Comparative Reactivity of Different Polyols in the PET Saponification Process

V. Sapunov, G. Dzhabarov, V. Shadrina, M. S. Voronov, R. Kozlovskiy, Pavel A. Orel, Lubov N. Magorina, Tatiana D. Izmailova, Elena V. Boldina
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Abstract

This work is concerned with polyethylene terephthalate (PET) saponification by different potassium compounds in various polyols as well as biodiesel’s main by-product, crude glycerol. It was established that reaction conditions (initial PET/K+ molar ratio, reaction time, etc.) could control the molecular weight of obtained oligomeric products. In ethylene glycol, depolymerization proceeds rapidly, and already at 10–30 min, PET is completely dissolved in the reaction mixture with the formation of liquid oligomers. Then, these oligomers react with potassium compounds, and after 200 min of the process, there are only solid, low-molecular-weight products (dipotassium terephthalate, monomers, and dimers). At the same time, PET saponification in pure glycerol is less effective, and solid polyether flakes could not fully decompose even after 200 min of the process. Crude glycerol takes the middle position between pure polyols. Based on the obtained data, an improved kinetic model was developed, and rate constants were estimated. This model takes into account PET saponification by potassium salts as well as direct PET glycolysis. Ethylene glycol is formed in situ by transesterification between fatty acid ethylene glycol esters and glycerol in the case of pure and crude glycerol.
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不同多元醇在PET皂化过程中的反应性比较
本文研究了不同钾化合物对聚对苯二甲酸乙二醇酯(PET)的皂化作用,以及生物柴油的主要副产物粗甘油。确定了反应条件(初始PET/K+摩尔比、反应时间等)可以控制所得低聚产物的分子量。在乙二醇中,解聚进行得很快,在10-30分钟内,PET完全溶解在反应混合物中,形成液体低聚物。然后,这些低聚物与钾化合物反应,经过200分钟的反应,只剩下固体的低分子量产物(对苯二甲酸二钾、单体和二聚体)。同时,PET在纯甘油中的皂化效果较差,固体聚醚片即使经过200 min也不能完全分解。粗甘油在纯多元醇之间处于中间位置。根据得到的数据,建立了改进的动力学模型,并估计了速率常数。该模型考虑了钾盐对PET皂化反应以及PET直接糖酵解反应。在纯甘油和粗甘油的情况下,乙二醇是由脂肪酸乙二醇酯和甘油之间的原位酯交换反应形成的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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