Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters
RESEARCH ARTICLE|Updated:2026-08-19
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Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters
Chinese Journal of Polymer ScienceVol. 44, Pages: 1-10(2026)
Affiliations:
a.MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, China
b.College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China
c.Key Laboratory of Medical Electronics and Digital Health of Zhejiang Province, Jiaxing University, Jiaxing 314001, China
Zhang, Z. R.; Bai, T. W.; Li, S. H.; Shen, T.; Zeng, J. J.; Chen, K. H.; Ling, J.; Ni, X. F. Chemoselective ring-opening copolymerization of CO2-based lactones towards functional polyesters. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3759-6
Zhuo-Rui Zhang, Tian-Wen Bai, Sheng-Hao Li, et al. Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10. DOI: 10.1007/s10118-026-3759-6.
Zhang, Z. R.; Bai, T. W.; Li, S. H.; Shen, T.; Zeng, J. J.; Chen, K. H.; Ling, J.; Ni, X. F. Chemoselective ring-opening copolymerization of CO2-based lactones towards functional polyesters. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3759-6DOI:
Zhuo-Rui Zhang, Tian-Wen Bai, Sheng-Hao Li, et al. Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10. DOI: 10.1007/s10118-026-3759-6.DOI:
Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters
A novel synthetic method towards recyclable polyesters rich in double bonds is highly desirable yet remains a considerable challenge.
α
-Ethylidene-
δ
-vinyl-
δ
-valerolactone (EVL)
a lactone derived from CO
2
and butadiene
is an attractive intermediate for the production of sustainable and functional copolymers. However
its anionic ring-opening polymerization (ROP) is significantly impeded by undesired conjugate addition of the tiglate groups. This study presents the chemoselective and controlled ring-opening copolymerization (ROCP) of EVL with
α
-(1-(alkylthio)ethyl)-
δ
-vinyl-
δ
-valerolactones (ATEVL)
which are derivatives of EVL and thiols
utilizing 1
5
7-triazabicyclo[4.4.0
]
dec-5-ene (TBD) as the catalyst. Conducted at temperatures ranging from –20 °C to 20 °C
the copolymerizations achieved 100% ROP selectivity with an initial EVL monomer content of less than 40 mol%. The resulting polyesters have number average molecular weights (
M
n
) between 3.8 and 11.0 kg/mol
low dispersities (
Đ
=1.15–1.28)
and preserve intact conjugated double bonds. The obtained copolymers can be modified by Michael addition and light-induced thio-ene click reactions to produce polyesters with various functional groups. A transparent polyester network was formed upon UV-induced crosslinking
exhibiting considerable shear strength and fluorescence properties
making it a promising candidate for use as a fluorescent photocuring adhesive. This method provides a convenient approach to achieve the chemoselective ROCP of
EVL
enabling the synthesis of linear CO
2
-based polyesters with numerous sites for post-polymerization modification.
关键词
Keywords
references
Tang, X.; Chen, E. Y.-X. Toward infinitely recyclable plastics derived from renewable cyclic esters. Chem 2019 , 5 , 284−312..
Xiong, W.; Lu, H. Recyclable polythioesters and polydisulfides with near-equilibrium thermodynamics and dynamic covalent bonds. Sci. China-Chem. 2023 , 66 , 725−738..
Hu, Z.; Li, M.; Chen, Y. Functional polyesters: tailoring structure and biomedical functions. Polym. Sci. Technol. 2025 , 1 , 299−313..
Nair, D. P.; Podgórski, M.; Chatani, S.; Gong, T.; Xi, W.; Fenoli, C. R.; Bowman, C. N. The thiol-Michael addition click reaction: a powerful and widely used tool in materials chemistry. Chem. Mater. 2013 , 26 , 724−744..
Ghosal, K.; Bhattacharyya, S. K.; Mishra, V.; Zuilhof, H. Click chemistry for biofunctional polymers: from observing to steering cell behavior. Chem. Rev. 2024 , 124 , 13216−13300..
Hardouin Duparc, V.; Shakaroun, R. M.; Slawinski, M.; Carpentier, J.-F.; Guillaume, S. M. Ring-opening (co)polymerization of six-membered substituted δ -valerolactones with alkali metal alkoxides. Eur. Polym. J. 2020 , 134 , 109858..
Rapagnani, R. M.; Dunscomb, R. J.; Fresh, A. A.; Tonks, I. A. Tunable and recyclable polyesters from CO 2 and butadiene. Nat. Chem. 2022 , 14 , 877−883..
Wu, X.; Yang, C.; Xi, J.; Shi, C.; Du, F.; Li, Z. Enabling closed-loop circularity of “non-polymerizable” α, β -conjugated lactone towards high-performance polyester with the assistance of cyclopentadiene. Angew. Chem. Int. Ed. 2024 , 136 , e202404179..
