文献类型：期刊文献

中文题名：氧气气氛中紫胶树脂的热分解动力学试验

英文题名：Thermal Decomposition and Kinetic Analysis of Lac Resin in Oxygen

作者：冀浩博[1] 李坤[2] 孙彦琳[3] 唐晓宁[3] 李凯[2] 郑华[2] 张弘[2]

第一作者：冀浩博

机构：[1]昆明冶金高等专科学校,昆明650033;[2]中国林业科学研究院资源昆虫研究所,国家林业局特色森林资源工程技术研究中心;[3]昆明理工大学

年份：2018

卷号：46

期号：10

起止页码：87-92

中文期刊名：东北林业大学学报

外文期刊名：Journal of Northeast Forestry University

收录：CSTPCD;;北大核心:【北大核心2017】；CSCD:【CSCD_E2017_2018】；

基金：云南省应用基础研究计划项目青年项目(2016FD063)；昆明冶金高等专科学校科研基金项目(2015XJQN002)。

语种：中文

中文关键词：紫胶树脂;氧气气氛;热分解;动力学

外文关键词：Lac resin;In oxygen;Thermal decomposition;Kinetic

分类号：TQ351.7;TQ351.4

摘要：采用热分解动力学研究方法,在氧气气氛中同时监测紫胶树脂由室温至高温条件范围内的热质量(TG)和差示扫描量热(DSC)曲线,应用相应软件绘制微分热质量(DTG)曲线,测定紫胶树脂有氧热分解过程的特征参数变化;根据TG、DTG曲线,采用4种不同数学方法(Kissinger法、Starink法、FWO法、FRL法)计算紫胶树脂在氧气气氛中的热分解活化能,对计算结果进行了线性相关性检验;应用Malek法计算并推断紫胶树脂在氧气气氛中的热分解数学模型。结果表明:紫胶树脂在氧气气氛中的热分解反应为两步反应,且热分解反应过程中,体系的放热量高于吸热量;由于紫胶树脂具有聚合物特性,其热分解反应最大分解速率温度随升温速率的增大而增大。由于热分解反应体系的反应复杂性,4种数学方法中仅有Kissinger法、Starink法的计算结果具有密切的线性相关性,计算的热分解反应活化能分别为287.192、287.294 k J/mol; FWO法、FRL法的计算结果不具有密切的线性相关性,FRL法的线性相关性较差,但仍可依据FWO法的计算结果并结合TG、DTG、DSC曲线形状进行热分解机理的推断分析。应用Malek法对热分解反应进行了最概然机理函数的计算,紫胶树脂在氧气气氛中的热分解反应最接近于J-M-A方程,依据此方程的反应机理为随机成核和随后生长。依据DSC曲线,紫胶树脂在10、15、20、25℃/min升温速率时,黏流转变的起始、终止及峰值温度平均值,分别为46.6、146.5、80.1℃;计算了紫胶树脂在相应升温速率时的黏流转变焓变和熵变,平均值分别为199.4 J/g、0.56 J/(g·K)。
By using the thermal decomposition kinetics,TG and DSC curves of lac resin from room temperature to high temperature were simultaneously monitored in oxygen atmosphere.DTG curves were plotted with corresponding software.The characteristic parameters of lac resin during aerobic thermal decomposition were determined.According to TG and DTG curves,the thermal decomposition activation energy of lac resin in oxygen atmosphere was calculated by four different mathematical methods(Kissinger,Starink,FWO,and FRL method),and the linear correlation test was carried out for the calculated results.Malek method was used to calculate and infer the thermal decomposition mathematical model of lac resin in oxygen atmosphere.The results show that the thermal decomposition reaction of lac resin in oxygen atmosphere is a two-step reaction,and the exothermic quantity of the system is higher than that of absorbed heat in the process of thermal decomposition.Because lac resin has polymer properties,the maximum decomposition rate temperature increases with the increase of heating rate.Because of the complexity of the thermal decomposition reaction system,only Kissinger and Starink methods have close linear correlation in the four mathematical methods,and the activation energies of thermal decomposition reaction are 287.192 and 287.294 kJ/mol,respectively.The results of FWO method and FRL method do not have close linear correlation,and FRL method is worse.However,the thermal decomposition mechanism can be inferred and analyzed according to the calculation results of FWO method and the shapes of TG,DTG and DSC curves.Malek method was used to calculate the most probable mechanism function of thermal decomposition reaction.The thermal decomposition reaction of lac resin in oxygen atmosphere was the closest to J-M-A equation.According to the reaction mechanism of this equation,random nucleation and subsequent growth were obtained.According to the curves of DSC,the average values of the beginning,ending and peak temperature of the viscous flow change of lac resin at the heating rates of 10,15,20,25℃/min are 46.6℃,146.5℃,and 80.1℃,respectively.The enthalpy and entropy changes of viscous flow transition at corresponding heating rate are calculated with the average values of 199.4 J/g and 0.56 J/(g·K),respectively.