新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯的合成及热分解动力学研究

Synthesis and Thermal Decomposition Kinetics of Novel Flame Retardant 1,3,5-Tris(5,5-dimethyl-1,3-dioxa-2-oxophosphorinanyl-2-oxy)benzene

以新戊二醇、三氯氧磷及1,3,5-三羟基苯等为原料,经过两步反应合成新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯,采用元素分析、FT-IR、MS及1HNMR等技术确定了标题化合物的分子结构.以TG-DTG为手段,研究该新型磷系阻燃剂在氮气气氛中的热分解动力学;利用Kissinger法、Flynn-Wall-Ozawa(FWO)法对其进行热分解动力学研究,求出该阻燃剂的热分解动力学参数;利用Coast-Redfern法研究该阻燃剂的热分解机理.结果表明,Kissinger法所求得的表观活化能为171.72kJ·mol-1,指前因子lnA为37.57;Flynn-Wall-Ozawa法所求得的表观活化能为172.05kJ·mol-1.标题化合物的热分解动力学方程g(α)=α1/4,反应级数n=1/4.

The novel flame retardant 1,3,5-tris（5,5-dimethyl-l,3-dioxa-2-oxophosphorinanyl-2-oxy）-benzene was synthesized via neopentyl alcohol, phosphous oxychloride and 1,3,5-trihydroxybenzene by a two step reaction, and its structure was identified and studied by elemental analysis, IR,^ 1H NMR and MS techniques. The thermal decomposition kinetics of the novel flame retardant were studied by TG-DTG techniques. The kinetic parameters, including the activation energy and frequency factor of the decomposition process for the title compound were calculated through the Kissinger and Flynn-Wall-Ozawa （FWO） method and the thermal decomposition mechanism was also studied with the Coast-Redfern method. The results show that the activation energy and pre-exponential factor are 171.72 kJ·mol^-1 and 37.57 s^-1 with the Kissinger method and 172.05 kJ·mol^-1 with the Flynn-Wall-Ozawa method respectively. The kinetic equation of the novel flame retardant can be expressed as g（α）=α^1/4, and the reaction order is n=1/4.