新型高能发射药表面处理技术研究

【作者】 陈余谦；

【导师】 黄振亚；

【作者基本信息】 南京理工大学 ， 材料学， 2012， 硕士

【摘要】 为了改善叠氮硝胺发射药(DA药)的初始燃气生成规律,改善其应用性能,本论文在1,3-偶极环加成反应原理的基础上提出了新的表面钝感处理方法,即采用端炔基化合物作为钝感剂前躯体,与叠氮硝胺反应生成聚三唑大分子,从而在降低DA药初始燃气生成速率和实现渐增性燃烧效果的同时确保钝感药良好的长储稳定性能。以均苯三甲酸和丙炔醇为原料,采用酰氯化法制备了1,3,5-苯三甲酸三炔丙酯(TPBC),并使用高效液相色谱、红外光谱和核磁共振对其纯度和结构进行了表征。以TPBC为钝感剂,采用转鼓钝感工艺对DA药进行表面处理,并以传统的小分子物质邻苯二甲酸二丁酯(DBP)和高分子物质聚己二酸丙二醇酯(PPA)作对比钝感剂,研究了钝感DA药的燃烧性能和长储稳定性。结果表明,采用DBP钝感的DA药在常温下放置3个月后燃烧性能就发生了很大的变化,采用PPA钝感的DA药在50℃下长储3个月后钝感剂也发生了明显的迁移,因此DBP和PPA都不能用作DA药的钝感剂。采用TPBC钝感的DA药,起始燃烧活度从未钝感DA药的6.3(MPa·s)-1降到3.3(MPa·s)-1,有效地降低了初始燃气生成速率；最大燃烧活度处的相对压力Bm为0.498,燃烧渐增性系数Pi为0.128(未钝感DA药的Pi为-0.176),具有明显的渐增性燃烧效果；在常温和50℃下长储3个月后,初始燃烧活度基本不变,仅在燃烧中后期活度稍有降低,具有良好的长储稳定性能。以三乙醇胺为原料,IPDI为桥联剂,丙炔醇为封端剂,成功地合成了端炔基三乙醇胺(ATTEA).以ATTEA为钝感剂,采用转鼓钝感工艺对DA药进行表面处理,结果表明：ATTEA对DA药具有很好的钝感阻燃效果,初始燃烧活度仅为1.5(MPa·s)-1左右；DA-ATTEA发射药具有较好的渐增性燃烧效果,其最大燃烧活度对应的相对压力Bm为0.406,燃烧渐增性系数Pi为0.754;热加速老化实验也表明DA-ATTEA发射药具有较好的长储稳定性能。论文研究结果表明,1,3-偶极环加成反应原理在叠氮硝胺发射药表面处理技术中具有广阔的应用前景,该方法值得深入研究。更多还原

【Abstract】 To improve the initial burning gas generating regulation and application properties of azidonitramine propellant (DA-propellant), a novel surface modification method was proposed in this paper based on the 1,3-dipolar cycloaddition reaction. A multiple acetylene-terminated compound was introduced as the deterrent precursor, it reacted with azidonitramine monomer to form polytriazole network, so that for one aspect the initial burning gas generating rate reduced and the effect of progressive burning was fulfilled, and the other aspect the long-storage stability of the deterred propellant was assured.Tripropargyl 1,3,5-benzenetricarboxylate (TPBC) was prepared by two steps with the raw materials of 1,3,5-benzenetricarboxyl acid and propargyl alcohol, and its purity and structure was characterized by HPLC, FTIR and 1H-NMR. TPBC was used as a deterrent, and the other two deterrents DBP (dibutyl phthalate) and PPA (poly(1,2-propylene glycol adipate)) were used as the comparative ones, DA-propellant was modified by rotating-drum technique to investigate their combustion property and long-storage stability. The results showed, the combustion property of DA-propellant deterred by DBP changed a lot after stored for 3 months under room temperature, and the deterrent of DA-propellant deterred by PPA migrated obviously after stored for 3 months under 50℃, so DBP and PPA could not be used as the deterrent for DA-propellant. For DA-propellant deterred by TPBC, the initial burning activity reduced from 6.3(MPa·s)-1 of undeterred DA-propellant to 3.3(MPa·s)-1,indicating that the initial burning gas generating rate was reduced obviously; the relative pressure Bm at the maximum burning activity was 0.498, the burning progressivity index Pi was 0.128 (Pi of undeterred DA-propellant was -0.176), demonstrating the effect of obvious progressive burning; the initial burning activity changed little after stored for 3 months under room temperature and 50℃, and the burning activity reduced a little just during the middle and late burning process, showing excellent long-storage stability.Acetylene-terminated triethylolamine (ATTEA) was synthesized successfully from raw material triethylolamine, bridge agent IPDI and capping agent propargyl alcohol. ATTEA was used as the deterrent, DA-propellant was modified by rotating-drum technique, the investigation results indicated:ATTEA showed good effect of deterring for DA-propellant, its initial burning activity was just about 1.5(MPa·s)-1; DA-propellant deterred by ATTEA had excellent effect of progressive burning, its relative pressure Bm at the maximum burning activity was 0.406, and its burning progressivity index Pi was 0.754; Heat accelerated aging test also demonstrated excellent long-storage stability of DA-propellant deterred by ATTEA.The results in this paper showed wide prospect of 1,3-dipolar cycloaddition reaction applied in the surface modification technique of azidonitramine propellant, and this approach was worthy of further investigation.更多还原