刚柔协同构建高强韧可循环聚(脲-聚氨酯)弹性体

陆健烨; 卢庆闯; 罗振扬; 罗艳龙

doi:10.11777/j.issn1000-3304.2025.25269

您当前的位置：

首页 >

文章列表页 >

刚柔协同构建高强韧可循环聚(脲-聚氨酯)弹性体

研究论文 | 更新时间：2026-02-11

- 刚柔协同构建高强韧可循环聚(脲-聚氨酯)弹性体
- Rigid-flexible Synergy for Constructing High-strength, Tough, and Recyclable Poly(urea-urethane) Elastomers
- 高分子学报 2026年57卷第3期页码：709-720
- 作者机构：
  
  南京林业大学理学院南京 210037
- 作者简介：
  
  E-mail: luoyanlong@njfu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 52573061)
- DOI：10.11777/j.issn1000-3304.2025.25269
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7524
- 收稿：2025-10-17，
  
  录用：2025-12-01，
  
  网络首发：2026-01-27，
  
  纸质出版：2026-03-20
- 稿件说明：
移动端阅览
陆健烨, 卢庆闯, 罗振扬, 罗艳龙. 刚柔协同构建高强韧可循环聚(脲-聚氨酯)弹性体. 高分子学报, 2026, 57(3), 709-720.

Lu, J. Y.; Lu, Q. C.; Luo, Z. Y.; Luo, Y. L. Rigid-flexible synergy for constructing high-strength, tough, and recyclable poly(urea-urethane) elastomers. Acta Polymerica Sinica (in Chinese), 2026, 57(3), 709-720.
陆健烨, 卢庆闯, 罗振扬, 罗艳龙. 刚柔协同构建高强韧可循环聚(脲-聚氨酯)弹性体. 高分子学报, 2026, 57(3), 709-720. DOI： 10.11777/j.issn1000-3304.2025.25269. CSTR： 32057.14.GFZXB.2025.7524.

Lu, J. Y.; Lu, Q. C.; Luo, Z. Y.; Luo, Y. L. Rigid-flexible synergy for constructing high-strength, tough, and recyclable poly(urea-urethane) elastomers. Acta Polymerica Sinica (in Chinese), 2026, 57(3), 709-720. DOI： 10.11777/j.issn1000-3304.2025.25269. CSTR： 32057.14.GFZXB.2025.7524.

摘要

针对高强韧聚氨酯(PU)难以循环利用的挑战，本工作通过在PU中引入超分子链段，构建刚柔协同的多级动态网络：刚性链段4

4′-二氨基苯甲酰胺(DABA)借助芳香环结构诱导形成强氢键体系以提供结构支撑、增强材料强度，柔性链段癸二酰肼(SPH)依托长链脂肪结构构建弱氢键体系，凭其链段迁移能力缓解应力集中并耗散能量，且二者引入的酰基氨基脲(ASCZ)基团赋予氢键网络动态可逆性. 所制备的PUU-DA-SPH

弹性体展现优异综合性能，拉伸强度达64.55 MPa、韧性为336.14 MJ·m

-3

，且经多次热压循环再加工后强度保留效率91%、韧性保留效率98%. 该研究为设计兼顾高强韧性与可循环利用的聚氨酯提供了新思路.

Abstract

To address the challenge of cyclic reprocessing of high-strength and tough polyurethane (PU)

this study introduces supramolecular segments into PU to construct a rigid-flexible synergistic multilevel dynamic network. The rigid segment 4

4′-diaminobenzamide (DABA) induces the formation of a strong hydrogen bond system

via

its aromatic ring structure to provide structural support and enhance material strength

whereas the flexible segment sebacoyl hydrazide (SPH) establishes a weak hydrogen bond system through its long-chain aliphatic structure

alleviating stress concentration and dissipating energy owing to its segment migration capability. Additional

the acylsemicarbazide (ASCZ) groups introduced by both segments endowed the hydrogen-bond network with dynamic reversibility. The prepared PUU-DA-SPH

elastomer exhibited excellent comprehensive properties

with a tensile strength of 64.55 MPa and toughness of 336.14 MJ·m

-3

. Moreover

it maintained a stable performance after multiple cycles of hot-press reprocessing (tensile strength retention rate of 91% and toughness retention rate of 98%). This study provides a novel approach for designing polyurethanes that integrate high strength

toughness

and cyclic reprocessability.

