200914408 九、發明說明 【發明所屬之技術領域】 本發明係關於藉由向全氟烯烴類加入硫醯二氟來製備 具有全氟烷基磺醯基基團的化合物之方法。 【先前技術】 磺醯基氟化物類是化學合成的中間產物。例如，藉由 水性鹼的水解作用和後續的酸處理，它們可被轉化爲全氟 烷基磺酸類。磺酸類是羧酸類的中間產物。磺醯基氟化物 類也可被用作爲殺蟲劑。二全氟烷基颯類適合作爲介電體 及溶劑。 GB-A 1 1 8956 1描述在二甘二甲醚中以批次方法製備 具有全氟化烷基基團的颯類以及全氟烷基磺醯基氟化物。 該處所描述之方法提供，使硫醯二氟（S 02F2 )加到特定 的氟取代的烯烴類。鹼金屬氟化物類與四級銨氟化物類被 指定爲觸媒；實例中以CsF操作。雖然其中提及所描述之 方法可能在大氣壓或超大氣壓下進行，由於可能的反應物 爲氣體或低沸點液體，使用超大氣壓將是令人滿意的。 WO 03/095422揭示以氟化鉀作爲催化劑在DMF中藉 由全氟乙烯與硫醯二氟的反應來製備全氟乙烷磺醯基氟化 物和二（全氟乙基）楓的混合物。 EP 0 73 6 5 24 A揭示以氟化鉀作爲催化劑在環丁颯中 藉由全氟丙烯與硫醯二氟的反應來製備全氟異丙基磺醯基 氟化物之方法。 200914408 【發明內容】 本發明之目標是提供製備磺醯基氟化物類以及颯類之 技術簡單之方法，係藉由將硫醯二氟加到多氟取代的烯烴 類或全氟烯烴類。本目標及其它目標是藉由本發明之方法 而達成的。 本發明用於製備多氟烷基磺醯基氟化物類或全氟烷基 磺醯基氟化物類的方法包括一步驟，其中硫醯二氟與多氟 取代的烯烴或全氟化的烯烴係在催化劑的存在下連續地反 應。術語“全氟化的烯烴”表示其中所有氫原子均被氟取代 的烯烴類。術語“多氟化的烯烴”表示其中至少50%的氫原 子被氟原子取代的烯烴類。一或多個其他氫原子可能被氯 原子，被具有1個或2個碳原子的未取代的、部分氟化的 或全氟化的烷基，或被具有1個或2個碳原子的未取代的 烷氧基，或被在末端碳原子上具有氟取代基的烷氧基所取 代’先決條件是，如上所述，該烯烴上至少5 0 %的氫原子 被氟取代。“未取代的”在這裏是指這些基團只被氫取代。 “部分氟化的”是指該烷基被至少一個氫原子取代，而其餘 的取代基爲氟原子。由碳和氟和任意地氫所組成的烯烴類 爲較佳的。全氟化的烯烴類爲特別佳的起始化合物。總體 上’具有2至12個碳原子的烯烴類可被用於本發明之方 法中。非常佳的烯烴類在下文將進一步詳細說明。 特別佳地，應用沸點（在1巴時）低於反應溫度的化 合物（因此，起始化合物是氣態或在蒸汽態）進行反應。 -6- 200914408 更佳地，以沸點在1巴（絕對値）等於或低於15 °C，特 別是等於或低於〇 ’和最佳地是等於或低於-1 0 °c的起 始化合物進行反應；例如’六氟丙烯，作爲特別佳的起始 化合物，的沸點爲-29°C。 本發明將針對此較佳的實施方案進一步詳細地解釋。 使硫醯二氟與氟化烯烴類’特別是六氟丙烯，連續反 應的出人意料效果是高產量。在GB 1,1 8 9,5 6 1的實例1 中，六氟丙烯與硫醯二氟是藉由硫醯二氟的間斷引入分批 方式進行反應。這是耗費時間的方法’因爲在發生壓力下 降後，額外的六氟丙烯被數次地引導至反應器。本發明之 快速地、簡單地連續方法產生相當量或甚至更多量的產物 〇 該反應可以在升高的壓力下進行。例如，壓力可以等 於或小於1 〇巴（絕對値）。較佳地，該反應在壓力等於 或小於5巴時進行，更佳地，等於或小於2巴（絕對値） ，特別佳地等於或小於1 · 5巴（絕對値），仍然更佳地在 等於或小於1 · 3巴（絕對値）時。較佳地，該壓力等於或 高於1巴（絕對値）。 例如，該反應可以在沒有增壓下進行。術語“沒有增 壓”表示一反應，其中除了環境壓力（大約1巴）之外沒 有外部壓力，反應物的傳送壓力，如果適用，惰性氣體如 氮氣的傳送壓力作用於反應混合物，並且滌氣器或洗漉器 作用於該反應混合物。該範圍通常是從1巴（絕對値）至 1 · 3巴（絕對値）。因此，在較佳的實施方案中，例如， 200914408 反應不是在自生壓力下進行。 在任何情況下，停留時間是小於一小時。 兩個反應方案是可能的，如以全氟化合物爲例： ISO2F2 + I全氟嫌烴全氟院基擴酿基氟化物 （I) 1 S02F2 + 2全氟烯烴> (二全氟烷基）硼 同樣的反應方案適用於多氟化合物： 1多氟烯烴+ 1 so2F2 >多氟烷基磺醯基氟化物 （111) 2多氟烯烴+ 1 S02F2 (二多氟烷基）颯 （IV) 在第一步驟中’生成1: 1加成物，即全氟烷基磺醯 基氟化物或個別的多氟化合物。在第二步驟中，如果烯烴 對硫醯二氟的莫耳比高到足以使未反應的烯烴仍然存在於 反應混合物中’生成2: 1的加成物，即（二全氟烷基） 颯或一（多氟院基）颯。通常，如果烯烴對硫醯二氟的莫 耳比爲大於1 ’則生成2 : 1加成物。如果期望藉由將中 間生成的磺醯基氟化物與烯烴進一步反應以生成碾作爲終 產物’烯烴對硫醯二氟的莫耳比較佳地爲等於或大於1.9 :1，更佳地等於或大於2: 1。因此，主要地並且甚至唯 一地’從所生成的磺醯基氟化物作爲中間產物生成颯類作 爲終產物。 因此’本發明方法的一實施方案提供，經由個別的多 氣院基磺酿基氟化物或全氟烷基磺醯基氟化物來製備多氟 院基颯類或全氟烷基颯類，並且包含一步驟，其中硫醯二 氣與多氟取代的烯烴或全氟化的烯烴以烯烴對硫醯二氟的 旲耳比大於1且在催化劑存在下連續地反應。用於此實施 8 - 200914408 方案的反應條件較佳地爲與上述製備1 : 1加成物的條件 相同。 因此，以所欲方式選擇烯烴與硫醯二氟的莫耳比，分 別用於製備磺醯基氟化物或颯。如果該莫耳比是在高於1 的範圍（理想的化學劑量比爲2 : 1 ) ’除了磺醯基氟化 物之外，生成楓，或如果烯烴對硫醯二氟的比率足夠高， 甚至颯是唯一的反應產物。如果莫耳比在較低的範圍（理 想的化學劑量比爲1 : 1 )內，生成磺醯基氟化物。有時 ，獲得兩種產物的混合物。 製備全氟烷基磺醯基氟化物是較佳的。因此，反應是 按照反應方案（I)與（Π)進行。對於此較佳的反應， S〇2F2與烯烴之間的莫耳比較佳地是等於或高於0.8:1。 對於此反應，so2F2與烯烴之間的較佳莫耳比等於或小於 1.2:1。 如上所述，僅有碳和氟組成的全氟化的烯烴類爲較佳 的。原則上，許多全氟化的烯烴類在本反應中適合作爲起 始化合物，例如，具有2至1 2個碳原子的直鏈或支鏈的 全氟化的烯烴類。可以藉由簡單的試驗來檢驗全氟烯烴（ 或多氟烯烴，當然）的適合性。在本發明之上下文中，全 氟化的烯烴類較佳地對應於式（III ) ，RLCFzCFR2。R1 和R2是相同或不同的並較佳地表示全氟化的C 1-C4烷基 或氟原子。R1較佳地是全氟甲基或全氟乙基，並且R2較 佳地表示氟、全氟甲基或全氟乙基。對於與硫醯二氟反應 生成全氟乙基磺醯基氟化物與全氟異丙基磺醯基氟化物而 -9- 200914408 曰’四氟乙嫌並且尤其是六氟丙烯是高度地適合於作爲起 始化合物。 該反應較佳地在非質子性有機溶劑中進行。