Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content

De-Xian Yin; Yu-Qiong Hu; Ya-Nan Cheng; Shuo Yan; Zi-Lin Liu; Yi-Qing Wang; Shi-Kai Hu; Xiu-Ying Zhao

doi:10.1007/s10118-026-3668-8

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Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content

RESEARCH ARTICLE | Updated：2026-07-27

- Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content
- Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content
- Chinese Journal of Polymer Science 2026年44卷第8期页码：2748-2757
- Affiliations：
  
  State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
- Author bio：
  
  wangyq1@mail.buct.edu.cn (Y.Q.W.)
  skhu@mail.buct.edu.cn (S.K.H.)
  zhaoxy@mail.buct.edu.cn (X.Y.Z.)
- Funds：
  
  This work was financially supported by the National Key Research and Development Program of China (No. 2024YFB3713000) and the National Natural Science Foundation of China (Nos. 52203003 and 52250357).;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3668-8.The data that support the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3668-8
  中图分类号：
- 收稿：2026-01-30，
  
  录用：2026-03-15，
  
  网络首发：2026-06-03，
  
  纸质出版：2026-08-15
- Accepted：
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Yin, D. X.; Hu, Y. Q.; Cheng, Y. N.; Yan, S.; Liu, Z. L.; Wang, Y. Q.; Hu, S. K.; Zhao, X. Y. Regulation of microphase separation in bio-based thermoplastic polyurethanes driven by hard segment content. Chinese J. Polym. Sci. 2026, 44, 2748–2757

De-Xian Yin, Yu-Qiong Hu, Ya-Nan Cheng, et al. Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2748-2757.
Yin, D. X.; Hu, Y. Q.; Cheng, Y. N.; Yan, S.; Liu, Z. L.; Wang, Y. Q.; Hu, S. K.; Zhao, X. Y. Regulation of microphase separation in bio-based thermoplastic polyurethanes driven by hard segment content. Chinese J. Polym. Sci. 2026, 44, 2748–2757 DOI： 10.1007/s10118-026-3668-8.

De-Xian Yin, Yu-Qiong Hu, Ya-Nan Cheng, et al. Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2748-2757. DOI： 10.1007/s10118-026-3668-8.

摘要

Regulating hard segment content in bio-based 1

4-phenylene diisocyanate (PPDI) polyurethanes optimizes microphase separation and induces ordered crystallization. This significantly enhances the 5% thermal deformation temperature to 230.2 °C and tensile strength to 22.6 MPa

providing a robust strategy for sustainable

high-performance elastomers.

Abstract

Regulation of the microphase-separated structure is critical for high-performance thermoplastic polyurethanes (TPUs). To address the limitations of poor heat resistance and reliance on petrochemical resources in traditional TPUs

bio-based TPUs were engineered using rigid 1

4-phenylene diisocyanate and bio-based poly(trimethylene ether) glycol. The results demonstrate that microstructural evolution

hydrogen bonding network formation

and tailoring of macroscopic properties in TPUs can be realized by varying the hard segment content. Increasing the hard segment content enhanced microstructural ordering

boosting the tensile strength from 6.1 MPa to 22.6 MPa while maintaining an elongation at break above 600%. Crucially

the robust crystalline network enhanced thermal stability of the TPUs

resulting in a maximum 5% thermal deformation temperature of 230.2 °C for TPUs. This work elucidates the structure-property relationships governing microphase separation

empowering the rational design of bio-based materials with exceptional toughness and thermal resistance.

关键词

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references

Balko, J.; Fernández-d’Arlas, B.; Pöselt, E.; Dabbous, R.; Müller, A. J.; Thurn-Albrecht, T. Clarifying the origin of multiple melting of segmented thermoplastic polyurethanes by fast scanning calorimetry. Macromolecules 2017 , 50 , 7672−7680..

Fei, Z. X.; Yin, C.; Sun, J. R.; Yuan, L.; Shi, L. Y. Healable and recyclable multiblock polyurethanes with mechanical performance tailorability based on hierarchical phase separation and dynamic bond interaction. Polymer 2023 , 289 , 126467..

Backes, E. H.; Harb, S. V.; Pinto, L. A.; de Moura, N. K.; de Morgado, G. F. M.; Marini, J.; Pessan, L. A. Thermoplastic polyurethanes: synthesis, fabrication techniques, blends, composites, and applications. J. Mater. Sci. 2024 , 59 , 1123−1152..

[Duval, A.; Sarbu, A.; Dalmas, F.; Albertini, D.; Avérous, L. 2,3-butanediol as a biobased chain extender for thermoplastic polyurethanes: influence of stereochemistry on macromolecular architectures and properties. Macromolecules 2022 , 55 , 5371−5381..

Rajput, B. S.; Forman, A.; Halloran, M. W.; Hai, T. A. P.; Scofield, G. B.; Burkart, M. D. Variation of aliphatic diisocyanates in bio-based TPUs. Macromolecules 2023 , 56 , 8813−8822..

