气固法合成氯磺化聚乙烯I.气-固相反应机理

以氯化聚乙烯为原料，氯气和二氧化硫为反应气体，紫外光引发，气固法合成了氯磺化聚乙烯。通过元素分析得出，氯磺化反应中不存在氯化和脱氯的副反应。在釜式反应器内研究了氯磺化反应的气固相反应机理，发现气体的内扩散和本征化学反应是氯磺化反应的控制步骤，升高温度（在30－50℃范围内）使氯磺化反应后期的速率显著提高，这是由氯化聚乙烯的共结晶的熔融引起的。还讨论了氯化聚乙烯的链结构和固态结构对氯磺化反应的影响。

Synthesis of Chlorosulfonated Polyethylene by Gas-solid Method I. Gas-solid Reaction Mechanism

Chlorosulfonated polyethylene (CSM) was synthesized by gas-solid method initiated by ultraviolet light using chlorinated polyethylene (CPE) and a gaseous mixture of chlorine and dioxide sulfur. It was discovered by element analysis that chlorination or dechlorination did not occur in the process of chlorosulfonation. The gas-solid reaction mechanism was studied in the tank reactor. It was found that the reaction rate was controlled by the interdiffusion and intrinsic chemical reaction. In addition, when temperature was raised within the range of from 30°C to 50°C, the rate of chlorosulfonation during the later reaction period was markedly increased, resulting from the melting of the cocrystalline of CPE. Finally, the effect of chain structure and solid state of chlorinated polyethylene on chlorosulfonation was discussed.