3,3-二叠氮甲基氧丁环与3-叠氮甲基-3-甲基氧丁环均聚物的嵌段共聚物热分解机理及非等温裂解动力学分析  

Thermal Decomposition Mechanism and Non-isothermal Pyrolysis Kinetic Analysis of BAMO-AMMO Copolymer

作　　者：宋秀铎[1] 赵凤起[1] 王江宁[1] 田军[1] 张腊莹[1] 甘孝贤[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《兵工学报》2011年第11期1320-1326,共7页Acta Armamentarii

摘　　要：3,3-二叠氮甲基氧丁环与3-叠氮甲基-3-甲基氧丁环均聚物的嵌段共聚物(BAMO-AM-MO)是一种含能黏合剂,为了解其受热分解机理及分解动力学情况,采用DSC法、TG-DTG法、固相原位池-FTIR联用技术和DSC-TG-MS联用技术探讨了BAMO-AMMO的热分解过程及机理。研究结果表明,BAMO-AMMO受热分解主阶段为叠氮基团分解,释放出N2,裂解过程中形成亚胺中间体,并放出大量的热,放热量为1 663 J/g.同时,由于叠氮基团分解引起其他基团的重排,而引起共聚物的深度分解。采用程序升温(升温速率为2.5、5、10、20℃/min)的DSC数据,根据非等温动力学方程Kissinger法、Ozawa法和Coats-Redfern法计算了BAMO-AMMO受热分解主阶段的非等温反应动力学参数。获得BAMO-AMMO分解主阶段的表观活化能为164.2 kJ/mol,指前因子为1014.14 s-1.计算结果表明,BAMO-AMMO受热分解具有局部化学反应特征,其分解动力学服从Avrami-Erofeyev成核与生长(n=1.5)过程。受热分解非等温动力学方程可表示为dα/dt=2.071×1014 exp(-1.975×104/T)(1-α)[-ln(1-α)1/3].The thermal decomposition process and mechanism of poly（BAMO）（3,3-diazidomethyl oxetane） and poly（AMMO）（3-azidomethyl-3-methyl oxetane）（BAMO-AMMO） copolymer were investigated by means of DSC,TG-DTG,heating in-situ cell/FTIR,and thermolysis/mass spectrograph.The decomposition mechanism of BAMO-AMMO was proposed.The results show that the break of C-N3 bond happens with the exothermic decomposition peak and releases N2 gas.The exothermic decomposition peak appears at 260.3 ℃,and the exothermic enthalpy is 1 663 J/g.Other decompositions arise from the break of C-N3 bond,and at last BAMO-AMMO is decomposed into CO2,N2,gas aldehyde compound and carbon.The thermal decomposition reaction kinetics of BAMO-AMMO was investigated by means of DSC in a temperature-programmed mode at the temperature rise rates of 2.5,5,10 and 20 ℃/min.The apparent activation energy and pre-exponential factor of the major decomposition reaction were calculated using Kissinger equation,Ozawa equation and Coats-Redfern equation.The apparent activation energy is 164.2 kJ/mol,and the pre-exponential factor is 1014.14 s-1.The results indicate that the major decomposition of BAMO-AMMO has the characteristic of local chemical reaction.And the reaction kinetics follow the Avrami-Erofeyev equation（n=1.5）.The kinetic equation of the decomposition process is expressed as： dα/dt=2.071×1014exp（-1.975×104/T）（1-α）[-ln（1-α）1/3].

关 键 词：分析化学 热分析 3 3-二叠氮甲基氧丁环与3-叠氮甲基-3-甲基氧丁环均聚物的嵌段共聚物 分解机理 非等温动力学 DSC 

分 类 号：O643[理学—物理化学]