Alternating Copolymerization of Dihydrocoumarin and Epoxides Catalyzed by 1-Ethyl-3-methylimidazolium Chloride

Jing-Jing Yu; Yong-Li Li; Xue Wu; Zhi-Dong Li; Ye-Fan Liu; Yang Zhang; Peng-Fei Song

doi:10.1007/s10118-025-3336-4

Your Location：

Home >

Browse articles >

Alternating Copolymerization of Dihydrocoumarin and Epoxides Catalyzed by 1-Ethyl-3-methylimidazolium Chloride

RAPID COMMUNICATION | Updated：2025-07-26

- Alternating Copolymerization of Dihydrocoumarin and Epoxides Catalyzed by 1-Ethyl-3-methylimidazolium Chloride
- Chinese Journal of Polymer Science Vol. 43, Issue 8, Pages: 1269-1276(2025)
- Affiliations：
  
  College of Chemistry and Chemical Engineering, Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Key Laboratory of Eco-environmental Polymer Materials of Gansu Province, Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Northwest Normal University, Lanzhou 730070, China
- Author bio：
  
  songpf@nwnu.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3336-4
  CLC：
- Received：07 January 2025，
  
  Revised：2025-03-08，
  
  Accepted：12 March 2025，
  
  Online First：14 May 2025，
  
  Published：01 August 2025
- Accepted：
Scan QR Code
Yu, J. J.; Li, Y. L.; Wu, X.; Li, Z. D.; Liu, Y. F.; Zhang, Y.; Song, P. F. Alternating copolymerization of dihydrocoumarin and epoxides catalyzed by 1-ethyl-3-methylimidazolium chloride. Chinese J. Polym. Sci. 2025, 43, 1269–1276

Jing-Jing Yu, Yong-Li Li, Xue Wu, et al. Alternating Copolymerization of Dihydrocoumarin and Epoxides Catalyzed by 1-Ethyl-3-methylimidazolium Chloride[J]. Chinese Journal of Polymer Science, 2025, 43(8): 1269-1276.
Yu, J. J.; Li, Y. L.; Wu, X.; Li, Z. D.; Liu, Y. F.; Zhang, Y.; Song, P. F. Alternating copolymerization of dihydrocoumarin and epoxides catalyzed by 1-ethyl-3-methylimidazolium chloride. Chinese J. Polym. Sci. 2025, 43, 1269–1276 DOI： 10.1007/s10118-025-3336-4.

Jing-Jing Yu, Yong-Li Li, Xue Wu, et al. Alternating Copolymerization of Dihydrocoumarin and Epoxides Catalyzed by 1-Ethyl-3-methylimidazolium Chloride[J]. Chinese Journal of Polymer Science, 2025, 43(8): 1269-1276. DOI： 10.1007/s10118-025-3336-4.

摘要

The ring-opening alternating copolymerization (ROAC) of 3

4-dihydrocoumarin (DHC) and epoxides was developed using an imidazolium salt of 1-ethyl-3-methylimidazolium chloride (EMIMCl) as a catalyst. The metal-free catalytic process was investigated by DFT calculations

and the synergistic catalytic mechanism of EMIMCl for ROAC of DHC and epoxides was demonstrated.

Abstract

The ring-opening alternating copolymerization (ROAC) of 3

4-dihydrocoumarin (DHC)/epoxides has been successfully developed using an imidazolium salt of 1-ethyl-3-methylimidazolium chloride (EMIMCl) as a catalyst. The resulting copolymer has a molecular weight of 13.7 kg·mol

–1

a narrow molecul

ar weight distribution of 1.03 and a strictly alternating structure. The MALDI-TOF MS characterization and DFT calculations including electrostatic potential (ESP)

hydrogen-atom abstraction (HAA)

independent gradient model based on hirshfeld partition (IGMH) and atoms-in-molecules (AIM) analysis were used to investigate the metal-free catalytic process. The synergistic effect of anions and cations of EMIMCl for ROAC of DHC and epoxides was demonstrated. This study provides a metal-free catalytic system for the facile synthesis of alternating polyesters from DHC.

