion polymerization of allyl sulfide copolymers for enhanced molar mass. Polym J (2025). https://doi.org/10.1038/s41428-025-01086-w

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