【作者】 王海波；

【导师】 邓剑如；

【作者基本信息】 湖南大学 ， 高分子物理与化学， 2007， 硕士

【摘要】 丁羟复合固体推进剂因其粘合剂具有生产工艺简单,价格便宜,本体粘度低,耐老化性好,能获得高固含量推进剂等特点,成为国内外普遍使用的推进剂品种。由于丁羟推进剂广阔的应用前景,国内外也有不少这方面的研究,不过基本上都是集中在改善丁羟复合推进剂力学、抗老化等工艺性能方面与应用方面的工作;却很少有关固化机理方面的基础理论研究。当然丁羟复合固体推进剂中组分较多,相互间作用复杂也给固化机理研究带了一定的困难;本课题选取丁羟复合固体推进剂中各含活泼氢组分作为研究对象,通过反应动力学、拉伸力学及溶胀性能的测试,针对它们在固化反应中的反应活性展开具体的研究。在反应动力学上,分别对端羟基聚丁二烯(HTPB)/苯异氰酸酯(PI),键合剂(BA-5)/PI和防老剂H(N,N′—二苯基对苯二胺)/PI在甲苯/二甲基亚砜混合溶液体系中进行了反应动力学研究,并计算了相应体系的反应速率和活化能。结果表明,在相同的条件下,这三种活泼氢组分的反应速率由大到小依次为;键合剂(BA-5)上的胺基、HTPB、BA-5上的羟基、防老剂H上的胺基。在对各活泼氢组分的力学及溶胀特性的研究上,对上述活泼氢组分按照实际丁羟推进剂固化条件,构成四个不同配方,用TDI固化并制成胶片,在同一恒定的固化温度下每隔24小时分别把四组胶片制成样片,进行了单向拉伸和溶胀比测试;力学性能和交联密度变化的结果不仅表明BA-5和防老剂H都能有效提高丁羟推进剂的力学性能;也验证了丁羟推进剂中各活泼氢组分的反应活性和反应顺序,同时也很好地说明了该实验结果在实际中的应用价值另外本课题研究的丁羟推进剂中各活泼氢组分的反应速率及活化能,各组分体现的力学性能,它们对交联网络的影响等结果对以后推进剂配方的研究和生产工艺的确定有参考意义。更多还原

【Abstract】 HTPB composite propellant has become a large used propellant abroad and in as for its simple productive technics, low cost, low bulk viscidity, good anti-aging performance and high solid content etc. Because of HTPB composite propellant’s good prosperity, now a lot of research has been taken on it. Most of them refer to HTPB propellant’s performance improving and application. But there are still few reports about its curing mechanism. By the way, HTPB composite propellant’s curing mechanism is more difficult for its complicated components and their inter-activity. So my research chooses the active hydrogen components from all propellant’s components as one part of curing mechanism, studies their reactive activity in curing system of HTPB propellant by kinetics, mechanical performance, swell ratio in detail.Kinetics of hydroxyl-terminated polybutadiene (HTPB) / phenyl isocyanate (PI) ,bonding agent(BA-5)/PI and antioxidant H/PI were studied in toluene/dimethyl sulphoxide solution. The rate constants and the activation parameters were calculated. The results showed that the reactionary rate of these three active hydrogen components decreased in same condition, the sequence of reactive activity was in following order: amine of BA-5>HTPB>hydroxyl of BA-5 > antioxidant H.Then four different formulations composed of these active hydrogen agents were cured with TDI and were made into rubber sheets. The effects of active hydrogen components on curing process were investigated by measurement of uniaxial tensile properties and swell ratio. Variety of rubber sheets’ mechanical properties and crosslink density proved the results of kinetics. The results also show that BA-5 and antioxidant H both can improve HTPB propellant’ mechanical properties effectively. And it will be well applied in real technical process.In addition, the research’ results, all active hydrogen components’ reactive activity and activation energy, influence on HTPB composite propellant’ mechanical properties and network structure will be as reference for the study of HTPB composite propellant’ formulation and productive technics.更多还原