Kinetic parameters of thermal destruction of the copolymer of polyethylene glycol fumarate with acrylic acid in inert medium

IF 0.3 Q4 CHEMISTRY, MULTIDISCIPLINARY Chemical Bulletin of Kazakh National University Pub Date : 2022-06-20 DOI:10.15328/cb1260
M. Burkeev, A. Bolatbay, D. Havlícek, Y. Tazhbayev, S. Davrenbekov, L. Zhaparova
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Abstract

Thermal decomposition of the copolymer of polyethylene glycol fumarate with acrylic acid (p-EGF:AA) of two different compositions synthesized earlier was studied in the present work. TG and DTG curves prove that decomposition takes place in several stages. According to thermogravimetric curves it has been found out that for the copolymer with higher content of acrylic acid the decomposition of the copolymer’s sample is started at higher temperatures. It has been shown the shift of the temperature of decomposition’s start to the higher area with the increase of heating rate which is necessary for the detorsion of macromolecular coil. Experimental data processed using graphical methods of Kissinger–Akahira–Sunose and Friedman allowed us to calculate the activation energy of the thermal decomposition process. It has been established that the copolymer with the composition of 21.03:78.97 mass.% has lower meaning of activation energy than the one with the composition of 68.96:31.04 mass.%. As a result of calculation one can see that the meanings found out using these methods depend slightly on conversion. Using Achar-Brindley-Sharp method and the method of invariant kinetic parameters the kinetic triplet of the decomposition process has been found which was used to build the calculated curve. The dependences of g(α) on α using these parameters showed a satisfactory agreement of calculated curves with the experimental ones. One can conclude that the decomposition process of the copolymer of polyethylene glycol fumarate with acrylic acid is well described with of D3 (three-dimensional diffusion) model.
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聚乙二醇-富马酸酯-丙烯酸共聚物在惰性介质中的热破坏动力学参数
研究了合成的两种不同组分的富马酸聚乙二醇与丙烯酸共聚物(p-EGF:AA)的热分解反应。TG和DTG曲线证明分解分几个阶段进行。根据热重曲线,已经发现对于具有较高丙烯酸含量的共聚物,共聚物样品的分解在较高温度下开始。研究表明,随着加热速率的增加,分解起始温度向较高区域移动,这是大分子线圈还原所必需的。使用Kissinger–Akahira–Sunose和Friedman的图解方法处理的实验数据使我们能够计算热分解过程的活化能。已经确定,组成为21.03:78.97质量%的共聚物比组成为68.96:31.04质量%的聚合物具有更低的活化能含义。计算结果表明,使用这些方法得出的含义略微取决于转化率。利用Achar-Brindley-Sharp方法和动力学参数不变方法,得到了分解过程的动力学三重态,并用它建立了计算曲线。使用这些参数的g(α)与α的依赖关系表明,计算曲线与实验曲线吻合良好。可以得出结论,用D3(三维扩散)模型很好地描述了富马酸聚乙二醇与丙烯酸共聚物的分解过程。
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审稿时长
10 weeks
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