Alternating Poly(ether-<italic style="font-style: italic">alt</italic>-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units

Yu-Tao Wang; Zheng-Fei Liu; Ye Liu; Xiao-Bing Lu

doi:10.1007/s10118-026-3726-2

Your Location：

Home >

Browse articles >

Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units

RESEARCH ARTICLE | Updated：2026-07-20

- Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-8(2026)
- Affiliations：
  
  State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
- Author bio：
  
  liuye@dlut.edu.cn (Y.L.)
  xblu@dlut.edu.cn (X.B.L.)
- Funds：
- DOI：10.1007/s10118-026-3726-2
  CLC：
- Received：03 April 2026，
  
  Accepted：23 April 2026，
  
  Online First：17 July 2026，
  
  Published：2026-06
- Accepted：
Scan QR Code
Wang, Y. T.; Liu, Z. F.; Liu, Y.; Lu, X. B. Alternating poly(ether-alt-ester)s with high glass transition temperature enabled by rotationally constrained biaryl units. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3726-2

Yu-Tao Wang, Zheng-Fei Liu, Ye Liu, et al. Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units[J/OL]. Chinese Journal of Polymer Science, 2026, 441-8. DOI: 10.1007/s10118-026-3726-2.
Wang, Y. T.; Liu, Z. F.; Liu, Y.; Lu, X. B. Alternating poly(ether-alt-ester)s with high glass transition temperature enabled by rotationally constrained biaryl units. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3726-2 DOI：

Yu-Tao Wang, Zheng-Fei Liu, Ye Liu, et al. Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units[J/OL]. Chinese Journal of Polymer Science, 2026, 441-8. DOI: 10.1007/s10118-026-3726-2. DOI：

摘要

Abstract

Incorporating different structural units into the polyester backbone constitutes a powerful strategy to tailor material performances. The integration of ether and ester moieties affords poly(ether-

alt

-ester)s with enhanced mechanical flexibility and tunable thermal properties. Nevertheless

the substrate scope available for the alternating copolymerization of epoxides with lactones remains considerably restricted

and the resulting polymers still suffer from inferior thermal resistance. Herein

we design a typical Bringmann’s lactone bearing a conformationally constrained biaryl axis and a helically distorted six-membered bridging scaffold. A binary catalyst system composed of simple Salen-Cr(III)-Cl and 7-methyl-1

7-triazabicyclo[4.4.0

]

dec-5-ene (MTBD) enables strictly alternating and controlled copolymerization with meso-epoxides

effectively suppressing the formation of ether-ether or ester-ester linked homopolymer sequences. This protocol yields alternating poly(ether-

alt

-ester)s with a high glass transition temperature of 114 °C

an enhancement of 57 °C relative to alternating copolymer derived from the flexible 3

4-dihydrocoumarin monomer. This approach provides a facile and practical strategy for advancing the performance of alternating poly(ether-

alt

-ester)s.

关键词

Keywords

references

Asri, N. A.; Sezali, N. A. A.; Ong, H. L.; Pisal, M. H. M.; Lim, Y. H.; Fang, J. Review on biodegradable aliphatic polyesters: development and challenges. Macromol. Rapid Commun. 2024 , 45 , 2400475..

MacLeod, M.; Arp, H. P. H.; Tekman, M. B.; Jahnke, A. The global threat from plastic pollution. Science 2021 , 373 , 61−65..

Tian, J.; Zhang, S.; Wang, Z.; Adl, M.; Lin, L.; Guler, H.; Cui, S. Synthesis of sustainable green bio-polycarbonates from bio-based feedstock and CO 2 toward carbon–neutral goals: opportunities and challenges. Bioresour. Technol. 2026 , 442 , 133701..

Rachita, E. D.; Yook, J.; Watts, A.; Ellison, C. J.; Hillmyer, M. A. Spiers memorial lecture: compostable plastics: promise and pitfalls. Faraday Discuss. 2026 , 262 , 12−45..

Sun, W.; Pang, Y.; He, Y.; Luo, Z.; Jia, P.; Zhou, Y.; Sha, Y. Chemically recyclable, fully biobased polyolefins with performance parity to low-density polyethylene. Green Chem. 2026 , 28 , 387−395..

Li, Y.; Wang, S.; Qian, S.; Liu, Z.; Weng, Y.; Zhang, Y. Depolymerization and re/upcycling of biodegradable PLA plastics. ACS Omega 2024 , 9 , 13509−13521..

Retnadhas, S.; Ducat, D. C.; Hegg, E. L. Nature-inspired strategies for sustainable degradation of synthetic plastics. JACS Au 2024 , 4 , 3323−3339..