关键词

Keywords

references

Tang X. J. ; Chen Z. H. ; Liu J. Y. ; Chen Z. Y. ; Xie W. M. ; Evrendilek F. ; Buyukada M. Dynamic pyrolysis behaviors, products, and mechanisms of waste rubber and polyurethane bicycle tires . J. Hazard. Mater. , 2021 , 402 , 123516 . doi: 10.1016/j.jhazmat.2020.123516 http://dx.doi.org/10.1016/j.jhazmat.2020.123516

Qian B. ; Wang Y. P. ; Wu Z. K. ; Jia Y. J. ; Liu M. ; Su J. L. ; Wang Y. H. ; Zhao Z. C. ; Wu J. N. ; Sun W. ; Tian M. ; You Z. W. Synergistic dual-dynamic covalent bonds enable robust, harsh environment-resistance, and structure evolution self-monitoring polyurethane adhesives . Adv. Funct. Mater. , 2025 , doi: 10.1002/adfm.202509916. http://dx.doi.org/10.1002/adfm.202509916.

Li C. L. ; Dong W. B. ; Li L. Y. ; Dou Z. L. ; Li Y. H. ; Wei L. H. ; Zhang Q. ; Fu Q. ; Wu K. A strain-reinforcing elastomer adhesive with superior adhesive strength and toughness . Mater. Horiz. , 2023 , 10 ( 10 ), 4183 - 4191 . doi: 10.1039/d3mh00966a http://dx.doi.org/10.1039/d3mh00966a

Xue Y. J. ; Zhang M. ; Huo S. Q. ; Ma Z. W. ; Lynch M. ; Tuten B. T. ; Sun Z. Q. ; Zheng W. ; Zhou Y. H. ; Song P. G. Engineered functional segments enabled mechanically robust, intrinsically fire-retardant, switchable, degradable PolyureThane adhesives . Adv. Funct. Mater. , 2024 , 34 ( 49 ), 2409139 . doi: 10.1002/adfm.202409139 http://dx.doi.org/10.1002/adfm.202409139

Li R. ; Li L. F. ; Qiu W. L. ; Zhu D. Y. ; Qiu X. Q. ; Ou R. X. ; Liu B. H. ; Liu W. F. Sustainable waterborne polyurethane adhesive with superstrong adhesion performance and excellent weatherability from biomass lignin and CO 2 -based polyols . Adv. Funct. Mater. , 2025 , 35 ( 34 ), 2422605 . doi: 10.1002/adfm.202422605 http://dx.doi.org/10.1002/adfm.202422605

Mahmood S. ; Khan A. ; Kant C. ; Chu C. W. ; Katiyar M. ; Lin H. C. Transparent, stretchable, and self-healable gas barrier films with 2D nanoplatelets for flexible electronic device packaging applications . Adv. Mater. Interfaces , 2023 , 10 ( 5 ), 2202093 . doi: 10.1002/admi.202202093 http://dx.doi.org/10.1002/admi.202202093

Yang Z. P. ; Zhang S. F. ; Chen Z. P. ; Lai X. J. ; Li H. Q. ; Zeng X. R. Self-healing and degradable polycaprolactone-based polyurethane elastomer for flexible stretchable strain sensors . ACS Appl. Polym. Mater. , 2024 , 6 ( 1 ), 905 - 914 . doi: 10.1021/acs.chemmater.3c00120 http://dx.doi.org/10.1021/acs.chemmater.3c00120

Zhao P. ; Zhang J. ; Lou Y. H. ; Li J. L. ; Han G. Q. ; Zeng S. Q. ; Wang Y. Y. ; Liu Y. Z. ; Yu H. P. Ultratough polyurethane elastomers for artificial ligaments . ACS Mater. Lett. , 2024 , 6 ( 8 ), 3226 - 3237 . doi: 10.1021/acsmaterialslett.4c00505 http://dx.doi.org/10.1021/acsmaterialslett.4c00505

Ramezani M. ; Monroe M. B. B. Biostable segmented thermoplastic polyurethane shape memory polymers for smart biomedical applications . ACS Appl. Polym. Mater. , 2022 , 4 ( 3 ), 1956 - 1965 . doi: 10.1021/acsapm.1c01808 http://dx.doi.org/10.1021/acsapm.1c01808

