201004933 六、發明說明： 【發明所屬之技術領域】 本發明係關於用於製備HF耗乏之氟化有機碳酸酯類 之方法。 【先前技術】 氟化有機碳酸酯類作爲溶劑或共溶劑是有用的，尤其 是用於Li離子電池的生產。例如，它們可以藉由與元素 氟的直接氟化作用、藉由與已分離氟的高價金屬氟化物（ 例如A g F 2 )反應、或藉由電化學氟化作用，從各自的非 氟化有機碳酸酯類予以製備。在這類方法中，一或多個C-H鍵被一或多個C-F鍵取代。形成氟化氫（HF )作爲副產 物。包含氟化氫的氟取代的有機碳酸酯類還可能以其他類 型的方法獲得。例如，在由碳酸伸乙基酯和元素氟生產碳 酸伸氟乙基酯時，加入HF作爲溶劑。當然，HF可能是有 害的，尤其是如果將該產物用於高科技應用中時，例如Li 離子電池中，並且因此必須被除去。 例如在 JP 2000309583 或 US-A 7,223,500 中所描述， 可以藉由用水沖洗而將H F從氟化有機碳酸酯類中除去。 對於具有CH-CF基團的化合物來說，與水接觸係不利的 ，因爲根據 US-A 7,268,238 (以美國專利申請公開號 2006/1 67279首次公開）’其似乎導致Hf從氟化有機碳 酸酯類中的分離。該美國專利揭示藉由蒸飽從碳酸伸氟乙 基酯中除去HF。 201004933 ΕΡ-Α-0 326〇54揭示使用矽膠或氧化鋁從2,2,3,3·四氣 氧咀（oxetane)中除去氟化氫以及三氟丙醯氟。本說明書聚 焦於提供與無機反應物接觸的氣態2,2,3,3-四氟氧u旦。 【發明內容】 本發明之目的係提供用於生產氟化有機碳酸酯類的簡 單可靠方法’該氟化有機碳酸酯類具有耗乏含量的HF。 根據本發明之方法，提供用於製備氟取代的有機碳酸 酯的方法，該氟取代的有機碳酸酯係HF耗乏，其中在分 子中包括至少一個CH-CF基團的HF污染的氟化有機碳酸 酯與包含Si〇2的無機反應物接觸，從而形成固體與HF耗 乏之氟化有機碳酸酯的混合物，並且將所得到的HF耗乏 之氟取代的有機碳酸酯從該固體中分離出。當進行HF的 消耗時’在氟取代的有機碳酸酯與無機反應物接觸期間， 該氟取代的有機碳酸酯保持在液態。當然，也可以將該方 法應用至包括兩種或多種氟取代的碳酸酯的混合物，或應 用至包括非氟化有機碳酸酯或兩種或多種非氟化碳酸酯與 一或多種氟取代的有機碳酸酯的混合物。因此，當使用單 數形式“碳酸酯”時，其也將表示複數形式。 結晶固體一般係適合的，例如含S i02的沸石類，或 玻璃質的材料，例如用玻璃製造的實體，例如玻璃珠。玻 璃珠應該以小顆粒的形式使用，例如具有在〇. 5 mm到2 0 m m之間的直徑（儘管，當然，該直徑可能小於0 · 5 m m或 大於20 mm)。較佳的是使用具有高表面積的固體’尤其 -6- 201004933 是非晶相固體矽石或含矽石的化合物。矽膠是非常佳的。 此類凝膠的高表面（其可以以成形實體的形式應用，例如 ，以珠粒的形式）提供快速除去HF的反應。 術語“氟化有機碳酸酯類”表示由至少一個氟原子取 代並且包含至少一個CH-CF基團的碳酸二烷基酯類以及 碳酸伸烷基酯類。 在碳酸—基醋類中’該等院基基團（它們中的至少 一者被至少一個氟原子取代）可能是相同或不同的。較佳 地，院基係c 1到C 3院基’尤其是甲基或乙基。例如，根 據本發明的方法’可以處理下列：碳酸氟甲基甲基酯、碳 酸二-(氟甲基）酯、碳酸二氟甲基甲基酯、碳酸二氟甲基氟 甲基酯、碳酸二-(二氟甲基）酯' 碳酸甲基三氟甲基酯、碳 酸氟甲基三氟甲基酯、碳酸二氟甲基三氟甲基酯、以及碳 酸二-(三氟甲基）酯。該等化合物可以藉由用元素氟直接氟 化碳酸二甲酯或從各自的氯取代的碳酸酯藉由氯-氟交換 反應（例如哈萊克斯（Halex)反應）進行製備。藉由蒸餾或 其他慣用方法進行分離係可能的。 在碳酸伸烷基酯類中，術語“伸烷基”較佳地表示 C 2到C 4伸烷基（被至少一個氟原子取代），尤其是伸乙 基、伸丙基（甲基伸乙基）、以及1，2 -二甲基伸乙基。“ 伸烷基”較佳地表示伸乙基或伸丙基。例如，碳酸伸4-氯-5-氟乙基酯（描述於JP-A 62-290072)、碳酸伸4 -氟-5 -甲基乙基酯' 碳酸伸4 -氟-4-甲基乙基酯、碳酸伸4,5-二 氟-5 -甲基乙基酯、碳酸伸4 -氯-5-氟-5 -甲基乙基酯（描述 -7- 201004933 於JP-A 62-290071)、碳酸伸4_氟甲基乙基酯、碳酸伸4-氟甲基-5,5-二甲基乙基酯、或碳酸伸4-(1-氟乙基）乙基酯 (描述於JP - A 0 9 - 2 5 1 8 6 1 )。較佳地，根據本發明的方法 ，處理下列：碳酸伸4-氟乙基酯；碳酸伸4,4-二氟乙基酯 、碳酸伸順式-4,5-二氟乙基酯以及碳酸伸反式-4,5-二氟乙 基酯；碳酸伸4,4,5-三氟乙基酯以及被至少一個氟原子取 代的碳酸伸甲基乙基酯（碳酸伸丙酯）、尤其是碳酸伸4-氟甲基乙基酯。該等氟化碳酸酯類可以由各自的非氟化的 化合物藉由在HF中的電化學氟化作用、藉由用高價金屬 氟化物處理、或較佳地藉由直接氟化作用（例如用惰性氣 體（尤其是氮）稀釋的元素氟）進行製備。碳酸伸丙酯的 直接氟化作用（例如）被描述於JP-A 07-3 1 2227中。具有 2個或更多個氟原子的化合物也可以藉由各自的碳酸酯類 的氟化作用進行製備，該等碳酸酯已藉由氟以較低程度的 取代作用予以取代。這（例如）被描述於^-八2000-3 44 7 63，其中碳酸伸氟乙基酯與氟反應，以提供二氟化的 產物。 在本發明的一具體例中，待處理的含HF之氟取代的 有機碳酸酯係是來自氟化反應之反應混合物。其可能包含 未氟化之起始材料、所欲之氟化的有機碳酸酯、以及過度 氟化的有機碳酸酯。較佳地，將該反應混合物進行預處® 以將HF含量減少至低於一個特定含量。較佳的是將HF 減至等於或低於2.5重量％。更佳地，如以下所詳述，將 HF含量減至等於或小於2重量％的待處理混合物。這減小 201004933 副反應可能發生的風險。 本發明之方法尤其適合於減少在碳酸伸單-、二-以及 三氟乙酯中的HF含量。鑑於從碳酸伸單氟乙酯（“ F1EC ”）中除去HF，將進一步詳細說明。 碳酸伸單氟乙酯可以藉由碳酸伸乙酯的直接氟化作用 而從碳酸伸乙酯予以製備。日本專利申請案JP-A 2000 309583揭示該反應可以在溶劑存在下或不存在予以進行。 美國專利US-A 7223500揭示碳酸伸乙酯和氟之間的反應 在碳酸伸氟乙酯作爲溶劑之存在下進行。美國專利US_A 726823 8揭示碳酸伸乙酯的直接氟化的方法，其中氟氣以 拉西環（Raschig ring)被分佈在配置於反應器內的管柱中。 在所有這些方法中，產生碳酸伸氟乙酯以及作爲副產 物之HF的混合物。較佳的是，在碳酸伸氟乙酯/HF混合 物與矽石接觸之前，將HF的含量減至等於或小於2.5重 量％(更佳地等於或小於2重量％，非常佳地等於或小於1 重量％，且最佳地等於或小於〇.5重量％)的待與去除HF 的反應物接觸的混合物。例如，大部分的HF可以藉由用 惰性氣體（例如用氮）汽提該溶液或藉由第一個蒸餾步驟 去除。較佳的是，以此前述步驟將HF的含量減至等於或 小於1重量％，更佳地等於或小於0 ·5重量％ ’且尤其佳地 等於或小於〇. 1重量％。當H F的含量減至所欲之含量時’ 將所得到的碳酸伸氟乙酯的混合物與矽膠（較佳的反應物 )接觸。