An Excellent Biobased Copolymerization Monomer Module: Synthesis of Biobased Copolymers with Excellent Heat Resistance and Hydrophilic Properties

Xiao-Jun Ma; Xiao-Qing Hao; Hong-Ji Wang; Han-Yu Yao; Zi-Qing Wang; Yin Lv

doi:10.1007/s10118-025-3433-4

Your Location：

Home >

Browse articles >

An Excellent Biobased Copolymerization Monomer Module: Synthesis of Biobased Copolymers with Excellent Heat Resistance and Hydrophilic Properties

RESEARCH ARTICLE | Updated：2025-10-30

- An Excellent Biobased Copolymerization Monomer Module: Synthesis of Biobased Copolymers with Excellent Heat Resistance and Hydrophilic Properties
- An Excellent Biobased Copolymerization Monomer Module: Synthesis of Biobased Copolymers with Excellent Heat Resistance and Hydrophilic Properties
- 高分子科学（英文） 2025年43卷第11期页码：2102-2109
- Affiliations：
  
  School of Chemistry and Chemical Engineering, State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi 832000, China
- Author bio：
  
  ag_125@163.com or Lvyin125@shzu.edu.cn
- Funds：
  
  This work was financially supported by the Provincial Project of Science and Technology (No. 2023112258), Tianshan Talent Training Program (No. 2024TSYCCX0112), Talent Introduction and Start Foundation for Young Scientists of Shihezi University (No. 2022ZK004), Program for Young Innovative Talents of Shihezi University (No. CXFZ202302).
- DOI：10.1007/s10118-025-3433-4
  中图分类号：
- 收稿：2025-07-13，
  
  录用：2025-08-11，
  
  网络首发：2025-10-16，
  
  纸质出版：2025-11-05
- Accepted：
Scan QR Code
Ma, X. J.; Hao, X. Q.; Wang, H. J.; Yao, H. Y.; Wang, Z. Q.; Lv, Y. An excellent biobased copolymerization monomer module: synthesis of biobased copolymers with excellent heat resistance and hydrophilic properties. Chinese J. Polym. Sci. 2025, 43, 2102–2109

Xiao-Jun Ma, Xiao-Qing Hao, Hong-Ji Wang, et al. An Excellent Biobased Copolymerization Monomer Module: Synthesis of Biobased Copolymers with Excellent Heat Resistance and Hydrophilic Properties[J]. Chinese Journal of Polymer Science, 2025, 43(11): 2102-2109.
Ma, X. J.; Hao, X. Q.; Wang, H. J.; Yao, H. Y.; Wang, Z. Q.; Lv, Y. An excellent biobased copolymerization monomer module: synthesis of biobased copolymers with excellent heat resistance and hydrophilic properties. Chinese J. Polym. Sci. 2025, 43, 2102–2109 DOI： 10.1007/s10118-025-3433-4.

Xiao-Jun Ma, Xiao-Qing Hao, Hong-Ji Wang, et al. An Excellent Biobased Copolymerization Monomer Module: Synthesis of Biobased Copolymers with Excellent Heat Resistance and Hydrophilic Properties[J]. Chinese Journal of Polymer Science, 2025, 43(11): 2102-2109. DOI： 10.1007/s10118-025-3433-4.

摘要

Incorporation of CBPC units markedly enhances PBCC copolymers’ thermal stability (Tm 225.8 °C

Td₅% 306.7 °C) and imparts excellent hydrophilicity

enabling a hydrophobic-to-hydrophilic transition. This work proposes a new strategy for designing high-performance bio-based polyesters

reducing reliance on finite fossil resources.

Abstract

The use of biomass feedstocks for the manufacture of high-performance polymers can help expand their range of applications and reduce their dependence on finite fossil resources. However

improving the heat resistance and hydrophilicity of bio-based polyesters remains a significant challenge. Herein

we introduce

trans

-1

4-cyclohexane-bis(pyrrolidone-4-methylcarboxylate) (CBPC)

a novel bio-based tricyclic dibasic ester synthesized from renewable dimethyl itaconic acid and

trans

-1

4-cyclohexane diamine

via

an aza-Michael addit

ion reaction. As a unique comonomer

CBPC features a rigid tricyclic backbone that significantly enhances chain packing and thermal stability

whereas its pyrrolidone side groups impart tunable polarity and improved hydrophilicity. Using CBPC

diphenyl carbonate

and 1

4-butylene glycol

a series of PBCC copolymers with 10 mol%–30 mol% CBPC was synthesized

via

ester-exchange and melt polycondensation methods. Incorporation of CBPC raised the melting temperature (

) from 56.8 °C to 225.8 °C and the initial decomposition temperature (

d5%

) from 258.0 °C to 306.7 °C

positioning PBCC among the most heat-resistant bio-based polyesters reported. Additionally

the pyrrolidone units enabled transformation from hydrophobic to hydrophilic. This study demonstrates that CBPC is an effective and innovative building block for the design of bio-based polymers with enhanced thermal and surface properties

offering a promising strategy for the development of high-performance sustainable materials.

