摘要
以聚叠氮缩水甘油醚(GAP)和4,4'-偶氮(4-氰基戊酸)(ACVA)为原料合成大分子引发剂(MI-GAP),用其引发氯乙酸乙烯酯自由基聚合,得到聚叠氮缩水甘油醚嵌段聚氯乙酸乙烯酯(GAP-bPVCA),最后将其叠氮化得到含能聚合物——聚叠氮缩水甘油醚嵌段聚叠氮乙酸乙烯酯(GAP-b-PVAA)。采用傅里叶变换红外光谱(FT-IR)、紫外-可见光谱(UV-Vis)、核磁共振氢谱(1H NMR)对GAPb-PVAA的结构进行了表征。利用差热分析(DTA)、热重分析(TG)和微分热重分析(DTG)对GAP-b-PVAA的热稳定性进行了研究。结果表明,GAP-b-PVAA在空气中200℃未见分解;GAP-b-PVAA具有两个热失重过程,其中最大质量损失发生在228~243℃范围内,失重率为68.74%。GAP-b-PVAA热分解动力学参数由不同升温速率下的DTA表征数据,通过Kissinger方法和Ozawa方法计算得到,两种方法得到的表观活化能Ea数值相近,表明GAP-b-PVAA热稳定性良好,有望用于熔铸炸药中作为一种含能黏结剂。
The given paper is inclined to introduce a novel energetic copolymer, poly （glycidyl azide）- b-poly （vinyl acetate azide） （ GAP - b - PVAA）, which can be successfully obtained through a three step synthesis. The above mentioned three-step synthesis include the separate esterification reaction, the radical polymerization reaction and the azidation reaction. To achieve the purpose of the three-step synthesis, we have carried out the esterification reaction by using the poly （glycidyl azide） （GAP） and 4,4＇-azobis-（4-cyanovaleric acid） （ACVA） as the main raw materials needed to prepare the 4- （dimethylamino） pyridine-p-toluenesulfonate （DPTS） as the catalyst and N,N＇-dicyclohexyl carbodiimide （DCC） as the dehydrate agent, through which we can obtain the macroinitiator MI - GAP. The afore- mentioned macroinitiator has taken a kind of highly viscous oily prod- uct in a color of pale yellow with a yield of 73.2 % . So far as the radical polymerization reaction we have conducted is concerned, we have managed to have prepared the poly （glycidyl azide ）-b-poly （vinyl chloroacetate） （GAP - b - PVCA ） copolymer by using the vinyl chloroacetate as the raw material and the MI - GAP as the macroinitiator, whose yield is expected to reach 64.2% in the form of a dark yellow solid. And, then, we have synthesized the target copolymer GAP- b - PVAA through the azidation reaction of GAP- b - PVCA with the sodium azide （Nal^l3 ） in the dimethyl sulfoxide （DMSO） solvent. The target copolymer we have worked out is to pro- duce a yield of 77.5 % in the form of a kind of black solid. The chemical structure of the copolymer GAP - b - PVAA has been made evaluated and characterized via the FF - IR, UV - Vis, 1H NMR spectra. The results of the analysis and characterization indicate that the targeted copolymer named GAP - b - PVAA can be successfully synthesized through the thermogravimetric （ TG ） analysis, digital thermogravimetry （DTG） and differential thermal analysis （DTA） methods. The TG and DTG curve analysis has shown that GAP- b - PVAA can have two weight-loss processes in a temperature range be- tween 228 - 243 ~C and 245 - 600 ~C . At the same time, the mass loss tends to be as high as 68.74 % and 31.26 %, respectively. In addition, we have found that the temperature of the maximum weight loss can be expected to reach as high as at 240 ~C , which can be at- tributed to the decomposition of the azide group. What is more, the DTA curves that can be obtained indicate that GAP - b - PVAA is endowed with excellent resistance to the thermal decomposition up to 200 ~C in the atmosphere. On the other hand, the kinetic parameters of the thermal decomposition of GAP - b - PVAA can also be ob- tained from the differential thermal analysis data by Kissinger and Ozawa-Doyle＇ s methods with Ea （the apparent activation energy） being 147.49 kJ/mol and 148.37 kJ/mol, respectively. Thus, the investigation results demonstrate that GAP - b - PVAA has excellent thermal stability and therefore is a promising energetic copolymer that can be applied to TNT-based melt-cast explosives.
出处
《安全与环境学报》
CAS
CSCD
北大核心
2015年第2期138-143,共6页
Journal of Safety and Environment
基金
国家自然科学基金项目(51372211)
关键词
安全工程
含能黏结剂
聚合物
热稳定性
合成
safety engineering
energetic binder
polymers
thermal stability
synthesis