201004933 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for preparing HF-depleted fluorinated organic carbonates. [Prior Art] Fluorinated organic carbonates are useful as solvents or co-solvents, especially for the production of Li-ion batteries. For example, they may be defluorinated from each by direct fluorination with elemental fluorine, by reaction with a high-valent metal fluoride (for example, A g F 2 ) from which fluorine has been separated, or by electrochemical fluorination. Organic carbonates are prepared. In such methods, one or more C-H bonds are replaced by one or more C-F bonds. Hydrogen fluoride (HF) is formed as a by-product. Fluorine-substituted organic carbonates containing hydrogen fluoride may also be obtained by other types of methods. For example, when a fluoroethyl carbonate is produced from ethyl carbonate and elemental fluorine, HF is added as a solvent. Of course, HF can be detrimental, especially if the product is used in high-tech applications, such as Li-ion batteries, and must therefore be removed. For example, as described in JP 2000309583 or US-A 7,223,500, HF can be removed from fluorinated organic carbonates by rinsing with water. In the case of a compound having a CH-CF group, contact with water is disadvantageous because it appears to result in Hf from fluorinated organic carbonates according to US-A 7,268,238 (published in US Patent Application Publication No. 2006/1 67279) Separation in the class. This U.S. patent discloses the removal of HF from fluoroethyl carbonate by steaming. 201004933 ΕΡ-Α-0 326〇54 discloses the removal of hydrogen fluoride and trifluoropropane fluoride from 2,2,3,3·tetraoxane nozzles using tannin or alumina. The present specification focuses on providing gaseous 2,2,3,3-tetrafluorooxo in contact with inorganic reactants. SUMMARY OF THE INVENTION The object of the present invention is to provide a simple and reliable method for producing fluorinated organic carbonates. The fluorinated organic carbonates have a depleted content of HF. According to the process of the present invention, there is provided a process for the preparation of a fluorine-substituted organic carbonate which is depleted of HF-contaminated fluorinated organic comprising at least one CH-CF group in the molecule The carbonate is contacted with an inorganic reactant comprising Si〇2 to form a mixture of solid and HF-depleted fluorinated organic carbonate, and the resulting HF-depleted fluorine-substituted organic carbonate is separated from the solid . When HF is consumed, the fluorine-substituted organic carbonate remains in a liquid state during contact of the fluorine-substituted organic carbonate with the inorganic reactant. Of course, the method can also be applied to a mixture comprising two or more fluorine-substituted carbonates, or to organics comprising a non-fluorinated organic carbonate or two or more non-fluorinated carbonates and one or more fluorine-substituted organic compounds. a mixture of carbonates. Thus, when the singular form "carbonate" is used, it