2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶形控制及其与HTPB推进剂组份的相容性

以2-羟甲基-2-硝基-1,3-丙二醇为起始原料,通过缩酮反应、氧化偶联反应、水解反应、硝化反应四步反应合成出了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(SMX),并采用红外光谱、元素分析及核磁共振谱进行了结构表征。采用Materials Studio Modeling软件中的Growth Morphology方法模拟了SMX晶体的生长形态和结晶习性,分析了重要构晶晶面的表面结构特征,研究了溶剂效应对晶体形貌的影响。采用乙酸乙酯/石油醚混合液对SMX进行重结晶实验。通过DSC法研究了SMX与端羟基聚丁二烯(HTPB)推进剂组份:HTPB、高氯酸铵(AP)、铝(Al)粉、奥克托今(HMX)、黑索今(RDX)和甲苯二异氰酸酯(TDI)的相容性。结果表明,乙酸乙酯/石油醚结晶体系可改善产品的晶体形貌,理论预测与实验结果相符。SMX与HMX、RDX、Al粉相容性较好,与AP轻微敏感,与HTPB和TDI不相容。

Synthesis, Crystal Morphology Control of SMX and Its Compatibility with the Components of HTPB Propellant

Bis(hydroxylmethyl)-2,3-dinitrobutane-1,4-diol tetranitrate(SMX) was synthesized via. ketal reaction, oxidative coupling, ketal deprotection and nitration etc. four step reaction using 2-(hydroxymethyl)-2-nitro-1,3-propanediol as starting material. The structure of SMX was characterized by elemental analyses,infrared spectroscopy and nuclear magnetic resonance spectroscopy. The crystal growth morphology and crystallization behavior of SMX were simulated by using Growth Morphology methods in Materials Studio Modeling softwar, the structure features of important crystal facets were analyzed, and the solvent effect on the crystal morphology was discussed. The recrystallization of SMX was carried out by using the mixed solution of ethyl acetate and petroleum ether. The compatibilities of SMX with hydroxy-terminated-polybutadiene(HTPB)propellant components, including HTPB, ammonium perchlorate(AP), aluminum powder,(Al powder)cyclotetramethylenetetramine(HMX), cyclotrimethylenetrinitramine(RDX), tolylene diisocyanate(TDI)were investigated by differential scanning calorimetry(DSC).Results show that the crystal morphology of the product was improved by the ethyl acetate/petroleum ether system. The theoretical predictions are in agreement with the experimental results. The mixed system of SMX with HMX, RDX and Al powder is compatible, with AP is slightly sensitive, and with HTPB and TDI is incompatible.