該溶劑必 須不以非所欲方式與起始材料反應；這可以藉由使合適的 溶劑與該起始材料簡單地混合來進行檢驗。較佳地，該溶 劑的沸點在環境壓力（1巴）時高於6 〇 〇C，更佳地高於 7〇 °C。可適用於本發明方法的溶劑的實例爲二烷基醚類， 特別是那些烷二醇類或聚烷二醇類、羧酸的二烷基醯胺， 較佳地是甲酸或在酸性基團上具有C1至C4烷基的羧酸 類的二烷基醯胺類，尤其是在酸性基團的烷基上具有J、 2或3個C原子的羧酸類的二烷基醯胺類，以及腈類與二 腈類。對於在此說明的溶劑，術語“烷基，，與“伸烷基”表示 具有1至4個碳原子的基團：例如，在二烷基醯胺類的醯 胺基團上的烷基爲具有1至4個碳原子的基團。乙二醇、 二乙二醇、三乙二醇與四乙二醇類的二甲醚類，甲酸、乙 酸、丙酸與丁酸的二烷基醯胺類，特別是個別的二甲基醯 胺類，和具有C1至C5烷基的腈類，己二腈或苄腈是非 常適合的。二甲基甲醯胺是特別佳的。 該催化劑可以是催化硫醯二氟加成到經氟取代的烯烴 上的任何已知催化劑。催化劑包括鹵離子，特別是溴或氟 離子，特別是鹼金屬氟化物類和具有1至4個碳原子的4 個烷基的季銨氟化物類，例如，氟化四甲基銨或氟化四乙 錢爲較佳的。K F與C s F是非常佳的’特別是K F。 根據本發明之方法較佳地在等於或大於5 (TC的溫度 -10- 200914408 進行的，較佳地等於或高於7〇°C。該上限是可變的。較 佳地，該反應在等於或小於170 °C的溫度進行的。非常適 宜的溫度範圍是70至10(TC。 有利地，反應物以分散形式進入溶劑。例如，其可以 通過玻璃料進入溶劑，特別是如果其是氣態或蒸汽態形式 。可替代地地或附加地，該反應器可以包括用以提高氣一 液接觸的裝置，特別是使氣體或蒸汽分散在液相中的裝置 ，例如，鮑爾環或拉西環或擾拌器。 本發明最佳地的實施方案是關於全氟異丙基磺醯基氟 化物的製備，其中硫醯二氟與六氟丙烯在催化劑存在下（ 較佳地KF或CsF )在非質子性溶劑中連續地反應。 該方法可以在單一反應器中進行。如果希望的話，爲 氣態或蒸汽形式的反應物可以通過含有溶劑與催化劑的二 個、三個、四個或更多個的連續反應器。此可以提高產量 〇 該產物的分離可以已知的方式進行。 氣體反應產物可以通過冷阱和在其中濃縮。如果希望 的話，其可以藉由蒸餾，藉由高壓蒸餾或深部溫度蒸餾予 以進一步純化。 具有較高沸點的反應產物也可以從溶劑中連續地分離 出來，例如藉由蒸餾。例如，反應混合物可以連續地從反 應器抽出，然後，所希望的產物可以被分離，如藉由蒸餾 ，並且剩餘物（大部分是溶劑）可以返回到反應器中。 根據本發明之方法給予高產率/空間與時間。較佳地 200914408 ，該空間一時間產率等於或高於〇.〇丨公斤/升反應器體積 與小時。更佳地，該空間一時間產率等於或高於〇 · 〇 5公 斤/升小時，特別佳地，等於或高於} 2公斤/升小時。 本發明之連續進行的方法的優點是出人意料地好的產 量。某些較佳的實施方案的另一優點是其可以在無需耐壓 的裝置中進行。 所製備的化合物可應用於任何其已知適用之目標。上 面提供一些應用領域爲。最佳的化合物，全氟異丙基磺醯 基氟化物，可以轉化爲通式（IV) (CF3)2CFS〇3_M +的鹽類 ’其中 M +代表 Li+、Na+、K+、Cs+、Rb+、R4P +或 R4N+ ( 在此，R代表Cl至C4烷基），如W003/0 20691所述。 這些鹽類適合作爲鋰離子電池的電解質鹽類。 當然’根據本發明之方法所獲得的磺醯基氟化物類可 能依據已知方法與另外的烯烴反應以形成颯類。 【實施方式】 以下實例將解釋本發明，而並非旨在限制它。 實例： 實例1:全氟異丙基磺醯基氟化物的製備 裝置：內部體積爲150ml的反應器藉由兩根輸入管線 與裝有六氟丙烯（HFP )和硫醯二氟（SOiF2 )的兩個耐 壓瓶相連。該反應器藉由輸出管線與裝有冷卻水的李比希 氏冷凝器相連。該李比希氏冷凝器與在冰浴中冷卻的燒瓶 -12- 200914408 相連。該燒瓶與冷卻到-7 8 r捕集阱相連。該反應器中有 1 15ml ( l〇8g )的二甲基甲醯胺（DMF )以及作爲催化劑 的 2.8g KF。 在引入起始化合物期間’溶劑的溫度被調整到大約 8 〇 t。起始化合物連續地通過該溶劑。離開反應器的氣態 反應混合物通過冷阱並在其中冷凝。在阱中不冷凝的氣態 成分離開阱進入滌氣器。 1_1. HFP 以 5_16 g/h( 0.034 mol/h)的速度被引入到 DMF 溶劑中，S〇2F2 以 3.2 g/h(0.031 mol/h) 的速度引入。產物與未反應的起始產物在冷阱中 冷凝。藉由低溫蒸餾分離該產物。根據HFP的 數量，產率是理論値的39.2%。 空間時間產量的計算結果爲0.05 5 7 kg/L*h。 1.2.重複實例1，但這次，HFP以13.14 g/h ( 0.088 mol/h)的速度引入，S02F2 以 10.50 g/h(0_103 mol/h )的速度弓丨入。這次，產率爲 3 8 · 8% ;空 間時間產率的計算結果爲0.1576 kg/L*h。 實例2:全氟異丙基磺醯基氟化物在2個連續的反應器中 的製備 裝置：內部體積爲1 5 〇 m 1的反應器藉由兩根輸入管線 與裝有六氟丙烯（HFP)和硫醯二氟（S02F2)的兩個耐 壓瓶相連。該反應器藉由輸出管線與裝有冷卻水的一李比 希氏冷凝器相連。該李比希氏冷凝器與在冰浴中冷卻的燒 -13- 200914408 瓶相連。該燒瓶與內部體積爲150ml的另一反應器相連， 該反應器藉由輸出管線與裝有冷卻水的李比希氏冷凝器相 連。該李比希氏冷凝器與在冰浴中冷卻的燒瓶相連。在每 個反應器中裝有115ml的DMF與2.8g的KF。兩個反應 器均保持在80 °C。在阱中不冷凝的氣態成分離開阱進入 漉氣器。 將HFP以35 g/h ( 0.23 mol/h )的量引導致第一反應 器中的溶劑與催化劑的混合物中，硫醯二氟以一個25 g/h (0.24 mol/h)的量引入。 產率爲理論値的 56.2%。空間時間產量爲 0.1587 kg/1 · h。 實例3:全氟異丙基磺醯基氟化物在3個連續的反應器中 的製備 重複實例2，但這次，反應是在三個連續的反應器中 進行。產率比實施2的高。 因爲來自冷阱的排氣端是開放管線，所以在實例i . ：! 與I·2中的反應器以及在實例2與3中的反應器是在約1 至1 .2巴（絕對値）的壓力操作。此證明，即使用氣態起 始材料’不需要施加壓力’因此，不需要壓力裝置，儘管 如此’仍可獲得高產率。但是即使在壓力下操作時，因爲 具有出人意料的高產量，該連續方法仍然是有利的。 -14-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a compound having a perfluoroalkylsulfonyl group by adding thiophosphoric difluoride to a perfluoroolefin. [Prior Art] Sulfonyl fluorides are intermediates of chemical synthesis. For example, they can be converted to perfluoroalkylsulfonic acids by hydrolysis of aqueous bases and subsequent acid treatment. Sulfonic acids are intermediates of carboxylic acids. Sulfonyl fluorides can also be used as insecticides. Diperfluoroalkyl hydrazines are suitable as dielectrics and solvents. GB-A 1 1 8956 1 describes the preparation of indoles having perfluorinated alkyl groups and perfluoroalkylsulfonyl fluorides in a batch process in diglyme. The process described herein provides for the addition of thioindole difluoride (S 02F2 ) to specific fluorine-substituted olefins. Alkali metal fluorides and quaternary ammonium fluorides are designated as catalysts; in the examples, CsF is operated. While it is mentioned that the process described may be carried out at atmospheric or superatmospheric pressure, the use of superatmospheric pressure would be satisfactory since the possible reactants are gases or low boiling liquids. WO 03/095422 discloses the preparation of a mixture of perfluoroethanesulfonyl fluoride and bis(perfluoroethyl) maple by the reaction of perfluoroethylene with thiophosphoric difluoride in DMF using potassium fluoride as a catalyst. EP 0 73 6 5 24 A discloses a process for preparing perfluoroisopropylsulfonyl fluoride by reacting perfluoropropene with thioindole difluorocarbon in cyclobutyl hydrazine using potassium fluoride as a catalyst. SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for preparing sulfonyl fluorides and hydrazines by adding thioxanthene difluoride to polyfluoro-substituted olefins or perfluoroolefins. This and other objects are achieved by the method of the present invention. The process for the preparation of polyfluoroalkylsulfonyl fluorides or perfluoroalkylsulfonyl fluorides of the present invention comprises a step wherein thioindole difluoro and polyfluoro substituted olefins or perfluorinated olefins The reaction is continuously carried out in the presence of a catalyst. The term "perfluorinated olefin" means an olefin in which all hydrogen atoms are replaced by fluorine. The term "polyfluorinated olefin" means an olefin in which at least 50% of hydrogen atoms are replaced by fluorine atoms. One or more other hydrogen atoms may be blocked by a chlorine atom, by an unsubstituted, partially fluorinated or perfluorinated alkyl group having one or two carbon atoms, or by a carbon having one or two carbon atoms. Substituted alkoxy groups, or substituted by alkoxy groups having a fluorine substituent at the terminal carbon atom, the prerequisite is that, as described above, at least 50% of the hydrogen atoms on the olefin are replaced by fluorine. "Unsubstituted" as used herein means that these groups are only replaced by hydrogen. "Partially fluorinated" means that the alkyl group is substituted with at least one hydrogen atom and the remaining substituents are fluorine atoms. Olefins composed of carbon and fluorine and optionally hydrogen are preferred. Perfluorinated