will also mean the plural. Crystalline solids are generally suitable, such as zeolites containing S02, or vitreous materials, such as entities made of glass, such as glass beads. The glass beads should be used in the form of small particles, for example having a diameter between mm 5 mm and 20 mm (although, of course, the diameter may be less than 0 · 5 m or greater than 20 mm). It is preferred to use a solid having a high surface area, especially -6-201004933, which is an amorphous phase solid vermiculite or a vermiculite-containing compound. Silicone is very good. The high surface of such gels, which may be applied in the form of shaped entities, for example in the form of beads, provides a rapid removal of HF. The term "fluorinated organic carbonates" means dialkyl carbonates and alkyl carbonates which are substituted by at least one fluorine atom and which contain at least one CH-CF group. In the carbonic acid-based vinegars, the athomo group groups (at least one of which is substituted by at least one fluorine atom) may be the same or different. Preferably, the yard base c 1 to C 3 is based on a methyl or ethyl group. For example, the process according to the invention can handle the following: fluoromethyl methyl carbonate, di-(fluoromethyl) carbonate, difluoromethyl methyl carbonate, difluoromethyl fluoromethyl carbonate, carbonic acid Di-(difluoromethyl)ester' methyl trifluoromethyl carbonate, fluoromethyl trifluoromethyl carbonate, difluoromethyl trifluoromethyl carbonate, and di-(trifluoromethyl) carbonate ester. These compounds can be prepared by directly fluorinating dimethyl carbonate with elemental fluorine or by a chlorine-fluorine exchange reaction (e.g., a Halex reaction) from a respective chlorine-substituted carbonate. Separation by distillation or other conventional methods is possible. In alkyl carbonates, the term "alkylene" preferably denotes C 2 to C 4 alkyl (substituted by at least one fluorine atom), especially ethyl, propyl (methyl) Base), and 1,2-dimethyl extended ethyl. "Alkylalkyl" preferably denotes an extended or extended propyl group. For example, carbonic acid 4-chloro-5-fluoroethyl ester (described in JP-A 62-290072), carbonic acid 4-fluoro-5-methylethyl ester 'carbonate extension 4-fluoro-4-methyl Base ester, 4,5-difluoro-5-methylethyl carbonate, 4-chloro-5-fluoro-5-methylethyl carbonate (Description -7-201004933 on JP-A 62-290071 ), 4-fluoromethyl ethyl carbonate, 4-fluoromethyl-5,5-dimethylethyl carbonate, or 4-(1-fluoroethyl)ethyl carbonate (described in JP - A 0 9 - 2 5 1 8 6 1 ). Preferably, according to the process of the present invention, the following treatments are carried out: 4-fluoroethyl carbonate, 4,4-difluoroethyl carbonate, cis--4,5-difluoroethyl carbonate, and carbonic acid Retino-4,5-difluoroethyl ester; 4,4,5-trifluoroethyl carbonate, and methyl ethyl carbonate (propylene carbonate) substituted by at least one fluorine atom, especially It is 4-fluoromethyl ethyl carbonate. The fluorinated carbonates may be derived from the respective non-fluorinated compounds