Ma Song, Fan Hongjie, Zhang Ning, Li Wenfeng, Li Yonghong, Li Yang, Huang Dianjun, Zeng Liyuan, Shi Xiaobing, Ran Xiulun, Xu Huixiang
Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.
Xi'an North Hui An Chemical Industries Co. Ltd., Xi'an 710302, China.
ACS Omega. 2020 Nov 18;5(47):30538-30548. doi: 10.1021/acsomega.0c04439. eCollection 2020 Dec 1.
In this work, a promising propellant binder using the energetic branched glycidyl azide polymer (B-GAP) as a matrix and the low-toxic dimer acid diisocyanate (DDI) as a curing agent was prepared, under the catalysis of dibutyl tin dilaurate. The curing kinetics considering the thermal diffusion effect and the reaction endpoint of B-GAP/DDI were investigated by the thermal analysis method and a newly proposed variance method, respectively. Moreover, the buildup of microstructures during curing and the tensile and dynamic mechanical performance of this binder were respectively explored. Results show that there exists an obvious induction period in the beginning of the curing reaction, and the autocatalytic model shows that thermal diffusion can effectively describe the curing process. Shore A hardness of sample stabilizes around 40.78 in the end of curing, and the reaction endpoint of B-GAP/DDI is in the time range of 156-168 h. There exist cross-linking, suspension, and free chains during the whole curing process, and the cross-linking density of the binder reaches approximately 4.0 × 10 mol·cm when the curing completes. Hydrogen bonding (H-bond) is found to be a strong binder: 53.3% of the carbonyls participates in forming the H-bond. Furthermore, this binder has better mechanical performance and lower glass-transition temperature than the GAP/N100 binder.
在这项工作中,制备了一种有前景的推进剂粘合剂,它以含能支化聚缩水甘油叠氮(B-GAP)为基体,低毒的二聚酸二异氰酸酯(DDI)为固化剂,并在二月桂酸二丁基锡的催化作用下进行反应。分别采用热分析方法和新提出的变分法研究了考虑热扩散效应的固化动力学以及B-GAP/DDI的反应终点。此外,还分别探究了固化过程中微观结构的形成以及该粘合剂的拉伸和动态力学性能。结果表明,固化反应开始时存在明显的诱导期,自催化模型表明热扩散能有效描述固化过程。固化结束时样品的邵氏A硬度稳定在40.78左右,B-GAP/DDI的反应终点在156 - 168小时的时间范围内。整个固化过程中存在交联、悬浮和自由链,固化完成时粘合剂的交联密度达到约4.0×10 mol·cm 。发现氢键(H键)是一种很强的粘合剂作用:53.3%的羰基参与形成氢键。此外,这种粘合剂比GAP/N100粘合剂具有更好的力学性能和更低的玻璃化转变温度。