JP2006348381A - Process for producing organic compounds by electrolytic fluorination - Google Patents
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Abstract
【課題】有機化合物の電解フッ素化によって、ペルフルオロ有機化合物を収率よく製造する方法を提供する。
【解決手段】有機化合物の電解フッ素化において、電解槽に電解液と共にフッ素化不活性溶媒を共存させて有機化合物を電解フッ素化することを特徴とするフッ素化有機化合物の製造方法であり、好ましくは、電解槽内で電解液層下側のフッ素化不活性溶媒を抜き出して電解液層側に供給することによって電解フッ素化反応ゾーンにフッ素化不活性溶媒を循環させて電解フッ素化を行う製造方法。
【選択図】なし
The present invention provides a method for producing a perfluoro organic compound with high yield by electrolytic fluorination of an organic compound.
A method for producing a fluorinated organic compound, characterized in that in the electrolytic fluorination of an organic compound, the organic compound is subjected to electrolytic fluorination in the presence of a fluorinated inert solvent together with an electrolytic solution in an electrolytic cell. Is a method of extracting fluorinated inert solvent below the electrolyte layer in the electrolytic bath and supplying it to the electrolyte layer side to circulate the fluorinated inert solvent in the electrolytic fluorination reaction zone to perform electrolytic fluorination Method.
[Selection figure] None
Description
本発明は、有機化合物の電解フッ素化によって、ペルフルオロ有機化合物を収率よく製造する方法に関する。 The present invention relates to a method for producing a perfluoro organic compound with high yield by electrolytic fluorination of an organic compound.
電解フッ素化によるペルフルオロ有機化合物の製造では、電解槽に原料の有機化合物と電解液の無水フッ酸を供給し、電解フッ素化反応によってペルフルオロ有機化合物を合成する。電解フッ素化反応が進むにつれて、生成物であるペルフルオロ有機化合物の濃度が増加し、溶解度を超えると電解液から分離する。生成したペルフルオロ有機化合物は比重が大きいため、電解槽の下部から抜き出すことが可能である。あるいは生成物の沸点が低い場合は、ペルフルオロ有機化合物が気体として電解槽から取り出され、これを吸収塔で回収することが可能である。 In the production of perfluoro organic compounds by electrolytic fluorination, raw organic compounds and electrolytic hydrofluoric acid are supplied to an electrolytic cell, and the perfluoro organic compounds are synthesized by electrolytic fluorination reaction. As the electrolytic fluorination reaction proceeds, the concentration of the product perfluoro organic compound increases, and when the solubility is exceeded, the product is separated from the electrolytic solution. Since the generated perfluoro organic compound has a large specific gravity, it can be extracted from the lower part of the electrolytic cell. Or when the boiling point of a product is low, a perfluoro organic compound is taken out from an electrolytic cell as gas, and this can be collect | recovered with an absorption tower.
一方、生成したペルフルオロ有機化合物が電解液中に滞留すると、さらなる電解反応を受けて分解し、収率が低下する。この問題を解決するため、例えば特許第２７５５４９号公報（特許文献１）や米国特許第５５７５９０６号明細書（特許文献２）には、電解液を電解槽から取り出してフッ素化不活性溶媒中に通し、生成したペルフルオロ有機化合物を連続的に抽出分離する方法が示されている。 On the other hand, when the generated perfluoro organic compound stays in the electrolytic solution, it undergoes further electrolytic reaction and decomposes, and the yield decreases. In order to solve this problem, for example, in Japanese Patent No. 275549 (Patent Document 1) and US Pat. No. 5,575,906 (Patent Document 2), an electrolytic solution is taken out from an electrolytic cell and passed through a fluorinated inert solvent. A method for continuously extracting and separating the produced perfluoro organic compound is shown.
ところが、特許文献１に記載されているように、生成したペルフルオロ有機化合物を速やかに電解槽から抜き出すと、過剰な電解反応による分解を防止できるものの、部分的に水素が残存する不完全フッ素化物が著しく増加し、生成物中の不完全フッ素化物の割合が３０％にまで達することが明らかにされている。さらに、この不完全フッ素化物を低減させるためには、電解フッ素化後に他のフッ素化工程が必要となることも記載されている。 However, as described in Patent Document 1, when the generated perfluoro organic compound is quickly extracted from the electrolytic cell, decomposition due to excessive electrolytic reaction can be prevented, but incomplete fluorinated products in which hydrogen remains partially exist. It has been shown that the proportion of incomplete fluorides in the product increases significantly up to 30%. Further, it is described that another fluorination step is required after electrolytic fluorination in order to reduce the incomplete fluorinated product.
また、特許文献２では、生成物の抽出によって分解が抑制されることが記載されており、生成物中の不完全フッ素化物の増加については言及されていないが、特許文献１の場合と同様に不完全フッ素化物が増加することは容易に推測される。
本発明は、電解フッ素化によるペルフルオロ有機化合物の製造において、不完全フッ素化物の含有量が少ないペルフルオロ有機化合物を収率よく製造する方法を提供するものである。 The present invention provides a method for producing a perfluoro organic compound having a low content of incomplete fluorinated compounds in a high yield in the production of a perfluoro organic compound by electrolytic fluorination.
本発明によれば、以下に示す構成によって上記課題を解決したペルフルオロ有機化合物の製造方法が提供される。
〔１〕有機化合物の電解フッ素化において、電解槽に電解液と共にフッ素化不活性溶媒を共存させて有機化合物を電解フッ素化する（スルトン化合物の電解フッ素化によってペルフルオロカルボニルスルホニル化合物を製造する方法を除く）ことを特徴とするフッ素化有機化合物の製造方法。
〔２〕電解槽内の反応ゾーンにフッ素化不活性溶媒を循環しながら電解フッ素化を行う上記(1)に記載する製造方法。
〔３〕電解槽内の電解液層とその下側のフッ素化不活性溶媒層とにおいて、電解槽内のフッ素化不活性溶媒を抜き出して電解液層に供給することによって電解フッ素化反応ゾーンにフッ素化不活性溶媒を循環させて電解フッ素化を行う上記(2)に記載する製造方法。
〔４〕抜き出したフッ素化不活性溶媒を、電解液層の電極間または電極近傍に、電解液層上側から供給して電解フッ素化反応ゾーンにフッ素化不活性溶媒を循環させる上記(3)に記載する製造方法。
〔５〕生成するペルフルオロ有機化合物のフッ酸に対する溶解度が１０％以上である上記(1)〜上記(4)の何れかに記載する製造方法。
〔６〕生成するペルフルオロ有機化合物の沸点が１２０℃以下である上記(1)〜上記(6)の何れかに記載する製造方法。
〔７〕生成したペルフルオロ有機化合物中の残存プロトン濃度が１０００ppm以下である上記(1)〜上記(6)の何れかに記載する製造方法。
〔８〕下記一般式(１)（式中、ｎは３〜６の整数）で表されるカルボニル化合物を電解フッ素化して、下記一般式(２)（式中、ｎは一般式(1)と同じ）で表されるペルフルオロジカルボニル化合物を製造する上記(1)〜上記(7)の何れかに記載する製造方法。
〔９〕下記一般式(３)（式中、ｎは１〜６の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるジカルボニル化合物を電解フッ素化して、下記一般式(４)（式中、ｎは一般式(3)と同じ）で表されるペルフルオロジカルボニル化合物を製造する上記(1)〜上記(7)の何れかに記載する製造方法。
ＸＣＯ（ＣＨ2）nＣＯＸ （３）
ＦＣＯ（ＣＦ2）nＣＯＦ （４）
〔１０〕下記一般式(５)（式中、ｎは１〜７の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるアルキルカルボニル化合物を電解フッ素化して、下記一般式(６)（式中、ｎは一般式(5)と同じ）で表されるペルフルオロアルキルカルボニル化合物を製造する上記(1)〜上記(7)の何れかに記載する製造方法。
ＣnＨ2n+1ＣＯＸ （５）
ＣnＦ2n+1ＣＯＦ （６）
〔１１〕下記一般式(７)（式中、ｎは１〜４の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるジスルホニル化合物を電解フッ素化して、下記一般式(８)（式中、ｎは一般式(7)と同じ）で表されるペルフルオロジスルホニル化合物を製造する上記(1)〜上記(7)の何れかに記載する製造方法。
ＸＳＯ2（ＣＨ2）nＳＯ2Ｘ （７）
ＦＳＯ2（ＣＦ2）nＳＯ2Ｆ （８）
〔１２〕下記一般式(９)（式中、ｎは１〜６の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるアルキルスルホニル化合物を電解フッ素化して、下記一般式(１０)（式中、ｎは一般式(9)と同じ）で表されるペルフルオロアルキルスルホニル化合物を製造する上記(1)〜上記(7)の何れかに記載する製造方法。
ＣnＨ2n+1ＳＯ2Ｘ （９）
ＣnＦ2n+1ＳＯ2Ｆ （１０）
〔１３〕下記化学式(１１)で表されるスルホニル化合物（スルホラン）を電解フッ素化して、下記化学式(１２)で表されるペルフルオロスルホニル化合物を製造する上記(1)〜上記(7)の何れかに記載する製造方法。
[1] In the electrolytic fluorination of an organic compound, the fluorinated inert solvent is allowed to coexist with the electrolytic solution in the electrolytic cell to electrofluorinate the organic compound (a method of producing a perfluorocarbonylsulfonyl compound by electrolytic fluorination of a sultone compound). A method for producing a fluorinated organic compound.
