Mechanistic Insights into Ring-opening Polymerization of <italic style="font-style: italic">β</italic>-Propiolactone Catalyzed by Organic Bases: Evidence for Alkyl-cleavage

Rui Yan; Chu-Han Deng; Yan-Jun Liu; Shuai-Shuai Zhao; Zong-Min Wu; Xiao-Mei Song; Guang-Peng Wu

doi:10.1007/s10118-026-3892-2

Your Location：

Home >

Browse articles >

Mechanistic Insights into Ring-opening Polymerization of β-Propiolactone Catalyzed by Organic Bases: Evidence for Alkyl-cleavage

RESEARCH ARTICLE | Updated：2026-10-28

- Mechanistic Insights into Ring-opening Polymerization of β-Propiolactone Catalyzed by Organic Bases: Evidence for Alkyl-cleavage
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-7(2026)
- Affiliations：
  
  a.CHN Energy Cornerstone Chemical Technology (Shanghai) Co., Ltd., Shanghai 201108, China
  b.MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang Key Laboratory of Advanced Organic Materials and Technologies, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, China
- Author bio：
  
  20121306@ceic.com (X.M.S.)
  gpwu@zju.edu.cn (G.P.W.)
- Funds：
- DOI：10.1007/s10118-026-3892-2
  CLC：
- Received：27 June 2026，
  
  Accepted：13 September 2026，
  
  Online First：28 October 2026，
  
  Published：2026-10
- Accepted：
Scan QR Code
Yan, R.; Deng, C. H.; Liu, Y. J.; Zhao, S. S.; Wu, Z. M.; Song, X. M.; Wu, G. P. Mechanistic insights into ring-opening polymerization of β-propiolactone catalyzed by organic bases: evidence for alkyl-cleavage. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3892-2

Rui Yan, Chu-Han Deng, Yan-Jun Liu, et al. Mechanistic Insights into Ring-opening Polymerization of β-Propiolactone Catalyzed by Organic Bases: Evidence for Alkyl-cleavage[J/OL]. Chinese Journal of Polymer Science, 2026, 441-7. DOI: 10.1007/s10118-026-3892-2.
Yan, R.; Deng, C. H.; Liu, Y. J.; Zhao, S. S.; Wu, Z. M.; Song, X. M.; Wu, G. P. Mechanistic insights into ring-opening polymerization of β-propiolactone catalyzed by organic bases: evidence for alkyl-cleavage. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3892-2 DOI：

Rui Yan, Chu-Han Deng, Yan-Jun Liu, et al. Mechanistic Insights into Ring-opening Polymerization of β-Propiolactone Catalyzed by Organic Bases: Evidence for Alkyl-cleavage[J/OL]. Chinese Journal of Polymer Science, 2026, 441-7. DOI: 10.1007/s10118-026-3892-2. DOI：

摘要

Abstract

Biodegradable aliphatic polyesters are promising alternatives to conventional plastics

which can be synthesized by the ring-opening polymerization (ROP) of the corresponding lactones. ROP of four-membered

-propiolactone (BPL) provides an efficient approach to poly(3-hydroxypropionate)

a class of polyhydroxyalkanoate materials. Although numerous organocatalytic systems

including those based on organic bases

have been exploited to achieve high efficiency and high molecular weights

the ring-opening mechanism of BPL and associated experimental evidence remain unclear. Specifically

for the ring-opening polymerization of BPL catalyzed by organic base/alcohol systems

further experimental evidence is required to elucidate the site that undergoes nucleophilic attack: attack at the carbonyl carbon versus the

-carbon of BPL results in acyl-oxygen cleavage and alkyl-oxygen cleavage of the monomer

respectively. The dominant reaction pathway for this system has not been definitively confirmed to date. In this work

using organic bases/alcohol as the catalytic system

we propose an experimental strategy to distinguish the ring-opening pathway of BPL by quenching the polymerization with benzyl bromide. The results illustrated that organic bases preferentially abstracted the

-proton of BPL

generating an acrylate anion as the actual initiator. The ROP of BPL is processed

via

an alkyl-cleavage mechanism

in which the acrylate initiator attacks the

-carbon of BPL. This research will facilitate the rational design of catalysts for the ROP of BPL in the future.

关键词

Keywords

references

Tong, R. New chemistry in functional aliphatic polyesters. Ind. Eng. Chem. Res. 2017 , 56 , 4207−4219..

Zhu, Y.; Romain, C.; Williams, C. K. Sustainable polymers from renewable resources. Nature 2016 , 540 , 354−362..

Kim, M. S.; Chang, H.; Zheng, L.; Yan, Q.; Pfleger, B. F.; Klier, J.; Nelson, K.; Majumder, E. L.; Huber, G. W. A review of biodegradable plastics: chemistry, applications, properties, and future research needs. Chem. Rev. 2023 , 123 , 9915−9939..

