聚全氟三嗪的合成研究Ⅰ.α,ω-二碘代全氟氧杂烷基三嗪单体的合成

以5-碘-3-氧杂-八氟戊碘酰氯(Ⅰ)为原料经八步合成得到三嗪单体——2-三氟甲基-4,6-二(4′-碘-2′-氧杂六氟丁基)-1,3,5-三嗪(Ⅸ).Ⅰ用亚硫酸钾还原生成亚磺酸盐Ⅱ,后者经氢碘酸处理生成5-碘-3-氧杂-六氟戊酸(Ⅲ)。化合物Ⅲ经相应的酯Ⅳ和酰胺Ⅴ转化为5-碘-3-氧杂-六氟戊腈Ⅵ。产物Ⅸ由亚胺脒Ⅷ经酰化脱水环化制备,后者则由腈Ⅵ和脒Ⅶ缩合而得。本文还研究了全氟羧酸的多种酯化方法并提出了一种全氟亚磺酸盐在氢碘酸作用下转化为全氟羧酸的可能机理。

STUDY ON THE SYNTHESIS OF POLYPERFLUOROTRIAZINE Ⅰ. The Synthsis of a Novel Di (ω-iodoperfluorooxaalkyl) s-Triazine Monomer

In order to investigate synthetic route of polyperfluorotriazine elastomer, 2-tri-fluoromethyl-4,6-bis (4'-iodo-2'-oxa-hexafluorobutyl)-1,3,5-triazine (Ⅸ), a novel tria-zine monomer, was synthesized from 5-iodo-3-oxa-octafluoropentanesulfonyl fluoride (Ⅰ) in eight-steps.Ⅰ was reduced by potassium sulfite to the sulfinat (Ⅱ), which was treated with hydriodic acid to yield 5-iodo-3-oxa-hexafluoropentanoic acid (Ⅲ). Compound III was transformed to 5-iodo-3-oxa-hexafluotopentanenitrile (Ⅵ) through the corresponding ester Ⅳ and amide Ⅴ. The desired product 99999999 was prepared by aeylationcyclodehydration of the imidoylamidine Ⅷ, obtained by condensation of the nitrile Ⅵ with the amidine Ⅶ. The various methods for the esterification of perfluoro-carboxylic acid were studied and a possible mechanism for the transformation of perfluorosulfina-te to the corresponding perfluorocarboxylic acid by hydriodic acid was proposed.