关键词

Keywords

references

Kunduru, K. R.; Hogerat, R.; Ghosal, K.; Shaheen-Mualim, M.; Farah, S. Renewable polyol-based biodegradable polyesters as greener plastics for industrial applications. Chem. Eng. J. 2023 , 459 , 141211..

Klajnert-Maculewicz, B.; Janaszewska, A.; Majecka, A. Dendrimersomes: biomedical applications. Chem. Commun. 2023 , 59 , 14611−14625..

Cai, Q.; Bai, T.; Zhang, H.; Yao, X.; Ling, J.; Zhu, W. Catalyst-free synthesis of polyesters via conventional melt polycondensation. Mater. Today 2021 , 51 , 155−164..

Katoh, T.; Ogawa, Y.; Ohta, Y.; Yokozawa, T. Synthesis of polyester by means of polycondensation of diol ester and dicarboxylic acid ester through ester-ester exchange reaction. J. Polym. Sci. 2021 , 59 , 787−797..

Li, Z.; Shen, Y.; Li, Z. Ring-opening polymerization of lactones to prepare closed-loop recyclable polyesters. Macromolecules 2024 , 57 , 1919−1940..

Bandelli, D.; Weber, C.; Schubert, U. S. Strontium isopropoxide: a highly active catalyst for the ring-opening polymerization of lactide and various lactones. Macromol. Rapid Commun. 2019 , 40 , 1900306..

Liu, X. Y.; Zhu, L.; Jie, S. Y.; Li, B. G. Controllable ring-opening polymerization of δ -valerolactone catalyzed by quinolinyl-urea/MTBD systems. Chinese J. Polym. Sci. 2024 , 42 , 1103−1110..

Vidal, F.; Smith, S.; Williams, C. K. Ring opening copolymerization of boron-containing anhydride with epoxides as a controlled platform to functional polyesters. J. Am. Chem. Soc. 2023 , 145 , 13888−13900..

Scharfenberg, M.; Hilf, J.; Frey, H. Functional polycarbonates from carbon dioxide and tailored epoxide monomers: degradable materials and their application potential. Adv. Funct. Mater. 2018 , 28 , 1704302..

Jung, H. J.; Goonesinghe, C.; Mehrkhodavandi, P. Temperature triggered alternating copolymerization of epoxides and lactones via presequenced spiroorthoester intermediates. Chem. Sci. 2022 , 13 , 3713−3718..

Geeti, D. K.; Niranjan, K. Environmentally benign bio-based waterborne polyesters: synthesis, thermal- and bio-degradation studies. Prog. Org. Coat. 2019 , 127 , 419−428..

Jindal, S.; Ghosal, K.; Khamaisi, B.; Kana'an, N.; Nassar-Marjiya, E.; Farah, S. Facile green synthesis of zingerone based tissue-like biodegradable polyester with shape-memory features for regenerative medicine. Adv. Funct. Mater. 2024 , 34 , 2405827..

Ghosal, K.; Bhattacharjee, U.; Sarkar, K. Facile green synthesis of bioresorbable polyester from soybean oil and recycled plastic waste for osteochondral tissue regeneration. Eur. Polym. J. 2020 , 122 , 109338..

Meng, X. B.; Zhou, T.; Yang, C.; Cheng, X. Y.; Wu, X. T.; Shi, C.; Du, F. S.; Li, Z. C. Thermally stable and chemically recyclable poly(ketal-ester)s regulated by floor temperature. J. Am. Chem. Soc. 2024 , 146 , 15428−15437..

Luo, W. F.; Ye, L. W.; Li, L.; Qian, P. C. Regio and diastereoselective synthesis of trans-3,4-diaryldihydrocoumarins via metal-free [4+2 ] annulation of ynamides with o -hydroxybenzyl alcohols. Chem. Commun. 2021 , 57 , 5032−5035..

Van Zee, N. J.; Coates, G. W. Alternating copolymerization of dihydrocoumarin and epoxides catalyzed by chromium salen complexes: a new route to functional polyesters. Chem. Commun. 2014 , 50 , 6322−6325..

Guo, Y.; Guo, G.; Liu, P.; You, Y.; Yuan, J.; Hu, G.; Dai, L.; North, M.; Xie, H.; Zheng, Q. The synthesis of multifunctional cellulose graft alternating copolymers of 3,4-dihydrocoumarin and epoxides in DBU/DMSO/CO 2 solvent system. Int. J. Bio. Macromol. 2023 , 252 , 126584..

