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

刘美琴; 袁鸿; 张博; 蒋迎忠; 赵玉梅; 石红翠

doi:10.14028/j.cnki.1003-3726.2025.25.180

您当前的位置：

首页 >

文章列表页 >

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

研究论文 | 更新时间：2025-10-30

- 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
- Effect of Small-molecule Diol Structure on Hydrogen Bonding Behavior of Polyester-based Polyurethanes During Hydrolytic Aging
- 高分子通报 2025年38卷第11期页码：1671-1684
- 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：
  
  E-mail: soniashc@163.com
- 基金信息：
  
  山西省高等学校科技创新项目(2023L5551);山西省教育科学“十四五”规划2022年度课题(GH-220230);山西省重点研发计划项目(202202040201013)
- DOI：10.14028/j.cnki.1003-3726.2025.25.180
  中图分类号：
- 收稿：2025-07-24，
  
  录用：2025-08-15，
  
  网络出版：2025-09-26，
  
  纸质出版：2025-11-20
- 稿件说明：
移动端阅览
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 gly

col (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

Boubakri, A. ; Elleuch, K. ; Guermazi, N. ; Ayedi, H. F . Investigations on hygrothermal aging of thermoplastic polyurethane material . Mater. Des. , 2009 , 30 ( 10 ), 3958 – 3965 .

Schneider, N. S. ; Dusablon, L. V. ; Spano, L. A. ; Hopfenberg, H. B. ; Votta, F . Sorption and diffusion of water in a rubbery polyurethane . J. Appl. Polym. Sci. , 1968 , 12 ( 3 ), 527 – 532 .

Panaitescu, I. ; Koch, T. ; Archodoulaki, V. M . Effects of temperature, humidity and automotive fluids exposure on glass fiber/polyurethane composites . Polym. Compos. , 2019 , 40 ( 6 ), 2357 – 2367 .

王义霞 , 梁书恩 , 宋宁宁 , 田春蓉 , 林晓艳 , 陈可平 . 硬段含量对聚氨酯弹性体的吸水动力学及力学性能的影响 . 高分子学报 , 2023 , 54 ( 2 ), 277 – 285 .

Yang, B. ; Huang, W. M. ; Li, C. ; Li, L . Effects of moisture on the thermomechanical properties of a polyurethane shape memory polymer . Polymer , 2006 , 47 ( 4 ), 1348 – 1356 .

de Oliveira, G. L. ; Ariza Gomez, A. J. ; Caire, M. ; Vaz, M. A. ; da Costa, M. F . Characterization of seawater and weather aged polyurethane elastomer for bend stiffeners . Polym. Test. , 2017 , 59 , 290 – 295 .

Zhou, R. ; Lu, D. H. ; Jiang, Y. H. ; Li, Q. N . Mechanical properties and erosion wear resistance of polyurethane matrix composites . Wear , 2005 , 259 ( 1-6 ), 676 – 683 .

Wang, Z. Y. ; Du, M. R. ; Fang, H. Y. ; Zhang, C. ; Li, M. J. ; Shi, M. S . Influence of different corrosion environments on mechanical properties of a roadbed rehabilitation polyurethane grouting material under uniaxial compression . Constr. Build. Mater. , 2021 , 301 , 124092 .

Rutkowska, M. ; Krasowska, K. ; Heimowska, A. ; Steinka, I. ; Janik, H . Degradation of polyurethanes in sea water . Polym. Degrad. Stab. , 2002 , 76 ( 2 ), 233 – 239 .

Pegoretti, A. ; Kolarik, J. ; Penati, A . Hydrolytic stability and mechanical properties of poly(ester urethanes) . Angew. Makromol. Chem. , 1994 , 220 ( 1 ), 49 – 60 .

Thompson, D. G. ; Osborn, J. C. ; Kober, E. M. ; Schoonover, J. R . Effects of hydrolysis-induced molecular weight changes on the phase separation of a polyester polyurethane . Polym. Degrad. Stab. , 2006 , 91 ( 12 ), 3360 – 3370 .

Mondal, S. ; Martin, D . Hydrolytic degradation of segmented polyurethane copolymers for biomedical applications . Polym. Degrad. Stab. , 2012 , 97 ( 8 ), 1553 – 1561 .

陈大俊 , 杨雪忠 . 对聚氨酯中氢键强度分布的理论探讨 . 中国纺织大学学报 , 1991 , 17 ( 1 ), 98 – 102 .

Deng, X. Y. ; Xie, H. ; Du, L. ; Fan, C. J. ; Cheng, C. Y. ; Yang, K. K. ; Wang, Y. Z . Polyurethane networks based on disulfide bonds: from tunable multi-shape memory effects to simultaneous self-healing . Sci. China Mater ., 2019 , 62 ( 3 ), 437 – 447 .

陈大俊 , 李瑶君 . 热塑性聚氨酯弹性体中的氢键作用: 动态力学分析 . 高等学校化学学报 , 2001 , 22 ( 5 ), 844 – 846 .

Yen, F. S. ; Hong, J. L . Hydrogen-bond interactions between ester and urethane linkages in small model compounds and polyurethanes . Macromolecules , 1997 , 30 ( 25 ), 7927 – 7938 .

