吡蚜酮二水合物脱溶剂机理及动力学研究

摘要利用TGA/DSC热分析技术对吡蚜酮二水合物热分解过程进行了研究。结果表明,氮气氛围下,吡蚜酮二水合物脱水焓变为154 kJ·mol^-1。脱溶剂机理高度吻合A₄三维成核生长模型(R²>0.99)。此外,使用Flynn-Wall-Ozawa方程,从转化率与升温速率2个维度进行拟合,分别得到了不等的表观活化能与指前因子。为消除不同拟合方法带来的误差,得到可靠的动力学参数,多升温速率法拟合所有升温速率下的各转化率的数据,结果为E_a:44.85 (±6.59) kJ·mol^-1(95%置信),lg(A/min^-1):9.54 (±1.08)(95%置信),R²=0.8141。为验证推算结果,比较拟合方法的准确性,引入Kissinger方法计算活化能及指前因子进行验证。验算结果支持多升温速率法结论。

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	陈巍
	姚其超
	吴迪
	纪旭
	林玮浩
	曲思源
	李九龙
	李唱
	周丽娜

关键词：吡蚜酮溶剂化物脱溶剂动力学热分析

Abstract： This research analyzed the thermal desolvation mechanism and kinetics of pymetrozine dihydrate by TGA/DSC. The result showed that in nitrogen atmosphere, the desolvation enthalpy of pymetrozine dihydrate desolvation is 154 kJ·mol^-1. The pymetrozine dihydrate’s desolvation process matched with the 3-dimensional nucleation and growth model (Avrami-Erofeev equation, n=4) well (R²>0.99) in this case. The Flynn-Wall-Ozawa equation was used to analyse the correlation of conversion rate and temperature changing rate, respectively. It revealed different apparent activation energy and pre-exponential factor A by two correlation methods. By fitting all the data of various temperature changing rates and conversion rates, the various heating rate method can fix the two fitting methods’ deviation and reveal credible data. It revealed apparent activation energy at 44.85 (±6.59) kJ·mol^-1 (95% confidence) and lg(A/min^-1) at 9.54(±1.08) (95% confidence), R²=0.8141. To certify the data and compare the fitting methods, Kissinger method was used to obtain apparent activation energy and a pre-exponential factor A. The verification sustained the conclusion by the various heating rate method.

Keywords： pymetrozine solvate desolvation kinetics thermal analysis

Received 2021-11-13;

Fund:天津市大学生创新创业训练计划项目(202010056216)。

Corresponding Authors: 陈巍,副教授,E-mail:chenwei@tju.edu.cn。 Email: chenwei@tju.edu.cn

About author: 陈巍(1974-),男,副教授,现从事工业结晶方面的研究。

引用本文:

陈巍, 姚其超, 吴迪, 纪旭, 林玮浩, 曲思源, 李九龙, 李唱, 周丽娜.吡蚜酮二水合物脱溶剂机理及动力学研究[J]. 化学工业与工程, 2023,40(5): 30-39

CHEN Wei, YAO Qichao, WU Di, JI Xu, LIN Weihao, QU Siyuan, LI Jiulong, LI Chang, ZHOU Lina.Desolvation mechanism and kinetics of pymetrozine dihydrate[J]. Chemcial Industry and Engineering, 2023,40(5): 30-39

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