Guillaume, S. M. Sustainable and degradable plastics. Nat. Chem. 2022 , 14 , 245−246..

Li, Y.; Maciel, D.; Rodrigues, J.; Shi, X.; Tomás, H. Biodegradable polymer nanogels for drug/nucleic acid delivery. Chem. Rev. 2015 , 115 , 8564−8608..

Xu, J.; Wang, X.; Liu, J.; Feng, X.; Gnanou, Y.; Hadjichristidis, N. Ionic H-bonding organocatalysts for the ring-opening polymerization of cyclic esters and cyclic carbonates. Prog. Polym. Sci. 2022 , 125 , 101484..

Penczek, S.; Cypryk, M.; Duda, A.; Kubisa, P.; Slomkowski, S. Living ring-opening polymerizations of heterocyclic monomers. Prog. Polym. Sci. 2007 , 32 , 247−282..

Zhang, X.; Fevre, M.; Jones, G. O.; Waymouth, R. M. Catalysis as an e nabling science for sustainable polymers. Chem. Rev. 2018 , 118 , 839−885..

Zhou, Y.; Zhang, H.; Duan, R.; Sun, Z.; Pang, X.; Chen, X. Recent developments of stereoselective ring-opening polymerization of lactides. Sci. Sin. Chim. 2020 , 50 , 806−815..

Ajellal, N.; Carpentier, J. F.; Guillaume, C.; Guillaume, S. M.; Helou, M.; Poirier, V.; Sarazin, Y.; Trifonov, A. Metal-catalyzed immortal ring-opening polymerization of lactones, lactides and cyclic carbonates. Dalton Trans. 2010 , 39 , 8363−8376..

Engel, J.; Cordellier, A.; Huang, L.; Kara, S. Enzymatic ring-opening polymerization of lactones: traditional approaches and alternative strategies. ChemCatChem 2019 , 11 , 4983−4997..

Kiesewetter, M. K.; Shin, E. J.; Hedrick, J. L.; Waymouth, R. M. Organocatalysis: opportunities and challenges for polymer synthesis. Macromolecules 2010 , 43 , 2093−2107..

Young, M. S.; LaPointe, A. M.; MacMillan, S. N.; Coates, G. W. Highly enantioselective polymerization of β-butyrolactone by a bimetal lic magnesium catalyst: an interdependent relationship between favored and unfavored enantiomers. J. Am. Chem. Soc. 2024 , 146 , 18032−18040..

Yang, J.; Wang, S. Y.; Lu, X. B.; Liu, Y. Intramolecular cooperation and exchange driven ring-opening polymerization toward functionalized polyhydroxyalkanoates with high ductility and robust adhesion. Macromolecules 2025 , 58 , 8622−8631..

Huang, H. Y.; Xiong, W.; Huang, Y. T.; Li, K.; Cai, Z.; Zhu, J. B. Spiro-salen catalysts enable the chemical synthesis of stereoregular polyhydroxyalkanoates. Nat. Catal. 2023 , 6 , 720−728..

Tian, J.-J.; Li, R.; Quinn, E. C.; Nam, J.; Chokkapu,E. R.; Zhang, Z.; Zhou, L.; Gowda, R. R.; Chen, E. Y. X. Stereodivergent transformation of a natural polyester to enantiopure PHAs. Nature 2025 , 643 , 967−974..

Huang, H. Y.; Xie, M.; Wang, S. Q.; Huang, Y. T.; Luo, Y. H.; Yu, D. G.; Cai, Z.; Zhu, J. B. Ultratough thermoplastic elastomers based on chemically recyclable cycloalkyl-substituted polyhydroxyalkanoates. J. Am. Chem. Soc. 2025 , 147 , 7788−7798..

Huang, H.; Xie, M.; Huang, Y.; Cui, J.; Cai, Z.; Zhu, J. Synthesis of stereoregular and functional polyhydroxyalkanoates via ring-opening polymerization mediated by spiro-salen complexes. Acta Chim. Sinica 2025 , 83 , 810..

Jaffredo, C. G.; Carpentier, J. F.; Guillaume, S. M. Controlled ROP of β-butyrolactone simply mediated by amidine, guanidine, and phosphazene organocatalysts. Macromol. Rapid Commun. 2012 , 33 , 1938−1944..

Shen, Y.; Xiong, W.; Li, Y.; Zhao, Z.; Lu, H.; Li, Z. Chemoselective polymerization of fully biorenewable α -methylene- γ -butyrolactone using organophosphazene/urea binary catalysts toward sustainable polyesters. CCS Chem. 2021 , 3 , 620−630..

Jain, I.; Malik, P. Advances in urea and thiourea catalyzed ring opening polymerization: a brief overview. Eur. Polym. J. 2020 , 133 , 109791..