关键词

Keywords

references

Krajovic, D. M.; Kumler, M. S.; Hillmyer, M. A. PLA block polymers: versatile materials for a sustainable future. Biomacromolecules. 2025 , 26 , 2761−2783..

[Tahara, A.; Yashiro, S.; Hokajo, T.; Kudo, S.; Yoshizaki, Y.; Konno, T.; Doi, T. Stereoselective polycondensation of levoglucosenone leading to water-degradable biopolymers. Polym. Chem . 2025 , 16 , 800−808..

Yang, R.; Yang, R.; Yang, S.; Zhang, K. Hydrogen bonding-rich bio-benzoxazine resin provides high-performance thermosets and ultrahigh-performance composites. ACS Sustain. Chem. Eng. 2024 , 12 , 1728−1739..

[Ma, X.; Wang, H.; Wang, Z.; Lv, Y.; Wei, Z. Synthesis and properties of biodegradable thiophene-based aliphatic polycarbonate/polyester copolymer: potential substitutes for terephthalic acid-based polymer. Eur. Polym. J . 2024 , 210 , 112972..

Kasmi, N.; Pinel, C.; Da Silva Perez, D.; Dieden, R.; Habibi, Y. Synthesis and characterization of fully biobased polyesters with tunable branched architectures. Polym. Chem. 2021 , 12 , 991−1001..

[Rajalakshmi, P.; Marie, J. M.; Maria Xavier, A. J. Castor oil-derived monomer ricinoleic acid based biodegradable unsaturated polyesters. Polym. Degrad. Stabil . 2019 , 170 , 109016..

[Feng, J.; Li, J.; Feng, J.; Wei, Z.; Wang, Z.; Song, X. Synthesis of aliphatic polycarbonates from diphenyl carbonate and diols over Zinc (II) acetylacetonate. Molecules 2022 , 27 , 8958..

Cai, X.; Yang, X.; Zhang, H.; Wang, G. Modification of biodegradable poly(butylene carbonate) with 1,4-cyclohexanedimethylene to enhance the thermal and mechanical properties. Polym. Degrad. Stabli. 2017 , 143 , 35−41..

Cai, X.; Yang, X.; Zhang, H.; Wang, G. Aliphatic-aromatic poly(carbonate- co -ester)s containing biobased furan monomer: synthesis and thermo-mechanical properties. Polymer 2018 , 134 , 63−70..

Zhu, C.; Liu, S.; Wang, Q.; Zhang, H.; Wang, G. Synthesis and properties of poly(butylene carbonate-co-spirocyclic carbonate). Chem. Res. Chin. Univ. 2019 , 35 , 729−734..

Chen, Y.; Wu, L.; Li, B. G. Colorless transparent cyclobutanediol-based copolyesters with excellent polymerization robustness, thermal stability, and high performance. ACS. Appl. Polym. Mater. 2022 , 4 , 2006−2016..

Liu, L.; Tu, Z.; Lu, Y.; Wei, Z. Scale synthesis of poly(butylene carbonate-co-terephthalate) and Its depolymerization–repolymerization recycling process. Ind. Eng. Chem. Res. 2023 , 62 , 4260−4270..

Würdemann, M. A.; Faber, T.; H arings, J. A. W.; Bernaerts, K. V.; Orru, R. V. A.; Pich, A. Post-modification of biobased pyrazines and their polyesters. Macromolecules 2021 , 54 , 10850−10859..

van der Maas, K.; Wang, Y.; Weinland, D. H.; van Putten, R.-J.; Wang, B.; Gruter, G. J. M. PISOX copolyesters─bio- and CO2-based marine-degradable high-performance polyesters. ACS Sustain. Chem. Eng. 2024 , 12 , 9822−9832..

Wang, H.; Ma, X.; Yao, H.; Chang, H.; Lv, Y.; Wei, Z. Synthesis of degradable polyester with high molecular weight and excellent mechanical properties through copolymerization modification of poly(butylene succinate). Polym. Chem. 2024 , 15 , 4570−4579..

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 , 9302−9314..

[Yu, Y.; Liu, S.; Liu, H.; Wei, Z. A renewable tricyclic building block towards synthesis of biobased polyesters with high-performance and hydrolyzability. Polym. Degrad. Stabil . 2023 , 217 , 110514..