[2] The production method according to the above (1), wherein electrolytic fluorination is performed while circulating a fluorinated inert solvent in the reaction zone in the electrolytic cell.
[3] In the electrolytic solution layer in the electrolytic cell and the fluorinated inert solvent layer below the electrolytic solution layer, the fluorinated inert solvent in the electrolytic cell is extracted and supplied to the electrolytic solution layer to enter the electrolytic fluorination reaction zone. The production method according to the above (2), wherein electrolytic fluorination is carried out by circulating a fluorinated inert solvent.
[4] In the above (3), the extracted fluorinated inert solvent is supplied between or near the electrodes of the electrolyte layer from above the electrolyte layer to circulate the fluorinated inert solvent in the electrolytic fluorination reaction zone. Manufacturing method to be described.
[5] The production method according to any one of (1) to (4), wherein the perfluoroorganic compound to be produced has a solubility in hydrofluoric acid of 10% or more.
[6] The production method according to any one of (1) to (6) above, wherein the perfluoroorganic compound to be produced has a boiling point of 120 ° C. or lower.
[7] The production method according to any one of (1) to (6) above, wherein the residual proton concentration in the generated perfluoroorganic compound is 1000 ppm or less.
[8] Electrolytic fluorination of a carbonyl compound represented by the following general formula (1) (where n is an integer of 3 to 6) gives the following general formula (2) (where n is the general formula (1) The production method according to any one of (1) to (7) above, wherein the perfluorodicarbonyl compound represented by (1) is produced.
[9] Electrolytic fluorination of a dicarbonyl compound represented by the following general formula (3) (wherein n is an integer of 1 to 6 and X is F, Cl or OH) to give the following general formula (4) (formula Wherein n is the same as in the general formula (3)). The production method according to any one of (1) to (7) above, wherein a perfluorodicarbonyl compound represented by the general formula (3) is produced.
XCO (CH 2 ) n COX (3)
FCO (CF 2 ) n COF (4)
[10] Electrolytic fluorination of an alkylcarbonyl compound represented by the following general formula (5) (wherein n is an integer of 1 to 7, X is F, Cl or OH), and the following general formula (6) (formula Wherein n is the same as in the general formula (5)). The production method according to any one of (1) to (7) above, wherein a perfluoroalkylcarbonyl compound represented by the general formula (5) is produced.
C n H 2n + 1 COX (5)
C n F 2n + 1 COF (6)
[11] A disulfonyl compound represented by the following general formula (7) (wherein n is an integer of 1 to 4 and X is F, Cl or OH) is subjected to electrolytic fluorination to give the following general formula (8) (formula Wherein n is the same as in the general formula (7)). The production method according to any one of (1) to (7) above, wherein the perfluorodisulfonyl compound represented by formula (7) is produced.
XSO 2 (CH 2 ) n SO 2 X (7)
FSO 2 (CF 2 ) n SO 2 F (8)
[12] Electrolytic fluorination of an alkylsulfonyl compound represented by the following general formula (9) (wherein n is an integer of 1 to 6 and X is F, Cl or OH) to give the following general formula (10) (formula Wherein n is the same as in the general formula (9)). The production method according to any one of (1) to (7) above, wherein a perfluoroalkylsulfonyl compound represented by formula (9) is produced.
C n H 2n + 1 SO 2 X (9)
C n F 2n + 1 SO 2 F (10)
[13] Any one of (1) to (7) above, wherein a sulfonyl compound (sulfolane) represented by the following chemical formula (11) is electrolytically fluorinated to produce a perfluorosulfonyl compound represented by the following chemical formula (12): The production method described in 1.
本発明の製造方法によれば、不完全フッ素化物の含有量が少ないペルフルオロ有機化合物を収率よく製造することができる。とくに本発明の製造方法において、好ましくは、電解槽内の反応ゾーンにフッ素化不活性溶媒を循環しながら電解フッ素化を行うことによって、具体的には、電解槽内のフッ素化不活性溶媒を抜き出して電解液層に供給し、例えば、抜き出したフッ素化不活性溶媒を、電解液層の電極間または電極近傍に、電解液層上側から供給して電解フッ素化反応ゾーンにフッ素化不活性溶媒を循環させながら電解フッ素化を行うことによって、生成したペルフルオロ有機化合物を効率よく不活性溶媒に抽出することができる。本発明の製造方法によって製造目的物であるペルフルオロ有機化合物を収率よく製造することができる理由として、電極が存在する反応ゾーンを不活性溶媒が流れることによって電極付近の生成物が不活性溶媒によって捕集されるので、生成物が電極に付着残留して過剰な電解反応によって分解することを防止する効果があるものと推定される。 According to the production method of the present invention, it is possible to produce a perfluoro organic compound with a low content of incomplete fluorinated compounds in a high yield. In particular, in the production method of the present invention, preferably, by performing electrolytic fluorination while circulating a fluorinated inert solvent in the reaction zone in the electrolytic cell, specifically, the fluorinated inert solvent in the electrolytic cell is reduced. Extracted and supplied to the electrolyte layer. For example, the extracted fluorinated inert solvent is supplied between or near the electrodes of the electrolyte layer from the upper side of the electrolyte layer and is supplied to the electrolytic fluorination reaction zone. By performing electrolytic fluorination while circulating the water, the generated perfluoro organic compound can be efficiently extracted into an inert solvent. The reason why the perfluoro organic compound, which is the production object, can be produced with high yield by the production method of the present invention is that the inert solvent flows through the reaction zone where the electrode is present, so that the product near the electrode is caused by the inert solvent. Since it is collected, it is presumed that there is an effect of preventing the product from adhering to the electrode and being decomposed by an excessive electrolytic reaction.
本発明の製造方法によれば、例えば、カルボニル化合物を原料としてペルフルオロカルボニル化合物やペルフルオロジカルボニル化合物を簡単な製造工程によって収率よく製造することができ、また、スルホニル化合物を原料としてペルフルオロスルホニル化合物やペルフルオロジスルホニル化合物を簡単な製造工程によって収率よく製造することができる。 According to the production method of the present invention, for example, a perfluorocarbonyl compound or a perfluorodicarbonyl compound can be produced in a high yield by a simple production process using a carbonyl compound as a raw material, and a perfluorosulfonyl compound or A perfluorodisulfonyl compound can be produced with high yield by a simple production process.
以下、本発明の製造方法について具体的に説明する。
本発明の製造方法は、有機化合物の電解フッ素化において、電解槽に電解液と共にフッ素化不活性溶媒（単に不活性溶媒と云う場合がある）を共存させて有機化合物を電解フッ素化することを特徴とするペルフルオロ有機化合物の製造方法である。
Hereinafter, the production method of the present invention will be specifically described.
