STUDIES ON THE RELATION BETWEEN THE STRUCTURAL DEFECTS AND THERMAL INSTABILITY OF POLY (VINYL CHLORIDE) 2. THE RELATION BETWEEN THE CONTENTS OF DIFFERENT STRUCTURAL DEFECTS AND DEHYDROCHLORINATION RATES OF PVC

HE Zuo-yun; HU Xing-zhou; PAN Jiang-qing

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STUDIES ON THE RELATION BETWEEN THE STRUCTURAL DEFECTS AND THERMAL INSTABILITY OF POLY (VINYL CHLORIDE) 2. THE RELATION BETWEEN THE CONTENTS OF DIFFERENT STRUCTURAL DEFECTS AND DEHYDROCHLORINATION RATES OF PVC

Research Article | 更新时间：2021-03-19

- STUDIES ON THE RELATION BETWEEN THE STRUCTURAL DEFECTS AND THERMAL INSTABILITY OF POLY (VINYL CHLORIDE) 2. THE RELATION BETWEEN THE CONTENTS OF DIFFERENT STRUCTURAL DEFECTS AND DEHYDROCHLORINATION RATES OF PVC
- Acta Polymerica Sinica Issue 1, Pages: 80-86(1993)
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- Published：20 February 1993，
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HE Zuo-yun, HU Xing-zhou, PAN Jiang-qing. STUDIES ON THE RELATION BETWEEN THE STRUCTURAL DEFECTS AND THERMAL INSTABILITY OF POLY (VINYL CHLORIDE) 2. THE RELATION BETWEEN THE CONTENTS OF DIFFERENT STRUCTURAL DEFECTS AND DEHYDROCHLORINATION RATES OF PVC. [J]. Acta Polymerica Sinica (1):80-86(1993)
DOI：

HE Zuo-yun, HU Xing-zhou, PAN Jiang-qing. STUDIES ON THE RELATION BETWEEN THE STRUCTURAL DEFECTS AND THERMAL INSTABILITY OF POLY (VINYL CHLORIDE) 2. THE RELATION BETWEEN THE CONTENTS OF DIFFERENT STRUCTURAL DEFECTS AND DEHYDROCHLORINATION RATES OF PVC. [J]. Acta Polymerica Sinica (1):80-86(1993) DOI：

摘要

本工作采用溴加成法、酚解法、FTIR法及臭氧裂解法分别测定了五种不饱和蒸气压下聚合的PVC样品(u-PVC)和五种商品PVC样品(s-PVC)的总双键、总不稳定氯、孤立双键和内部双键的含量.通过研究结构缺陷和PVC的平均分子量及脱HCl速率的相互关系

揭示了不饱和总双键值

总不稳定氯和孤立双键含量彼此的相关性是建立在它们分别与1/Mn的相关性基础之上

从而得出了这三种定量值测得的主要都是端基烯丙基氯结构.根据三者对脱HCl速率的良好线性相关性

首次提出了端基烯丙基氯结构在HCl催化作用下异构化成内部烯丙基氯从而成为脱HCl速率主要原因的机理.

Abstract

The contents of diferent structural deftects of five PVC samples，obtained by polymeri-zation at monomer unsaturation vapor pressure，and five commercial PVC samples were deter-mined．The total number of double bonds(C=CT) and labile chlorine atoms (ClL) were deter mined by bromine addition and phenolysis methods，respectively．The determination of inter-nal double bonds (C=Cint) and isolated doubl bonds(C=Ciso) was carried out by means of ozonlysis and FTIR methods．It was found tha：the dehvdrochlorination rates of PVC samples depended linearly on the contentof ClL，C=CT and (C=C)lso，respectively．In addition，the con-tents of these three structural defects were all correlated linearly with 1／Mn，so most parts of them would be the same defect——terminal allyl chlorine．Therefore，the main source of thermal dehydrochlorination of PVC could be attributed to the presence of terminal allyl chlorine groups．A mechanism．that in the presence of HCl as eatalyst the terminal allyl chlorine can be isomerized into internal allyl chlorine．was proposed to explain the main role of terminal allyl chlorine in the thermal dehvdrochlorination of PVC．

关键词

聚氯乙烯结构缺陷脱氯化氢热不稳定性

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