【摘要】 偏氟乙烯能够分别与四氯化碳和全氟叔丁基碘进行自由基的调聚反应,得到新型的调聚物CCl₃（CH₂CF₂）_nCl（n=1～6）和（CF₃）₃C（CH₂CF₂）_nI（n=1,2）。调聚物的结构由核磁共振谱、红外光谱、元素分析和化学转化所证实。反应中亲电自由基·CCl₃与·C（CF₃）₃主要进攻偏氟乙烯上无氟碳原子,亦即在偏氟乙烯的自由基加成中,极性因素对加成方向起决定性作用。调聚产物CCl₃CH₂CF₂Cl、CCl₃CH₂CF₂CH₂CF₂Cl和（CF₃）₃CCH₂CF₂I用三乙胺脱卤化氢,得到烯烃CCl₂=CHCF₂Cl、CCl₂=CHCF₂CH₂CF₂Cl和（CF₃）₃CCH=CF₂·化合物（CF₃）₃CCH₂CF₂I和（CF₃）₂CFCH₂CF₂I先后用乙二胺和水处理,得到含氟酰胺,（CF₃）₃CCH₂CON（C₂H₅）₂和（CF₃）₂C=CHCON（C₂H₅）₂。（CF₃）₃CCH₂CF₂I先后用氢氧化钾和水处理,得到新的含氟羧酸（CF₃）₃CCH₂COOH,在较低温度下,用氟氯化锑处理CCl₂=CHCF₂Cl,只得到氟化产物CCl₂=CH₂CF₃,而没有得到重排产物。调聚物Cl（CF₂CH₂）_nCCl₃（n=1～6）在强酸介质中,能水解成相应的羧酸Cl（CF₂CH₂）_nCOOH,这些酸的碱金属盐Cl（CF₂CH₂）_nCOOM（n=3～5）是良好的表面活性剂,可作为含氟烯烃聚合的乳化剂。更多还原

【Abstract】 Vinylidene fluoride has been successfully telomerized with carbon tetrachloride and perfluoro-t-butyl iodide as telogens; various new telomerization products and new compounds derived therefrom have been identified by NMR, IR, elemental analyses and chemical transformations. In agreement with our view that polar factors play an important part in deciding the orientation of free radical additions to vinylidene fluoride, it has been shown that the elcotrophilic radicals·CCl₃ and （CF₃）₃C·add to the methylene end of the alkene.Triethylamine has been used as the dehydrohalogenating agent in the following three reactions: （1） from CCl₃CH₂CF₂Cl （1） to the known compound CCl₁2 = CHCF₂Cl （5）; （2） from CCl₃CH₂CF₂CH₂CF₂Cl （6） to a mixture of CCl₂=CHCF₂CH₂CF₂Cl （7） and CCl₃ CH₂CF₂CH = CF₂ （8） ; and （3） from （CF₃）₃CCH₂CF₂I （3） to （CF₃）₃CCH = CF₂ （9）.The reaction of diethylamine with the iodide 3 and （CF₃）₂CFCH₂CF₂I afforded the amides （CF₃）₃CCH₂CON （C₂H₅）₂ （10） and （CF₃）₂C=CH—CON （C₂H₅）₂ respectively. Dehydroiodination of 3 by KOH followed by hydrolysis yielded the perfluoro-t- butyl substituted acetic acid, （CF₃）₃CCH₂CO₂H（11）.The exchange reaction of CCl₃CH₂CF₂Cl （1） with antimony fluorides was found to be able to proceed at relatively low temperature, fielding a mixture of CF₃CH₂CF₂Cl （18） and CF₂ClCH₂CF₂Cl （12）. An unrearranged product, CCl₂=CHCF₃ （14） was obtained when the same reaction was applied to the alkene CCl₂ = CHCF₂Cl （5）.The telomerization products Cl （CF₂CH₂）_nCCl₃ have been hydrolyzed in the strong acid medium to the corresponding carboxylic acids, Cl （CF₂CH₂）_nCOOH （n = 1～6）.The alkaline salts of these acids Cl（CF₂CH₂）_nCOOM （n=3～5） have been proved to be good surfactants for emulsion polymerization of fluoro-olefins.更多还原