Johansen M. B. ; Donslund B. S. ; Kristensen S. K. ; Lindhardt A. T. ; Skrydstrup T. Tert-amyl alcohol-mediated deconstruction of polyurethane for polyol and aniline recovery . ACS Sustainable Chem. Eng. , 2022 , 10 ( 34 ), 11191 - 11202 . doi: 10.1021/acssuschemeng.2c02797 http://dx.doi.org/10.1021/acssuschemeng.2c02797

Wang L. P. ; Zhang K. Q. ; Zhang X. X. ; Tan Y. ; Guo L. F. ; Xia Y. G. ; Wang X. Mismatched supramolecular interactions facilitate the reprocessing of super-strong and ultratough thermoset elastomers . Adv. Mater. , 2024 , 36 ( 28 ), 2311758 . doi: 10.1002/adma.202311758 http://dx.doi.org/10.1002/adma.202311758

Yin X. S. ; Huang Z. Y. ; Zhao X. ; Li B. T. ; Wu J. X. ; Kuang Y. L. ; Sun Y. J. ; Lin X. F. ; Lin W. J. ; Ji L. ; Yi G. B. Mismatched hydrogen bond donor-acceptor stoichiometry strategy enables high-strength, crack-resistant, and recyclable thermosetting polyurethane elastomer . Adv. Funct. Mater. , 2025 , doi: 10.1002/adfm.202514438. http://dx.doi.org/10.1002/adfm.202514438.

Xu Y. W. ; Zhou S. ; Wu Z. H. ; Yang X. Y. ; Li N. ; Qin Z. H. ; Jiao T. F. Room-temperature self-healing and recyclable polyurethane elastomers with high strength and superior robustness based on dynamic double-crosslinked structure . Chem. Eng. J. , 2023 , 466 , 143179 . doi: 10.1016/j.cej.2023.143179 http://dx.doi.org/10.1016/j.cej.2023.143179

Liang H. R. ; Xu Y. F. ; Song J. ; Cui Y. X. ; Chen Y. B. ; Cao Y. ; An Q. L. ; Yin L. X. ; Bu T. A. ; Wang Z. High-performance easy-degradable and recyclable thermosetting polyurethanes via dynamic cross-linking and abundant hydrogen bonding for foam sensor applications . Chem. Eng. J. , 2025 , 514 , 163277 . doi: 10.1016/j.cej.2025.163277 http://dx.doi.org/10.1016/j.cej.2025.163277

Wang X. Y. ; Xu J. ; Zhang X. R. ; Yang Z. H. ; Zhang Y. M. ; Wang T. M. ; Wang Q. H. Molecularly engineered unparalleled strength and supertoughness of poly(urea-urethane) with shape memory and clusterization-triggered emission . Adv. Mater. , 2022 , 34 ( 45 ), 2205763 . doi: 10.1002/adma.202205763 http://dx.doi.org/10.1002/adma.202205763

Zhang C. R. ; Lu Q. C. ; Song M. ; Luo Z. Y. ; Duan L. ; Luo Y. L. Mechanically robust and highly transparent polyurethane elastomer with excellent adhesion enabled by hierarchical hydrogen bonds . J. Appl. Polym. Sci. , 2025 , 142 ( 32 ), e 57281 . doi: 10.1002/app.57281 http://dx.doi.org/10.1002/app.57281

Lu Q. C. ; Duan L. ; Liu Y. ; Zhang C. R. ; Zhang Z. B. ; Luo Z. Y. ; Li C. H. ; Luo Y. L. Dragonfly wing-inspired reticular hierarchical structure enables strong and tough supramolecular elastomers . Adv. Funct. Mater. , 2025 , 35 ( 36 ), 2506282 . doi: 10.1002/adfm.202506282 http://dx.doi.org/10.1002/adfm.202506282

Wang D. ; Wang Z. F. ; Ren S. Y. ; Xu J. H. ; Wang C. ; Hu P. ; Fu J. J. Molecular engineering of a colorless, extremely tough, superiorly self-recoverable, and healable poly(urethane-urea) elastomer for impact-resistant applications . Mater. Horiz. , 2021 , 8 ( 8 ), 2238 - 2250 . doi: 10.1039/d1mh00548k http://dx.doi.org/10.1039/d1mh00548k

