目的 将动态亚胺键引入生物基水性聚氨酯（WPU）主链,探索兼具优异自修复性能与较高力学强度的生物基WPU涂层材料,明确其实际应用潜力。方法 以蓖麻油（CO）与山梨醇单油酸酯（SP）作为生物基混合多元醇,通过调节含动态亚胺键扩链剂HBA-AP与1,4-丁二醇（BDO）的投料比例,采用预聚体分散法成功合成了一系列水性聚氨酯乳液;研究过程中重点探究了动态键含量与薄膜力学性能、热分解行为及自修复效率之间的结构-性能关联规律。结果 随着HBA-AP添加量的逐步增加,WPU薄膜的力学性能与热稳定性能均得到显著提升。其中,WPU-20% HBA-AP薄膜的拉伸强度最高可达到19.71 MPa,热失重特征温度T10%和T50%分别较WPU-0% HBA-AP提高了11.6 ℃和9.2 ℃。在80 ℃恒温条件下修复12 h后,WPU-20% HBA-AP薄膜的拉伸强度与断裂伸长率最大修复效率分别达到83.97%和81.05%,展现出优良的自修复效率。结论 基于动态亚胺键的可逆交换反应机理,本研究成功制备出兼具高力学强度、良好热稳定性及优异自修复功能的生物基WPU材料。该研究不仅为解决传统涂层因表面微裂纹产生而导致使用寿命缩短的实际问题,提供了一种有效的技术策略,同时也为高性能环保涂层材料的分子结构设计,提供了可靠的实验数据支撑与理论参考。
Abstract
The work aims to introduce dynamic imine bonds into the backbone of bio-based waterborne polyurethane (WPU) to explore bio-based WPU coating materials that combine excellent self-healing properties with high mechanical strength, thereby clarifying their practical application potential. With castor oil (CO) and sorbitol monooleate (SP) as bio-based polyol blends, a series of waterborne polyurethane dispersions were successfully synthesized via the prepolymer dispersion method by adjusting the feed ratio of the chain-extender HBA-AP, which contained dynamic imine bonds, and 1,4-butanediol (BDO). As the HBA-AP additions gradually increased, both the mechanical properties and thermal stability of the WPU films improved significantly. Specifically, the tensile strength of the WPU-20% HBA-AP films reached a maximum of 19.71 MPa, while the characteristic temperature T10% and T50% of the thermal gravimetric analysis increased by 11.6 ℃ and 9.2 ℃, respectively, compared with the WPU-0% HBA-AP film. After 12 hours of recovery at 80 ℃, the maximum healing efficiency of tensile strength and elongation at break for the WPU-20% HBA-AP film reached 83.97% and 81.05%, respectively, demonstrating excellent self-healing efficiency. Based on the reversible exchange reaction mechanism of dynamic imine bonds, bio-based WPU materials that combine high mechanical properties, excellent thermal stability, and good self-healing capability are successfully prepared. This work not only provides an effective technical strategy for addressing the practical issue of reduced service life in traditional coatings caused by surface microcracks, but also offers reliable experimental data and theoretical references for the molecular structural design of high-performance, environmentally friendly coating materials.
关键词
生物基水性聚氨酯 /
亚胺键 /
蓖麻油 /
山梨醇单油酸酯 /
自修复
Key words
bio-based waterborne polyurethane /
imine bonds /
castor oil /
sorbitan monooleate /
self-healing
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基金
“广东特支计划”青年拔尖人才项目（2024TQ08C172）; 广东省科技创新战略专项资金（大学生科技创新培育）项目（pdjh2026bk041）; 国家级大学生创新创业训练计划项目（202510564006S）; 韶关市科技计划项目（873003）; 清远市科技计划项目（2024BQW017）
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