by electrochemical fluorination in HF, by treatment with high-valent metal fluorides, or preferably by direct fluorination (eg, The inert gas (especially nitrogen) diluted elemental fluorine) is prepared. The direct fluorination of propylene carbonate (for example) is described in JP-A 07-3 1 2227. Compounds having 2 or more fluorine atoms can also be prepared by fluorination of the respective carbonates which have been replaced by a lower degree of substitution by fluorine. This is described, for example, in ^-八 2000-3 44 7 63, in which fluoroethyl carbonate is reacted with fluorine to provide a difluorinated product. In one embodiment of the invention, the HF-substituted fluoro-substituted organic carbonate to be treated is a reaction mixture from a fluorination reaction. It may contain unfluorinated starting materials, desired fluorinated organic carbonates, and over-fluorinated organic carbonates. Preferably, the reaction mixture is pretreated to reduce the HF content below a specific level. It is preferred to reduce HF to equal to or lower than 2.5% by weight. More preferably, the HF content is reduced to equal to or less than 2% by weight of the mixture to be treated as detailed below. This reduces the risk of a possible side reaction to 201004933. The process of the present invention is particularly suitable for reducing the HF content in mono-, di- and trifluoroethyl carbonates. In view of the removal of HF from the monofluoroethyl carbonate ("F1EC"), this will be described in further detail. The monofluoroethyl carbonate can be prepared from ethyl acetate by direct fluorination of ethyl carbonate. Japanese Patent Application No. JP-A 2000 309583 discloses that the reaction can be carried out in the presence or absence of a solvent. U.S. Patent No. 7,223,500 discloses the reaction between ethyl acetate and fluorine in the presence of fluoroethyl carbonate as a solvent. U.S. Patent No. 7,726,823 discloses a process for the direct fluorination of ethyl carbonate, wherein the fluorine gas is distributed in a column disposed in the reactor in a Raschig ring. In all of these processes, a mixture of fluoroethyl carbonate and HF as a by-product is produced. Preferably, the content of HF is reduced to equal to or less than 2.5% by weight (more preferably equal to or less than 2% by weight, very preferably equal to or less than 1) before the fluoroethyl carbonate/HF mixture is contacted with vermiculite. % by weight, and optimally equal to or less than 5% by weight of the mixture to be contacted with the HF-removed reactant. For example, most of the HF can be removed by stripping the solution with an inert gas (e.g., with nitrogen) or by a first distillation step. Preferably, the content of HF is reduced to equal to or less than 1% by weight, more preferably equal to or less than 0.5% by weight and particularly preferably equal to or less than 0.1% by weight. When the content of H F is reduced to the desired level, the resulting mixture of fluoroethyl carbonate is contacted with a silicone (preferably a reactant).