In the production method of the present invention, in the electrolytic fluorination of an organic compound, an electrolytic fluorination of an organic compound is carried out in the presence of a fluorinated inert solvent (sometimes referred to simply as an inert solvent) together with an electrolytic solution in an electrolytic cell. It is a manufacturing method of the perfluoro organic compound characterized.
本発明の製造方法の基本となる特願２００５−１４３９５５号の方法は、スルトン化合物の電解フッ素化によってペルフルオロカルボニルスルホニル化合物を製造する方法であるが、本発明の製造方法はスルトン化合物を原料とする場合に限らず、生成物としてペルフルオロカルボニルスルホニル化合物に限定されない製造方法である。なお、上記基本方法に基づく他の製造方法との相違を明確にするため、本発明の製造方法はスルトン化合物を原料とし、その電解フッ素化によってペルフルオロカルボニルスルホニル化合物を製造する方法を除いたものである。 The method of Japanese Patent Application No. 2005-143955, which is the basis of the production method of the present invention, is a method of producing a perfluorocarbonylsulfonyl compound by electrolytic fluorination of a sultone compound. The production method of the present invention uses a sultone compound as a raw material. The production method is not limited to a perfluorocarbonylsulfonyl compound as a product. In order to clarify the difference from other production methods based on the above basic method, the production method of the present invention excludes a method of producing a perfluorocarbonylsulfonyl compound by electrolytic fluorination using a sultone compound as a raw material. is there.
本発明の製造方法の対象となる化合物は、通常の電解フッ素化反応により合成される化合物であれば特に限定されないが、生成するペルフルオロ化合物のフッ酸に対する溶解度が１０％以上である場合に特に効果的である。一般に電解液中のペルフルオロ有機化合物の濃度が高くなると電解電圧が上昇しやすく、反応の継続が困難になったり、生成物の分解を生じるため、収率が低下するが、本発明の製造方法においては、生成したペルフルオロ化合物が不活性溶媒に効率よく抽出されるので、電解液であるフッ酸に対する溶解度が１０％以上のペルフルオロ化合物についても高い収率で製造することができる。 The compound that is the subject of the production method of the present invention is not particularly limited as long as it is a compound synthesized by a normal electrolytic fluorination reaction, but is particularly effective when the solubility of the resulting perfluoro compound in hydrofluoric acid is 10% or more. Is. In general, when the concentration of the perfluoro organic compound in the electrolytic solution increases, the electrolytic voltage tends to increase, and the continuation of the reaction becomes difficult or the product is decomposed, resulting in a decrease in yield. Since the produced perfluoro compound is efficiently extracted into an inert solvent, a perfluoro compound having a solubility in hydrofluoric acid as an electrolyte of 10% or more can be produced in a high yield.
電解液に対する溶解度が１０％以上であるペルフルオロ有機化合物の例として、下記一般式(４)（式中、ｎは１〜６の整数）で表されるペルフルオロジカルボニル化合物や、下記一般式(８)（式中、ｎは１〜４の整数）で表されるペルフルオロジスルホニル化合物等が挙げられる。
ＦＣＯ（ＣＦ2）nＣＯＦ （４）
ＦＳＯ2（ＣＦ2）nＳＯ2Ｆ （８）
Examples of perfluoro organic compounds having a solubility in an electrolytic solution of 10% or more include perfluorodicarbonyl compounds represented by the following general formula (4) (where n is an integer of 1 to 6), and the following general formula (8 ) (Wherein n is an integer of 1 to 4), and the like.
FCO (CF 2 ) n COF (4)
FSO 2 (CF 2 ) n SO 2 F (8)
また、本発明の製造方法の対象となる化合物は、生成されるペルフルオロ有機化合物の沸点が１２０℃以下である場合にも特に効果的である。生成物であるペルフルオロ有機化合物の沸点が低い場合は、通常の電解フッ素化では、気化した生成物が副生ガスあるいはキャリアガスに同伴されて損失になりやすいが、本発明の製造方法では、生成物を不活性溶媒に連続的に抽出することによって、ガスに同伴される損失を防ぐことができる。 Moreover, the compound used as the object of the production method of the present invention is particularly effective even when the generated perfluoro organic compound has a boiling point of 120 ° C. or lower. When the boiling point of the product perfluoro organic compound is low, the vaporized product tends to be lost due to the by-product gas or carrier gas in normal electrolytic fluorination, but in the production method of the present invention, By continuously extracting the product into an inert solvent, loss associated with the gas can be prevented.
沸点が１２０℃以下であるペルフルオロ有機化合物の例として、下記一般式(６)（式中、ｎは１〜７の整数）で表されるペルフルオロアルキルカルボニル化合物や、下記一般式(１０)（式中、ｎは１〜６の整数）で表されるペルフルオロアルキルスルホニル化合物等が挙げられる。
ＣnＦ2n+1ＣＯＦ （６）
ＣnＦ2n+1ＳＯ2Ｆ （１０）
Examples of perfluoro organic compounds having a boiling point of 120 ° C. or lower include perfluoroalkylcarbonyl compounds represented by the following general formula (6) (where n is an integer of 1 to 7), and the following general formula (10) (formula And n is an integer of 1 to 6).
C n F 2n + 1 COF (6)
C n F 2n + 1 SO 2 F (10)
さらに、本発明の製造方法は、生成物中の残存プロトン濃度を低くすることができる。これは、本発明の製造方法では、フッ素化不活性溶媒を電解槽中で電解液と共存させるため、中間体として生成する不完全フッ素化物がフッ素化不活性溶媒に抽出されても、これが分配平衡によってフッ素化不活性溶媒から電解液側に移動され、再び電解液中でフッ素化反応が進むので完全フッ素化物の割合を高めることができるものと推定される。 Furthermore, the production method of the present invention can reduce the residual proton concentration in the product. In the production method of the present invention, since the fluorinated inert solvent coexists with the electrolytic solution in the electrolytic cell, even if the incomplete fluorinated product generated as an intermediate is extracted into the fluorinated inert solvent, it is distributed. It is presumed that the ratio of the completely fluorinated product can be increased because the fluorination inert solvent moves from the fluorinated inert solvent to the electrolyte side by equilibrium and the fluorination reaction proceeds again in the electrolyte.
ここで、残存プロトン濃度とは、有機化合物中のプロトン(水素)の重量濃度を示す値であり、内部標準物質を用いてペルフルオロ有機化合物の核磁気共鳴分析（1Ｈ−ＮＭＲ）を行うことによって測定できる。具体的には、本発明の製造方法によれば、残存プロトン濃度が１０００ppm以下であるフッ素化率の高いペルフルオロ有機化合物を製造することができる。 Here, the residual proton concentration is a value indicating the weight concentration of proton (hydrogen) in the organic compound, and by performing a nuclear magnetic resonance analysis ( 1 H-NMR) of the perfluoroorganic compound using an internal standard substance. It can be measured. Specifically, according to the production method of the present invention, it is possible to produce a perfluoro organic compound having a high fluorination rate with a residual proton concentration of 1000 ppm or less.
本発明の製造方法は、電解槽に電解液と共にフッ素化不活性溶媒を共存させて電解フッ素化を行う方法である。このフッ素化不活性溶媒とは、電解フッ素化条件下において実質的に分解または変性を起こさないフッ素化化合物であって、電解フッ素化条件下で、電解液の無水フッ酸とは異なる相を形成する液状化合物である。 The production method of the present invention is a method of performing electrolytic fluorination in the presence of a fluorinated inert solvent together with an electrolytic solution in an electrolytic cell. This fluorinated inert solvent is a fluorinated compound that does not substantially decompose or denature under electrolytic fluorination conditions, and forms a phase different from anhydrous hydrofluoric acid in the electrolytic solution under electrolytic fluorination conditions. Liquid compound.
