固体推进剂用硝酸酯增塑剂的热安定机制研究进展  

Progress on thermal stability mechanism of nitrate esters plasticizers for solid propellant

作　　者：曹华文 唐秋凡 郑启龙 屈蓓[1] 李吉祯[1] CAO Huawen;TANG Qiufan;ZHENG Qilong;QU Bei;LI Jizhen(Xi'an Modern Chemistry Research Institute,Xi'an710065,China)

机构地区：[1]西安近代化学研究所,西安710065

出　　处：《固体火箭技术》2023年第6期854-865,共12页Journal of Solid Rocket Technology

摘　　要：从硝酸酯在固体推进剂中的应用角度综述了硝酸酯的热分解机理和热安定机制的国内外研究进展。硝酸酯的热分解机理国内外均集中于非等温高温热分解行为和热分解动力学研究,对于使用温度下的硝酸酯的等温热分解机理、反应动力学和产物分布等方向研究相对较少;对于硝酸酯热安定机制的研究主要集中于苯胺型和苯脲型安定剂的初步安定效果探索,其后期安定机理、整体反应动力学过程以及安定剂和硝酸酯的定量配比关系的研究未见文献报道。截至目前,国内外已形成硝酸酯两步热分解机制——硝酸酯键的断裂与硝酸酯的自催化;初步探索出苯胺型和苯脲型安定剂前期安定作用过程,其中,苯胺型安定剂初步安定机制为安定剂氨基上的氢与二氧化氮结合生成HNO_(2)和N自由基,而后安定剂的N自由基结合NO,苯脲型安定剂安定机制为安定剂发生C-硝化和N-硝化吸收氮氧化物。但上述国内外研究成果尚不足以支撑硝酸酯热安定控制技术及固体推进剂高温可靠使用调控技术等研究。基于此,文章提出应将使用温度下的硝酸酯等温热分解热行为和热安定机制作为硝酸酯基础应用的重点研究方向的研究建议。From the application perspective of nitrate ester in solid propellant,the research progress on the thermal decomposi-tions and thermal stability mechanisms of nitrate esters at home and abroad was reviewed.Research on the thermal decomposition mechanism of nitrate esters was focused on the non-isothermal high-temperature thermal decomposition behaviors and kinetics,but the isothermal thermal decomposition mechanism,reaction kinetics and product distribution of nitrate esters at the operating temper-ature was seldom investigated.Studies on the thermal stability mechanism of nitrate esters mainly concentrated on the exploration of the initial stability effect of phenylamine type and phenylurea type stabilizers,the later stability mechanism,the overall reaction ki-netic process and the quantitative ratio relationship between stabilizers and nitrate esters has not been reported in the literature.Up to now,a two-step thermal decomposition mechanism of nitrate has been formed at home and abroad,namely the breaking of nitrate esters bond and the self-catalysis of nitrate esters;the initial stability process of phenylamine type and phenylurea type stabilizers was preliminarily obtained.The initial stability mechanism of phenylamine type stabilizers was that hydrogen on the amino group of stabilizers was combined with nitrogen dioxide to generate HNO_(2) and N free radicals,and then the N free radicals of stabilizer was combined with NO.The stability mechanism of phenylurea type stabilizers was C-nitration and N-nitration absorption of nitrogen ox-ides.However,the above research results at home and abroad were not enough to support the research on the control technology of nitrate esters stability and the high temperature reliable use control technology of solid propellant and others.Henceforth,further re-search on the isothermal decomposition behaviors as well as the stability mechanism of nitrate esters at the operating temperature should be advocated as critical direction for academic investigation.

关 键 词：固体推进剂 硝酸酯 安定剂 热分解 安定机理 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]