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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/M_n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.
In this work, the bromine addition method, phenolysis method, FTIR method and ozone cracking method were used to determine the total amount of unsaturated poly (v-PVC) samples and u-PVC samples Bond, total unstable chlorine, isolated double bonds and internal double bonds.The relationship between the structural defects and the average molecular weight of PVC and the rate of removal of HCl revealed that the total unsaturated double bond value, the total unstable chlorine and the isolated double The correlations of the key contents are based on their correlation with 1 / M_n, respectively, and it is concluded that the three quantitatively measured values are mostly terminal allyl chloride structures. HCl ratio, the mechanism of isomerization of end-allyl chloride structure to internal allyl chloride under the action of HCl catalysis was proposed for the first time.