Jiang, X.; Zhao, N.; Li, Z. Stereoselective ring-opening polymerization of rac -lactide catalyzed by squaramide derived organocatalysts at room temperature. Chin. J. Chem. 2021 , 39 , 2403−2409..

Connor, E. F.; Nyce, G. W.; Myers, M.; Möck, A.; Hedrick, J. L. First example of N-heterocyclic carbenes as catalysts for living polymerization: organocatalytic ring-opening polymerization of cyclic esters. J. Am. Chem. Soc. 2002 , 124 , 914−915..

Yan, R.; Li, S.; Li, M. J.; Li, B.; Wu, G. P. Hydrogen bonding-driven ring-opening polymerization of β -lactones to polyhydroxyalkanoates using aminocyclopropenium carboxylates. Macromolecules 2025 , 58 , 2379−2388..

Dunn, E. W.; Lamb, J. R.; LaPointe, A. M.; Coates, G. W. Carbonylation of ethylene oxide to β -propiolactone: a facile route to poly(3-hydroxypropionate) and acrylic acid. ACS Catal. 2016 , 6 , 8219−8223..

Yang, L.; Zhang, Y. Y.; Yang, G. W.; Xie, R.; Wu, G. P. Controlled ring-opening polymerization of β -butyrolactone via bifunctional organoboron catalysts. Macromolecules 2021 , 54 , 5509−5517..

Li, W. B.; Ren, B. H.; Gu, G. G.; Lu, X. B. Controlled random terpolymerization of β -propiolactone, epoxides, an d CO 2 via regioselective lactone ring opening. CCS Chem. 2022 , 4 , 344−355..

Thomas, C.; Peruch, F.; Bibal, B. Ring-opening polymerization of lactones using supramolecular organocatalysts under simple conditions. RSC Adv. 2012 , 2 , 12851−12856..

Pratt, R. C.; Lohmeijer, B. G. G.; Long, D. A.; Waymouth, R. M.; Hedrick, J. L. Triazabicyclodecene: a simple bifunctional organocatalyst for acyl transfer and ring-opening polymerization of cyclic esters. J. Am. Chem. Soc. 2006 , 128 , 4556−4557..

Rodríguez, H. A.; Bickelhaupt, F. M.; Fernández, I. Origin of the Bürgi-dunitz angle. ChemPhysChem 2023 , 24 , e202300379..

Philip, T.; Cook, R. L.; Malloy, T. B., Jr.; Allinger, N. L.; Chang, S.; Yuh, Y. Molecular mechanics calculations and experimental studies of conformations of.delta.-valerolactone. J. Am. Chem. Soc. 1981 , 103 , 2151−2156..

Domiński, A.; Konieczny, T.; Zięba, M.; Klim, M.; Kurcok, P. Anionic polymerization of β -butyrolactone ini tiated with sodium phenoxides. the effect of the initiator basicity/nucleophilicity on the ROP mechanism. Polymers 2019 , 11 , 1221..

Li, S.; Liu, S.; Yan, R.; Xie, R.; Xue, Q.; Li, B.; Wu, G.-P. Sulfur-containing salen-type chromium complexes for selective carbonylation of epoxides: a pathway to polyesters and cyclic lactones. Chem. Eur. J. 2025 , 31 , e202500571..

Yamashita, Y.; Ito, K.; Nakakita, F. Initiation mechanism for the anionic polymerization of β-propiolactone by pyridine. Makromol. Chem. 1969 , 127 , 292−295..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

CO2-Sourced Poly(chloropropylene carbonate) with High Flame-Retardant Performance

Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers

Facile Synthesis of Polycarbonate DiolviaCopolymerization of CO2and Cyclohexene Oxide Catalysed by a Combination of One-Component Phosphonium Borane Lewis Pair and Water

Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters

Advances in Polymer-based Circularly Polarized Luminescent Materials

Related Author

Yue Gong

Xiao-Feng Zhu

Guan-Wen Yang

Meng Ma

Xu Wang

Jie Xu

Xin Shu

Guang-Peng Wu

Related Institution

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Key Laboratory of Adsorption and Separation Materials & Technologies of Zhejiang Province, Department of Polymer Science and Engineering, Zhejiang University

Zhejiang Key Laboratory of Plastic Modification and Processing Technology, College of Materials Science and Engineering, Zhejiang University of Technology

Shanxi Coal Chemical Industry Technology Research Institute Co., Ltd.

Faculty of Materials Science and Engineering, South China University of Technology

State Key Laboratory Base of Eco-Chemical Engineering; College of Chemical Engineering, Qingdao University of Science and Technology

⁰

Mechanistic Insights into Ring-opening Polymerization of β-Propiolactone Catalyzed by Organic Bases: Evidence for Alkyl-cleavage

DOI：10.1007/s10118-026-3892-2

摘要

Abstract

关键词

Keywords

references