Xie, D. M.; Zhang, Y. X.; Li, Y. D.; Weng, Y.; Zeng, J. B. Castor oil-derived sustainable poly(urethane urea) covalent adaptable networks with tunable mechanical properties and multiple recyclability based on reversible piperidine-urea bond. Chem. Eng. J. 2022 , 446 , 137071..

Mei, X.; Lu, W.; Dong, J. R.; Pan, K. H.; Tan, J. J.; Yan, H. Y.; Chen, H. X. Influence of soft segment length on the dielectric polarization behavior of ketal-containing polyurethane elastomer. Chinese J. Polym. Sci. 2025 , 44 , 189−197..

He, Y.; Xie, D.; Zhang, X. The structure, microphase-separated morphology, and property of polyurethanes and polyureas. J. Mater. Sci. 2014 , 49 , 7339−7352..

Qiu, J.; Zhao, H.; Luan, S.; Wang, L.; Shi, H. Recent advances in functional polyurethane elastomers: from structural design to biomedical applications. Biomater. Sci. 2025 , 13 , 2526−2540..

Li, K.; Yan, X.; Wang, Y.; Ai, T.; Niu, Y.; Chen, Y. Design and modification mechanism of a novel high-viscosity thermoplastic polyurethane modified asphalt. Constr. Build. Mater. 2024 , 433 , 136585..

Zeng, Y.; Chen, Y.; Sha, D.; Wu, Y.; Qiu, R.; Liu, W. Highly stretchable fatty acid chain-dangled thermoplastic polyurethane elastomers enabled by H-bonds and molecular chain entanglements. ACS Sustainable Chem. Eng. 2022 , 10 , 11524−11532..

Xu, W.; Zhang, R.; Liu, W.; Zhu, J.; Dong, X.; Guo, H.; Hu, G. H. A multiscale investigation on the mechanism of shape recovery for IPDI to PPDI hard segment substitution in polyurethane. Macromolecules 2016 , 49 , 5931−5944..

Wu, Y.; Xu, C.; Gan, M.; Zhai, M.; Chen, Z.; Shou, T.; Hu, G. H. Multifunctional bio-based waterborne polyurethane with excellent transparency, strength, abrasion resistance, and antimicrobia l properties. Prog. Org. Coat. 2024 , 195 , 108671..

Jia, Y.; Guan, Q.; Chu, C.; Zhang, L.; Neisiany, R. E.; Gu, S.; You, Z. A fluorine-based strong and healable elastomer with unprecedented puncture resistance for high performance flexible electronics. Sci. Bull. 2024 , 69 , 1875−1886..

Shen, A.; Xuan, H.; Jia, Y.; Gu, S.; Neisiany, R. E.; Shu, W.; You, Z. Dynamic healing-assembly for biocompatible, biodegradable, stretchable and self-healing triboelectric nanogenerators. Chem. Eng. J. 2024 , 491 , 151896..

Zhang, W.; Xuan, H.; Xu, X.; Lou, J.; Guan, Q.; You, Z. Multiple dynamic bonds enable high mechanical strength and efficient room-temperature self-healable polyurethane for triboelectric nanogenerators. Sci. China Chem. 2025 , 68 , 1468−1477..

Jia, Y.; Chu, C.; Wu, Z.; Ni, Y.; Cao, S.; Liao, T.; You, Z. Simultaneous improvement of mechanical strength, toughness, and self-healability of elastomers enabled by F─H-bond-based nanoconfinement. Angew. Chem. Int. Ed. 2025 , 64 , e202505848..

[Jia, Y.; Chu, C.; Cao, S.; Wu, Z.; Gu, S.; Chen, Z.; You, Z. Self-confined effects induced by F─H bonds simultaneously enhance mechanical strength, conductivity, and self-healability of ionic elastomers. Adv. Funct. Mater . 2025 , 36 , e26628..

Gaymans, R. J. Segmented copolymers with monodisperse crystallizable hard segments: Novel semi-crystalline materials. Prog. Polym. Sci. 2011 , 36 , 713−748..

Amirkhosravi, M.; Yue, L.; Ju, T.; Manas-Zloczower, I. Designing thermal annealing to control mechanical performance of thermoplastic polyurethane elastomers. Polymer 2021 , 214 , 123254..

Yang, J. X.; Qian, H. J.; Gong, Z.; Lu, Z. Y.; Cui, S. X. Stretching elasticity and flexibility of single polyformaldehyde chain. Chinese J. Polym. Sci. 2022 , 40 , 333−337..

Pérez-Camargo, R. A.; Meabe, L.; Liu, G.; Sardon, H.; Zhao, Y.; Wang, D.; Müller, A. J. Even–odd effect in aliphatic polycarbonates with different chain lengths: From poly (hexamethylene carbonate) to poly (dodecamethylene carbonate). Macromolecules 2020 , 54 , 259−271..

