Comparative Analysis of Thermal Decomposition Kinetics of Copolymers Based on Polyethylene Glycol Fumarate with Methacrylic Acid

Ulygbek B. Tuleuov, A. Kazhmuratova, Abylaihan N. Bolatbay, Ermaut Nassikhatuly, Aizhan R. Koishugulova
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Abstract

The thermal properties of a copolymer based on polyethylene glycol fumarate with methacrylic acid in a ni-trogen atmosphere were studied in this paper. Four various heating rates and two types of a polyester resin composition were used. The analysis of thermal decomposition kinetics was implemented. Three kinetics methods namely Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose and Friedman were applied. Curves of a thermogravimetric analysis demonstrated that the thermal decomposition of copolymers with different molar ratios was observed. It was determined that the kinetic data depends on the studied copolymers’ composition. The obtained data showed a good convergence in various heating rates. Also, the thermodynamic characteris-tics were calculated namely the changes in the Gibbs energy (ΔG), enthalpy (ΔH) and entropy of activation (ΔS). The Achar-Brindley-Sharp method was used to find the invariant kinetic parameters of decomposition. Thus, the the kinetic compensation effect was applied to define a reaction model and a pre-exponential factor. A main phase of the copolymer decomposition in a narrow temperature range was determined. It was attested by a peak on the differential curve. An insignificant mass loss of the volatile-matter yield was observed in the range of 30–150 °C.
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富马酸聚乙二醇与甲基丙烯酸共聚物热分解动力学的比较分析
研究了富马酸聚乙二醇与甲基丙烯酸共聚物在氮气气氛中的热性能。使用了四种不同的加热速率和两种类型的聚酯树脂组合物。进行了热分解动力学分析。采用了Flynn-Wall-Ozawa、Kissinger-Akahira-Sunose和Friedman三种动力学方法。热重分析曲线表明,不同摩尔比的共聚物发生了热分解。确定了动力学数据取决于所研究的共聚物的组成。所得数据在不同升温速率下具有良好的收敛性。同时计算了反应的热力学特性,即吉布斯能(ΔG)、焓(ΔH)和活化熵(ΔS)的变化。采用Achar-Brindley-Sharp方法求出分解的不变动力学参数。因此,应用动力学补偿效应定义了反应模型和指前因子。确定了共聚物在较窄温度范围内分解的主相。微分曲线上的一个峰可以证明这一点。在30-150°C范围内,挥发物产率的质量损失不显著。
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