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=2.071×1014exp(-1.975×104/T)(1-α)[- ln(1-α)1/3].%The thermal decomposition process and mechanism of poly (BAMO) (3 ,3-diazidomethyl oxet-ane) 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-Erof-eyev equation(n = 1.5). The kinetic equation of the decomposition process is expressed as; dα/dt =2.071 x 1014 exp( -1.975 x104/T)(l-α)[ -ln(l -α)1/3].
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