矽石含量係非常可變的；最小量取決於可接受的HF -9- 201004933 殘餘量。矽石應該以在合理的時間內提供所欲之純度水平 的含量使用。通常，取決於HF的濃度，每1〇〇 g的碳酸 伸氟乙酯/HF混合物使用等於或小於4 g的矽石。可以使 用較高含量，但有可能的是，一些矽石和/或所欲之產物 可能被浪費掉。專家可以進行簡單的試驗，以找出最理想 含量的矽石。 在含HF的混合物與矽石接觸期間的溫度不是非常關 鍵，尤其是考慮到通常使用的小含量。溫度應高於各自碳 酸酯的熔點並且不會高至非所欲之副反應發生。原則上， 該接觸可以在碳酸酯或碳酸酯混合物的固化溫度和相當高 的溫度（例如，高達 U 〇 °C或甚至更高）之間進行。較佳 地，該溫度等於或高於1 (TC。例如，該接觸可以在環境溫 度下進行。 根據一具體例，待處理的反應混合物與矽石之間的接 觸係在低於5 0°C的溫度下進行。在這樣低的溫度（尤其是 在從1 0 °C到5 0 °C範圍內）允許溫和處理。 根據另一具體例’該接觸溫度係等於或高於5 0 °C，更 佳地等於或高於8 0 °C。較佳地，其等於或低於1 〇 〇 °C。8 0 °C到1 00 °C的溫度範圍係非常有利的，尤其是當待用無機 反應物處理的氟化合物在此高溫下離開另一處理過程時（ 例如汽提過程，其中HF在此溫度範圍內藉由用惰性氣體 汽提除去）。 接觸時間應長至所需的時間，但不應過度延長。較佳 地’其等於或小於6 0分鐘，更佳地等於或小於3 0分鐘。 -10- 201004933 較佳地’其等於或大於丨分鐘，更佳地等於或大於5分鐘 〇 尤其是如果在較高範圍的溫度下進行處理時，例如在 5 0 °C到1 0 0 °C (並且尤其是8 0 °C到1 0 0 °c )的範圍內，有 利的是可以應用輕度真空。假定此有助於除去所有水，並 且因此防止由水引起的副反應。 有可能應用任何所欲之形式的矽石材料，例如作爲珠 粒或擠出物。 在一具體例中，砂石係以散裝材料（bulk material)的 形式與氟化的化合物進行接觸。在接觸之後，藉由已知的 方法，例如藉由過濾、傾析、離心或蒸餾，從該反應混合 物中除去固體。 在另一較佳的具體例中，矽石，尤其是矽膠珠粒被， 被包含在過濾器中，其中待接觸的氟化的化合物通過該過 濾器。過濾器的優點係在接觸期間矽石被包裹在其中並且 保留在該過濾器中。因此’其不必在處理之後在分離步驟 中從該有機化合物中去除。 藉由應用矽石，尤其是矽膠，HF的含量可以減至等 於或小於300重量ppm。 經常較佳的是進一步純化該液體’特別是藉由蒸餾。 尤其是如果包括例如碳酸伸氟乙酯、HF、起始材料（在此 案例中，碳酸伸乙酯）和/或較高氟化的產物（在此案例 中，碳酸伸二氟乙酯類）的原產物係根據本發明的方法予 以純化的案例。因此，可以進一步將HF含量減至等於或 -11 - 201004933 小於30重量ppm ’並且甚至到等於或小於1 〇重量ppm。 在本發明的一較佳具體例中，矽石處理係在蒸餾管柱 的底部進行；當分批進行蒸餾時，這個替代方案係尤其可 行的。此具體例還具有另外的優點，即排除分離步驟。鑒 於水（其係在處理期間形成的）在碳酸伸氟乙酯中引起副 反應’非常出人意料的是，鑑於蒸餾期間該碳酸伸氟乙酯 上的熱應力’此具體例完全非常令人滿意地工作。 用矽石的處理較佳地用前面的汽提步驟（其中藉由在 高度下將惰性氣體引導至該原料而除去HF )和/或隨後的 蒸餾步驟進行。此組合具有以下優點：加熱氟化的有機化 合物所需要的能量可以用於數個處理步驟。 矽石從有機化合物中除去HF的用途主要是從美國專 利US-A 625 2 1 05中得知的。假定Si〇2與HF反應形成 SiF4 (氣態產物），然後SiF4形成H2SiF6和水。碳酸伸 氟乙酯對脫氟化氫作用似乎是敏感的。水（如在US-A 726823 8所指出）被認爲引起HF從碳酸伸氟乙酯中的分 離；因此，專家將預期，含Si02的化合物應該不適合作 爲用於從該等化合物中除去HF的試劑：HF與矽石的反應 形成水，形成的水引起從碳酸伸氟乙酯形成HF，因此形 成的HF引起從矽石形成水等等；結果，人們會預期對產 量和純度兩者皆有不利的作用。非常出人意料的是，矽石 (或含矽石的化合物）可以作爲純化試劑以完全去除HF ，尤其是用於碳酸伸氟乙酯’而且還用於上面所提及的其 他氟化碳酸酯類。 -12- 201004933 現在，將藉由實例描述本發明，該等實例對本發明進 行進一步說明但無意對其限制。 一般說明：所有的％係面積％，除了 H F (以重量％表 達）以外。 待處理的該等混合物係根據描述於WO 2004/076439 的過程來合成：加入碳酸伸乙酯在碳酸伸氟乙酯中的溶液 中，當反應進行時引入用氮稀釋的氟。 【實施方式】 實例1 : 1 000 g的混合物於室溫下在塗覆ΡΕ的反應器中攪拌 ，該混合物包括：4-氟-1,3-二氧唓（dioxolane)-2-酮（碳酸 伸單氟乙酯，F1EC; 50%，4.7 mol) 、（4R，5R)-4,5-二氟-1，3-二氧陳-2-酮（反式-F2EC，24°/。，1.9 mol) 、（4S，5R)-4,5 -二氟-1,3 -二氧嗦-2-酮（順式-F2EC，18%，1.5 mol) 、4,4 -二氟-1，3 -二氧嗦-2 -酮（4,4-F2EC; 6%，0.5 mol) 、碳酸伸乙酯（EC ; 1·2%，0.1 mol )、以及無水氟化氫 (HF ； 0.8 % » 0.4 mol)。 將 1 5 g ( 0.25 mol )的 SiΟ2 (矽膠’60，81§111&-Aldrich，CAS No. 1 1 2926-00-8 )逐滴加入。在加入矽膠 期間，溫度保持在2 5 °C到3 0 °C之間。 在氣體形成（S i F 4 )結束後，藉由氣相層析法分析該 混合物的樣品。未能檢測到氟化的化合物的顯著分解。該 混合物係藉由在減壓下蒸餾而予以分離。藉由蒸餾除去從 -13- 201004933 H F與S i Ο 2反應所形成的水。 實例2 : 1 000 g的混合物於室溫下在ΡΕ塗覆的反應器中攪样 ，該混合物包括：4-氟-〗，3-二氧唓-2-酮（碳酸伸單氟乙醋 .F1EC > 55% - 5.2 mol ) 、（ 4 R, 5 R) - 4,5 -二氟 1，3 -二氧唓 _ 2 -酮（反式-F2EC，5%，0.4 mol) 、（4S，5R)-4,5 -二氟 _ 1，3 -二氧唓-2 -酮（順式-F 2 E C，4 %，0 _ 3 m ο 1 ) 、4，4 -二氟 _ 1，3 -二氧唓-2 -酮（4,4-F2EC，1%，0_1 mol)、碳酸伸乙 酯（3 5 % ’ 4 · 0 m ο 1 )、以及無水氟化氫（H F，2 · 5 %，1 . 3 mol)。 將 50 g ( 0.8 mol )的 Si02 (矽膠，60，31811^-Aldrich，CAS No. 112926-00-8)逐滴力口入。在力口入砂膠 期間，藉由該反應器的外部冷卻將溫度保持在25 t到3 0 °C之間。 在氣體形成（SiF4 )結束後，藉由氣相層析法分析混 合物的樣品。未能檢測到氟化的化合物的顯著分解。在 S i Ο 2中和後，該混合物的H F含量係< 3 0 0 p p m H F。 藉由減壓蒸餾分離該混合物。