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    Fluorosulfonate containing polyfluorocarbonyl compounds
    1.
    发明授权
    Fluorosulfonate containing polyfluorocarbonyl compounds 失效
    含氟磺酸盐的多氟羰基化合物

    公开(公告)号：US4603017A

    公开(公告)日：1986-07-29

    申请号：US720163

    申请日：1985-04-05

    申请人： Hans Millauer ,  Gunter Siegemund ,  Werner Schwertfeger

    发明人： Hans Millauer ,  Gunter Siegemund ,  Werner Schwertfeger

    IPC分类号： C07C69/708 ,  C07C45/54 ,  C07C49/167 ,  C07C51/00 ,  C07C51/373 ,  C07C53/50 ,  C07C59/21 ,  C07C59/347 ,  C07C59/58 ,  C07C59/88 ,  C07C67/00 ,  C07C67/313 ,  C07C69/716 ,  C07C301/00 ,  C07C303/00 ,  C07C305/00 ,  C07C305/26 ,  C25B3/00 ,  C25B3/02 ,  C07C141/00

    CPC分类号： C07C45/54 ,  C07C305/26 ,  C07C49/167 ,  C07C51/00 ,  C07C59/21

    摘要： Perfluorocarbonyl compounds of the formulae IV and V ##STR1## in which R.sub.f denotes perfluoroalkyl, R'.sub.f denotes perfluoroalkylene, R denotes F, Cl, perfluoroalkyl or --OR"' (R"'=alkyl, aryl or aralkyl) and n denotes a number from 0 to 10, are prepared, starting from compounds of the formula I ##STR2## in which R.sub.f, R'.sub.f and n have the same meaning as in the formulae IV and V and R" is F, Cl or perfluoroalkyl, by electrolysis in an electrolyte consisting of fluorosulfonic acid/alkali metal fluorosulfonate and, if necessary, esterification with R"'OH, and decomposition ##STR3## in the presence of catalytic amounts of alkali metal fluorides and/or aprotic N-bases. Most of the compounds IV and V are new; the latter are, above all, valuable heat transfer fluids, lubricating oils or intermediates for the preparation of other F-organic compounds.

    摘要翻译： （IV）的全氟羰基化合物其中Rf表示全氟烷基，R'f表示全氟亚烷基，R表示F，Cl，全氟烷基或-OR“（R”'） =烷基，芳基或芳烷基），n表示0至10的数，从其中R f，R'f和n与式（I）中相同含义的式I的化合物 IV和V和R“是F，Cl或全氟烷基，通过在由氟磺酸/碱金属氟代磺酸盐组成的电解质中电解并在需要时与R”OH进行酯化，并在催化剂存在下分解“IMAGE” 碱金属氟化物和/或非质子N-碱的量。 大多数化合物IV和V是新的; 后者首先是有价值的传热流体，润滑油或用于制备其它F-有机化合物的中间体。

    .omega.-Fluorosulfato-perfluorocarboxylic acid derivatives and processes for their preparation
    2.
    发明授权
    .omega.-Fluorosulfato-perfluorocarboxylic acid derivatives and processes for their preparation 失效
    ω-氟磺酸 - 全氟羧酸衍生物及其制备方法

    公开(公告)号：US4460512A

    公开(公告)日：1984-07-17

    申请号：US482570

    申请日：1983-04-06

    申请人： Hans Millauer ,  Werner Schwertfeger

    发明人： Hans Millauer ,  Werner Schwertfeger

    IPC分类号： C07C305/26 ,  C07C67/00 ,  C07C301/00 ,  C07C303/00 ,  C07C305/00 ,  C07C325/00 ,  C25B3/00 ,  C25B3/02 ,  C07C141/00

    CPC分类号： C07C305/10 ,  C07C305/00 ,  C25B3/02

    摘要： The present invention relates to novel .omega.-fluorosulfato-perfluorocarboxylic acid derivatives of the formula I ##STR1## in which A denotes halogen, preferably Cl or F, and in particular F, or the group OR wherein R is alkyl, aryl or aralkyl with preferably up to 10 C atoms, in particular CH.sub.3 or C.sub.2 H.sub.5, m denotes a number from 1 to 10, preferably from 1 to 8 and in particular from 1 to 6, and n denotes a number from 0 to 10, preferably from 0 to 4 and in particular 0 or 1, which are prepared by electrolysis of .omega.-H-perfluorocarboxylic acid halides of the formula II ##STR2## in which A'=halogen and m and n have the same meaning as in formula I, in an electrolyte consisting of fluorosulfonic acid/alkali metal fluorosulfonate, the compounds of the formula III being formed: ##STR3## in which A' has the same meaning as in formula II and m and n have the same meaning as in formulae I and II, these compounds then also being esterified with an organic hydroxy compound of the formula IVROH (IV)in which R has the meaning given in the case of formula I, to give compounds I in which A=OR.The compounds of the present invention are valuable intermediate products particularly suitable for the preparation of perfluorinated vinyl compounds with an additional functional group wherein the vinyl compounds can in turn be processed to valuable oligomers and polymers which are very stable to heat and chemicals and can be used in many ways.

