基于TG分析的杯[8]芳烃热解机理与动力学分析  

Pyrolysis mechanism and kinetics of calixarene based on TG analysis

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,河北廊坊065000 [2]中国人民警察大学科研处,河北廊坊065000

出　　处：《中国塑料》2022年第1期92-99,共8页China Plastics

基　　金：国家自然科学基金资助项目(21472241);河北省自然科学基金资助项目(E2016507027);中国人民警察大学优秀硕士学位论文培育工程(JDYP202106)。

摘　　要：运用热失重分析法对杯[8]芳烃和对叔丁基杯[8]芳烃氮气氛围下的热解状况与热解机理进行了探究,同时采用热分解动力学方法求解了二者热解过程对应的反应活化能和最优的机理函数方程。结果表明,对叔丁基杯[8]芳烃由于结构中的C—Hσ键以及C=Cπ键的强相互作用力,整体结构更为稳定,杯[8]芳烃具备优良的成炭性能,对叔丁基杯[8]芳烃具备优良的热稳定性能,二者的分解温度对于高分子材料的适应性较强;依照Kissinger方法和Flynn-Wall-Ozawa计算的杯[8]芳烃的反应活化能分别为179.14 kJ/mol和192.84 kJ/mol,对叔丁基杯[8]芳烃的反应活化能分别为291.61 kJ/mol和312.14 kJ/mol;依照Coats-Redfern方法计算的杯[8]芳烃的热解机理函数为g(α)=[-ln(1-α)]^(1/3),反应级数n=1/3,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[8]芳烃的热解机理函数为g(α)=α^(1/3),反应级数n=1/3。Thermogravimetry analysis was conducted to investigate the pyrolysis status and mechanism of calixarene and 4-tert-butylcalixarene under a nitrogen atmosphere.Meanwhile,the reaction activation energy and the optimal mechanism function equation of the two pyrolysis processes were obtained using a thermal decomposition kinetics method.The results indicated that the overall structure of 4-tert-butylcalixarene was more stable due to the strong interaction between the C—Hσand C=Cπbonds.Calixarene exhibited excellent char forming performance,and 4-tert-butylcalixarene presented an excellent thermal stability.Their decomposition temperatures are very suitable for the use of polymer materials,Moreover,the pyrolysis kinetic analysis demonstrated that the activation energies of calixarene were determined to be 179.14 and 192.84 kJ/mol through calculation using the Kissinger’s and Flynn-wall-Ozawa’s methods,respectively.The activation energies of 4-tert-butylcalixarene were calculated to be 291.61 and 312.14 kJ/mol using the Kissinger’s and Flynn-wall-Ozawa’s methods,respectively.According to the Coats-Redfern method,the pyrolysis mechanism function of calixarene was determined to be g(α)=[-ln(1-α)]^(1/3) and its reaction order n was 1/3.Its non-isothermal pyrolysis mechanism belongs to random nucleation and subsequent growth reaction.The pyrolysis mechanism function of 4-tert-butylcalixarene was g(α)=α^(1/3) and its reaction order n was 1/3.

关 键 词：杯[8]芳烃 对叔丁基杯[8]芳烃 热失重 热分解 动力学 

分 类 号：TQ314.2[化学工程—高聚物工业]