Wang L. P. ; Guo L. F. ; Zhang K. Q. ; Xia Y. G. ; Hao J. C. ; Wang X. Development of tough thermoplastic elastomers by leveraging rigid-flexible supramolecular segment interplays . Angew. Chem. Int. Ed. , 2023 , 62 ( 29 ), e 202301762 . doi: 10.1002/anie.202301762 http://dx.doi.org/10.1002/anie.202301762

Song Y. H. ; Li J. L. ; Song G. J. ; Li X. R. Tough and self-healing waterborne polyurethane elastomers via dynamic hydrogen bonds design for flexible conductive substrate applications . ACS Appl. Mater. Interfaces , 2024 , 16 ( 2 ), 2683 - 2691 . doi: 10.1021/acsami.3c12688 http://dx.doi.org/10.1021/acsami.3c12688

Wei J. ; Ma Y. C. ; Hu Y. ; Zhu J. L. ; Gou H. L. ; Qian D. ; Fan H. Enhanced mechanical strength and water resistance in waterborne polyurethanes through hydroxyl-functionalized MQ silicone resin modification . Prog. Org. Coat. , 2024 , 194 , 108555 . doi: 10.1016/j.porgcoat.2024.108555 http://dx.doi.org/10.1016/j.porgcoat.2024.108555

Dong F. H. ; Yang X. X. ; Guo L. Z. ; Wang Y. Q. ; Shaghaleh H. ; Huang Z. ; Xu X. ; Wang S. F. ; Liu H. Self-healing polyurethane with high strength and toughness based on a dynamic chemical strategy . J. Mater. Chem. A , 2022 , 10 ( 18 ), 10139 - 10149 . doi: 10.1039/d2ta00802e http://dx.doi.org/10.1039/d2ta00802e

Guo Y. F. ; Chen S. ; Sun L. J. ; Yang L. ; Zhang L. Z. ; Lou J. M. ; You Z. W. Degradable and fully recyclable dynamic thermoset elastomer for 3D-printed wearable electronics . Adv. Funct. Mater. , 2021 , 31 ( 9 ), 2009799 . doi: 10.1002/adfm.202009799 http://dx.doi.org/10.1002/adfm.202009799

Li Z. Q. ; Zhu Y. L. ; Niu W. W. ; Yang X. ; Jiang Z. Y. ; Lu Z. Y. ; Liu X. K. ; Sun J. Q. Healable and recyclable elastomers with record-high mechanical robustness, unprecedented crack tolerance, and superhigh elastic restorability . Adv. Mater. , 2021 , 33 ( 27 ), 2101498 . doi: 10.1002/adma.202101498 http://dx.doi.org/10.1002/adma.202101498

Liu Z. X. ; Guo W. ; Wang W. Y. ; Guo Z. J. ; Yao L. F. ; Xue Y. ; Liu Q. ; Zhang Q. Y. Healable strain sensor based on tough and eco-friendly biomimetic supramolecular waterborne polyurethane . ACS Appl. Mater. Interfaces , 2022 , 14 ( 4 ), 6016 - 6027 . doi: 10.1021/acsami.1c21987 http://dx.doi.org/10.1021/acsami.1c21987

Xiao X. Z. ; Zhou S. K. ; Gu L. Clusterization-triggered emission of waterborne polyurethane: the role of carboxyl groups . Macromolecules , 2024 , 57 ( 1 ), 88 - 97 . doi: 10.1021/acs.macromol.3c02393 http://dx.doi.org/10.1021/acs.macromol.3c02393

Ye T. ; Liu J. Y. ; Sun J. J. ; Tan J. L. ; Chen X. ; Yin Y. J. ; Wang C. X. Healable, luminescent, notch-insensitive waterborne polyurethane via noncovalent crosslinking with hydrogen bonds and ionic interactions . Chem. Eng. J. , 2023 , 475 , 146393 . doi: 10.1016/j.cej.2023.146393 http://dx.doi.org/10.1016/j.cej.2023.146393

Zheng Z. H. ; Liang D. S. ; Deng H. H. ; Xie F. ; Chen X. M. ; Luo Y. ; Zhang C. Q. Castor oil-based, robust, non-leaching and durable antibacterial waterborne polyurethane/polyhexamethylene guanidine composites prepared via an electrostatic self-assembly strategy . Chem. Eng. J. , 2023 , 462 , 142060 . doi: 10.1016/j.cej.2023.142060 http://dx.doi.org/10.1016/j.cej.2023.142060

