Diverse polymers with chemical recyclability via regioirregular polymerization of a single monomer

Nature Materials (2026)Cite this article The development of polymer products with a circular economy lifecycle represents a path to alleviate the growing plastic waste and energy crisis. However, long-standing challenges include synthesis scalability, tunable material performance and the feasibility of chemical recycling from mixed products. Here we developed a facile regioirregular polymerization strategy to access diverse polymer structures from a single monomer via regioselectivity and dynamic covalent bond exchange. We were able to synthesize polyurethanes (PUx, where x represents the percentage of urethane linkages in the polymer) with tailored urethane contents by modulating the reaction time for the regioirregular polymerization of tetramethylene urethane. The resulting PUx products showcase remarkable composition-dependent material performance, illustrating high strength, toughness and gas barriers comparable with commercial plastics. In particular, PU57 exhibits superior adhesive strength, outperforming commercial glues. Notably, these diverse PUx products could be converted back to a single monomer, representing a proof-of-concept process for a ‘single monomer ↔ multiple polymers’ closed loop.This is a preview of subscription content, access via your institution Access Nature and 54 other Nature Portfolio journals Get Nature+, our best-value online-access subscription $32.99 / 30 days cancel any timeSubscribe to this journal Receive 12 print issues and online access $259.00 per yearonly $21.58 per issueBuy this articleUSD 39.95Prices may be subject to local taxes which are calculated during checkoutThe data supporting the findings of this study are provided in the article and the Supplementary Information and are available from the authors upon request.Geyer, R., Jambeck, J. R. & Law, K. L. Production, use, and fate of all plastics ever made. Sci. Adv. 3, e1700782 (2017).Article PubMed PubMed Central Google Scholar Jambeck, J. R. et al. Plastic waste inputs from land into the ocean. Science 347, 768–771 (2015).Article CAS PubMed Google Scholar Mohanty, A. K. et al. Sustainable polymers. Nat. Rev. Methods Primers 2, 46 (2022).Article CAS Google Scholar Vidal, F. et al. Designing a circular carbon and plastics economy for a sustainable future. Nature 626, 45–57 (2024).Article CAS PubMed Google Scholar Jehanno, C. et al. Critical advances and future opportunities in upcycling commodity polymers. Nature 603, 803–814 (2022).Article CAS PubMed Google Scholar Law, K. L. & Narayan, R. Reducing environmental plastic pollution by designing polymer materials for managed end-of-life. Nat. Rev. Mater. 7, 104–116 (2022).Article CAS Google Scholar Zuin, V. G. & Kümmerer, K. Chemistry and materials science for a sustainable circular polymeric economy. Nat. Rev. Mater. 7, 76–78 (2022).Article PubMed PubMed Central Google Scholar De Hoe, G. X., Şucu, T. & Shaver, M. P. Sustainability and polyesters: beyond metals and monomers to function and fate. Acc. Chem. Res. 55, 1514–1523 (2022).Article PubMed PubMed Central Google Scholar Coates, G. W. & Getzler, Y. D. Y. L. Chemical recycling to monomer for an ideal, circular polymer economy. Nat. Rev. Mater. 5, 501–516 (2020).Article CAS Google Scholar Shi, C., Quinn, E. C., Diment, W. T. & Chen, E. Y.-X. Recyclable and (bio)degradable polyesters in a circular plastics economy. Chem. Rev. 124, 4393–4478 (2024).Article CAS PubMed Google Scholar Sun, Y. et al. New sustainable polymers with on-demand depolymerization property. Sci. China Chem. 67, 2803–2841 (2024).Article CAS Google Scholar Bo, Q. & Xi, Z. On depolymerization. CCS Chem. 6, 297–312 (2024).Article Google Scholar Haque, F. M. et al. Defining the macromolecules of tomorrow through synergistic sustainable polymer research. Chem. Rev. 122, 6322–6373 (2022).Article CAS PubMed Google Scholar Hong, M. & Chen, E. Y.-X. Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nat. Chem. 8, 42–49 (2016).Article CAS PubMed Google Scholar Zhu, J.-B., Watson, E. M., Tang, J. & Chen, E. Y.-X. A synthetic polymer system with repeatable chemical recyclability. Science 360, 398–403 (2018).Article CAS PubMed Google Scholar Tu, Y.-M., Gong, F.-L., Wu, Y.-C., Cai, Z. & Zhu, J.-B. Insights into substitution strategy towards thermodynamic and property regulation of chemically recyclable polymers. Nat. Commun. 