Dehydrochlorination of PVC at low-temperatures and the pyrolysis behavior of dechlorinated PVC

Jiayou Sun, Tianyang Ding, Xue Zhao, Pengcheng Wang, Wen Chen, Jie Yu
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Abstract

In this study, the dehydrochlorination reaction of polyvinyl chloride (PVC) was thoroughly investigated at various temperatures and reaction times. Ultraviolet–visible (UV–Vis) and Raman spectroscopies were employed to analyze the conjugated polyene sequences, and Fourier transform infrared spectroscopy (FTIR) was utilized to characterize the functional groups present in the intermediates. The results reveal that in the very initial stages, the dehydrochlorination reaction forms soluble and colored intermediates, primarily consisting of conjugated polyene sequences without crosslinking. As dehydrochlorination progresses, the products become completely insoluble and transform into highly crosslinked black hard chucks. The obtained dehydrochlorinated intermediates were then pyrolysed using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to reveal their structures and decomposition mechanism. The core structure of the crosslinked intermediates is likely composed of cyclohexenes or cyclohexadienes. Among the aromatic compounds, benzenes and naphthalenes are the predominant categories with benzene being the most abundant. The crosslinking reaction inhibits benzene formation, leading to increased production of alkyl-aromatic compounds. This study proposes the structure of dehydrochlorinated intermediates and their decomposition mechanism, providing valuable insights for PVC recycling.

Graphical abstract

Abstract Image

聚氯乙烯的低温脱氯及脱氯后的热解行为
本文研究了聚氯乙烯(PVC)在不同温度和反应时间下的脱氢氯化反应。利用紫外可见光谱(UV-Vis)和拉曼光谱(Raman)对共轭多烯序列进行分析,利用傅里叶变换红外光谱(FTIR)对中间体中的官能团进行表征。结果表明,在脱氢氯化反应的最初阶段,形成可溶性和有色中间体,主要由共轭多烯序列组成,没有交联。随着脱氢氯化反应的进行,产物完全不溶,转化为高度交联的黑色硬卡盘。利用热解-气相色谱/质谱(Py-GC/MS)对得到的脱氯中间体进行热解分析,揭示其结构和分解机理。交联中间体的核心结构可能由环己烯或环己二烯组成。在芳香族化合物中,苯和萘是主要的种类,其中苯的含量最多。交联反应抑制苯的生成,导致烷基芳香族化合物的产量增加。本研究提出了脱氢氯化中间体的结构及其分解机理,为PVC的回收利用提供了有价值的见解。图形抽象
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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