olefins are particularly preferred starting compounds. The olefins having generally 2 to 12 carbon atoms can be used in the process of the present invention. Very preferred olefins are described in further detail below. Particularly preferably, the reaction is carried out using a compound having a boiling point (at 1 bar) lower than the reaction temperature (hence, the starting compound is gaseous or in a vapor state). -6- 200914408 More preferably, the boiling point is 1 bar (absolute 値) equal to or lower than 15 °C, especially equal to or lower than 〇' and is preferably equal to or lower than -1 0 °c. The compound is subjected to a reaction; for example, 'hexafluoropropylene, as a particularly preferred starting compound, has a boiling point of -29 °C. The invention will be explained in further detail with respect to this preferred embodiment. The surprising effect of continuous reaction of thioindole difluoro with fluorinated olefins, particularly hexafluoropropylene, is high yield. In Example 1 of GB 1,1 8 9,5 6 1 , hexafluoropropylene and thioindole difluoride were reacted in a batchwise manner by intermittent introduction of thioindole difluoro. This is a time consuming method' because additional hexafluoropropylene is directed to the reactor several times after the pressure drop has occurred. The rapid, simple continuous process of the present invention produces a substantial or even greater amount of product. The reaction can be carried out under elevated pressure. For example, the pressure can be equal to or less than 1 〇 (absolute 値). Preferably, the reaction is carried out at a pressure equal to or less than 5 bar, more preferably equal to or less than 2 bar (absolute 値), particularly preferably equal to or less than 7.5 bar (absolute 値), still better at When equal to or less than 1 · 3 bar (absolute 値). Preferably, the pressure is equal to or higher than 1 bar (absolute 値). For example, the reaction can be carried out without pressurization. The term "without pressurization" means a reaction in which there is no external pressure other than the ambient pressure (about 1 bar), the transfer pressure of the reactants, if applicable, the transfer pressure of an inert gas such as nitrogen acts on the reaction mixture, and the scrubber Or a scrubber acts on the reaction mixture. The range is usually from 1 bar (absolute 値) to 1 · 3 bar (absolute 値). Thus, in a preferred embodiment, for example, the 200914408 reaction is not carried out under autogenous pressure. In any case, the residence time is less than one hour. Two reaction schemes are possible, such as perfluorochemicals: ISO2F2 + I perfluorocarbons, perfluorocarbons, extended fluorides (I) 1 S02F2 + 2 perfluoroolefins (diperfluoroalkyl) The same reaction scheme for boron is applicable to polyfluoro compounds: 1 polyfluoroolefin + 1 so2F2 > polyfluoroalkylsulfonyl fluoride (111) 2 polyfluoroolefin + 1 S02F2 (dipolyfluoroalkyl) fluorene (IV In the first step, '1:1 