Zeng, C.; Ren, J.; Shen, W.; Zhang, S.; Ji, P.; Wang, C.; Wang, H. Synthesis of thermal-resistant polyester-polycarbonate with fully rigid structure from biobased isosorbide. Macromolecules 2024 , 57 , 6284−6294..

Wang, Y.; Xie, R.; Xu, J.; Li, Z.; Guo, M.; Yang, F.; Wu, J.; Wang, H. Strong, tough, and heat-resistant isohexide-based copolycarbonates: an ecologically safe alternative for bisphenol-a polycarbonate. ACS Sustain. Chem. Eng. 2024 , 12 , 7553−7565..

Wang, T.; Wang, Q.; Quan, Y.; Liao, X.; Sun, R.; Ding, L.; Xie, M. Efficient Synthesis of high-molecular-weight biobased polycarbonates by lithium lactate. ACS Appl. Polym. Mater. 2023 , 5 , 8296−8304..

Zhang, Z.; Xu, F.; Zhang, Y.; Li, C.; He, H.; Yang, Z.; Li, Z. A non-phosgene process for bioderived polycarbonate with high molecular weight and advanced property profile synthesized using amino acid ionic liquids as catalysts. Green Chem. 2020 , 22 , 2534−2542..

Morand, C.; Mantione, D.; Dove, A. P.; Sardón, H.; Jehanno, C. Controlling the cis/trans content of biobased unsaturated polyesters by judicious choice of a biosourced catalyst. ACS Sustain. Chem. Eng. 2025 , 13 , 6176−6185..

Han, C.; Liu, J.; Li, C.; Xiao, Y.; Wu, S.; Du, M. FDCA bio-based copolyester PBFA: synthesis, properties, and fluorescence regulation. Polym. Chem. 2025 , 16 , 2254−2262..

[Li, J.; Yu, Y.; Zhang, X. Synthesis of renewable and seawater-degradable polyesters based on a fully biobased diester. Polym. Degrad. Stabil . 2024 , 230 , 111015..

[Zhang, X.; Yin, M.; Wang, J.; Pang, C.; Liu, X.; Zhu, J. Biobased high barrier copolyesters derived from furandicarboxylic acid and citric acid. Eur. Polym. J . 2024 , 213 , 113075..

[Zarei, M.; El Fray, M. Synthesis of Hydrophilic Poly(butylene succinate-butylene dilinoleate) (PBS-DLS) copolymers containing poly(ethylene glycol) (PEG) of variable molecular weights. Polymers 2021 , 13 , 3177..

[Zhu, H.; Hu, H.; Luan, Q.; Lin, C.; Xu, J.; Wang, J.; Ying, W. B.; Zhu, J. Highly crystalline, heat resistant and biodegradable copolyesters from fully bio-based bis(pyrrolidone) monomer. Giant 2024 , 18 , 100276..

Yu, Y.; Liu, S.; Wei, Z. Improving Thermal, Mechanical, and crystalline properties of poly(butylene succinate) copolyesters from a renewable rigid diester. ACS Sustain. Chem. Eng. 2023 , 11 , 15091−15101..

Yu, Y.; Liu, H.; Li, J.; Song, H.; Wei, Z. Tricyclic diester and 2,5-furandicarboxylic acid for the synthesis of biobased hydrolysis copolyesters with high glass transition temperatures. Biomacromolecules 2023 , 24 , 5105−5115..

Hu, H.; Li, J.; Tian, Y.; Chen, C.; Li, F.; Ying, W. B.; Zhang, R.; Zhu, J. Experimental and theoretical study on glycolic acid provided fast bio/seawater-degradable poly(butylene succinate- co -glycolate). ACS Sustain. Chem. Eng. 2021 , 9 , 3850−3859..

Park, S.-A.; Choi, J.; Ju, S.; Jegal, J.; Lee, K. M.; Hwang, S. Y.; Oh, D. X.; Park, J. Copolycarbonates of bio-based rigid isosorbide and flexible 1,4-cyclohexanedimethanol: merits over bisphenol-a based polycarbonates. Polymer 2017 , 116 , 153−159..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Synergistic Effects of Poly(propylene carbonate) Content and Pre-stretching on the Strength, Toughness, and Heat Resistance of Polylactide/Poly(propylene carbonate) Blends

Heat-resistant Microporous Star-shaped Casting Polyurethane for Airless Electric Bicycle Tires

Synthesis and Characterization of α-End Functionalized 3,4-Polyisoprene Using Fe(acac)3/IITP/AliBu3 Catalyst

Molecularly Engineered Polyimide Films with Switchable Cavitation for Bidirectional Passive Thermal Regulation

Tunable Circularly Polarized Luminescence of Helical Poly(phenylacetylene)s via Side-chain-to-Backbone Förster Resonance Energy Transfer