Api, A. M.; Belsito, D.; Botelho, D.; Bruze, M.; Burton, G. A.; Buschmann, J.; Cancellieri, M. A.; Dagli, M. L.; Date, M.; Dekant, W.; Deodhar, C.; Fryer, A. D.; Jones, L.; Joshi, K.; Kumar, M.; Lapczynski, A.; Lavelle, M.; Lee, I.; Liebler, D. C.; Moustakas, H.; Na, M.; Penning, T. M.; Ritacco, G.; Romine, J.; Sadekar, N.; Schultz, T. W.; Selechnik, D.; Siddiqi, F.; Sipes, I. G.; Sullivan, G.; Thakkar, Y.; Tokura, Y. RIFM fragrance ingredient safety assessment, dihydrocoumarin, CAS Registry Number 119-84-6. Food Chem. Toxicol. 2021 , 156 , 112557..

Uenishi, K.; Sudo, A.; Endo, T. Anionic alternating copolymerizability of epoxide and 3,4-dihydrocoumarin by imidazole. Macromolecules 2007 , 40 , 6535−6539..

Sudo, A.; Uenishi, K.; Endo, T. Imidazole-promoted copolymerization of epoxide and 3,4-dihydrocoumarin and its application to a high-performance curing system. J. Polym. Sci. A: Polym. Chem. 2007 , 45 , 3798−3802..

Gruszka, W.; Garden, J. A. Advances in heterometallic ring-opening (co)polymerization catalysis. Nat. Commun. 2021 , 12 , 3252..

Diment, W. T.; Williams, C. K. Chain end-group selectivity using an organometallic Al(III)/K(I) ring-opening copolymerization catalyst deliv ers high molar mass, monodisperse polyesters. Chem. Sci. 2022 , 13 , 8543−8549..

Zhao, D.; Li, Z.; Shen, Y.; Li, Z. Crystalline stereoregular poly(ether-ester) via MeAl[Salen ] -catalyzed well-controlled ring-opening polymerization of enantiopure cyclic ether-ester monomer. Macromolecules 2023 , 56 , 6019−6026..

Deacy, A. C.; Moreby, E.; Phanopoulos, A.; Williams, C. K. Co(III)/Alkali-metal(I) heterodinuclear catalysts for the ring-opening copolymerization of CO 2 and propylene oxide. J. Am. Chem. Soc. 2020 , 142 , 19150−19160..

Duan, R. L.; Zhou, Y. C.; Sun, Z. Q.; Huang, Y. Z.; Pang, X.; Chen, X. S. The effect of oxygen to salen-Co complexes for the copolymerization of PO/CO 2 . Chinese J. Polym. Sci. 2020 , 38 , 1124−1130..

Liu, Y.; Guo, J. Z.; Lu, H. W.; Wang, H. B.; Lu, X. B. Making various degradablepolymers from epoxides using a versatile dinuclear chromium catalyst. Macromolecules 2018 , 51 , 771−778..

Lin, L.; Liang, J.; Xu, Y.; Wang, S.; Xiao, M.; Sun, L.; Meng, Y. Fully alternating sustainable polyesters from epoxides and cyclic anhydrides: economical and metal-free dual catalysis. Green Chem. 2019 , 21 , 2469−2477..

Ávila Gonçalves, S.; Rodrigues, P. R.; Pioli Vieira, R. Metal-free organocatalyzed atom transfer radical polymerization: synthesis, applications, and future perspectives. Macromol. Rapid Commun. 2021 , 42 , 2100221..

Zhu, S.; Zhao, Y.; Ni, M.; Xu, J.; Zhou, X.; Liao, Y.; Wang, Y.; Xie, X. One-step and metal-free synthesis of triblock quaterpolymers by concurrent and switchable polymerization. ACS Macro Lett. 2020 , 9 , 204−209..

Zhang, Y. Y.; Yang, G. W.; Lu, C.; Zhu, X. F.; Wang, Y.; Wu, G. P. Organoboron-mediated polymerizations. Chem. Soc. Rev. 2024 , 53 , 3384−3456..

