Diels-Alder型自修复聚氨酯胶粘剂的制备及其性能  

Preparation and Properties of Self-healing Polyurethane Adhesives with Diels-Alder Bonds

作　　者：石碧茹 武浩浩 谢昊圃 田新欣 孙莹潞 刘向东[1] 杨宇明[1,2] SHI Bi-Ru;WU Hao-Hao;XIE Hao-Pu;TIAN Xin-Xin;SUN Ying-Lu;LIU Xiang-Dong;YANG Yu-Ming(Key Laboratory of High-Performance Synthetic Rubber and Its Composite Materials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;University of Science and Technology of China,Hefei 230026,China;Xi'an Northern Hui-An Chemical Industry Co.Ltd.,Xi'an 710302,China)

机构地区：[1]中国科学院长春应用化学研究所,高性能合成橡胶及其复合材料重点实验室,长春130022 [2]中国科学技术大学,合肥230026 [3]西安北方惠安化学工业有限公司,西安710300

出　　处：《应用化学》2023年第2期277-287,共11页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(No.22175171)资助。

摘　　要：目前,针对珍贵零件粘接后难以回收重复使用的问题,将可逆共价键引入胶粘体系成为解决问题的方向。研究使用糠醇(FA)和N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺(BMI)制备了含有Diels-Alder(DA)键的二元醇(DA diol),使用六亚甲基二异氰酸酯(HDI)分别与聚四氢呋喃二醇(PTMG-2000)和DA diol反应封端,最后使用1,1,1-三(羟甲基)丙烷(TMP)与封端产物反应形成交联结构的聚氨酯材料(DPU)。结果表明,DPU具备优异的机械性能、热稳定性和粘接性能。DA键在DPU中具有可逆性且DA逆反应(r-DA)的最佳温度为135℃。DA键含量最多的DPU-Ⅳ的修复效率最高可达到89.0%。DPU-Ⅲ、DPU-Ⅳ粘接性能优异,对不锈钢粘接的剪切强度分别可达到(6.41±0.41)和(2.89±0.34)MPa;DPU-Ⅳ具有重复粘接使用的能力,对不锈钢基材重复粘接的3次的剪切强度分别为(2.89±0.34)、(1.91±0.15)和(1.68±0.20)MPa。粘接性能测试体现出胶膜自身强度与粘接的剪切强度、修复效率与重复粘接能力间的相关性。DA diol containing Diels-Alder(DA)bond is firstly prepared by one-step method.HDI is then used to terminate Poly-tetrahydrofuran(PTMG-2000)and DA diol.Finally,1,1,1-tris(hydroxymethyl)propane(TMP)reacts with the NCO-end products to form a crosslinked polyurethane material(DPU).The reversibility and the excellent thermal properties of DA structure in DPU is successfully detected.The DA reverse reaction(r-DA)temperature is proven to be 135℃.DPU-Ⅳwith the highest content of DA bond has the highest self-healing efficiency of 89.0%along DPU.DPU-Ⅳand DPU-Ⅳboth show excellent adhesive properties,DPU-Ⅲpossesses great matrix tolerance and DPU-Ⅳhas the ability of repeated bonding which could be used as repeated PU adhesive.

关 键 词：狄尔斯-阿尔德反应 交联聚氨酯 自修复胶粘剂 高剪切强度 

分 类 号：O631[理学—高分子化学]