三唑结构交联体的合成、表征及固化反应热动力学研究

The alkyne terminated curing agents will be designed, synthesized and characterized, and then energetic triazole crosslinked polymeric binders were synthesized via 1,3-dipolar cycloaddition reaction between the azido groups of azide prepolymer and the triple bonds of alkyne terminated curing agent. The structure and physical properties of energetic triazole crosslinked polymeric binders will be characterized. The thermokinetics of the curing reactions between alkyne terminated curing agents and azide prepolymer will be studied by using a microcalorimeter. On the basis of experimental and calculated results, the thermodynamics parameters (the activation enthalpies, the activation entropies, the activation free energies), the rate constant, the thermokinetic parameters (the activation energies, the pre-exponential constant and the reaction order) and the enthalpies of the curing reactions will be obtained. Furthermore, the corresponding kinetic equation describing the relationship between the rate of curing reaction and the molar ratio of triple bonds to azide groups will also be obtained. We can obtain the relationship between the rate of curing reaction and the structures of alkyne terminated curing agents and azide prepolymers, the mechanism of curing reaction between triple bonds and azide groups, the best curing conditions. Finally, according to the characterization of mechanical and thermal properties of the curing system, we will select a new triazole crosslinked polymeric binder which has better curing, mechanical and thermal properties.

设计并合成出几种新型端炔基固化剂，选择出数种叠氮预聚物与上述固化剂配伍，按照1,3-偶极环加成反应机理得到含有三唑结构的含能交联体，并对其进行结构鉴定和性能表征；开展炔基固化剂、叠氮预聚物以及三唑交联体与固体推进剂主要组分的相互作用研究；借助微量热技术，进行端炔基与叠氮基发生固化反应的热动力学研究，获得固化反应的热动力学参数，建立固化反应速率常数与端炔基固化剂/叠氮预聚物质量比之间的热动力学方程，明确端炔基固化剂和叠氮预聚物的结构与固化速率之间的关系，揭示炔基与叠氮基的固化反应机理，确定其最佳固化反应参数，结合力学性能和热性能的测试结果，筛选出具有应用前景的黏合剂体系，为新型推进剂开发设计提供重要的理论依据和技术支持。

针对端羟基预聚物/异氰酸酯黏合体系稳定性差、与新型绿色含能材料ADN不相容的问题，开展了新型端炔基固化剂和叠氮预聚物的合成与表征，二者发生1,3-偶极环加成反应得到了含能三唑交联弹性体，对其进行了结构和物化性能表征；完成了含能三唑交联弹性体与固体推进剂主要组分的相互作用研究，结果表明含能三唑交联弹性体与固体推进剂主要组分相容性良好；完成了三唑交联聚合物的溶胀性能研究，获得了不同结构三唑交联聚合物的溶度参数，通过Flory-Huggins 理论进一步计算了所制备三唑交联聚合物的交联密度及表观分子量；采用微量热技术开展了端炔基固化剂与叠氮预聚物发生固化反应的热动力学研究，获得了固化反应的热动力学参数（n，lnk，E，ΔG≠，ΔH≠，ΔS≠），建立固化速率常数与端炔基固化剂/叠氮预聚物质量比之间的热动力学方程，揭示了端炔基固化剂与叠氮预聚物的结构与固化速率之间的关系，从而确定了其最佳固化条件（固化温度和固化时间）；完成了不同结构、不同质量比的端炔基固化剂/叠氮预聚物体系力学性能研究，获得了不同类型的聚三唑交联弹性体的力学性能，筛选出了力学性能相对较好的聚三唑交联弹性体。最后完成了不同类型的聚三唑交联弹性体的热性能研究，获得了其热分解行为和热分解机理。结合上述研究结果，优选出了具有较好应用前景的含能三唑交联黏合剂体系，为ADN和叠氮预聚物的广泛应用提供了基础数据，为新型推进剂开发设计提供重要的理论依据和技术支持。