フッ素化不活性溶媒は生成したペルフルオロ有機化合物の抽出溶媒としての作用を有するので、生成したペルフルオロ有機化合物に対して相溶性を有し、かつ電解液と分離して回収できるように、電解液の無水フッ酸よりもやや比重の大きいものが用いられる。このフッ素化不活性溶媒は、１種類の化合物でもよく、２種類以上の混合物でもよい。混合物の場合は混合物として液体状であればよい。 Since the fluorinated inert solvent has an action as an extraction solvent for the produced perfluoro organic compound, the fluorinated inert solvent is compatible with the produced perfluoro organic compound and is separated from the electrolyte so that it can be recovered separately. Those having a specific gravity slightly higher than that of anhydrous hydrofluoric acid are used. This fluorinated inert solvent may be one kind of compound or a mixture of two or more kinds. In the case of a mixture, the mixture may be liquid.
フッ素化不活性溶媒は電解液である無水フッ酸に対する溶解度が小さいほうが好ましい。具体的には、０℃における無水フッ酸への飽和溶解度が２０質量％以下であることが好ましく、１０質量％以下がより好ましく、５質量％以下が特に好ましい。また、フッ素化不活性溶媒と無水フッ酸との２相系において、生成物の分配係数がフッ素化不活性溶媒側で大きいことが好ましい。 The fluorinated inert solvent preferably has a low solubility in anhydrous hydrofluoric acid, which is an electrolytic solution. Specifically, the saturated solubility in anhydrous hydrofluoric acid at 0 ° C. is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Further, in a two-phase system of a fluorinated inert solvent and hydrofluoric anhydride, it is preferable that the distribution coefficient of the product is large on the fluorinated inert solvent side.
また、フッ素化不活性溶媒の沸点としては、幅広い沸点の溶媒が使用可能であるが、操作の容易性から、沸点の範囲としては、大気圧下での沸点が３０℃〜２５０℃の範囲が好ましく、５０℃〜２００℃の範囲がより好ましい。なお、生成物との蒸留分離が容易な溶媒が特に好ましく、生成物との沸点差が３℃以上、あるいは５℃以上、さらには１０℃以上である溶媒が特に好ましい。 Moreover, as the boiling point of the fluorinated inert solvent, a wide range of boiling point solvents can be used, but from the viewpoint of ease of operation, the boiling point range is from 30 ° C. to 250 ° C. in terms of boiling point under atmospheric pressure. Preferably, the range of 50 ° C to 200 ° C is more preferable. A solvent that can be easily separated from the product by distillation is particularly preferable, and a solvent having a boiling point difference from the product of 3 ° C. or higher, 5 ° C. or higher, and further 10 ° C. or higher is particularly preferable.
以上のような特性を示すフッ素化不活性溶媒としては、例えばペルフルオロ炭化水素化合物が挙げられ、分子内に酸素や窒素等のヘテロ原子が含まれていてもよく、フッ素原子の一部が塩素原子や水素原子で置換されていてもよい。 Examples of the fluorinated inert solvent exhibiting the above characteristics include perfluorohydrocarbon compounds, and the molecule may contain heteroatoms such as oxygen and nitrogen, and a part of the fluorine atoms are chlorine atoms. Or a hydrogen atom.
本発明で用いられるフッ素化不活性溶媒の例としては、以下の化合物が挙げられる。
（Ａ）ペルフルオロヘキサン、ペルフルオロシクロヘキサン、ペルフルオロクタン、ペルフルオロデカン等のペルフルオロアルカン類
（Ｂ）ペルフルオロトリブチルアミン等のペルフルオロアミン類
（Ｃ）ペルフルオロブチルテトラヒドロフランやペルフルオロポリエーテル（例えば、ガルデン：ソルベイソレクシス社製品の登録商標名）等のペルフルオロエーテル類等
（Ｄ）上記化合物の部分塩素置換体（例えば、フッ素原子の１〜３個が塩素原子で置換されたもの）
（Ｅ）上記化合物の部分水素原子置換体（例えば、フッ素原子の１〜３個が水素原子で置換されたもの）
Examples of the fluorinated inert solvent used in the present invention include the following compounds.
(A) Perfluoroalkanes such as perfluorohexane, perfluorocyclohexane, perfluorooctane, and perfluorodecane (B) Perfluoroamines such as perfluorotributylamine (C) Perfluorobutyltetrahydrofuran and perfluoropolyethers (for example, Galden: Solvay Solexis products) (D) Partially chlorine-substituted products of the above compounds (for example, those in which 1 to 3 fluorine atoms are substituted with chlorine atoms)
(E) Partial hydrogen atom substitution product of the above compound (for example, one in which 1 to 3 fluorine atoms are substituted with hydrogen atoms)
本発明の製造方法において、フッ素化不活性溶媒は、電解フッ素化中、電解槽中に無水フッ酸と２層分離した状態で存在していればよいが、機械的撹拌や窒素バブリング等により系内で撹拌されていることが好ましい。さらには、電解液層の電極が設置されている電解フッ素化反応ゾーンにフッ素化不活性溶媒を循環することが特に好ましい。 In the production method of the present invention, the fluorinated inert solvent may be present in an electrolytic bath in a state separated from anhydrous hydrofluoric acid in two layers during electrolytic fluorination. It is preferable that it is stirred inside. Furthermore, it is particularly preferable to circulate a fluorinated inert solvent in the electrolytic fluorination reaction zone in which the electrode of the electrolyte layer is installed.
具体的には、電解槽から抜き出したフッ素化不活性溶媒層を、ポンプを用いて電解槽に戻してやればよい。一般に、フッ素化不活性溶媒層は電解液の無水フッ酸層より下側にあるので、抜き出したフッ素化不活性溶媒を電解槽上部から導入することによって、無水フッ酸層を通過させればよい。さらに、好ましくは、抜き出したフッ素化不活性溶媒を、電解液層の電極間または電極近傍に、電解液層上側からを供給するとよい。なお、電解槽から抜き出したフッ素化不活性溶媒は、生成物を蒸留分離したものを電解槽に戻してもよい。 Specifically, the fluorinated inert solvent layer extracted from the electrolytic cell may be returned to the electrolytic cell using a pump. Generally, since the fluorinated inert solvent layer is below the anhydrous hydrofluoric acid layer of the electrolyte, it is only necessary to pass the anhydrous hydrofluoric acid layer by introducing the extracted fluorinated inert solvent from the upper part of the electrolytic cell. . Further, preferably, the extracted fluorinated inert solvent is supplied from the upper side of the electrolyte layer between or near the electrodes of the electrolyte layer. The fluorinated inert solvent extracted from the electrolytic cell may be returned to the electrolytic cell by distilling and separating the product.
本発明の製造方法における電解フッ素化は、一般的な条件下で行うことができ、特には制限されない。すなわち、電解槽としては、ニッケルまたはニッケル合金の陽極および陰極を備えた、鉄、ステンレス、モネル等の金属製もしくはフッ素樹脂等の角型や円筒型等の通常の電解槽を用いることができる。また、電解フッ素化は、通常のように原料の有機化合物を無水フッ酸に溶解または分散させ、この溶液に通電することによって行われる。無水フッ酸中の原料の濃度は０.５〜８０質量％が好ましく、特に1〜４０質量％の範囲が好ましい。この電解フッ素化はバッチ方式で行ってもよく、または原料を連続的もしくは間欠的に投入しながら行ってもよい。反応中、必要があれば無水フッ酸を補充してもよい。 The electrolytic fluorination in the production method of the present invention can be performed under general conditions and is not particularly limited. That is, as an electrolytic cell, a normal electrolytic cell made of metal such as iron, stainless steel, monel, or a square or cylindrical type made of fluororesin, having an anode and a cathode of nickel or a nickel alloy can be used. In addition, electrolytic fluorination is performed by dissolving or dispersing a raw material organic compound in anhydrous hydrofluoric acid as usual and energizing this solution. The concentration of the raw material in hydrofluoric anhydride is preferably 0.5 to 80% by mass, and particularly preferably 1 to 40% by mass. This electrolytic fluorination may be performed in a batch system, or may be performed while continuously or intermittently adding raw materials. During the reaction, if necessary, anhydrous hydrofluoric acid may be supplemented.