Guo R. ; Zhang Q. ; Wu Y. S. ; Chen H. B. ; Liu Y. H. ; Wang J. J. ; Duan X. L. ; Chen Q. ; Ge Z. S. ; Zhang Y. F. Extremely strong and tough biodegradable poly(urethane) elastomers with unprecedented crack tolerance via hierarchical hydrogen-bonding interactions . Adv. Mater. , 2023 , 35 ( 21 ), 2212130 . doi: 10.1002/adma.202212130 http://dx.doi.org/10.1002/adma.202212130

Chen X. C. ; Tian Y. T. ; Lin M. ; Zhu D. D. ; Wang X. L. Reusable ultratough supramolecular polyurethane-urea elastomer via rigid-flexible mismatched hard segments and a "train coupling mechanism" . Macromolecules , 2025 , 58 ( 16 ), 8777 - 8785 . doi: 10.1021/acs.macromol.5c01718 http://dx.doi.org/10.1021/acs.macromol.5c01718

Li Y. P. ; Jin Y. ; Zeng W. H. ; Jin H. Y. ; Shang X. ; Zhou R. Bioinspired fast room-temperature self-healing, robust, adhesive, and AIE fluorescent waterborne polyurethane via hierarchical hydrogen bonds and use as a strain sensor . ACS Appl. Mater. Interfaces , 2023 , 15 ( 29 ), 35469 - 35482 . doi: 10.1021/acsami.3c05699 http://dx.doi.org/10.1021/acsami.3c05699

Du Y. M. ; Wang H. ; Li X. F. ; Liu J. C. ; Liu Y. Y. ; Zhang W. ; Liu Q. ; Da Y. S. ; Li H. ; Sun Z. P. ; Dong Y. ; Tian X. Y. Ethanol-assisted room-temperature rapid self-healing polydimethylsiloxane-polyurea/carbon composite elastomers for energy harvesters and smart sensors . J. Mater. Chem. A , 2024 , 12 ( 4 ), 2024 - 2035 . doi: 10.1039/d3ta05217f http://dx.doi.org/10.1039/d3ta05217f

Kim S. ; Felsenthal L. M. ; Sala O. ; Welz O. ; Bergeler M. ; Alsbaiee A. ; Dichtel W. R. Reprocessing thermoset polyurethane foams using their residual polymerization catalysts . J. Am. Chem. Soc. , 2025 , 147 ( 39 ), 35655 - 35663 . doi: 10.1021/jacs.5c11319 http://dx.doi.org/10.1021/jacs.5c11319

Fu D. H. ; Pu W. L. ; Escorihuela J. ; Wang X. R. ; Wang Z. H. ; Chen S. Y. ; Sun S. J. ; Wang S. ; Zuilhof H. ; Xia H. S. Acylsemicarbazide moieties with dynamic reversibility and multiple hydrogen bonding for transparent, high modulus, and malleable polymers . Macromolecules , 2020 , 53 ( 18 ), 7914 - 7924 . doi: 10.1021/acs.macromol.0c01667 http://dx.doi.org/10.1021/acs.macromol.0c01667

Yang X. ; Wang Y. D. ; Zhang X. K. ; Jian Z. W. ; Lu X. L. ; Wang Z. H. ; Xia H. S. Carbon fiber reinforced epoxy resin composites with excellent recyclable performance via dynamic acylsemicarbazide moieties . ACS Appl. Polym. Mater. , 2023 , 5 ( 7 ), 5189 - 5199 . doi: 10.1021/acsapm.3c00658 http://dx.doi.org/10.1021/acsapm.3c00658

Wang S. ; Fu D. H. ; Wang X. R. ; Pu W. L. ; Martone A. ; Lu X. L. ; Lavorgna M. ; Wang Z. H. ; Amendola E. ; Xia H. S. High performance dynamic covalent crosslinked polyacylsemicarbazide composites with self-healing and recycling capabilities . J. Mater. Chem. A , 2021 , 9 ( 7 ), 4055 - 4065 . doi: 10.1039/d0ta11251h http://dx.doi.org/10.1039/d0ta11251h

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

空间位阻对氢键构筑的嵌段共聚物微相分离结构的影响

氢键构筑的甲壳型液晶高分子的设计合成和自组装

聚苯乙烯-聚（4-乙烯基吡啶）嵌段共聚物LB膜结构形态的研究

具有形状记忆性能的P(MMA-co-HEA)/PDMS-OH 氢键复合物的研究