Tang, X.; Hong, M.; Falivene, L.; Caporaso, L.; Cavallo, L.; Chen, E. Y.-X. The quest for converting biorenewable bifunctional α -methylene- γ -butyrolactone into degradable and recyclable polyester: controlling vinyl-addition/ring-opening/cross-linkingpathways. J. Am. Chem. Soc. 2016 , 138 , 14326−14337..
Li, J.; Liu, F.; Liu, Y.; Shen, Y.; Li, Z. Functionalizable and chemically recyclable thermoplastics from chemoselective ring-opening polymerization of bio-renewable bifunctional α -methylene- δ -valerolactone. Angew. Chem. Int. Ed. 2022 , 61 , e202207105..
[Yan, Q.; Ma, J.; Pei, W.; Zhang, Y.; Zhong, R.; Liu, S.; Shen, Y.; Li, Z. Chemoselective ring-opening polymerization of α -methylene- δ -valerolactone catalyzed by a simple organoaluminum complex to prepare closed-loop recyclable functional polyester. Angew. Chem. Int. Ed . 2024, 64 , e202418488..
Artz, J.; Muller, T. E.; Thenert, K.; Kleinekorte, J.; Meys, R.; Sternberg, A.; Bardow, A.; Leitner, W. Sustainable conversion of carbon dioxide: an integrated review of catalysis and life cycle assessment. Chem. Rev. 2018 , 118 , 434−504..
Nozaki, K. New polymers made from carbon dioxide and alkenes. Bull. Chem. Soc. Jpn. 2021 , 94 , 984−988..
[Rapagnani, R. M.; Tonks, I. A. 3-Ethyl-6-vinyltetrahydro-2H-pyran-2-one (EVP): a versatile CO 2 -derived lactone platform for polymer synthesis. Chem. Commun . 2022, 58 , 9586−9593..
Tang, S.; Nozaki, K. Advances in the synthesis of copolymers from carbon dioxide, dienes, and olefins. Acc. Chem. Res. 2022 , 55 , 1524−1532..
Chen, K.; Mei, Y.; Zhang, Z.; Ling, J.; Ni, X. How to open the ring of a di-ene-substituted-delta-valerolactone: from carbon dioxide and 1,3-butadiene to functional polyesters. Chempluschem 2023 , 88 , e202300022..
Eagan, J. M. The divergent reactivity of lactones derived from butadiene and carbon dioxide in macromolecular synthesis. Macromol. Rapid Commun. 2023 , 44 , e2200348..
Tang, S.; Lin, B.; Tonks, I.; Eagan, J. M.; Ni, X.; Nozaki, K. Sustainable copolymer synthesis from carbon dioxide and butadiene. Chem. Rev. 2024 , 124 , 3590−3607..
Dinjus, E.; Leitner, W. New ins ights into the palladium-catalysed synthesis of δ -lactones from 1,3-dienes and carbon dioxide. Appl. Organomet. Chem. 1995 , 9 , 43−50..
Nakano, R.; Ito, S.; Nozaki, K. Copolymerization of carbon dioxide and butadiene via a lactone intermediate. Nat. Chem. 2014 , 6 , 325−31..
Chen, L.; Li, Y.; Yue, S.; Ling, J.; Ni, X.; Shen, Z. Chemoselective RAFT polymerization of a trivinyl monomer derived from carbon dioxide and 1,3-butadiene: from linear to hyperbranched. Macromolecules 2017 , 50 , 9598−9606..
Ferretti, F.; Sharif, M.; Dastgir, S.; Ragaini, F.; Jackstell, R.; Beller, M. Selective palladium-catalysed synthesis of diesters: alkoxycarbonylation of a CO 2 -butadiene derived δ -lactone. Green Chem. 2017 , 19 , 3542−3548..
Liu, M.; Sun, Y.; Liang, Y.; Lin, B. Highly Efficient Synthesis of functionalizable polymers from a CO 2 /1,3-butadiene-derived lactone. ACS Macro Lett. 2017 , 6 , 1373−1378..
Chen, L.; Ling, J.; N i, X.; Shen, Z. Synthesis and properties of networks based on thiol-ene chemistry using a CO 2 -based delta-lactone. Macromol. Rapid Commun. 2018 , 39 , e1800395..
Tang, S.; Zhao, Y.; Nozaki, K. Accessing divergent main-chain-functionalized polyethylenes via copolymerization of ethylene with a CO 2 /butadiene-derived lactone. J. Am. Chem. Soc. 2021 , 143 , 17953−17957..
