青岛科技大学高分子科学与工程学院 青岛 266045
山东星宇手套有限公司 潍坊 261500
03280@qust.edu.cn
收稿:2026-02-27,
录用:2026-03-30,
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李浩然, 许鸿泽, 王耀东, 黄文旭, 周立娟. 纤维素纳米晶剥离二硫化钨纳米片协同海藻酸钠构筑高固含水性聚氨酯及其3D打印应用. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.089
Li, H. R.; Xu, H. Z.; Wang, Y. D.; Huang, W. X.; Zhou, L. J. Construction of high-solid water-based polyurethanes using cellulose nanocrystals and tungsten disulfide nanosheets in synergy with sodium alginate, and 3D printing applications. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.089
李浩然, 许鸿泽, 王耀东, 黄文旭, 周立娟. 纤维素纳米晶剥离二硫化钨纳米片协同海藻酸钠构筑高固含水性聚氨酯及其3D打印应用. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.089 DOI:
Li, H. R.; Xu, H. Z.; Wang, Y. D.; Huang, W. X.; Zhou, L. J. Construction of high-solid water-based polyurethanes using cellulose nanocrystals and tungsten disulfide nanosheets in synergy with sodium alginate, and 3D printing applications. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.089 DOI:
针对传统水性聚氨酯(WPU)乳液固含量低、干燥收缩大及3D打印层间结合弱等瓶颈问题,提出了一种基于纤维素纳米晶体辅助剥离二硫化物纳米片与海藻酸钠(SA)协同稳定的Pickering乳液策略,成功制备了固含量高达70 wt%的高性能WPU乳液,并赋予WPU乳液卓越流变特性:剪切变稀行为、高黏度(1972.8 Pa·s)以及快速的触变恢复性。高固含量设计不仅显著抑制了干燥过程中的水分迁移与体积收缩,使打印构件的尺寸误差控制在12%以内,更促进了打印细丝间的分子链扩散与界面融合,实现了优异的层间黏合。力学性能测试表明,纳米粒子的均匀分散与多重氢键作用赋予WPU弹性体优异的力学性能,其拉伸强度达45.1 MPa,断裂伸长率高达617.8%。本研究通过微观界面工程与宏观流变调控的协同,为高性能WPU复杂结构的精密制造及功能化应用提供了新范式。
To address the bottlenecks of traditional waterborne polyurethane (WPU) emulsions
including low solid content
significant drying shrinkage
and poor interlayer adhesion in 3D printing
this study proposes a Pickering emulsion strategy. This approach utilizes cellulose nanocrystals to assist in the exfoliation of disulfide-bonded nanosheets
which are synergistically stabilized with sodium alginate (SA).This strategy successfully yielded a high-performance WPU emulsion with a solid content of 70 wt%
endowing it with exceptional rheological properties
shear thinning behavior
high viscosity (1972.8 Pa·s)
and rapid thixotropic recovery. The high solid content design not only significantly suppresses moisture migration and volume shrinkage during drying
maintaining dimensional errors of printed components within 12%
but also promotes molecular chain diffusion and interfacial fusion between printed filaments
achieving outstanding interlayer adhesion. Mechanical testing revealed that uniform nanoparticle dispersion and multiple hydrogen bonding interactions endowed the WPU elastomer with remarkable mechanical properties: tensile strength reached 45.1 MPa
while elongation at break soared to 617.8%. By synergizing micro-interface engineering with macroscale rheological control
this study establishes a novel paradigm for the precision manufacturing and functional applications of high-performance WPU in complex structures.
Cheng, B. X. ; Gao, W. C. ; Ren, X. M. ; Ouyang, X. Y. ; Zhao, Y. ; Zhao, H. ; Wu, W. ; Huang, C. X. ; Liu, Y. ; Liu, X. Y. ; Li, H. N. ; Li, R. K. Y . A review of microphase separation of polyurethane: characterization and applications . Polym. Test. , 2022 , 107 , 107489 .
Santamaria-Echart, A. ; Fernandes, I. ; Barreiro, F. ; Corcuera, M. A. ; Eceiza, A . Advances in waterborne polyurethane and polyurethane-urea dispersions and their eco-friendly derivatives: a review . Polymers , 2021 , 13 ( 3 ), 409 .
Salzano de Luna, M . Recent trends in waterborne and bio-based polyurethane coatings for corrosion protection . Adv. Mater. Interfaces , 2022 , 9 ( 11 ), 2101775 .
