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：2026-06-04

- Regulation of Microphase Separation in Bio-based Thermoplastic Polyurethanes Driven by Hard Segment Content
- Chinese Journal of Polymer Science Vol. 44, Issue 8, Pages: 2748-2757(2026)
- 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：
- DOI：10.1007/s10118-026-3668-8
  CLC：
- Received：30 January 2026，
  
  Accepted：15 March 2026，
  
  Online First：03 June 2026，
  
  Published：15 August 2026
- 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.

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references

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