本工作用核磁共振、红外光谱、裂解气相色谱和示差扫描量热等技术研究了粉末固相氯化聚乙烯(CPE)的结构。结果表明,在氯含量达到50％以前的氯化过程是受阻型取代机理,所得CPE的分子链主要以—CH_2—和—CHCl—基团组成;在氯含量超过50％以后,有—CCl_2—基团产生,但量极少,反应机理较为复杂。氯化后试样的结晶性能的变化不同于水相悬浮氯化的产物,亦不同于溶液氯化的产物。 In this work, the structure of powder CPE was studied by NMR, FTIR, pyrolysis gas chromatography and differential scanning calorimetry. The results showed that the chlorination process before the content of chlorine reached 50% was a hindered substitution mechanism. The molecular chain of the resulting CPE mainly consisted of -CH_2- and -CHCl- groups. After the content of chlorine exceeded 50% Groups generated, but the amount is minimal, the reaction mechanism is more complicated. The crystallization behavior of the sample after chlorination is different from the product of the suspension chlorination in the aqueous phase and also different from the chlorination of the solution.