Hill, M. R.; Tang, S.; Masada, K.; Hirooka, Y.; Nozaki, K. Incorporation of CO 2 -derived bicyclic lactone into conventional vinyl polymers. Macromolecules 2022 , 55 , 3311−3316..
Song, J.; Chen, K.; Feng, Y.; Ni, X.; Ling, J. One-pot orthogonal thiol-ene click polymerization and ring-opening grafting reaction of CO 2 -based disubstituted δ -valerolactone. J. Polym Sci. 2022 , 60 , 2352−2361..
Wang, Z.; Zheng, W.; Yue, S.; Chen, K.; Ling, J.; Ni,X. Random terpolymer of carbon dioxide, butadiene and epoxides: synthesis, functionalization and degradability. Chin. J. Chem. 2024 , 42 , 1630−1636..
Garcia Espinosa, L. D.; Williams-Pavlantos, K.; Turney, K. M.; Wesdemiotis, C.; Eagan, J. M. Degradable polymer structures from carbon dioxide and butadiene. ACS Macro Lett. 2021 , 10 , 1254−1259..
Chen, K.; Zhu, Z.; Bai, T.; Mei, Y.; Shen, T.; Ling, J.; Ni, X. A topology-defined polyester elastomer from CO 2 and 1,3-butadiene: a one-pot-one-step "scrambling polymerizations" strategy. Angew. Chem. Int. Ed. 2022 , 61 , e202213028..
Chen, K.; Bai, T.; Lin, Y.; Ling, J.; Ni, X. Synthesis and functionalization of sustainable poly(ester- co -carbonate) from carbon dioxide, 1,3-butadiene, and biosourced diols. Macromolecules 2025 , 58 , 575−584..
Zhao, Y.; Zhang, X.; Li, Z.; Li, Z.; Tang, S. Functional and degradable polyester- co -polyethers from CO 2 , butadiene, and epoxides. ACS Macro Lett. 2024 , 13 , 315−321..
Lou, Y.; Xu, L.; Gan, N.; Sun, Y.; Lin, B. Chemically recyclable polyesters from CO 2 , H 2 , and 1,3-butadiene. Innovation 2022 , 3 , 100216..
Lou, Y.; Xu, J.; Xu, L.; Chen, Z.; Lin, B. Chemically recyclable CO 2 -based solid polyesters with facile property tunability. Macromol. Rapid Commun. 2022 , 43 , e2200341..
Zhang, Z.; Shen, T.; Chen, K.; Zeng, J.; Mei, Y.; Ling, J.; Ni, X. Polyester platform with high refractive indices and closed-loop recyclability from CO 2 , 1,3-butadiene, and thiols. ACS Macro Lett. 2024 , 13 , 741−746..
Xu, J.; Niu, Y.; Lin, B. Monomer-recyclable polyester from CO 2 and 1,3-butadiene. Macromol. Rapid Commun. 2024 , 45 , 2400163..
Zhang, J.; Jiang, L.; Liu, S.; Shen, J.; Braunstein, P.; Shen, Y.; Kang, X.; Li, Z. Bifunctional and recyclable polyesters by chemoselective ring-opening polymerization of a δ -lactone derived from CO 2 and butadiene. Nat. Commun. 2024 , 15 , 8698..
Shen, J.; Zhang, J.; Kong, W.; Ma, Y.; Liu, S.; Li, Z. Synthesis of bifunctional copolyesters via chemoselective ring-opening copolymerization of δ -lactone derived from CO 2 and butadiene with ε -caprolactone. Macromolecules 2025 , 58 , 3497−3508..
Wang, J.; Feng, X.; Song, J.; Gao, Z.; Wang, W.; Bao, M. The ultrasmall palladium nanoparticles catalyzed telomerization of CO 2 with 1,3-butadiene at room temperature: selective synthesis of δ -lactone. ChemistrySelect 2020 , 5 , 9404−9408..
Shin, E. J.; Brown, H. A.; Gonzalez, S.; Jeong, W.; Hedrick, J. L.; Waymouth, R. M. Zwitterionic copolymerization: synthesis of cyclic gradient copolymers. Angew. Chem. Int. Ed. 2011 , 50 , 6388−6391..
Chu, B.; Zhang, H.; Hu, L.; Liu, B.; Zhang, C.; Zhang, X.; Tang, B. Altering chain flexibility of aliphatic polyesters for yellow-green clusteroluminescence in 38 % quantum yield. Angew. Chem. Int. Ed. 2021 , 61 , e202114117..
Tao, S.; Zhu, S.; Feng, T.; Zheng, C.; Yang, B. Cross link-enhanced emission effect on luminescence in polymers: advances and perspectives. Angew. Chem. Int. Ed. 2020 , 59 , 9826−9840..
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