Obtaining phthalate substituted post-consumer polyethylene terephthalate and its isothermal crystallization

K. Kirshanov, A. Gervald, R. Toms, A. Lobanov
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引用次数: 3

Abstract

Objects. Due to the polymer waste accumulation, the search for new directions for their utilization is urgent. Chemical recycling methods are of considerable interest, which allow one to obtain the original monomers or change the compositions of the copolymers. From the point of view of building a circular economy, a promising material is polyethylene terephthalate (PET), on the basis of which amorphous copolyesters can be obtained. The study aimed to analyze the simultaneous glycolysis and interchain exchange reactions of PET in the presence of the oligoethylene phthalate modifier with hydroxyl end groups and the study of isothermal crystallization of poly(ethylene phthalate-co-terephthalates) with different phthalate contents obtained in this way.Methods. Oligoethylene phthalate is synthesized by polycondensation. Poly(ethylene phthalateco-terephthalates) were obtained by the interaction of post-consumer PET with oligoethylene phthalate. The composition of the oligomer and copolymers was confirmed using Fourier-transform infrared spectroscopy, thermal characteristics and crystallization half-times were determined by differential scanning calorimetry.Results. In this work, the use of the post-consumer PET chemical recycling process, aimed at obtaining copolyesters under the influence of small modifier amounts was proposed. The process consisted in carrying out the combined interchain exchange and degradation with a complex oligoester different from PET. Poly(ethylene phthalate-co-terephthalate) copolymers were obtained via reaction of post-consumer poly(ethylene terephthalate) flakes and synthesized oligoethylene phthalate resin in the melt phase in the absence of catalyst. The effect of phthalate concentration in polymer on the isothermal crystallization of phthalate substituted poly(ethylene terephthalate) was estimated.Conclusions. The hypothesis about the possibility of using an oligoester modifier to obtain the PET-based copolymer at the high rate and without reducing the molecular weight to values characteristic of a monomer or oligomer has been confirmed. The process can be used to obtain random copolyesters based on post-consumer PET. The phthalate unit concentration increase is followed by decrease in the glass transition temperature, temperature and heat of fusion, and increase in crystallization half-times. Phthalate has a better ability to retard PET crystallization than 2-methyl-1,3-propanediol or furandicarboxylic acid, but is inferior to some of the other modifiers known.
邻苯二甲酸酯取代消费后聚对苯二甲酸乙二醇酯及其等温结晶
对象。由于聚合物废弃物的积累,寻找其利用的新方向迫在眉睫。化学再循环方法是相当有趣的,它允许人们获得原始单体或改变共聚物的组成。从建立循环经济的角度来看,有前途的材料是聚对苯二甲酸乙二醇酯(PET),在此基础上可以得到非晶共聚酯。本研究旨在分析在端羟基邻苯二甲酸酯改性剂存在下PET的同时糖解和链间交换反应,并研究以这种方式得到的不同邻苯二甲酸酯含量的聚(邻苯二甲酸乙酯-共对苯二甲酸酯)的等温结晶。用缩聚法合成了邻苯二甲酸低聚乙烯酯。聚(邻苯二甲酸乙二醇酯-对苯二甲酸乙酯)是通过消费后PET与邻苯二甲酸乙二醇酯的相互作用得到的。用傅里叶变换红外光谱法确定了低聚物和共聚物的组成,用差示扫描量热法测定了其热特性和结晶半次。在这项工作中,提出了利用消费后PET化学回收工艺,旨在获得在小改性剂用量影响下的共聚酯。该过程是用一种不同于PET的复合低聚酯进行联合链间交换和降解。在没有催化剂的情况下,用消费后的聚对苯二甲酸乙酯薄片与熔体相合成的邻苯二甲酸低聚乙烯树脂反应得到聚邻苯二甲酸乙酯共聚物。考察了聚合物中邻苯二甲酸酯浓度对邻苯二甲酸酯取代聚对苯二甲酸乙酯等温结晶的影响。关于使用低聚酯改性剂在不降低分子量到单体或低聚物特征值的情况下以高速率获得pet基共聚物的可能性的假设已经得到证实。该工艺可用于获得基于消费后PET的随机共聚酯。随着邻苯二甲酸盐单位浓度的增加,玻璃化转变温度、熔合温度和熔合热降低,结晶率增加一半。邻苯二甲酸酯比2-甲基-1,3-丙二醇或呋喃二甲酸具有更好的延缓PET结晶的能力,但不如其他一些已知的改性剂。
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