Millican, J. M.; Agarwal, S. Plastic pollution: a material problem. Macromolecules 2021 , 54 , 4455−4469..

Velasquez, S. T. R.; Hu, Q.; Kramm, J.; Santin, V. C.; Völker, C.; Wurm, F. R. Plastics of the future? An interdisciplinary review on biobased and biodegradable polymers: progress in chemistry, societal views, and environmental implications. Angew. Chem., Int. Ed. 2025 , 64 , e202423406..

Sahu, P.; Sharma, L.; Dawsey, T.; Gupta, R. K. Fully biobased high-molecular-weight polyester with impressive elasticity, thermo-mechanical properties, and enzymatic biodegradability: replacing terephthalate. Macromolecules 2024 , 57 , 10086−10100..

Pion, F.; Ducrot, P. H.; Allais, F. Renewable alternating aliphatic-aromatic copolyesters derived from biobased ferulic acid, diols, and diacids: sustainable polymers with tunable thermal properties. Macromol. Chem. Phys. 2014 , 215 , 431−439..

Moser, B. R.; Doll, K. M.; Price, N. P. Comparison of aliphatic polyesters prepared by acyclic diene metathesis and thiol-ene polymerization of alpha,omega-polyenes arising from oleic acid-based 9-decen-1-ol. J. Am. Oil Chem. Soc. 2022 , 100 , 149−162..

Reddy, S. K. K.; Valsange, N. G.; Nguyen, T. T.; Liu, G. J.; Liu J.; Guo, Z. W.; Anderhell, M.; Wahlberg, J.; Zhang B. Z.; Jannasch, P. Tailoring biobased aliphatic polyesters for high T g , scalable production, processability, biodegradability, and closed-loop chemical recyclability. Chem. Eng. J. 2025 , 526 , 170788..

Hillmyer, M. A.; Tolman, W. B. Catalysis as an enabling science for sustainable polymers. Chem. Rev. 2018 , 118 , 232−428..

Xu, Z.; Hu, C.; Vargun, E.; Rojas, G.; Coates, G. W.; Chen, E. Y. X. Closed-loop recyclable and nonpersistent polyethylene-like po lyesters. Acc. Chem. Res. 2024 , 57 , 153−164..

van der Maas, K.; Wang, Y.; Weinland, D. H.; van Putten, R. J.; Wang, B.; Gruter, G. J. M. PISOX copolyesters—bio- and CO 2 -based marine-degradable high-performance polyesters. ACS Sustainable Chem. Eng. 2024 , 12 , 9822−9832..

Craze, A. R.; Kerr, R. W. F.; McGuire, T. M.; Wille, L.; Williams, C. K. Toughened commercial poly(l-lactide) (PLLA) using degradable and recyclable poly(ester- alt -ether)- b -PLLA. Green Chem. 2025 , 27 , 9495−9511..

Kerr, R. W. F.; Craze, A. R.; Williams, C. K. Cyclic ether and anhydride ring opening copolymerisation delivering new ABB sequences in poly(ester- alt -ethers). Chem. Sci. 2024 , 15 , 11617−11625..

Guan, J.; Wang, M.; Ding, Z.; Wang, B.; Li, Y. Floor temperature-regulated poly(ether- alt -ester) with thermal stability and chemical recyclability. Angew. Chem., Int. Ed. 2026 , 64 , e202509468..

Wang, M.; Ding, Z.; Shi, X.; Ma, Z.; Wang, B.; Li, Y. Modulating polymerization behaviors of ether-ester monomers and physicochemical properties of poly(ether- alt -ester)s by heteroatom substitutions. Macromolecules 2024 , 57 , 869−879..

Le Luyer, S.; Quiienne, B.; Bouzaid, M.; Guégan, P.; Caillol, S.; Illy, N. Bio-based poly(ester- alt -thioether)s synthesized by organo-catalyzed ring-opening copolymerizations of eugenol-based epoxides and N-acetyl homocysteine thiolactone. Green Chem. 2021 , 23 , 7743−7750..

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

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

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

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..

Ren, W. M.; Gao, H. J.; Yue, T. J. Flexible gradient poly(ether-ester) from the copolymerization of epoxides and ε -caprolactone mediated by a hetero-bimetallic complex. Chinese J. Polym. Sci. 2021 , 39 , 1013−1019..

Ren, F.; Liang, Z. Z.; Niu, M. X.; Hu, C. Y.; Pang, X. Preparation of chemically recyclable poly(ether- alt -ester) by the ring opening polymerization of cyclic monomers synthesized by coupling glycolide and epoxides. Chinese J. Polym. Sci. 2024 , 42 , 168−175..

