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

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...

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

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].