Frka-Petesic, B. ; Parton, T. G. ; Honorato-Rios, C. ; Narkevicius, A. ; Ballu, K. ; Shen, Q. C. ; Lu, Z. H. ; Ogawa, Y. ; Haataja, J. S. ; Droguet, B. E. ; Parker, R. M. ; Vignolini, S . Structural color from cellulose nanocrystals or chitin nanocrystals: self-assembly, optics, and applications . Chem. Rev. , 2023 , 123 ( 23 ), 12595 – 12756 .
Mantala, K. ; Crespy, D . Waterborne polyurethane transparent coatings for self-healing at room temperature . Macromolecules , 2025 , 58 ( 7 ), 3450 – 3459 .
Aramayo, M. A. F. ; Fernandes, R. F. ; Dias, M. S. ; Bozzo, S. ; Steinberg, D. ; da Silva, M. R. D. ; Maroneze, C. M. ; Silva, C. C. C . Eco-friendly waterborne polyurethane coating modified with ethylenediamine-functionalized graphene oxide for enhanced anticorrosion performance . Molecules , 2024 , 29 , 4163 .
Pichon, E. ; De Smet, D. ; Rouster, P. ; Freulings, K. ; Pich, A. ; Bernaerts, K. V . Bio-based non-isocyanate polyurethane(urea) waterborne dispersions for water resistant textile coatings . Mater. Today Chem. , 2023 , 34 , 101822 .
Wei, P. R. ; Cipriani, C. ; Hsieh, C. M. ; Kamani, K. ; Rogers, S. ; Pentzer, E . Go with the flow: rheological requirements for direct ink write printability . J. Appl. Phys. , 2023 , 134 ( 10 ), 100701 .
Zheng, R. J. ; Binks, B. P. ; Cui, Z. G . Pickering emulsions of hydrophilic silica particles and symmetrical organic electrolytes . Langmuir , 2020 , 36 ( 17 ), 4619 – 4629 .
Wan, X. ; Xiao, Z. M. ; Tian, Y. J. ; Chen, M. ; Liu, F. ; Wang, D. ; Liu, Y. ; Da Silva Bartolo, P. J. ; Yan, C. Z. ; Shi, Y. S. ; Zhao, R. R. ; Qi, H. J. ; Zhou, K . Recent advances in 4D printing of advanced materials and structures for functional applications . Adv. Mater. , 2024 , 36 ( 34 ), 2312263 .
Yu, Z. Y. ; Sun, X. ; Zhu, Y. L. ; Zhou, E. ; Cheng, C. F. ; Zhu, J. Y. ; Yang, P. ; Zheng, D. Y. ; Zhang, Y. F. ; Panahi-Sarmad, M. ; Jiang, F . Direct ink writing 3D printing elastomeric polyurethane aided by cellulose nanofibrils . ACS Nano , 2024 , 18 ( 41 ), 28142 – 28153 .
Vadillo, J. ; Larraza, I. ; Calvo-Correas, T. ; Gabilondo, N. ; Derail, C. ; Eceiza, A . Design of a waterborne polyurethane—Urea ink for direct ink writing 3D printing . Materials , 2021 , 14 ( 12 ), 3287 .
Lin, Z. W. ; Qiu, X. W. ; Cai, Z. ; Li, J. L. ; Zhao, Y. N. ; Lin, X. P. ; Zhang, J. M. ; Hu, X. L. ; Bai, H . High internal phase emulsions gel ink for direct-ink-writing 3D printing of liquid metal . Nat. Commun. , 2024 , 15 , 4806 .
Vadillo, J. ; Larraza, I. ; Calvo-Correas, T. ; Gabilondo, N. ; Derail, C. ; Eceiza, A . Bioactive inks suitable for 3D printing based on waterborne polyurethane urea, cellulose nanocrystals and Salvia extract . React. Funct. Polym. , 2022 , 175 , 105286 .
Narukulla, R. ; Ojha, U. ; Sharma, T . Effect of NaCl concentration on s tability of a polymer—Ag nanocomposite based Pickering emulsion: validation via rheological analysis with varying temperature . RSC Adv. , 2020 , 10 ( 36 ), 21545 – 21560 .
Abrahamsen, G. M. ; Lequeux, Z. A. B. ; Kemp, L. K. ; Wedgeworth, D. N. ; Rawlins, J. W. ; Newman, J. K. ; Morgan, S. E . Morphology control in waterborne polyurethane dispersion nanocomposites through tailored structure, formulation, and processing . Langmuir , 2025 , 41 ( 16 ), 10383 – 10393 .
