紫胶树脂的热分解过程及动力学研究  

On Thermal Decomposition and Kinetics of Lac Resin

作　　者：董国华 冀浩博 张弘[3] 郑华[3] 李凯[3] 李坤[3] 

机构地区：[1]云南工艺美术学校教务处,云南昆明650223 [2]昆明冶金高等专科学校科技处,云南昆明650033 [3]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,云南昆明650224

出　　处：《昆明冶金高等专科学校学报》2017年第5期63-69,共7页Journal of Kunming Metallurgy College

基　　金：昆明冶金高等专科学校科研基金项目:紫胶树脂与羟丙基甲基纤维素共混成膜研究(2015XJQN002);云南省应用基础研究计划项目青年项目:紫胶树脂与聚乙烯醇共混改性研究(2016FD063)

摘　　要：紫胶树脂的无氧热分解动力学参数对其加工应用及拓展新的应用领域具有重要的指导作用。通过紫胶树脂在升温速率为5、10、20、40 K/min时,升温终止温度为883 K的热重试验,得出紫胶树脂无氧热分解反应为一步反应,且其热分解反应的起始、终止、最大分解速率温度均随着升温速率的升高而升高;应用Kissinger法和Starink法估算的紫胶树脂无氧热分解反应活化能分别为249.49 k J/mol和260.46 k J/mol,通过FWO法和FRL法的进一步计算,确定其值为(254.52±31)k J·mol-1;通过Malek法确定了紫胶树脂的无氧热分解机理满足J-M-A方程,其机理为随机成核、随后生长,并计算了紫胶树脂无氧热分解反应的n及lg A值的范围,分别在0.069 6~0.075 6和13.38~14.53之间;通过升温速率为5、10、20、40 K/min时,升温终止温度为843 K的差示扫描量热试验,测得紫胶树脂在该升温速率下的粘流转变起始、终止及峰值温度的平均值分别为328.0 K、341.4 K、356.5 K,其4种升温速率下的粘流转变焓变和熵变平均值分别为58.41 J/g和0.17 J/g·K。The kinetic parameters of lac resin's thermal decomposition play an important role in its application and expanding application fields. By the thermogravimetric experiment with separate testing heating rates of 5,10,20,40 K/min and final temperature of 883 K,this paper draws the conclusions as follows:the thermal decomposition of lac resin is a one-step reaction,with its maximum decomposition temperature increased by heating rates both atthe start and the end of the reaction; the activation energies of lac resin thermal decomposition reaction are 249. 49 k J/mol and 260. 46 k J/mol calculated separately by Kissinger and Starink methods; further calculation by FWO and FRL,it gets the value of( 254. 52 ± 31) k J·mol-1; by Malek,it confirms that the mechanism of thermal decomposition reaction matches the J-M-A equation: the nucleation and growth at random. Accordingly,the range of n and lg A calculated is between 0. 069 6 ~0. 075 6 and 13. 38 ~ 14. 53. By the same thermogravimetric experiment with final temperature of 843 K,the start,end and peaking temperatures at viscous flow transition are measured separately at 328. 0 K,341. 4 K and 356. 5 K and the enthalpy and entropy changes at viscous flow transition are averagely at 58. 41 J/g and0. 17 J/g·K under the 4 heating rates mentioned above.

关 键 词：紫胶树脂 热解 动力学 反应机理 热力学 

分 类 号：TQ321[化学工程—合成树脂塑料工业] O643.12[理学—物理化学]