Effect of Small-molecule Diol Structure on Hydrogen Bonding Behavior of Polyester-based Polyurethanes During Hydrolytic Aging

LIU Mei-qin; YUAN Hong; ZHANG Bo; JIANG Ying-zhong; ZHAO Yu-mei; SHI Hong-cui

doi:10.14028/j.cnki.1003-3726.2025.25.180

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Effect of Small-molecule Diol Structure on Hydrogen Bonding Behavior of Polyester-based Polyurethanes During Hydrolytic Aging

更新时间：2025-10-30

- Effect of Small-molecule Diol Structure on Hydrogen Bonding Behavior of Polyester-based Polyurethanes During Hydrolytic Aging
- Polymer Bulletin Vol. 38, Issue 11, Pages: 1671-1684(2025)
- 作者机构：
  
  1.山西铁道职业技术学院，太原 030013
  2.山西省应用化学研究所(有限公司)，太原 030027
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.180
  CLC：
- Received：24 July 2025，
  
  Accepted：15 August 2025，
  
  Published Online：26 September 2025，
  
  Published：20 November 2025
- 稿件说明：
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刘美琴, 袁鸿, 张博, 蒋迎忠, 赵玉梅, 石红翠. 小分子二元醇结构对水老化过程中聚酯型聚氨酯氢键作用的影响. 高分子通报, 2025, 38(11), 1671-1684.

Liu, M. Q.; Yuan, H.; Zhang, B.; Jiang, Y. Z.; Zhao, Y. M.; Shi, H. C. Effect of small-molecule diol structure on hydrogen bonding behavior of polyester-based polyurethanes during hydrolytic aging. Polym. Bull. (in Chinese), 2025, 38(11), 1671-1684.
刘美琴, 袁鸿, 张博, 蒋迎忠, 赵玉梅, 石红翠. 小分子二元醇结构对水老化过程中聚酯型聚氨酯氢键作用的影响. 高分子通报, 2025, 38(11), 1671-1684. DOI： 10.14028/j.cnki.1003-3726.2025.25.180.

Liu, M. Q.; Yuan, H.; Zhang, B.; Jiang, Y. Z.; Zhao, Y. M.; Shi, H. C. Effect of small-molecule diol structure on hydrogen bonding behavior of polyester-based polyurethanes during hydrolytic aging. Polym. Bull. (in Chinese), 2025, 38(11), 1671-1684. DOI： 10.14028/j.cnki.1003-3726.2025.25.180.

摘要

合成了氨基甲酸酯基/脲键摩尔比分别为10/90、25/75和40/60的聚酯型聚氨酯(PU)，系统研究了小分子二元醇结构与氨基甲酸酯基/脲键的摩尔比对PU在水老化过程中氢键作用、吸水行为及力学性能的影响。结果表明：聚酯型PU在水浸初期24 h，水分子优先与软段酯羰基形成氢键作用，酯羰基的氢键化比例呈较大幅度上升趋势，游离酯羰基比例呈下降趋势；随着老化时间延长至720 h，氨酯羰基与水之间形成多种新型氢键，由结构对称性强的小分子二元醇(如1

4-丁二醇(BDO)、乙二醇(EG)、新戊二醇(NPG))合成的PU-B1、PU-E1和PU-N1，表现出更为显著的氢键重构现象，而由结构不对称、结晶性弱的1

2-丙二醇(PG)合成的PU-P系列则以原有氢键断裂为主。吸水率随浸泡老化时间延长持续增加，且小分子二元醇的结晶性对PU的吸水能力具有较强抑制作用。当氨基甲酸酯基/脲键摩尔比为40/60时，PU-B3吸水率最低(3.34%)，PU-P3最高(8.43%)。力学性能测试结果显示，老化720 h后，PU-B1、PU-E1与PU-N1仍保持较高的拉伸强度和应力响应，表现出典型的拉伸硬化行为；而PU-P2与PU-P3则应力-应变曲线趋于平缓，力学性能显著下降。上述性能劣化主要源于原有氢键的断裂或其结合强度的降低，导致聚氨酯分子间作用力减弱。同时，水分子对部分硬段相微区的侵蚀以及软段的增塑效应亦对性能下降起协同作用。

Abstract

Polyester-based polyurethanes (PU) with different urethane/urea molar ratios of 10/90

25/75

and 40/60 were synthesized using structurally diverse small-molecule diols. Hydrogen bonding dynamics

water uptake behavior

and mechanical properties were investigated to elucidate the effects of diol architecture and urethane/urea during immersion hydrothermal aging. The results revealed that water molecules preferentially interacted with the ester carbonyl groups in the soft segments during the initial 24 h

and the proportion of hydrogen-bonded ester carbonyl groups (

) was significantly enhanced

free ester carbonyl fraction (

) was reduced. Upon prolonged aging for up to 720 h

urethane carbonyls engage in various newly formed hydrogen bonds with water molecules. PU-B1

PU-E1

and PU-N1

synthesized from

small-molecule diols (

e.g.

4-butanediol (BDO)

ethylene glycol (EG)

neopentyl glycol (NPG))

exhibited a more pronounced hydrogen bond reorganization. In contrast

the PU-P series exhibited cleavage of the original hydrogen bonds derived primarily from asymmetric and low-crystallinity PG. Water uptake continuously increased with aging time

and the higher crystallinity of small-molecule diols markedly suppressed PU’s water absorption of PU. At a urethane/urea molar ratio of 40/60

PU-B3 exhibited the lowest water uptake (3.34%)

while PU-P3 exhibited the highest water uptake (8.43%). This difference is attributed to the higher crystallinity of the diol used in PU-B3 compared to the amorphous nature of PU-P3. Mechanical testing revealed that after 720 h of aging

PU-B1

PU-E1

and PU-N1 retained high tensile strength and stress responsiveness

exhibiting typical strain-hardening behavior. In contrast

PU-P2 and PU-P3 exhibited flattened stress-strain curves

indicating significant mechanical degradation. Performance degradation is primarily caused by hydrogen bond breakage or weakening of the original hydrogen bonds

resulting in reduced intermolecular forces. Meanwhile

water-induced erosion of certain hard segment microdomains and the plasticization effect on soft segments synergistically contribute to the performance decline.

关键词

Keywords

references

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