Jiang, H. ; Sheng, Y. F. ; Ngai, T . Pickering emulsions: Versatility of colloidal particles and recent applications . Curr. Opin. Colloid Interface Sci. , 2020 , 49 , 1 – 15 .
He, X. ; Lu, Q. Y . A review of high internal phase Pickering emulsions: stabilization, rheology, and 3D printing application . Adv. Colloid Interface Sci. , 2024 , 324 , 103086 .
Qiu, C. ; Wang, C. X. ; Li, X. J. ; Sang, S. Y. ; McClements, D. J. ; Chen, L. ; Long, J. ; Jiao, A. Q. ; Wang, J. P. ; Jin, Z. Y . Preparation of high internal phase Pickering emulsion gels stabilized by glycyrrhizic acid-zein composite nanoparticles: gelation mechanism and 3D printing performance . Food Hydrocoll. , 2023 , 135 , 108128 .
Minas, C. ; Carnelli, D. ; Tervoort, E. ; Studart, A. R . 3D printing of emulsions and foams into hierarchical porous ceramics . Adv. Mater. , 2016 , 28 ( 45 ), 9993 – 9999 .
Bruel, C. ; Tavares, J. R. ; Carreau, P. J. ; Heuzey, M. C . The structural amphiphilicity of cellulose nanocrystals characterized from their cohesion parameters . Carbohydr. Polym. , 2019 , 205 , 184 – 191 .
Liu, Y. X. ; Wei, H. X. ; Liu, Z. W. ; Liu, X. R. ; Fang, Y. J. ; Jiang, M. ; Li, M. J. ; Zhou, L. J. ; Zhang, J. M . Ultrafast and energy-saving extraction of cellulose nanocrystals . Green Chem. , 2022 , 24 ( 18 ), 6823 – 6829 .
Liu, Q. L. ; Peng, Q. Q. ; Ma, C. ; Jiang, M. ; Zong, L. ; Zhang, J. M . Efficient transition metal dichalcogenides exfoliation by cellulose nanocrystals for ultrabroad-pH/temp stable aqueous dispersions and multi-responsive photonic films . Chem. Eng. J. , 2022 , 428 , 132594 .
Saalah, S. ; Abdullah, L. C. ; Aung, M. M. ; Salleh, M. Z. ; Awang Biak, D. R. ; Basri, M. ; Jusoh, E. R. ; Mamat, S. ; Osman Al Edrus, S. S . Chemical and thermo-mechanical properties of waterborne polyurethane dispersion derived from jatropha oil . Polymers , 2021 , 13 ( 5 ), 795 .
Zhou, X. ; Fang, C. Q. ; Chen, J. ; Li, S. J. ; Li, Y. ; Lei, W. Q . Correlation of raw materials and waterborne polyurethane properties by sequence similarity analysis . J. Mater. Sci. Technol. , 2016 , 32 ( 7 ), 687 – 694 .
Chang, C. W. ; Chang, J. P. ; Lu, K. T . Synthesis of linseed oil-based waterborne urethane oil wood coatings . Polymers , 2018 , 10 ( 11 ), 1235 .
Lei, W. Q. ; Zhou, X. ; Fang, C. Q. ; Song, Y. H. ; Li, Y. G . Eco-friendly waterborne polyurethane reinforced with cellulose nanocrystal from office waste paper by two different methods . Carbohydr. Polym. , 2019 , 209 , 299 – 309 .
Lin, X. ; Hao, M. Y. ; Ying, J. Y. ; Wang, R. G. ; Lu, Y. L. ; Gong, M. ; Zhang, L. Q. ; Wang, D. R. ; Zhang, L . An insight into the tensile anisotropy of 3D-printed thermoplastic polyurethane . Addit. Manuf. , 2022 , 60 , 103260 .
Huang, X. M. ; Peng, S. Q. ; Zheng, L. H. ; Zhuo, D. X. ; Wu, L. X. ; Weng, Z. X . 3D printing of high viscosity UV-curable resin for highly stretchable and resilient elastomer . Adv. Mater. , 2023 , 35 ( 49 ), 2304430 .
Peng, S. Q. ; Thirunavukkarasu, N. ; Chen, J. ; Zheng, X. X. ; Long, C. Z. ; Huang, X. M. ; Weng, Z. X. ; Zheng, L. H. ; Wang, H. P. ; Peng, X. F. ; Wu, L. X . Vat photopolymerization 3D printing of transparent, mechanically robust, and self-healing polyurethane elastomers for tailored wearable sensors . Chem. Eng. J. , 2023 , 463 , 142312 .
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