    摘要翻译： 本发明涉及式I（I）的新型ω-氟磺酸 - 全氟羧酸衍生物，其中A表示卤素，优选Cl或F，特别是F，或OR基团，其中R是烷基，芳基或 优选至多10个C原子的芳烷基，特别是CH 3或C 2 H 5，m表示1至10，优选1至8，特别是1至6的数，n表示0至10的数，优选0 至4，特别是0或1，其通过电解其中A'=卤素和m和n具有与式I中相同含义的式IIA（II）的ω-H-全氟羧酸酰卤制备 在由氟磺酸/碱金属氟代磺酸盐组成的电解质中，形成式III的化合物：其中A'具有与式II相同的含义，m和n具有与下式相同的含义： 通式I和II，然后这些化合物也与有机羟基化合物进行酯化 R IV（R）其中R具有式I给出的含义，得到其中A = OR的化合物I。 本发明的化合物是有价值的中间产品，特别适用于制备具有附加官能团的全氟化乙烯基化合物，其中乙烯基化合物又可加工成对热和化学品非常稳定的有价值的低聚物和聚合物，并且可以使用 在许多方面。

    Process for the preparation of fluorocarbon polymers containing carboxyl groups, and certain starting materials required for this, and the fluoro-sulfato compounds formed as intermediate products in the process
    4.
    发明授权
    Process for the preparation of fluorocarbon polymers containing carboxyl groups, and certain starting materials required for this, and the fluoro-sulfato compounds formed as intermediate products in the process 失效
    制备含有羧基的氟碳聚合物的方法，以及所需的某些原料以及在该方法中形成为中间产物的氟 - 硫酸酯化合物

    公开(公告)号：US4471076A

    公开(公告)日：1984-09-11

    申请号：US467179

    申请日：1983-02-16

    申请人： Peter Blickle ,  Johannes Brandrup ,  Hans Millauer ,  Werner Schwertfeger ,  G/u/ nter Siegemund

    发明人： Peter Blickle ,  Johannes Brandrup ,  Hans Millauer ,  Werner Schwertfeger ,  G/u/ nter Siegemund

    IPC分类号： C08F8/12 ,  B01J39/20 ,  C08F8/34

    CPC分类号： C08F8/12 ,  C08F2800/10

    摘要： Substantially non-crosslinked fluorocarbon polymers containing carboxyl groups are prepared starting from non-crosslinked and in some cases new, fluorocarbon polymers in which the linear macromolecules carry side chains containing the end group --CHFX (X is F or CF.sub.3). The starting polymers are first reacted with peroxodisulfuryl difluoride FSO.sub.2 O--OSO.sub.2 F to give the corresponding fluorosulfato derivatives containing the side chain end groups. ##STR1## In the event that X is F, these derivaties are then converted into the corresponding carboalkoxy derivatives by means of an alcohol, the fluorosulfato group being split off, and these carboalkoxy derivatives are then converted by saponification into the products containing the free carboxyl groups; the fluorosulfato derivatives can also be hydrolyzed with water, if appropriate in the presence of an inert solvent and/or bases, to give, without further treatment, the products containing the free carboxyl groups.The fluorosulfato derivatives in which X is CF.sub.3 in the side chain end groups are first decomposed in the presence of catalytic amounts of alkali metal fluorides and/or aprotic nitrogen bases to give the products containing the side chain end groups ##STR2## and the latter are then hydrolyzed to give the products containing the free carboxyl group.Virtually non-crosslinked fluorocarbon polymers containing carboxyl groups are of industrial importance in the form of cation exchanger membranes in electrolytic cells, particularly in chlor-alkali electrolysis.

    摘要翻译： 含有羧基的基本上非交联的碳氟化合物聚合物是从非交联的，在某些情况下，新的含有端基-CHFX（X是F或CF 3）的侧链的大分子的氟碳聚合物开始制备的。 起始聚合物首先与过氧二硫代氟化二氟FSO 2 O-OSO 2 F反应，得到含有侧链端基的相应的氟代磺酰基衍生物。 （X是F或CF3）。 在X为F的情况下，这些衍生物然后通过醇转化成相应的烷氧基衍生物，将氟代磺酰基分解，然后将这些烷氧羰基衍生物通过皂化转化成含有游离羧基的产物; 如果在惰性溶剂和/或碱存在的情况下，氟磺酸衍生物也可以用水水解，得到含有游离羧基的产物，无需进一步处理。 在侧链端基中X为CF 3的氟代硫脲衍生物首先在催化量的碱金属氟化物和/或非质子氮碱的存在下分解，得到含有侧链端基的产物，并且后者为 然后水解，得到含有游离羧基的产物。 含有羧基的几乎不交联的碳氟化合物聚合物在电解槽中的阳离子交换膜的形式具有工业上的重要性，特别是在氯碱电解中。