杯[6]芳烃热解及热动力学特性分析  

Pyrolysis and Thermokinetic Characteristics of Calixarene

作　　者：张丁然 卢林刚 ZHANG Dingran;LU Lingang(Graduate School,China People´s Police University,Langfang 065000,China;Office of Academic Research,China People´s Police University,Langfang 065000,China)

机构地区：[1]中国人民警察大学研究生院,廊坊065000 [2]中国人民警察大学科研处,廊坊065000

出　　处：《中国塑料》2021年第11期104-110,共7页China Plastics

基　　金：基于杯芳烃模块的新型单组分磷氮膨胀型阻燃剂的合成及阻燃机理研究(21472241);以磷腈为核的多模块协同阻燃剂的合成及阻燃机理研究(E2016507027);中国人民警察大学优秀硕士学位论文培育工程(JDYP202106)。

摘　　要：在氮气氛围中,利用热失重分析方法对杯[6]芳烃与对叔丁基杯[6]芳烃的热解特性进行了研究,同时采用热分解动力学分析方法计算了反应过程对应的活化能以及最优机理函数方程。结果表明,对叔丁基杯[6]芳烃由于叔丁基的不稳定性导致其初始热分解温度同杯[6]芳烃相比提前约160℃,此之后的分解过程同杯[6]芳烃基本一致(即发生桥联的亚甲基断裂与母体苯环的热裂解),整体上残炭量杯[6]芳烃略高10%;热解动力学分析表明,依据Kissinger和Flynn⁃Wall⁃Ozawa方法求出的杯[6]芳烃反应活化能分别是387.87 kJ/mol和376.28 kJ/mol,对叔丁基杯[6]芳烃脱叔丁基过程的化学反应活化能分别为223.56 kJ/mol和240.97 kJ/mol;依据Coats⁃Redfern方法求出杯[6]芳烃热解机理函数为g(α)=[-ln(1-α)]2/5,反应级数n=2/5,对应非等温热解机理为随机成核和随后生长反应,对叔丁基杯[6]芳烃脱叔丁基过程的热解机理函数为g(α)=[-ln(1-α)]1/2,反应级数n=1/2,对应非等温热解机理为随机成核和随后生长反应。The pyrolysis characteristics of calixarene and 4⁃tert⁃butylcalixarene were investigated by thermogravimetric analysis under a nitrogen atmosphere.Their activation energy and optimal mechanism function equation of the reaction process were studied using a thermal decomposition kinetic analysis method.The results indicated that 4⁃tert⁃butylcali⁃xarene exhibited the same initial thermal decomposition temperature as calixarene due to the instability of tert butyl groups.Hydrocarbons presented a decomposition temperature of about 160℃earlier than calixarene.Their subsequent decomposition process was almost the same with calixarene(namely the bridged methylene cleavage occurs and the ther⁃mal cracking of the parent benzene ring).The residual char of 4⁃tert⁃butylcalixarene was slightly higher than calixarene by 10%.The pyrolysis kinetic analysis demonstrated that the calixarene exhibited activation energy of 387.87 and 376.28 kJ/mol according to the Kissinger and Flynn⁃wall⁃Ozawa methods,respectively.According to the Coats⁃Red⁃fern method,the pyrolysis mecha⁃nism function of calixarene was determined to be g(α)=[-ln(1-α)]2/5,and the reac⁃tion order n was 2/5.Based on this result,the non⁃isothermal pyrolysis mechanism was determined as a random nucle⁃ation and subsequent growth reaction.The pyrolysis mechanism function of 4⁃tert⁃butylcalixarene was deterined to be g(α)=[-ln(1-α)]1/2,and the reaction order n was 1/2,assigned to the non⁃isothermal pyrolysis mechanism as a re⁃sult of the random nucleation and subsequent growth reaction.

关 键 词：杯[6]芳烃 芳烃 热失重分析 升温速率 热分解动力学 

分 类 号：TQ325[化学工程—合成树脂塑料工业]