14, 3198 (2023).Article CAS PubMed PubMed Central Google Scholar Sathe, D. et al. Olefin metathesis-based chemically recyclable polymers enabled by fused-ring monomers. Nat. Chem. 13, 743–750 (2021).Article CAS PubMed Google Scholar Kariyawasam, L. S., Rolsma, J. & Yang, Y. Chemically recyclable dithioacetal polymers via reversible entropy-driven ring-opening polymerization. Angew. Chem. Int. Ed. 62, e202303039 (2023).Article CAS Google Scholar Meng, X.-B. et al. Thermally stable and chemically recyclable poly(ketal-ester)s regulated by floor temperature. J. Am. Chem. Soc. 146, 15428–15437 (2024).Article CAS PubMed Google Scholar Abel, B. A., Snyder, R. L. & Coates, G. W. Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals. Science 373, 783–789 (2021).Article CAS PubMed Google Scholar Xiong, W. et al. Geminal dimethyl substitution enables controlled polymerization of penicillamine-derived β-thiolactones and reversed depolymerization. Chem 6, 1831–1843 (2020).Article CAS Google Scholar Su, Y.-L. et al. Chemically recyclable polymer system based on nucleophilic aromatic ring-opening polymerization. J. Am. Chem. Soc. 145, 13950–13956 (2023).Article CAS PubMed PubMed Central Google Scholar Sullivan, K. P. et al. Mixed plastics waste valorization through tandem chemical oxidation and biological funneling. Science 378, 207–211 (2022).Article CAS PubMed Google Scholar Shi, C., Diment, W. & Chen, E. Y.-X. Closed-loop recycling of mixed plastics of polyester and CO2-based polycarbonate to a single monomer. Angew. Chem. Int. Ed. 63, e202405083 (2024).Article CAS Google Scholar Si, G. & Chen, C. Cyclic–acyclic monomers metathesis polymerization for the synthesis of degradable thermosets, thermoplastics and elastomers. Nat. Synth. 1, 956–966 (2022).Article CAS Google Scholar Elsayed, R. & Teow, Y. H. Advanced functional polymer materials for biomedical applications. J. Appl. Polym. Sci. 142, e56391 (2025).Article CAS Google Scholar Westerman, C. R., McGill, B. C. & Wilker, J. J. Sustainably sourced components to generate high-strength adhesives. Nature 621, 306–311 (2023).Article CAS PubMed Google Scholar Feist, J. D., Lee, D. C. & Xia, Y. A versatile approach for the synthesis of degradable polymers via controlled ring-opening metathesis copolymerization. Nat. Chem. 14, 53–58 (2022).Article CAS PubMed Google Scholar Sulley, G. S. et al. Switchable catalysis improves the properties of CO2-derived polymers: poly(cyclohexene carbonate-b-ε-decalactone-b-cyclohexene carbonate) adhesives, elastomers, and toughened plastics. J. Am. Chem. Soc. 142, 4367–4378 (2020).Article CAS PubMed PubMed Central Google Scholar Fu, X.-Y. et al. A powerful strategy for synthesizing block copolymers via bimetallic synergistic catalysis. Angew. Chem. Int. Ed. 63, e202401926 (2024).Article CAS Google Scholar Guo, Y.-T. et al. Closed-loop recyclable aliphatic poly(ester-amide)s with tunable mechanical properties. Macromolecules 55, 4000–4010 (2022).Article CAS Google Scholar Rapagnani, R. M., Dunscomb, R. J., Fresh, A. A. & Tonks, I. A. Tunable and recyclable polyesters from CO2 and butadiene. Nat. Chem. 14, 877–883 (2022).Article CAS PubMed Google Scholar Sha, Y. et al. Biorenewable and circular polyolefin thermoplastic elastomers. Nat. Commun. 15, 8480 (2024).Article CAS PubMed PubMed Central Google Scholar Dreiling, R. J., Huynh, K. & Fors, B. P. Degradable thermosets via orthogonal polymerizations of a single monomer. Nature 638, 120–125 (2025).Article CAS PubMed Google Scholar Shi, C., Clarke, R. W., McGraw, M. L. & Chen, E. Y.-X. Closing the ‘one monomer–two polymers–one monomer’ loop via orthogonal (de)polymerization of a lactone/olefin hybrid. J. Am. Chem. Soc. 144, 2264–2275 (2022).Article CAS PubMed Google Scholar Stößer, T., Mulryan, D. & Williams, C. K. Switch catalysis to deliver multi-block polyesters from mixtures of propene oxide, lactide, and phthalic anhydride. Angew. Chem. Int. Ed. 57, 16893–16897 (2018).Article Google Scholar Zhou, Z., LaPointe, A. M., Shaffer, T. D. & Coates, G. W. Nature-inspired methylated polyhydroxybutyrates from C1 and C4 feedstocks. Nat. Chem. 15, 856–861 (2023).Article CAS PubMed Google Scholar Wang, M.-Y. et al. High-performance recyclable polymers enabled by stereo- and sequence-controlled polymerization. Nat. Chem. 17, 1119–1128 (2025).Article CAS PubMed Google Scholar Kloxin, C. J., Scott, T. F., Adzima, B. J. & Bowman, C. N. Covalent adaptable networks (CANs): a unique paradigm in cross-linked polymers. Macromolecules 43, 2643–2653 (2010).Article CAS PubMed PubMed Central Google Scholar Wojtecki, R. J., Meador, M. A. & Rowan, S. J. Using the dynamic bond to access macroscopically responsive structurally dynamic polymers. Nat. Mater. 