adduct, ie perfluoroalkylsulfonyl fluoride or individual polyfluoro compound, is formed. In the second step, if the molar ratio of olefin to thioindole difluoro is high enough that unreacted olefin is still present in the reaction mixture 'generates a 2:1 adduct, ie (diperfluoroalkyl) hydrazine Or one (polyfluoride-based) 飒. Generally, a 2:1 adduct is formed if the molar ratio of olefin to thioindole difluoro is greater than 1 '. If it is desired to further react by reacting the intermediately formed sulfonyl fluoride with an olefin to form a mill as a final product, the mole of olefin thiopurine difluoro is preferably equal to or greater than 1.9:1, more preferably equal to or greater than twenty one. Therefore, hydrazines are mainly and even exclusively produced from the produced sulfonyl fluoride as an intermediate product as an end product. Thus, an embodiment of the method of the present invention provides for the preparation of polyfluoro-based steroids or perfluoroalkyl hydrazines via individual multi-gas-based sulfonyl fluorides or perfluoroalkylsulfonyl fluorides, and A step is included wherein the sulfonium diene and the polyfluorinated olefin or perfluorinated olefin have an arsenic ratio of olefin to sulfonium difluoride greater than 1 and are continuously reacted in the presence of a catalyst. The reaction conditions used in this embodiment 8 - 200914408 are preferably the same as those described above for the preparation of the 1:1 adduct. Therefore, the molar ratio of olefin to thiophosphoric difluoride is selected in the desired manner for the preparation of sulfonyl fluoride or hydrazine, respectively. If the molar ratio is in the range above 1 (ideal stoichiometric ratio is 2:1) 'in addition to the sulfonyl fluoride, generate maple, or if the ratio of olefin to thiopurine difluoro is sufficiently high, even Ruthenium is the only reaction product. If the molar ratio is in the lower range (ideal chemical dose ratio is 1:1), sulfonyl fluoride is formed. Sometimes a mixture of the two products is obtained. It is preferred to prepare a perfluoroalkylsulfonyl fluoride. Therefore, the reaction is carried out in accordance with the reaction schemes (I) and (Π). For this preferred reaction, the molar between S〇2F2 and the olefin is preferably equal to or higher than 0.8:1. For this reaction, the preferred molar ratio between so2F2 and olefin is equal to or less than 1.2:1. As described above, only perfluorinated olefins composed of carbon and fluorine are preferred. In principle, many perfluorinated olefins are suitable as starting compounds in the present reaction, for example, linear or branched perfluorinated olefins having 2 to 12 carbon atoms. The suitability of perfluoroolefins (or polyfluoroolefins, of course) can be tested by simple tests. In the context of the present invention, perfluorinated olefins preferably correspond to formula (III), RLCFzCFR2. R1 and R2 are the same or different and preferably represent a