電解温度は−２０〜＋４０℃が好ましく、−１０〜＋２０℃がさらに好ましい。電解温度が低過ぎると電圧が上昇したり副反応が増加する傾向があり、一方、電解温度が高過ぎると無水フッ酸の損失量が多くなり好ましくない。反応液を冷却する場合、外部に冷却槽を設けて循環して行ってもよいし、電解槽の内部もしくは外部から冷却を行ってもよい。 The electrolysis temperature is preferably -20 to + 40 ° C, more preferably -10 to + 20 ° C. If the electrolysis temperature is too low, the voltage tends to increase or the side reaction tends to increase. On the other hand, if the electrolysis temperature is too high, the loss of hydrofluoric anhydride is undesirably increased. When cooling the reaction solution, a cooling bath may be provided outside and circulated, or cooling may be performed from inside or outside the electrolytic bath.
電流密度は０.０１〜２０Ａ/ｄm2が好ましく、０.１〜１０Ａ/ｄm2がさらに好ましい。電流密度がこれより低いと製造効率が低くなり、高くなると原料や生成物の分解を生じやすい。 The current density is preferably 0.01~20A / dm 2, more preferably 0.1 to 10 A / dm 2. If the current density is lower than this, the production efficiency is lowered, and if it is higher, the raw materials and products are likely to be decomposed.
〔製造例１〕
本発明の製造方法によって、下記一般式(１)（式中、ｎは３〜６の整数）で表されるカルボニル化合物を電解フッ素化して、下記一般式(２)（式中、ｎは一般式(1)と同じ）で表されるペルフルオロジカルボニル化合物を製造することができる。
According to the production method of the present invention, a carbonyl compound represented by the following general formula (1) (where n is an integer of 3 to 6) is electrolytically fluorinated, and the following general formula (2) (where n is a general formula) A perfluorodicarbonyl compound represented by the same formula (1) can be produced.
〔製造例２〕
本発明の製造方法によって、下記一般式(３)（式中、ｎは１〜６の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるジカルボニル化合物を電解フッ素化して、下記一般式(４)（式中、ｎは一般式(3)と同じ）で表されるペルフルオロジカルボニル化合物を製造することができる。
ＸＣＯ（ＣＨ2）nＣＯＸ （３）
ＦＣＯ（ＣＦ2）nＣＯＦ （４）
[Production Example 2]
According to the production method of the present invention, a dicarbonyl compound represented by the following general formula (3) (wherein n is an integer of 1 to 6, X is F, Cl or OH) is subjected to electrolytic fluorination, and the following general formula ( 4) A perfluorodicarbonyl compound represented by the formula (wherein n is the same as in formula (3)) can be produced.
XCO (CH 2 ) n COX (3)
FCO (CF 2 ) n COF (4)
〔製造例３〕
本発明の製造方法によって、下記一般式(５)（式中、ｎは１〜７の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるアルキルカルボニル化合物を電解フッ素化して、下記一般式(６)（式中、ｎは一般式(5)と同じ）で表されるペルフルオロアルキルカルボニル化合物を製造することができる。
ＣnＨ2n+1ＣＯＸ （５）
ＣnＦ2n+1ＣＯＦ （６）
[Production Example 3]
According to the production method of the present invention, an alkylcarbonyl compound represented by the following general formula (5) (wherein n is an integer of 1 to 7, X is F, Cl or OH) is electrolytic fluorinated, and the following general formula ( 6) A perfluoroalkylcarbonyl compound represented by the formula (wherein n is the same as in formula (5)) can be produced.
C n H 2n + 1 COX (5)
C n F 2n + 1 COF (6)
〔製造例４〕
本発明の製造方法によって、下記一般式(７)（式中、ｎは１〜４の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるジスルホニル化合物を電解フッ素化して、下記一般式(８)（式中、ｎは一般式(7)と同じ）で表されるペルフルオロジスルホニル化合物を製造することができる。
ＸＳＯ2（ＣＨ2）nＳＯ2Ｘ （７）
ＦＳＯ2（ＣＦ2）nＳＯ2Ｆ （８）
[Production Example 4]
According to the production method of the present invention, a disulfonyl compound represented by the following general formula (7) (wherein n is an integer of 1 to 4 and X is F, Cl or OH) is subjected to electrolytic fluorination, and the following general formula ( 8) A perfluorodisulfonyl compound represented by the formula (wherein n is the same as in formula (7)) can be produced.
XSO 2 (CH 2 ) n SO 2 X (7)
FSO 2 (CF 2 ) n SO 2 F (8)
〔製造例５〕
本発明の製造方法によって、下記一般式(９)（式中、ｎは１〜６の整数、ＸはＦ、ＣｌまたはＯＨ）で表されるアルキルスルホニル化合物を電解フッ素化して、下記一般式(１０)（式中、ｎは一般式(9)と同じ）で表されるペルフルオロアルキルスルホニル化合物を製造することができる。
ＣnＨ2n+1ＳＯ2Ｘ （９）
ＣnＦ2n+1ＳＯ2Ｆ （１０）
[Production Example 5]
According to the production method of the present invention, an alkylsulfonyl compound represented by the following general formula (9) (wherein n is an integer of 1 to 6 and X is F, Cl or OH) is subjected to electrolytic fluorination, and the following general formula ( 10) A perfluoroalkylsulfonyl compound represented by the formula (wherein n is the same as in formula (9)) can be produced.
C n H 2n + 1 SO 2 X (9)
C n F 2n + 1 SO 2 F (10)
〔製造例６〕
本発明の製造方法によって、下記化学式(１１)で表されるスルホニル化合物（スルホラン）を電解フッ素化して、下記化学式(１２)で表されるペルフルオロスルホニル化合物を製造することができる。
[Production Example 6]
The perfluorosulfonyl compound represented by the following chemical formula (12) can be produced by electrolytic fluorination of the sulfonyl compound (sulfolane) represented by the following chemical formula (11) by the production method of the present invention.
以下、本発明の実施例を比較例と共に示す。また、実施例と比較例の結果を表１に示す。 Examples of the present invention are shown below together with comparative examples. Table 1 shows the results of Examples and Comparative Examples.
［実施例１］
−５５℃の還流冷却器を備えた容量１５００mlの鉄製電解槽にニッケル製の電極（陽極９枚、陰極１０枚、極板総面積１．９７ｄm2/枚）を極板間隔４ｍｍで取り付け、この電解槽に無水フッ酸９００ｇ、１−プロパンスルホニルフロライド４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を５〜１０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出し、電解槽上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１３３７Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して８８０ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のペルフルオロ−１−プロパンスルホニルフロライドのＧＣによる純度は９８％であり、１Ｈ−ＮＭＲによるプロトン濃度は１８５ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留してペルフルオロ−１−プロパンスルホニルフロライド４５５ｇを得た。原料１−プロパンスルホニルフロライドに対する収率は５０％であった。
[Example 1]
Nickel electrodes (9 anodes, 10 cathodes, total area of electrode plates 1.97 dm 2 / sheet) were attached to an iron electrolytic cell with a capacity of 1500 ml equipped with a reflux condenser at −55 ° C., with an electrode plate interval of 4 mm. Supply 900 g of anhydrous hydrofluoric acid and 450 g of 1-propanesulfonyl fluoride to the electrolytic cell, add 380 g of perfluorotributylamine and keep the temperature at 5 to 10 ° C., and remove the perfluorotributylamine from the lower part of the electrolytic cell with a pump. Circulation was performed at a flow rate of 500 ml / min so as to return to the upper part of the tank.
The electrolysis was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 1337 Ahr (theoretical energization amount) was energized. The lower layer was extracted from the bottom of the electrolytic cell to recover 880 g of a perfluorotributylamine layer. The purity of the perfluoro-1-propanesulfonyl fluoride of the product extracted in the perfluorotributylamine layer was 98% by GC, and the proton concentration by 1H-NMR was 185 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer, the dissolved anhydrous hydrofluoric acid is removed, sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain perfluoro-1-propanesulfonyl fluoride. 455 g was obtained. The yield based on the raw material 1-propanesulfonyl fluoride was 50%.