10, 14–27 (2011).Article CAS PubMed Google Scholar Pal, S. et al. Recyclable surgical, consumer, and industrial adhesives of poly(α-lipoic acid). Science 385, 877–883 (2024).Article CAS PubMed Google Scholar Li, L., Peng, X., Zhu, D., Zhang, J. & Xiao, P. Recent progress in polymers with dynamic covalent bonds. Macromol. Chem. Phys. 224, 2300224 (2023).Article CAS Google Scholar Zheng, N., Xu, Y., Zhao, Q. & Xie, T. Dynamic covalent polymer networks: a molecular platform for designing functions beyond chemical recycling and self-healing. Chem. Rev. 121, 1716–1745 (2021).Article CAS PubMed Google Scholar Scheutz, G. M., Lessard, J. J., Sims, M. B. & Sumerlin, B. S. Adaptable crosslinks in polymeric materials: resolving the intersection of thermoplastics and thermosets. J. Am. Chem. Soc. 141, 16181–16196 (2019).Article CAS PubMed Google Scholar Lei, Z. et al. New advances in covalent network polymers via dynamic covalent chemistry. Chem. Rev. 124, 7829–7906 (2024).Article CAS PubMed Google Scholar Kušan, J., Keul, H. & Höcker, H. Cationic ring-opening polymerization of tetramethylene urethane. Macromolecules 34, 389–395 (2001).Article Google Scholar Du, Y. et al. Highly regioselective ring-opening polymerization of an asymmetric diester. Macromolecules 57, 11476–11487 (2024).Article CAS Google Scholar Qiu, W. & Tang, X. Regioselective ring-opening polymerization of asymmetric cyclic dimers for polyester-based alternating copolymers. Chem. Eur. J. 31, e02142 (2025).Article CAS PubMed Google Scholar Hardy, C., Kociok-Köhn, G. & Buchard, A. Variations around the presence and position of sulfur in sugar-derived cyclic monomers: influence on polymerisation thermodynamics, polymer sequence and thermal properties. Polym. Chem. 14, 623–632 (2023).Article CAS Google Scholar Han, C.-T. et al. Circular polymer designed by regulating entropy: spiro-valerolactone-based polyesters with high gas barriers and adhesion strength. J. Am. Chem. Soc. 147, 4511–4519 (2025).Article CAS PubMed Google Scholar Chen, L. et al. Selective, catalytic oxidations of C–H Bonds in polyethylenes produce functional materials with enhanced adhesion. Chem 7, 137–145 (2021).Article CAS Google Scholar Huang, R. et al. Microconfinement effect on gas barrier and mechanical properties of multilayer rigid/soft thermoplastic polyurethane films. J. Appl. Polym. Sci. 132, 41849 (2015).Article Google Scholar Ni, Y. et al. One-step fabrication of ultrathin porous Janus membrane within seconds for waterproof and breathable electronic skin. Sci. Bull. 70, 712–721 (2025).Article Google Scholar Download referencesThis work was supported by the National Key R&D Program of China (2021YFA1501700), the National Natural Science Foundation of China (22301197 and 22371194) and the Fundamental Research Funds from Sichuan University (2023SCUNL103). We thank P.-C. Deng, D. Deng and J. Li for compound testing.These authors contributed equally: Hua-Zhong Fan, Jia-An-Qi Zhou, Yi-Min Tu.National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), State Key Laboratory of Advanced Polymer Materials, College of Chemistry, Sichuan University, Chengdu, People’s Republic of ChinaHua-Zhong Fan, Jia-An-Qi Zhou, Yi-Min Tu, Jia-Hao Chen, Jun-Ming Liu, Zhongzheng Cai & Jian-Bo ZhuSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarJ.-B.Z. conceived the project. Z.C. and J.-B.Z. directed the research. H.-Z.F., J.-A.-Q.Z. and Y.-M.T designed and conducted experiments related to monomer synthesis, polymer synthesis, polymer characterizations and depolymerization. J.-H.C. and J.-M.L. conducted experiments related to monomer and polymer synthesis. Z.C. and J.-B.Z. wrote the initial paper. All authors contributed to data analysis and discussions and to paper revision.Correspondence to Zhongzheng Cai or Jian-Bo Zhu.J.-B.Z., Z.C., J.-A.-Q.Z. and H.-Z.F. are inventors on China patent application 202511895019.1, submitted by Sichuan University, which covers the synthetic strategy of polymers with diverse functional linkages. The other authors declare no competing interests.Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.Supplementary Text, Figs. 1–90, Scheme 1 and Tables 1–23.Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.Reprints and permissionsFan, HZ., Zhou, JAQ., Tu, YM. et al. Diverse polymers with chemical recyclability via regioirregular polymerization of a single monomer. Nat. Mater. (2026). https://doi.org/10.1038/s41563-026-02498-6Download citationReceived: 08 July 2025Accepted: 15 January 2026Published: 12 February 2026Version of record: 12 February 2026DOI: https://doi.org/10.1038/s41563-026-02498-6Anyone you share the following link with will be able to read this content:Sorry, a shareable link is not currently available for this article. Provided by the Springer Nature SharedIt content-sharing initiative