Zhao, D.; Li, T.; Jiang, L.; Li, Z.; Li, Z. Selective synthesis and polymerization of methyl-1,4-dioxan-2-one toward closed-loop recyclable poly(ether- alt -ester) from methyl glycolate and propylene oxide. Biomacromolecules 2026 , 27 , 2125−2136..

Chwatko, M.; Lynd, N. A. Statistical copolymerization of epoxides and lac tones to high molecular weight. Macromolecules 2017 , 50 , 2714−2723..

Lochee, Y.; Hurry, D.; Bhaw-Luximon, A.; Kalangos, A. Biodegradable poly(ester-ether)s: ring-opening polymerization of D,L-3-methyl-1,4-dioxan-2-one using various initiator systems. Polym. Int. 2010 , 59 , 1310−1318..

Raquez, J. M.; Degée, P.; Narayan, R.; Dubois, P. Some thermodynamic, kinetic, and mechanistic aspects of the ring-opening polymerization of 1,4-dioxan-2-one initiated by Al(OiPr) 3 in bulk. Macromolecules 2001 , 34 , 8419−8425..

Raquez, J. M.; Degée, P.; Narayan, R.; Dubois, P. Synthesis of melt-stable and semi-crystalline poly(1,4-dioxan-2-one) by ring-opening (co)polymerisation of 1,4-dioxan-2-one with different lactones. Polym. Degrad. Stabil. 2004 , 86 , 159−169..

Isnard, F.; Carratu, M.; Lamberti, M.; Venditto, V.; Mazzeo, M. Copolymerization of cyclic esters, epoxides and anhydrides: evidence of the dual role of the monomers in the reaction mixture. Catal. Sci. Technol. 2018 , 8 , 5034−5043..

[Severson, S. M.; Fresh, A. A.; Limin, L.; Young, M. S.; LaPointe, A. M.; Coates, G. W. Synthesis of phenyl-substituted poly(3-hydroxybutyrates) with high and tunable glass transition temperatures via sequential catalytic transformations. J. Am. Chem. Soc . 2026 , 148 , 3, 2870−2875..

Chen, G. Q.; Lin, B. J.; Huang, J. M.; Zhao, L. Y.; Chen, Q. S.; Jia, S. P.; Yin, Q.; Zhang, X. M. Design and synthesis of chiral oxa-spirocyclic ligands for ir-catalyzed direct asymmetric reduction of bringmann’s lactones with molecular H 2 . J. Am. Chem. Soc. 2018 , 140 , 8064−8068..

Bringmann, G.; Breuning, M.; Pfeifer, R.-M.; Schenk, W. A.; Kamikawa, K.; Uemura, M. The lactone concept-a novel approach to the metal-assisted atroposelective construction of axially chiral biaryl systems. J. Organomet. Chem. 2002 , 661 , 31−47..

Cao, Q.; Tu, Y. M.; Fan, H. Z.; Shan, S. Y.; Cai, Z.; Zhu, J. B. Torsional strain enabled ring-opening polymerization towards axially chiral semiaromatic polyesters with chemical recyclability. Angew. Chem. Int. Ed. 2024 , 63 , e202400196..

Rao, D. Y.; Li, B.; Zhang, R.; Wang, H.; Lu, X. B. Binding of 4-( N,N -dimethylamino)pyridine to Salen- and Salan-Cr(III) cations: a mechanistic understanding on the difference in their catalytic activity for CO 2 /epoxide copolymerization. Inorg. Chem. 2009 , 48 , 2830−2836..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Machine Learning-assisted Prediction of Polymer Glass Transition Temperature: A Structural Feature Approach

Precise Pentamers with Diverse Monomer Sequences and Their Thermal Properties

Physical Properties of Polymers under Soft and Hard Nanoconfinement: A Review

Nanoparticle Dispersion and Glass Transition Behavior of Polyimide-grafted Silica Nanocomposites

Research on the Glass Transition Temperature and Mechanical Properties of Poly(vinyl chloride)/Dioctyl Phthalate (PVC/DOP) Blends by Molecular Dynamics Simulations

Related Author

Hadi Shirali

Bardia Afsordeh

Jiang-Tao Xu

Kun-Kun Guo

Lei Zhang

Rui-Zhe Liu

Ming-Chao Ma

Yun-Long Guo

Related Institution

Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, PO Box 15875-441, Tehran

Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran

College of Materials Science and Engineering, Hunan University

School of Chemical Engineering, UNSW Sydney

University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University

⁰

Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units

DOI：10.1007/s10118-026-3726-2

摘要

Abstract

关键词

Keywords

references