Tailoring Block Sequence Length Enhances the Mechanical Properties of Thermoplastic Polyurethane Elastomers

Jia-xin Shi; Bao-hua Guo; Jun Xu

doi:10.11777/j.issn1000-3304.2025.25028

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Tailoring Block Sequence Length Enhances the Mechanical Properties of Thermoplastic Polyurethane Elastomers

Research Article | 更新时间：2025-08-28

- Tailoring Block Sequence Length Enhances the Mechanical Properties of Thermoplastic Polyurethane Elastomers
- Acta Polymerica Sinica Vol. 56, Issue 9, Pages: 1537-1545(2025)
- 作者机构：
  
  清华大学化学工程系先进材料教育部重点实验室北京 100084
- 作者简介：
  
  Jun Xu, E-mail: jun-xu@mail.tsinghua.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25028
  CLC：
- CSTR：32057.14.GFZXB.2025.7379
- Received：26 January 2025，
  
  Accepted：06 March 2025，
  
  Published Online：22 April 2025，
  
  Published：20 September 2025
- 稿件说明：
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史家昕, 郭宝华, 徐军. 调控嵌段序列长度提升热塑性聚氨酯的力学性能. 高分子学报, 2025, 56(9), 1537-1545

Shi, J. X.; Guo, B. H.; Xu, J. Tailoring block sequence length enhances the mechanical properties of thermoplastic polyurethane elastomers. Acta Polymerica Sinica, 2025, 56(9), 1537-1545
史家昕, 郭宝华, 徐军. 调控嵌段序列长度提升热塑性聚氨酯的力学性能. 高分子学报, 2025, 56(9), 1537-1545 DOI： 10.11777/j.issn1000-3304.2025.25028. CSTR： 32057.14.GFZXB.2025.7379.

Shi, J. X.; Guo, B. H.; Xu, J. Tailoring block sequence length enhances the mechanical properties of thermoplastic polyurethane elastomers. Acta Polymerica Sinica, 2025, 56(9), 1537-1545 DOI： 10.11777/j.issn1000-3304.2025.25028. CSTR： 32057.14.GFZXB.2025.7379.

摘要

热塑性聚氨酯(TPU)作为广泛应用的材料，其结构-性能关系与高性能设计备受关注. 本研究针对具有氢键阵列的酰肼基TPU弹性体，通过预聚-扩链法控制嵌段序列长度制备了软硬段比例相同但是软硬段的序列长度不同的材料. 结果表明，长序列可以通过强化微相分离和氢键分级响应来实现性能的显著提高，包括强度、韧性、流动温度、抗松弛等. 序列长度调控这一方法为高性能TPU设计提供了新颖的思路，也加深了对TPU结构-性能关系的认识.

Abstract

Thermoplastic polyurethane (TPU) has become a pivotal engineering material due to its unique combination of elasticity and processability. Recent research has focused on elucidating the structure-property relationship to guide high-performance TPU design. This study innovatively explores the impact of segment sequence length on material performance through a systematic synthesis strategy. Using pre-polymerization and chain extension techniques

we developed a series of hydrazide-based TPU elastomers with identical hard/soft segment ratios but varying sequence lengths. Characterization results reveal that extending the sequence lengths induces two critical structural modifications: enhanced microphase separation between hard and soft domains

and optimized hierarchical hydrogen bonding networks. These structural changes collectively elevate material performance

with long-sequence TPUs exhibiting a 50% increase in tensile strength (from 50 MPa to 80 MPa)

and significantly higher flow temperatures (Δ

45 ℃) compared to short-sequence counterparts. Notably

stress relaxation tests demonstrate that extended sequences increase the relaxation time significantly

indicating superior dimensional stability. The performance enhancements stem from the dual reinforcement mechanism: microphase separation creates robust physical crosslinks while hierarchical hydrogen bonds enable energy dissipation. This sequence engineering approach provides a paradigm shift from traditional composition-focused design to topological structure optimization

offering a viable pathway for developing TPUs that simultaneously satisfy conflicting requirements of mechanical robustness and processing efficiency in industrial applications.

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references

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