perfluorinated C1-C4 alkyl group or a fluorine atom. R1 is preferably a perfluoromethyl group or a perfluoroethyl group, and R2 preferably represents fluorine, perfluoromethyl or perfluoroethyl. For the reaction with thioindole difluorocarbon to form perfluoroethylsulfonyl fluoride and perfluoroisopropylsulfonyl fluoride and -9- 200914408 曰 'tetrafluoroethylene and especially hexafluoropropylene is highly suitable for As a starting compound. The reaction is preferably carried out in an aprotic organic solvent. The solvent must not react with the starting material in an undesired manner; this can be verified by simply mixing a suitable solvent with the starting material. Preferably, the solvent has a boiling point higher than 6 〇 〇 C, more preferably higher than 7 〇 ° C at ambient pressure (1 bar). Examples of solvents which may be suitable for use in the process of the invention are dialkyl ethers, especially those which are alkanediols or polyalkylene glycols, carboxylic acids, preferably formic acid or in acidic groups. a dialkyl decylamine having a carboxylic acid having a C1 to C4 alkyl group, particularly a dialkyl decylamine having a carboxylic acid having J, 2 or 3 C atoms on an alkyl group of an acidic group, and a nitrile Classes and dinitrile. For the solvents described herein, the terms "alkyl," and "alkyl" refer to a group having from 1 to 4 carbon atoms: for example, an alkyl group on a guanamine group of a dialkyl decylamine is a group having 1 to 4 carbon atoms. Dimethyl ether of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, dialkyl hydrazine of formic acid, acetic acid, propionic acid and butyric acid Amines, especially individual dimethyl decylamines, and nitriles having a C1 to C5 alkyl group, adiponitrile or benzonitrile are very suitable. Dimethylformamide is particularly preferred. Is any known catalyst which catalyzes the addition of sulfhydryl difluoro to a fluorine-substituted olefin. The catalyst comprises a halide, in particular a bromine or fluoride ion, in particular an alkali metal fluoride and 4 having 1 to 4 carbon atoms. Alkyl quaternary ammonium fluorides, for example, tetramethylammonium fluoride or tetraethylammonium fluoride are preferred. KF and CsF are very good 'particularly KF. The method according to the invention is preferred. The ground is at or above 5 (temperature of TC-10-200914408, preferably equal to or higher than 7 〇 ° C. The upper limit is variable. Preferably, the reaction is carried out at a temperature equal to or lower than 170 ° C. A very suitable temperature range is 70 to 10 (TC. Advantageously, the reactants enter the solvent in a dispersed form. For example, it can enter the solvent through the glass frit, In particular if it is in the form of a gaseous or vaporous state. Alternatively or additionally, the reactor may comprise means for increasing the gas-liquid contact, in particular means for dispersing the gas or vapor in the liquid phase, for example Pall ring or