［実施例２］
実施例１と同様の装置を使用し、無水フッ酸９００ｇ、スルホラン４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を５〜１０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出し、電解槽上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１８０９Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して９５０ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のペルフルオロ−１−ブタンスルホニルフロライドのＧＣによる純度は９５％であり、１Ｈ−ＮＭＲによるプロトン濃度は３７６ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留してペルフルオロ−１−ブタンスルホニルフロライド５０８ｇを得た。原料スルホランに対する収率は４５％であった。
[Example 2]
Using the same apparatus as in Example 1, 900 g of anhydrous hydrofluoric acid and 450 g of sulfolane were supplied, and further 380 g of perfluorotributylamine was added, and while maintaining the temperature at 5 to 10 ° C., perfluorotributylamine was pumped from the bottom of the electrolytic cell. The sample was extracted and circulated at a flow rate of 500 ml / min so as to return to the upper part of the electrolytic cell.
The electrolytic reaction was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 1809 Ahr (theoretical required amount of electricity) was applied. The lower layer was extracted from the bottom of the electrolytic cell to recover a 950 g perfluorotributylamine layer. The purity of perfluoro-1-butanesulfonyl fluoride of the product extracted into the perfluorotributylamine layer was 95% by GC, and the proton concentration by 1H-NMR was 376 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer, the dissolved anhydrous hydrofluoric acid is removed, sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain perfluoro-1-butanesulfonyl fluoride. 508 g was obtained. The yield based on the raw material sulfolane was 45%.
［実施例３］
実施例１と同様の装置を使用し、無水フッ酸９００ｇ、１−ヘキサンスルホニルフロライド４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を５〜１０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出して電解槽上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１８６８Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して９３７ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のペルフルオロ−１−ヘキサンスルホニルフロライドのＧＣによる純度は９５％であり、１Ｈ−ＮＭＲによるプロトン濃度は４３１ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留してペルフルオロ−１−ヘキサンスルホニルフロライド５１７ｇを得た。原料１−ヘキサンスルホニルフロライドに対する収率は４８％であった。
[Example 3]
Using the same apparatus as in Example 1, 900 g of hydrofluoric acid and 450 g of 1-hexanesulfonyl fluoride were supplied, and 380 g of perfluorotributylamine was further added, and the perfluorotributylamine was pumped while maintaining the temperature at 5 to 10 ° C. Was extracted from the lower part of the electrolytic cell and circulated at a flow rate of 500 ml / min so as to return to the upper part of the electrolytic cell.
The electrolytic reaction was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 1868 Ahr (theoretical required energization amount) was energized. The lower layer was extracted from the bottom of the electrolytic cell to recover 937 g of a perfluorotributylamine layer. The purity of perfluoro-1-hexanesulfonyl fluoride of the product extracted into the perfluorotributylamine layer was 95% by GC, and the proton concentration by 1H-NMR was 431 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer, the dissolved anhydrous hydrofluoric acid is removed, the sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain perfluoro-1-hexanesulfonyl fluoride. 517 g was obtained. The yield based on the raw material 1-hexanesulfonyl fluoride was 48%.
［実施例４］
実施例１と同様の装置を使用し、無水フッ酸９００ｇ、１，３−プロパンビススルホニルフロライド４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を５〜１０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出して電解槽上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、６９８Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して８２６ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物の１，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ビススルホニルフロライドのＧＣによる純度は９６％であり、１Ｈ−ＮＭＲによるプロトン濃度は２８６ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留して、１，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ビススルホニルフロライド４１６ｇを得た。原料１，３−プロパンビススルホニルフロライドに対する収率は６１％であった。
[Example 4]
Using the same apparatus as in Example 1, 900 g of hydrofluoric acid and 450 g of 1,3-propanebissulfonyl fluoride were supplied, and further 380 g of perfluorotributylamine was added, and the temperature was maintained at 5 to 10 ° C. with a pump. Perfluorotributylamine was circulated at a flow rate of 500 ml / min so as to extract from the lower part of the electrolytic cell and return to the upper part of the electrolytic cell.
The electrolysis reaction was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 698 Ahr (theoretical energization amount) was energized. The lower layer was extracted from the bottom of the electrolytic cell to recover 826 g of a perfluorotributylamine layer. The purity of 1,1,2,2,3,3-hexafluoropropane-1,3-bissulfonyl fluoride of the product extracted in the perfluorotributylamine layer by GC is 96%, and the proton by 1H-NMR The concentration was 286 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer, dissolved anhydrous hydrofluoric acid is removed, sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain 1,1,2,2 , 3,3-hexafluoropropane-1,3-bissulfonyl fluoride 416 g was obtained. The yield based on the raw material 1,3-propanebissulfonyl fluoride was 61%.
［実施例５］
実施例１と同様の装置を使用し、無水フッ酸９００ｇ、ε−カプロラクトン４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を５〜１０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出して電解槽の上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、２１１５Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して１０６５ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のペルフルオロブタン−１，４−ジカルボニルフロライドのＧＣによる純度は２５％であり、１Ｈ−ＮＭＲによるプロトン濃度は７７ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留して電解生成物５４８ｇを得た。この電解生成物のペルフルオロブタン−１，４−ジカルボニルフロライドの純度は３０％であった。原料ε−カプロラクトンに対する収率は１４％であった。
[Example 5]
Using the same apparatus as in Example 1, 900 g of hydrofluoric acid and 450 g of ε-caprolactone were supplied, and further 380 g of perfluorotributylamine was added, and while maintaining the temperature at 5 to 10 ° C., perfluorotributylamine was electrolyzed with a pump. It was circulated at a flow rate of 500 ml / min so as to be extracted from the lower part and returned to the upper part of the electrolytic cell.
The electrolytic reaction was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 2115 Ahr (theoretical required amount of electricity) was applied. The lower layer was extracted from the bottom of the electrolytic cell to recover 1065 g of a perfluorotributylamine layer. The purity of perfluorobutane-1,4-dicarbonyl fluoride of the product extracted into the perfluorotributylamine layer by GC was 25%, and the proton concentration by 1H-NMR was 77 ppm.
Sodium fluoride 30 g was added to the perfluorotributylamine layer to remove dissolved hydrofluoric acid, sodium fluoride was filtered off, and the filtrate was subjected to atmospheric distillation to obtain 548 g of an electrolytic product. The purity of perfluorobutane-1,4-dicarbonyl fluoride of this electrolytic product was 30%. The yield based on the raw material ε-caprolactone was 14%.
［実施例６］
実施例１と同様の装置を使用し、無水フッ酸９００ｇ、ｎ−酪酸４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を−５〜０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出して電解槽上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、２４６６Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して８２２ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のｎ−ヘプタフルオロブチリルフロライドのＧＣによる純度は９６％であり、１Ｈ−ＮＭＲによるプロトン濃度は４４４ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留してｎ−ヘプタフルオロブチリルフロライド（ｂｐ.０℃）４０１ｇを得た。原料ｎ−酪酸に対する収率は３６％であった。
[Example 6]
Using the same apparatus as in Example 1, 900 g of hydrofluoric acid and 450 g of n-butyric acid were supplied, and 380 g of perfluorotributylamine was further added, and perfluorotributylamine was electrolyzed with a pump while keeping the temperature at -5 to 0 ° C. It was circulated at a flow rate of 500 ml / min so as to be extracted from the lower part of the tank and returned to the upper part of the electrolytic cell.
The electrolysis was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 2466 Ahr (theoretical energization amount) was energized. The lower layer was extracted from the bottom of the electrolytic cell to recover 822 g of perfluorotributylamine layer. The purity of n-heptafluorobutyryl fluoride of the product extracted into the perfluorotributylamine layer was 96% by GC, and the proton concentration by 1H-NMR was 444 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer, the dissolved anhydrous hydrofluoric acid is removed, sodium fluoride is filtered off, and the filtrate is subjected to atmospheric distillation to give n-heptafluorobutyryl fluoride. 401 g (bp. 0 ° C.) was obtained. The yield based on the raw material n-butyric acid was 36%.
