Abstract: 1,1,1,3,3-pentachloropropane was prepared by radical addition between carbon tetrachloride and vinyl chloride in the presence of iron powder and tributyl phosphate. The effects of such factors as catalyst，co-catalyst，ferric chloride，reaction temperature，material mole ratio and reaction time on the reaction were investigated. The origin of ferrous chloride was also explored. The proper reaction condition of synthetic process of 1,1,1,3,3-pentachloropropane was as follows：material mole ratio n(CCl4)∶n(VnCl)=1∶(0.1—0.4)，reaction temperature 110—115 ℃，reaction time 4—5 h，catalyst iron powder 0.6%—0.9% of the total quantity of raw materials. Tributyl phosphate was selected as co-catalyst，and its molar weight was equal to that of iron powder. The yield of 1,1,1,3,3- pentachloropropane was 85.2% and the purity of product was 99.8%.

Key words: 1,1,1,3,3-pentachloropropane, synthesis, optimization, catalyst, ferrous chloride, ferric chloride

摘要： 以氯乙烯与四氯化碳为原料，在铁粉催化剂与磷酸三丁酯助催化剂作用下，通过自由基加成反应合成1,1,1,3,3-五氯丙烷。考察了催化剂、助催化剂、氯化铁、反应温度、反应时间、原料摩尔比对反应的影响，以及氯化亚铁的生成来源。研究获得反应的最佳工艺条件为：原料摩尔比n(四氯化碳)∶n(氯乙烯)=1∶(0.1～0.4)，反应温度110～115 ℃，反应时间4～5 h，采用铁粉作催化剂，用量为总物料质量的0.6%～0.9%，助催化剂磷酸三丁酯与铁粉的摩尔量比为1∶1。1,1,1,3,3-五氯丙烷的收率为85.2%，产品纯度为99.8％。

关键词: 1, 1, 1, 3, 3-五氯丙烷, 合成, 优化, 催化剂, 氯化亚铁, 氯化铁