Raschig ring or scrambler. A preferred embodiment of the invention relates to the preparation of perfluoroisopropylsulfonyl fluoride, wherein thioindole difluoro and hexafluoropropylene are present in the presence of a catalyst Preferably, KF or CsF) is continuously reacted in an aprotic solvent. The process can be carried out in a single reactor. If desired, the reactants in gaseous or vapor form can pass through two or three solvents and catalysts. Four or more continuous reactors. This can increase the yield. The separation of the product can be carried out in a known manner. The gaseous reaction product can be passed through a cold trap and concentrated therein. If desired, it can be further purified by distillation by high pressure distillation or deep temperature distillation. The reaction product having a higher boiling point can also be continuously separated from the solvent, for example by distillation. For example, the reaction mixture can be continuously The extract is withdrawn from the reactor and the desired product can be separated, for example by distillation, and the remainder (mostly solvent) can be returned to the reactor. The process according to the invention gives high yield/space and time. Preferably, in 200914408, the space-time yield is equal to or higher than 〇.〇丨kg/liter of reactor volume and hours. More preferably, the space-time yield is equal to or higher than 〇·〇5 kg/liter hour. Particularly preferably, equal to or higher than 2 kg/L. The advantage of the continuously carried out process of the present invention is an unexpectedly good yield. Another advantage of certain preferred embodiments is that it can be carried out in a device that does not require pressure. The compounds prepared can be applied to any of their known targets. Some application areas are provided above. The best compound, perfluoroisopropylsulfonyl fluoride, can be converted into a salt of the general formula (IV) (CF3)2CFS〇3_M + where M + represents Li+, Na+, K+, Cs+, Rb+, R4P + or R4N+ (wherein R represents Cl to C4 alkyl) as described in W003/0 20691. These salts are suitable as electrolyte salts for lithium ion batteries. Of course, the sulfonyl fluorides obtained according to the process of the present invention may be reacted with additional olefins according to known methods to form hydrazines. [Embodiment] The following examples will explain the present invention and are not intended to limit it. EXAMPLES Example 1: Preparation of Perfluoroisopropylsulfonyl Fluoride: A reactor with an internal volume of 150 ml was supplied by two input lines with hexafluoropropylene (HFP) and thioindole difluoride (SOiF2). Two pressure bottles are connected. The reactor was connected to a Liebig condenser equipped with cooling water via an output line. The Liebig condenser was connected to a flask -12-200914408 cooled in an ice bath. The flask was connected to a trap cooled to -7 8 r. The reactor contained 1 15 ml (10 〇 8 g) of dimethylformamide (DMF) and 2.8 g of KF as a catalyst. The temperature of the solvent was adjusted to about 8 〇 t during the introduction of the starting compound. The starting compound is continuously passed through the solvent. The gaseous reaction mixture leaving the reactor passes through a cold trap and condenses therein. The gaseous components that do not condense in the trap exit the trap and enter the scrubber. 