［実施例７］
実施例１と同様の装置を使用し、無水フッ酸９００ｇ、アジピン酸クロライド４５０ｇを供給し、さらにペルフルオロトリブチルアミン３８０ｇを加え、温度を５〜１０℃に保ちながら、ポンプでペルフルオロトリブチルアミンを電解槽下部から抜き出して電解槽上部に戻るよう、５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１０５３Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して１００６ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のペルフルオロブタン−１，４−ジカルボニルフロライドのＧＣによる純度は２４％であり、１Ｈ−ＮＭＲによるプロトン濃度は９０ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留して電解生成物４８１ｇを得た。この電解生成物のペルフルオロブタン−１，４−ジカルボニルフロライドの純度は３０％であった。原料アジピン酸クロライドに対する収率は２０％であった。
[Example 7]
Using the same apparatus as in Example 1, 900 g of anhydrous hydrofluoric acid and 450 g of adipic acid chloride were supplied, and further 380 g of perfluorotributylamine was added, and while maintaining the temperature at 5 to 10 ° C., perfluorotributylamine was electrolyzed with a pump. It was circulated at a flow rate of 500 ml / min so as to be extracted from the lower part and returned to the upper part of the electrolytic cell.
The electrolytic reaction was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 1053 Ahr (theoretical required energization amount) was applied. The lower layer was extracted from the bottom of the electrolytic cell to recover 1006 g of a perfluorotributylamine layer. The purity of the perfluorobutane-1,4-dicarbonyl fluoride of the product extracted into the perfluorotributylamine layer by GC was 24%, and the proton concentration by 1H-NMR was 90 ppm.
Sodium fluoride 30 g was added to the perfluorotributylamine layer to remove dissolved hydrofluoric acid, sodium fluoride was filtered off, and the filtrate was subjected to atmospheric distillation to obtain 481 g of an electrolytic product. The purity of perfluorobutane-1,4-dicarbonyl fluoride of this electrolytic product was 30%. The yield based on the raw material adipic acid chloride was 20%.
［比較例１］
実施例１と同様の装置を使用し、無水フッ酸１１００ｇ、１−プロパンスルホニルフロライド４５０ｇを供給した後、ペルフルオロトリブチルアミンを加えずに、電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１３３７Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出して３０５ｇの粗生成物を回収した。粗生成物中のペルフルオロ−１−プロパンスルホニルフロライドのＧＣによる純度は９６％であり、１Ｈ−ＮＭＲによるプロトン濃度は２００ppmであった。
上記で得た粗生成物にフッ化ナトリウム１５ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留して、ペルフルオロ−１−プロパンスルホニルフロライド２６５ｇを得た。原料１−プロパンスルホニルフロライドに対する収率は２９％であった。
[Comparative Example 1]
Using the same apparatus as in Example 1, 1100 g of hydrofluoric acid and 450 g of 1-propanesulfonyl fluoride were supplied, and then no current value was 26.6 A (current density 1.5 A / dm 2) without adding perfluorotributylamine. The electrolytic reaction was performed at a constant current of 1), and the electrolysis was stopped when 1337 Ahr (theoretical required amount of electricity) was applied. The lower layer was extracted from the bottom of the electrolytic cell to recover 305 g of a crude product. The purity by GC of perfluoro-1-propanesulfonyl fluoride in the crude product was 96%, and the proton concentration by 1H-NMR was 200 ppm.
To the crude product obtained above, 15 g of sodium fluoride is added, the dissolved hydrofluoric acid is removed, sodium fluoride is removed by filtration, and the filtrate is distilled at atmospheric pressure to obtain perfluoro-1-propane. 265 g of sulfonyl fluoride was obtained. The yield based on the raw material 1-propanesulfonyl fluoride was 29%.
［比較例２］
実施例１と同様の装置を使用し、無水フッ酸１１００ｇ、スルホラン４５０ｇを供給した後、ペルフルオロトリブチルアミンを加えずに、電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１８０９Ahr（理論必要通電量）通電した時点で電解を停止した。電解槽の底部から下層を抜き出したところ３２８ｇの粗生成物を回収した。粗生成物中のペルフルオロ−１−ブタンスルホニルフロライドのＧＣによる純度は９５％であり、１Ｈ−ＮＭＲによるプロトン濃度は３９９ppmであった。
上記粗生成物にフッ化ナトリウム１５ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留してペルフルオロ−１−ブタンスルホニルフロライド３０６ｇを得た。原料スルホランに対する収率は２７％であった。
[Comparative Example 2]
Using the same apparatus as in Example 1, after supplying 1100 g of hydrofluoric acid and 450 g of sulfolane, without adding perfluorotributylamine, at a constant current of 26.6 A (current density 1.5 A / dm 2 ). The electrolysis was carried out, and the electrolysis was stopped when 1809 Ahr (theoretical required energization amount) was energized. When the lower layer was extracted from the bottom of the electrolytic cell, 328 g of a crude product was recovered. The purity of perfluoro-1-butanesulfonyl fluoride in the crude product by GC was 95%, and the proton concentration by 1H-NMR was 399 ppm.
Sodium fluoride (15 g) is added to the above crude product to remove dissolved anhydrous hydrofluoric acid, sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain 306 g of perfluoro-1-butanesulfonyl fluoride. Got. The yield based on the raw material sulfolane was 27%.
［比較例３］
実施例１の電解槽に外部抽出手段として容量５００mlの鉄製受槽を付設した装置を用い、電解槽に無水フッ酸９００ｇ、１−プロパンスルホニルフロライド４５０ｇを供給し、一方、外部抽出手段の受槽にペルフルオロトリブチルアミン３８０ｇと無水フッ酸２００ｇを供給し、温度を５〜１０℃に保ちながら、ポンプで電解槽下部から受槽下部、受槽上部から電解槽上部へ電解槽にペルフルオロトリブチルアミンが混入しないように５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、１３３７Ahr（理論必要通電量）通電した時点で電解を停止した。受槽の底部から下層を抜き出して８５０ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物のペルフルオロ−１−プロパンスルホニルフロライドのＧＣによる純度は８０％であり、１Ｈ−ＮＭＲによるプロトン濃度は２０５０ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留して、ペルフルオロ−１−プロパンスルホニルフロライド３５０ｇを得た。原料１−プロパンスルホニルフロライドに対する収率は３９％であった。
[Comparative Example 3]
Using an apparatus provided with an iron receiving tank having a capacity of 500 ml as an external extraction means in the electrolytic cell of Example 1, 900 g of anhydrous hydrofluoric acid and 450 g of 1-propanesulfonyl fluoride were supplied to the electrolytic tank, while the external extraction means was used as a receiving tank. While supplying 380 g of perfluorotributylamine and 200 g of hydrofluoric acid and keeping the temperature at 5 to 10 ° C., prevent perfluorotributylamine from entering the electrolytic cell from the lower part of the electrolytic cell to the lower part of the electrolytic cell and from the upper part of the electrolytic cell to the upper part of the electrolytic cell with a pump. Circulation was performed at a flow rate of 500 ml / min.
The electrolysis was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 1337 Ahr (theoretical energization amount) was energized. The lower layer was extracted from the bottom of the receiving tank to recover 850 g of a perfluorotributylamine layer. The purity of the perfluoro-1-propanesulfonyl fluoride of the product extracted into the perfluorotributylamine layer was 80% by GC, and the proton concentration by 1H-NMR was 2050 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer to remove dissolved hydrofluoric acid, sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain perfluoro-1-propanesulfonyl fluoride. 350 g of ride was obtained. The yield based on the raw material 1-propanesulfonyl fluoride was 39%.