藉由蒸餾除去從HF與 Si02反應所形成的水。 實例3 : 使用類似於實例2的另一混合物，不同之處在於HF 的濃度係 5.4% ( 2_7 mol )。 -14- 201004933 爲了除i °C到30°C之 析法分析該ί； 氟化的碳酸^ 形成。 5 HF，逐滴加入100 g Si〇2。溫度保持在25 間。在氣體形成（SiF4 )結束後’藉由氣相層 己合物的樣品。結果指明在G C跡線上有更高 肖乙醋衍生物的分解以及新的未經確認的峰的 -15-The vermiculite content is very variable; the minimum amount depends on the acceptable residual amount of HF -9- 201004933. Vermiculite should be used at a level that provides the desired level of purity in a reasonable amount of time. Generally, depending on the concentration of HF, vermiculite equal to or less than 4 g is used per 1 g of the fluoroethyl carbonate/HF mixture. Higher levels can be used, but it is possible that some vermiculite and/or desired products may be wasted. Experts can perform simple tests to find the most ideal meteorite. The temperature during contact of the HF-containing mixture with vermiculite is not critical, especially in view of the small amounts typically used. The temperature should be above the melting point of the respective carbonate and not so high as undesired side reactions. In principle, the contacting can be carried out between the curing temperature of the carbonate or carbonate mixture and a relatively high temperature (e.g., up to U 〇 ° C or even higher). Preferably, the temperature is equal to or higher than 1 (TC. For example, the contact can be carried out at ambient temperature. According to a specific example, the contact between the reaction mixture to be treated and the vermiculite is below 50 °C. Performing at such a low temperature (especially in the range from 10 ° C to 50 ° C) allows gentle treatment. According to another specific example, the contact temperature is equal to or higher than 50 ° C, More preferably equal to or higher than 80 ° C. Preferably, it is equal to or lower than 1 〇〇 ° C. The temperature range of 80 ° C to 100 ° C is very advantageous, especially when inorganic is to be used The reactant-treated fluorine compound leaves the other treatment process at this elevated temperature (for example, a stripping process in which HF is removed by stripping with an inert gas). The contact time should be as long as necessary, but It should not be excessively extended. Preferably it is equal to or less than 60 minutes, more preferably equal to or less than 30 minutes. -10-201004933 Preferably, it is equal to or greater than 丨 minutes, more preferably equal to or greater than 5 minutes. 〇 especially if it is processed at a higher temperature range, for example In the range of 50 ° C to 1 0 0 ° C (and especially 80 ° C to 100 ° C), it is advantageous to apply a mild vacuum. This is assumed to help remove all water and thus prevent Side reactions caused by water. It is possible to apply any desired form of vermiculite material, for example as beads or extrudates. In one embodiment, the sandstone is in the form of a bulk material and fluorinated. The compound is contacted. After contacting, the solid is removed from the reaction mixture by known methods, for example by filtration, decantation, centrifugation or distillation. In another