四氟乙烯与乙二醇单甲醚和乙二醇二甲醚调聚产物的结构

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四氟乙烯分别与乙二醇单甲醚及乙二醇二甲醚在过氧化叔丁基引发下,于115°~130℃调聚。在单甲醚系列中得1~3产物;在二甲醚系列中得4和5产物。由红外光谱、核磁共振谱和化学转化证明产物的结构。1经铬酸氧化生成1-甲氧基-3,3,4-四氟-2-丁酮;2经铬酸氧化生成2甲氧基-3,3,4,4-四氟丁酸,3氧化得ω-氢四氟丙酸,1和2分别经氧化银和碘甲烷甲醚化,均生成4,而3则生成5。用癸硼氢和碘部份水解4和5,分别得2和3。这些结论分别通过化合物的~1H和~(19)F核磁共振谱而得验证。初步精馏结果表明,调聚反应中,甲基和次甲基均可发生反应,次甲基活性大于甲基。两个基团的相对活洼约为2~4:1。 Tetrafluoroethylene with ethylene glycol monomethyl ether and ethylene glycol dimethyl ether in t-butyl peroxide initiator, at 115 ° ~ 130 ° C telomerization. 1 to 3 products in the monomethyl ether series and 4 and 5 products in the dimethyl ether series. The structure of the product was confirmed by infrared spectroscopy, nuclear magnetic resonance spectroscopy and chemical transformation. 1 by chromic acid oxidation of 1-methoxy-3,3,4-tetrafluoro-2-butanone; 2 by chromic acid oxidation 2 methoxy -3,3,4,4-tetrafluorobutyric acid, 3 oxidation of ω-hydrogen tetrafluoropropionic acid, 1 and 2, respectively silver oxide and methyl iodide methyl etherate, are generated 4, 3 is generated 5. Hydrolysis of 4 and 5 with decabromohydrin and iodine gave 2 and 3, respectively. These conclusions are validated by ~ 1H and ~ (19) F nuclear magnetic resonance spectroscopy of the compounds, respectively. The preliminary rectification results show that both the methyl group and the methine group can react in the telomerization reaction, and the methine activity is greater than the methyl group. The relative living waits of the two groups are about 2 to 4: 1.
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