Kong, Z. Y. ; Qiang, T. ; Zhang, R. Y. ; Yin, J. B. ; Lei, S. ; Ying, W. B. ; Han, H. ; Yao, C. K. ; Kai, W. ; Jin, Z . Reexamination of the microphase separation in MDI and PTMG based polyurethane: fast and continuous association/dissociation processes of hydrogen bonding . Polymer , 2019 , 185 , 121943 .

Wang, W. ; Jin, Y. ; Su, Z. H . Spectroscopic study on water diffusion in poly(ester urethane) block copolymer matrix . J. Phys. Chem. B , 2009 , 113 ( 48 ), 15742 – 15746 .

Kanapitsas, A. ; Pissis, P. ; Gomez Ribelles, J. L. ; Pradas, M. M. ; Privalko, E. G. ; Privalko, V. P . Molecular mobility and hydration properties of segmented polyurethanes with varying structure of soft- and hard-chain segments . J. Appl. Polym. Sci. , 1999 , 71 ( 8 ), 1209 – 1221 .

Diao, S. ; Zhang, Y. Q. ; Zhao, C. D. ; Wang, M. Y. ; Yu, J. C . Preparation of waterborne polyurethane with high solid content: the crystallinity control of soft segment and the organosilicon modification . Polym. Bull. , 2024 , 81 ( 1 ), 317 – 333 .

Xu, D. H. ; Liu, F. ; Pan, G. ; Zhao, Z. G. ; Yang, X. ; Shi, H. C. ; Luan, S. F . Softening and hardening of thermal plastic polyurethane blends by water absorbed . Polymer , 2021 , 218 , 123498 .

Xu, D. H. ; Craig, S. L . Strain hardening and strain softening of reversibly cross-linked supramolecular polymer networks . Macromolecules , 2011 , 44 ( 18 ), 7478 – 7488 .

Possart, W. ; Zimmer, B . Water in polyurethane networks: physical and chemical ageing effects and mechanical parameters . Continuum Mech. Thermodyn. , 2024 , 36 ( 2 ), 261 – 287 .

Blackwell, J. ; Nagarajan, M. R. ; Hoitink, T. B . Structure of polyurethane elastomers: effect of chain extender length on the structure of MDI/diol hard segments . Polymer , 1982 , 23 ( 7 ), 950 – 956 .

Salazar, M. R. ; Thompson, S. L. ; Laintz, K. E. ; Pack, R. T . Degradation of a poly(ester urethane) elastomer. I. Absorption and diffusion of water in Estane ® 5703 and related polymers . J. Polym. Sci. B Polym. Phys. , 2002 , 40 ( 2 ), 181 .

Salazar, M. R. ; Thompson, S. L. ; Laintz, K. E. ; Meyer, T. O. ; Pack, R. T . Degradation of a poly(ester urethane) elastomer. IV. Sorption and diffusion of water in PBX 9501 and its components . J. Appl. Polym. Sci. , 2007 , 105 ( 3 ), 1063 – 1076 .

赵玉梅 , 张博 , 刘美琴 , 石红翠 . 氨基甲酸酯基/脲键对混合TDI聚酯-聚氨酯树脂羰基氢键作用的影响 . 高分子通报 , 2023 , 36 ( 3 ), 355 – 365 .

Idolor, O. ; Guha, R. D. ; Berkowitz, K. ; Geiger, C. ; Davenport, M. ; Grace, L . Polymer-water interactions and damage detection in polymer matrix composites . Compos. Part B Eng. , 2021 , 211 , 108637 .

曹高华 , 夏正斌 , 张燕红 , 李伟 . AAS/DMPA对水性聚氨酯胶膜结晶性能的影响 . 化工学报 , 2013 , 64 ( 7 ), 2672 – 2678 .

Cohen, M. H. ; Turnbull, D . Molecular transport in liquids and glasses . J. Chem. Phys. , 1959 , 31 ( 5 ), 1164 – 1169 .

Wang, Z. F. ; Wang, B. ; Ding, X. M. ; Zhang, M. ; Liu, L. M. ; Qi, N. ; Hu, J. L . Effect of temperature and structure on the free volume and water vapor permeability in hydrophilic polyurethanes . J. Membr. Sci. , 2004 , 241 ( 2 ), 355 – 361 .

Musto, P. ; Ragosta, G. ; Mascia, L . Vibrational spectroscopy evidence for the dual nature of water sorbed into epoxy resins . Chem. Mater. , 2000 , 12 ( 5 ), 1331 – 1341 .

Zhou, J. M. ; Lucas, J. P . Hygrothermal effects of epoxy resin. Part II: Variations of glass transition temperature . Polymer , 1999 , 40 ( 20 ), 5513 – 5522 .

Paik Sung, C. S. ; Smith, T. W. ; Sung, N. H . Properties of segmented polyether poly(urethaneureas) based of 2, 4-toluene diisocyanate. 2. infrared and mechanical studies . Macromolecules , 1980 , 13 ( 1 ), 117 – 121 .

Sheth, J. P. ; Klinedinst, D. B. ; Wilkes, G. L. ; Yilgor, I. ; Yilgor, E . Role of chain symmetry and hydrogen bonding in segmented copolymers with monodisperse hard segments . Polymer , 2005 , 46 ( 18 ), 7317 – 7322 .

浏览量

524

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

高强韧水凝胶纤维研究进展

高韧性两性离子聚合物水凝胶研究进展

有机蒙脱土改性聚乙烯醇缩丁醛透明高分子薄膜的研究

两个典型橡胶树品种制备烟片胶的结构与性能研究