二氟氨基齐聚物增塑剂结构与性能的关系及可控合成

Difluoroamino oligomer plasticizer is one of the important development directions of energetic plasticizers using in solid propellants. In order to fulfill the demands of the difluoroamino energetic binder systems in high energy propellants, the work is carried out based on the former researches of design and synthesis of difluoroamino binders. The structures of difluoroamino oligomer plasticizers can be designed by setting the kind of monomers, initiators and end groups and the degree of polymerization as variables. By using quantum chemistry and molecular dynamics computing methods, the theoretical performances would be analyzed and the rules between structures and performances could be established for better understandings of performance evaluation and structure optimization. The synthetic routes, mechanisms and processes of the chosen difluoroamino oligomer plasticizers are designed, analyzed and optimized, respectively. The controllable synthesis methods would be explored, followed by structure characterization and performance research. The anticipative results can not only reveal the relationships between structures and performances of difluoroamino oligomer plasticizers, and achieve the controllable synthesis methods of the chosen species, but also can improve the difluoroamino energetic binder systems, and provide a research orientation for high energy difluoroamino-based solid propellants.

齐聚物含能增塑剂是固体推进剂用含能增塑剂的重要发展方向之一。针对高能推进剂对二氟氨基含能粘合剂体系的需求，在前期已初步完成新型二氟氨基粘合剂设计与合成的基础上，项目以二氟氨基齐聚物增塑剂为研究对象，将单体、引发剂、末端基团及聚合度作为结构变量开展分子结构设计，通过量子化学及分子动力学计算，完善系列二氟氨基齐聚物增塑剂性能的理论分析，构建二氟氨基齐聚物增塑剂的性能随内在结构变化的规律，开展性能评估与结构优选。对优选的二氟氨基齐聚物增塑剂进行合成路线设计、机理分析及工艺优化，探索其可控合成方法，开展结构表征与基础性能研究。本项目研究成果预计可揭示二氟氨基齐聚物含能增塑剂结构与性能的关系，获得结构优选的增塑剂的可控合成方法，既是对二氟氨基含能粘合剂体系的完善，又可为二氟氨基固体推进剂的高能化发展提供一种研究方向。

二氟氨基齐聚物增塑剂作为一种新型的二氟氨基类含能增塑剂，有望在二氟氨基类含能粘合剂体系中配伍使有。本项目以新戊基结构的二氟氨基化合物为单体，设计出了80种新型二氟氨基齐聚物增塑剂。在B3PW91/6-31G(d,p)基组上，应用密度泛函理论，从生成热、电子结构稳定性、热稳定性和爆轰性能等方面对设计的二氟氨基齐聚物增塑剂进行结构筛选，同时应用分子动力学理论，模拟得到其玻璃化转变温度，完成其构效关系的建立，获得了最优的结构，即以丙三醇为引发剂、3-二氟氨甲基-3-甲基氧杂环丁烷为单体、聚合度为3、末端基团为硝酸酯基。最后，基于阳离子溶液聚合及硝化反应，获得了目标化合物，并完成了其结构表征与基础性能研究。本项目揭示了二氟氨基齐聚物含能增塑剂结构与性能的关系，获得了结构优选的增塑剂的可控合成方法，既是对新型二氟氨基含能增塑剂种类的扩充，又可为二氟氨基含能粘合剂体系的发展提供一种研究方向。