1_1. HFP was introduced into the DMF solvent at a rate of 5_16 g/h (0.034 mol/h) and S〇2F2 was introduced at a rate of 3.2 g/h (0.031 mol/h). The product is condensed with the unreacted starting product in a cold trap. The product was isolated by cryogenic distillation. According to the amount of HFP, the yield is 39.2% of the theoretical enthalpy. The calculation of the space time yield is 0.05 5 7 kg/L*h. 1.2. Repeat Example 1, but this time, HFP was introduced at a rate of 13.14 g/h (0.088 mol/h) and S02F2 was inserted at a rate of 10.50 g/h (0_103 mol/h). This time, the yield was 3 8 · 8%; the calculation of the space time yield was 0.1576 kg/L*h. Example 2: Preparation of Perfluoroisopropylsulfonyl Fluoride in 2 Continuous Reactors: Reactor with an internal volume of 15 〇m 1 with two input lines and with hexafluoropropylene (HFP) ) is connected to two pressure bottles of sulphur difluoride (S02F2). The reactor was connected to a Libye condenser equipped with cooling water by an output line. The Liebig condenser was connected to a burnt -13-200914408 bottle cooled in an ice bath. The flask was connected to another reactor having an internal volume of 150 ml, which was connected to a Liebig condenser equipped with cooling water by an output line. The Liebig condenser was connected to a flask cooled in an ice bath. Each reactor was charged with 115 ml of DMF and 2.8 g of KF. Both reactors were maintained at 80 °C. The gaseous components that do not condense in the trap exit the trap and enter the helium. The introduction of HFP at a rate of 35 g/h (0.23 mol/h) resulted in a mixture of solvent and catalyst in the first reactor, and thiophosphoric difluoride was introduced in an amount of 25 g/h (0.24 mol/h). The yield was 56.2% of the theoretical enthalpy. The space time yield is 0.1587 kg/1 · h. Example 3: Preparation of perfluoroisopropylsulfonyl fluoride in 3 consecutive reactors Example 2 was repeated, but this time the reaction was carried out in three consecutive reactors. The yield was higher than that of Example 2. Since the exhaust end from the cold trap is an open line, the reactors in the examples i.:! and I·2 and the reactors in the examples 2 and 3 are between about 1 and 1.2 bar (absolute). Pressure operation. This proves that the use of the gaseous starting material 'no need to apply pressure' therefore does not require a pressure device, although a high yield can still be obtained. However, this continuous process is advantageous even when operating under pressure, because of the unexpectedly high throughput. -14-