preferred embodiment, vermiculite, especially It is a silicone bead that is contained in a filter through which the fluorinated compound to be contacted passes. The advantage of the filter is that the vermiculite is encapsulated therein during the contact and remains in the filter. It does not have to be removed from the organic compound in the separation step after the treatment. By using vermiculite, especially silicone, the content of HF can be reduced to equal to or less than 300 ppm by weight. It is often preferred to further purify the liquid. By distillation, especially if it includes, for example, fluoroethyl carbonate, HF, starting materials (in this case, ethyl carbonate) and/or higher fluorinated products (in this case, carbonic acid) The original product of fluoroethyl ester) is a case of purification according to the method of the present invention. Therefore, the HF content can be further reduced to be equal to or -11 - 201004933 to less than 30 ppm by ppm 'and even to equal to or less than 1 〇 by weight ppm. In a preferred embodiment of the invention, the vermiculite treatment is carried out at the bottom of the distillation column; this alternative is particularly feasible when the distillation is carried out batchwise. This specific example also has the additional advantage of eliminating separation. step. In view of the fact that water, which is formed during the treatment, causes side reactions in the fluoroethyl carbonate, it is very surprising that, in view of the thermal stress on the fluoroethyl carbonate during distillation, this specific example is completely very satisfactory. jobs. The treatment with vermiculite is preferably carried out using a previous stripping step in which HF is removed by directing the inert gas to the feedstock at a level and/or a subsequent distillation step. This combination has the advantage that the energy required to heat the fluorinated organic compound can be used in several processing steps. The use of vermiculite to remove HF from organic compounds is primarily known from U.S. Patent No. 625 2 051. It is assumed that Si〇2 reacts with HF to form SiF4 (gaseous product), and then SiF4 forms H2SiF6 and water. The fluoroethyl carbonate appears to be sensitive to dehydrofluorination. Water (as indicated in US-A 726 823 8) is believed to cause separation of HF from fluoroethyl carbonate; therefore, experts would expect that SiO2-containing compounds should not be suitable as a means for removing HF from such compounds. Reagent: The reaction of HF with vermiculite forms water, and the formed water causes formation of HF from fluoroethyl carbonate. Therefore, the formed HF causes water to form from vermiculite, etc. As a result, it is expected that both yield and purity are expected. Unfavorable effect. Quite surprisingly, vermiculite (or vermiculite-containing compounds) can be used as a purification reagent to completely remove HF, especially for fluoroethyl carbonate, and also for other fluorinated carbonates mentioned above. The invention will now be described