新型阻燃聚丙烯腈共聚物在空气中的非等温热分解动力学

Non-isothermal Decomposition Kinetics of Novel Fire Retarded Polyacrylonitrile Copolymer in Air

用O,O-二乙基-O-烯丙基硫代磷酸酯(DATP)与丙烯腈共聚合成了新型阻燃聚丙烯腈共聚物(FR-PAN),对其在空气中的非等温动力学通过TG-DTG技术进行了研究,并通过极限氧指数法(LOI)考查了FR-PAN的阻燃性能;利用Kissinger方法和Flynn-Wall-Ozawa(FWO)方法计算出了FR-PAN热降解过程中的表观活化能;采用Satava-Sestak方法通过对不同机理模型的选取,确定了FR-PAN的热降解机理.结果表明,由Kissinger法和FWO法所计算得到的FR-PAN的表观活化能分别为119.62和123.99 kJ·mol-1;FR-PAN的热降解反应属于随机成核和随后增长机理,其机理函数为G(α)=-ln(1-α),反应级数n=1.

A novel fire retarded polyacrylonitrile copolymer （FR-PAN） was obtained via copolymerization of acrylonitrile with O,O-diethyl-O-allyl thiophosphate （DATP）. The non-isothermal decomposition kinetics of the FR-PAN in O2 were studied by TG-DTG techniques, and the fire retardance of the FR-PAN was investigated by the limiting oxygen index （LOI） method. The activation energies of the major thermal decomposition of the FR-PAN were determined by using the Kissinger method and Flynn-Wall-Ozawa （FWO） method, respectively. With the selection of different mechanism models, the decomposition mechanism of the FR-PAN was obtained by using the Satava-Sestak method. The results show that the activation energies for the major thermal decomposition step of the FR-PAN are 119.62 kJ·mol^-1 with the Kissinger method and 123.99 kJ·mol^-1 with the FWO method, respectively. And the thermal decomposition mechanism of the major decomposition step of the FR-PAN is random nucleation and growth, with the mechanism function being G（α）= -ln（1 -α）, and the reaction order being 1.