Pseudo-living radical polymerization of vinyl halide chain transfer agent and method of making agent
申请人:The Geon Company
公开号:EP0974604A2
公开(公告)日:2000-01-26
The present invention to a method of synthesizing poly(vinyl halide) by means of a free radical polymerization which mimics a "living" radical polymerization in the presence of an iodine containing chain transfer agent containing at least one iodine atom bonded to a primary carbon atom and having the formula:
R-CH2 I (I)
R-CHX I (II),
R-CH(X)-CH2 I (III),
R-CH(X)-CHX I (IV), or
R-CH(X)-CH2-CHX I (V),
wherein X is fluorine, chlorine, bromine, or iodine, R is hydrogen, C1, C2, C3, C4, C5 alkyl, any of which are linear or branched, cyanoalkyl, cyclohexyl, methyl cyclohexyl, phenyl, benzyl, and halogenated or oxygenated derivatives thereof.
In accordance with the invention there is further provided a method of synthesizing 1-halo-1-iodoethane by reacting hydrogen iodide with vinyl chloride or vinyl fluoride in the presence of an iodine generating catalyst under certain specified conditions. The resulting product of the reaction is a high yield, high purity 1-chloro-1-iodoethane or 1-fluoro-1-iodoethane. The poly(vinyl halide) resin is obtainable under conventional temperatures of polymerization and the chain transfer agents included herein perform consistently over repeated runs, hence useful for commercial manufacturing. The resin obtained has reduced molecular weight and polydispersity, good thermal stability, and enhanced mechanical properties, compared to poly(vinyl halide) conventionally formed by free radical methods at higher temperatures and/or with the use of conventional chain transfer agents for vinyl halide polymer.
本发明涉及一种通过自由基聚合合成聚(卤化
乙烯基)的方法,该方法是在含
碘链转移剂的存在下模拟 "活 "自由基聚合,该含
碘链转移剂含有至少一个与主碳原子键合的
碘原子,具有以下式子:
R-
CH2 I (I)
R-CHX I (II)、
R-CH(X)- I (III)、
R-CH(X)-CHX I (IV),或
R-CH(X)- -CHX I (V)、
其中 X 为
氟、
氯、
溴或
碘,R 为氢、C1、C2、C3、C4、C5 烷基(其中任何一个为直链或支链)、
氰基烷基、环己基、甲基环己基、苯基、苄基以及它们的卤代或氧代衍
生物。
根据本发明,还提供了一种合成 1-卤代-1-
碘乙烷的方法,即在一定的特定条件下,在
碘催化剂存在下,
碘化氢与
氯乙烯或
氟化乙烯反应。反应产物是高产率、高纯度的 1-
氯-1-
碘乙烷或 1-
氟-1-
碘乙烷。这种聚(卤化
乙烯)
树脂可在常规聚合温度下获得,其中的链转移剂在重复运行时性能稳定,因此可用于商业生产。与在较高温度下和/或使用卤化
乙烯基聚合物的常规链转移剂通过自由基方法形成的聚卤化
乙烯基树脂相比,所获得的
树脂具有较低的分子量和多分散性、良好的热稳定性和更强的机械性能。