by way of examples, which are further described but not intended to be limiting. General Note: All % area %, except for H F (expressed in weight %). The mixtures to be treated are synthesized according to the procedure described in WO 2004/076439: the addition of ethyl carbonate in a solution of fluoroethyl carbonate, and the introduction of fluorine diluted with nitrogen as the reaction proceeds. [Examples] Example 1: A mixture of 1 000 g was stirred at room temperature in a crucible-coated reactor comprising: 4-fluoro-1,3-dioxolane-2-one (carbonic acid) Monofluoroethyl ester, F1EC; 50%, 4.7 mol), (4R, 5R)-4,5-difluoro-1,3-dioxo-2-one (trans-F2EC, 24°/., 1.9 mol), (4S, 5R)-4,5-difluoro-1,3-dioxo-2-one (cis-F2EC, 18%, 1.5 mol), 4,4-difluoro-1, 3 -dioxan-2-one (4,4-F2EC; 6%, 0.5 mol), ethyl carbonate (EC; 1.2%, 0.1 mol), and anhydrous hydrogen fluoride (HF; 0.8% » 0.4 mol) ). 1 5 g (0.25 mol) of SiΟ2 (silicone '60, 81 § 111 & - Aldrich, CAS No. 1 1 2926-00-8) was added dropwise. During the addition of the silicone, the temperature is maintained between 25 ° C and 30 ° C. After the end of gas formation (S i F 4 ), a sample of the mixture was analyzed by gas chromatography. A significant decomposition of the fluorinated compound could not be detected. This mixture was separated by distillation under reduced pressure. The water formed by the reaction of -13-201004933 H F with S i Ο 2 was removed by distillation. Example 2: A 1 000 g mixture was stirred at room temperature in a ruthenium coated reactor comprising: 4-fluoro-, 3-dioxo-2-one (carbonated monofluoroacetic acid). F1EC > 55% - 5.2 mol ), ( 4 R, 5 R) - 4,5 - difluoro 1,3 -dioxan-2-one (trans-F2EC, 5%, 0.4 mol), (4S , 5R)-4,5-difluoro_ 1,3 -dioxan-2-one (cis-F 2 EC, 4 %, 0 _ 3 m ο 1 ), 4,4-difluoro _ 1, 3-dioxan-2-one (4,4-F2EC, 1%, 0_1 mol), ethyl carbonate (35 % '4 · 0 m ο 1 ), and anhydrous hydrogen fluoride (HF, 2 · 5 %) , 1.3 mol). 50 g (0.8 mol) of SiO 2 (silicone, 60, 31811^-Aldrich, CAS No. 112926-00-8) was added dropwise. The temperature is maintained between 25 t and 30 ° C by external cooling of the reactor during the force in the sand. After the end of gas formation (SiF4), a sample of the mixture was analyzed by gas chromatography. A significant decomposition of the fluorinated compound could not be detected. After neutralization of S i Ο 2, the H F content of the mixture is < 3 0 0 p p m H F . The mixture was separated by distillation under reduced pressure. The water formed by the reaction of HF and SiO 2 is removed by distillation. Example 3: Another mixture similar to Example 2 was used, except that the concentration of HF was 5.4% (2-7 mol). -14- 201004933 For the analysis of the analysis of i °C to 30 ° C, the fluorinated carbonic acid was formed. 5 HF, 100 g Si〇2 was added dropwise. The temperature is maintained at 25. A sample of the hexamide by the gas phase layer after the end of gas formation (SiF4). The results indicate that there is a higher decomposition of the acetonitrile derivative on the G C trace and a new unconfirmed peak -15-