Zhang, L.; Huang, H.; Sun, L.; Ma, X.; Tan, H.; You, Z. Sequence-controlled dynamic covalent units enable decoupling of mechanical and self-healing performance of polymers. Sci. China Chem. 2024 , 68 , 745−753..

Cheng, B. X.; Gao, W. C.; Ren, X. M.; Ouyang, X. Y.; Zhao, Y.; Zhao, H.; Li, R. K. A review of microphase separation of polyurethane: Characterization and applications. Polym. Test. 2022 , 107 , 107489..

Gao, X.; Qian, H.; Wang, J.; Hong, Y.; Chen, Y.; Zhao, L.; Hu, D. Self-reinforced thermoplastic polyurethane composite with excellent mechanical properties, heat resistance and sustainable recycling. Compos. Part B Eng. 2025 , 297 , 112342..

Farid, M. I.; Wu, W.; Li, G.; Zheng, A.; Zhao, Y. Superior tensile properties of FDM 3D-printed TPU/E-TPU layered structure. J. Mater. Res. 2024 , 39 , 2051−2066..

Ti, Y.; Chen, D. Temperature dependence of hydrogen bond in fe-OCAP/polyurethane blends. J. Appl. Polym. Sci. 2013 , 130 , 2265−2271..

Sofla, R. L. M.; Rezaei, M.; Babaie, A.; Nasiri, M. Preparation of electroactive shape memory polyurethane/graphene nanocomposites and investigation of relationship between rheology, morphology and electrical properties. Compos. Part B Eng. 2019 , 175 , 107090..

Chen, Z.; Wang, J.; Zhao, W.; Hu, S.; Yin, D.; Zhao, X. Synergistic dual-crosslinking and multilevel hydrogen-bond engineering for high-damping polyurethanes. Constr. Build. Mater. 2026 , 514 , 145569..

Yin, D.; Liu, Y.; Wang, X.; Hu, S.; Liu, L.; Zhao, X.; Zhang, L. Novel bio-based polyurethane elastomers for adjustable room-temperature damping property. Compos. Commun. 2024 , 49 , 101975..

Ning, N.; Qin, H.; Wang, M.; Sun, H.; Tian, M.; Zhang, L. Improved dielectric and actuated performance of thermoplastic polyurethane by blending with XNBR as macromolecular dielectrics. Polymer 2019 , 179 , 121646..

Wang, X.; Yin, D.; Chen, Z.; Hu, Y.; Hu, S.; Zhao, X. CO 2 -based polyurethane elastomers with enhanced mechanical and tunable room-temperature damping performances. Eur. Polym. J. 2024 , 220 , 113499..

Wang, H.; Li, Y.; Zhang, H.; Lang, X.; Wang, X.; Cao, L.; Zong, C. Effects of soft segment molecular weight on the properties of recyclable polyurethanes with low-temperature multiple shape memory. J. Polym. Sci. 2024 , 63 , 121−132..

Gong, X.; Liu, Q.; Chen, P.; Wang, H.; Liu, X.; Chen, S.; Wu, S. Modification mechanism of green polyurethane modified asphalt prepared by in-situ polymerization. Constr. Build. Mater. 2024 , 448 , 138243..

Fernández-d’Arlas, B.; Ugarte, L.; Eceiza, A.; Müller, A. J. Chemical composition and mechanical deformation define lamellar sizes in aliphatic triblock-based polyurethane elastomers. Macromolecules 2024 , 57 , 7755−7767..

Huang, M.; Li, Z.; Xu, W.; He, S.; Liu, W.; Jiang, L.; Liu, H. Visualization and quantification of microphase separation in thermoplastic polyurethanes under different hard segment contents and its effect on the mechanical properties. Polym. Test. 2024 , 131 , 108329..

Amjed, N.; Bhatti, I. A.; Simon, L.; Castel, C. D.; Zia, K. M.; Zuber, M.; Murtaza, M. A. Preparatio n and characterization of thermoplastic polyurethanes blended with chitosan and starch processed through extrusion. Int. J. Biol. Macromol. 2022 , 208 , 37−44..

Xiao, Y.; Jiang, L.; Liu, Z.; Yuan, Y.; Yan, P.; Zhou, C.; Lei, J. Effect of phase separation on the crystallization of soft segments of green waterborne polyurethanes. Polym. Test. 2017 , 60 , 160−165..

Hu, S.; He, S.; Wang, Y.; Wu, Y.; Shou, T.; Yin, D.; Zhang, L. Self-repairable, recyclable and heat-resistant polyurethane for high-performance automobile tires. Nano Energy 2022 , 95 , 107012..

Lukoschek, S.; Frankenbach, L. A.; Kruppke, I.; Cherif, C. Biobased TPU for melt spun multifilament yarns as a sustainable alternative for conventional fossil based TPU. J. Polym. Environ. 2025 , 33 , 1934−1946..

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