Ji, H. Y.; Song, D. P.; Wang, B.; Pan, L.; Li, Y. S. Organic lewis pairs for selective copolymerization of epoxides with anhydrides to access sequence-controlled block copolymers. Green Chem. 2019 , 21 , 6123−6132..

Hu, S.; Dai, G. ; Zhao, J.; Zhang, G. Ring-opening alternating copolymerization of epoxides and dihydrocoumarin catalyzed by a phosphazene superbase. Macromolecules 2016 , 49 , 4462−4472..

Zhang, H.; Hu, S.; Zhao, J.; Zhang, G. Phosphazene-catalyzed alternating copolymerization of dihydrocoumarin and ethylene oxide: weaker is better. Macromolecules 2017 , 50 , 4198−4205..

Zhang, H.; Hu, S.; Zhao, J.; Zhang, G. Expanding the scope of organocatalysis for alternating copolymerization of dihydrocoumarin and styrene oxide. Eur. Polym. J. 2017 , 95 , 693−701..

Song, Y. J.; He, J. H.; Zhang, Y. T. Mechanistic study on the synthesis of dihydrocoumarin-based polyester catalyzed by N-heterocyclic olefins-based lewis pairs. Acta Polymerica Sinica (in Chinese) 2022 , 53 , 1112−1122..

Migowski, P.; Lozano, P.; Dupont, J. Imidazolium based ionic liquid-phase green catalytic reactions. Green Chem. 2023 , 25 , 1237−1260..

Chapman Varela, J.; Sankar, K.; Hino, A.; Lin, X.; Chang, W.; Coker, D.; Grinstaff, M. Pip eridinium ionic liquids as electrolyte solvents for sustained high temperature supercapacitor operation. Chem. Commun. 2018 , 54 , 5590−5593..

Leite, M. J.; Agner, T.; Machado, F.; Neto, B. A. D.; Araujo, P. H. H.; Sayer, C. ε-Caprolactone ring-opening polymerization catalyzed by imidazolium-based ionic liquid under mild reaction conditions. J. Polym. Res . 2022 , 29 , 56..

Liao, L.; Liu, L.; Zhang, C.; Gong, S. Microwave-assisted ring-opening polymerization of ε -caprolactone in the presence of ionic liquid. Macromol. Rapid Commun. 2006 , 27 , 2060−2064..

Song, P.; Chen, Y.; Li, Y.; Ma, J.; Wang, L.; Wang, R. A one-pot strategy to synthesize block copolyesters from monomer mixtures using a hydroxy-functionized ionic liquid. Macromol. Rapid Commun. 2020 , 41 , 2000436..

Wu, X.; Li, Y.; Yu, J.; Liu, Y.; Li, Z.; Zhang, Y.; Song, P. Switchable copolymerization of mixed monomers catalyzed by imidazolium ionic liquids. Polym. Chem. 2024 , 15 , 1475−1483..

Lu, T.; Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 2011 , 33 , 580−592..

Emamian, S.; Lu, T.; Kruse, H.; Emamian, H. Exploring nature and predicting strength of hydrogen bonds: a correlation analysis between atoms-in-molecules descriptors, binding energies, and energy components of symmetry-adapted perturbation theory. J. Comput. Chem. 2019 , 40 , 2868−2881..

Views

196

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

The Effect of Oxygen to Salen-Co Complexes for the Copolymerization of PO/CO2

Synthesis of Polycarbonate Block Terpolymers Using Robust Cobalt Catalyst Systems

DFT Studies on the Origin of Regioselective Ring-opening of Terminal Epoxides during Copolymerization with CO2

Epoxy-functionalized Cyclohexane-based Ricinoleate Plasticizer: Synthesis, Performance Evaluation, and Plasticizing Mechanism

End-group and Side-chain Dual-engineering of Selenium-fused Acceptors for 20.08% Efficiency Polymer Solar Cells with Low Energy Loss

Related Author

Yan-Chuan Zhou

Ran-Long Duan

Zhi-Qiang Sun

Yue-Zhou Huang

Xuan Pang

Xue-Si Chen

Xiao-Bing Lu

Ying-Jie Jiang

Related Institution

Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

University of Science and Technology of China

State Key Laboratory of Fine Chemicals, Dalian University of Technology

⁰