［比較例４］
比較例３と同様の装置を使用し、電解槽に無水フッ酸９００ｇ、１，３−プロパンビススルホニルフロライド４５０ｇを供給し、一方、外部抽出手段の受槽にペルフルオロトリブチルアミン３８０ｇと無水フッ酸２００ｇを供給し、温度を５〜１０℃に保ちながら、ポンプで電解槽下部から受槽下部、受槽上部から電解槽上部へ電解槽にペルフルオロトリブチルアミンが混入しないように５００ml/minの流量で循環した。
電流値２６.６Ａ（電流密度１.５Ａ/ｄm2）の定電流で電解反応を行い、６９８Ahr（理論必要通電量）通電した時点で電解を停止した。受槽の底部から下層を抜き出して８００ｇのペルフルオロトリブチルアミン層を回収した。ペルフルオロトリブチルアミン層に抽出された生成物の１，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ビススルホニルフロライドのＧＣによる純度は７５％であり、１Ｈ−ＮＭＲによるプロトン濃度は１８００ppmであった。
上記ペルフルオロトリブチルアミン層にフッ化ナトリウム３０ｇを投入して、溶解している無水フッ酸を除去し、フッ化ナトリウムを濾別し、この濾液を常圧蒸留して、１，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ビススルホニルフロライド２７３ｇを得た。原料１，３−プロパンビススルホニルフロライドに対する収率は４０％であった。
[Comparative Example 4]
Using the same apparatus as in Comparative Example 3, 900 g of anhydrous hydrofluoric acid and 450 g of 1,3-propanebissulfonyl fluoride were supplied to the electrolytic cell, while 380 g of perfluorotributylamine and 200 g of anhydrous hydrofluoric acid were received in the receiving tank of the external extraction means. While maintaining the temperature at 5 to 10 ° C., the pump was circulated at a flow rate of 500 ml / min from the lower part of the electrolytic cell to the lower part of the electrolytic cell and from the upper part of the electrolytic cell to the upper part of the electrolytic cell so as not to mix perfluorotributylamine.
The electrolysis reaction was carried out at a constant current of 26.6 A (current density 1.5 A / dm 2 ), and the electrolysis was stopped when 698 Ahr (theoretical energization amount) was energized. The lower layer was extracted from the bottom of the receiving tank to recover 800 g of a perfluorotributylamine layer. The purity of 1,1,2,2,3,3-hexafluoropropane-1,3-bissulfonyl fluoride of the product extracted in the perfluorotributylamine layer by GC is 75%, and the proton by 1H-NMR The concentration was 1800 ppm.
30 g of sodium fluoride is added to the perfluorotributylamine layer, dissolved anhydrous hydrofluoric acid is removed, sodium fluoride is filtered off, and the filtrate is distilled at atmospheric pressure to obtain 1,1,2,2 , 3,3-hexafluoropropane-1,3-bissulfonyl fluoride was obtained. The yield based on the raw material 1,3-propanebissulfonyl fluoride was 40%.
[実施例８、９]
フッ素化不活性溶媒としてペルフルオロアミンであるペルフルオロトリブチルアミンに代えて、ペルフルオロアルカンであるペルフルオロデカンを使用した他は実施例１と同様にして電解フッ素化を行った（実施例８）。また、フッ素化不活性溶媒としてペルフルオロエーテルであるガルデンＤシリーズ（ソルベイソレクシス社製品、登録商標名）を使用した他は実施例１と同様にして電解フッ素化を行った（実施例９）。これらの結果を表１に示した。
[Examples 8 and 9]
Electrofluorination was carried out in the same manner as in Example 1 except that perfluorodecane, which is a perfluoroalkane, was used instead of perfluorotributylamine, which is a perfluoroamine, as a fluorinated inert solvent (Example 8). Further, electrolytic fluorination was carried out in the same manner as in Example 1 except that Galden D series (product of Solvay Solexis, registered trademark), which is a perfluoroether, was used as a fluorinated inert solvent (Example 9). These results are shown in Table 1.
本発明の方法によれば、不完全フッ素化物の含有量が少ないペルフルオロ有機化合物を収率よく製造することができる。
According to the method of the present invention, a perfluoro organic compound having a low content of incomplete fluorinated compounds can be produced with high yield.
Claims (13)
In electrolytic fluorination of organic compounds, electrolytic fluorination of organic compounds in the electrolytic cell in the presence of a fluorinated inert solvent together with the electrolytic solution (excluding methods for producing perfluorocarbonylsulfonyl compounds by electrolytic fluorination of sultone compounds) The manufacturing method of the perfluoro organic compound characterized by these.
The production method according to claim 1, wherein the electrolytic fluorination is performed while circulating a fluorinated inert solvent in the reaction zone in the electrolytic cell.
In the electrolytic solution layer in the electrolytic cell and the fluorinated inert solvent layer below the electrolytic solution layer, the fluorinated inert solvent in the electrolytic cell is extracted and supplied to the electrolytic solution layer. The production method according to claim 2, wherein electrolytic fluorination is carried out by circulating an active solvent.
The manufacturing method according to claim 3, wherein the extracted fluorinated inert solvent is supplied from above the electrolyte layer between or near the electrodes of the electrolyte layer, and the fluorinated inert solvent is circulated in the electrolytic fluorination reaction zone. .
The manufacturing method according to any one of claims 1 to 4, wherein the perfluoroorganic compound to be produced has a solubility in hydrofluoric acid of 10% or more.
The manufacturing method according to claim 1, wherein the perfluoroorganic compound to be produced has a boiling point of 120 ° C. or lower.
The manufacturing method according to any one of claims 1 to 6, wherein a residual proton concentration in the generated perfluoro organic compound is 1000 ppm or less.
Electrolytic fluorination of a carbonyl compound represented by the following general formula (1) (where n is an integer of 3 to 6) gives the following general formula (2) (where n is the same as in general formula (1)) The manufacturing method in any one of Claims 1-7 which manufactures the perfluoro dicarbonyl compound represented by these.
ＸＣＯ（ＣＨ2）nＣＯＸ （３）
ＦＣＯ（ＣＦ2）nＣＯＦ （４）
A dicarbonyl compound represented by the following general formula (3) (where n is an integer of 1 to 6 and X is F, Cl or OH) is subjected to electrolytic fluorination to give the following general formula (4) (where n Is the same as the general formula (3)), the production method according to any one of claims 1 to 7, wherein the perfluorodicarbonyl compound represented by the general formula (3) is produced.
XCO (CH 2 ) n COX (3)
FCO (CF 2 ) n COF (4)
ＣnＨ2n+1ＣＯＸ （５）
ＣnＦ2n+1ＣＯＦ （６）
An alkylcarbonyl compound represented by the following general formula (5) (wherein n is an integer of 1 to 7, X is F, Cl or OH) is subjected to electrolytic fluorination to give the following general formula (6) (where n Is the same as the general formula (5)). The production method according to any one of claims 1 to 7, wherein a perfluoroalkylcarbonyl compound represented by the general formula (5) is produced.
C n H 2n + 1 COX (5)
C n F 2n + 1 COF (6)
ＸＳＯ2（ＣＨ2）nＳＯ2Ｘ （７）
ＦＳＯ2（ＣＦ2）nＳＯ2Ｆ （８）
A disulfonyl compound represented by the following general formula (7) (where n is an integer of 1 to 4 and X is F, Cl or OH) is subjected to electrolytic fluorination to give the following general formula (8) (where n Is the same as the general formula (7)). The production method according to any one of claims 1 to 7, wherein a perfluorodisulfonyl compound represented by the general formula (7) is produced.
XSO 2 (CH 2 ) n SO 2 X (7)
FSO 2 (CF 2 ) n SO 2 F (8)
ＣnＨ2n+1ＳＯ2Ｘ （９）
ＣnＦ2n+1ＳＯ2Ｆ （１０）
An alkylsulfonyl compound represented by the following general formula (9) (where n is an integer of 1 to 6 and X is F, Cl or OH) is subjected to electrolytic fluorination to give the following general formula (10) (where n Is the same as the general formula (9)). The production method according to any one of claims 1 to 7, wherein a perfluoroalkylsulfonyl compound represented by the general formula (9) is produced.
C n H 2n + 1 SO 2 X (9)
C n F 2n + 1 SO 2 F (10)
The production method according to any one of claims 1 to 7, wherein a perfluorosulfonyl compound represented by the following chemical formula (12) is produced by electrolytic fluorination of a sulfonyl compound (sulfolane) represented by the following chemical formula (11).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109750314A (en) * | 2018-12-29 | 2019-05-14 | 中船重工（邯郸）派瑞特种气体有限公司 | A kind of preparation method of the double acyl fluorides of perfluoroalkyl |
| WO2021141120A1 (en) * | 2020-01-08 | 2021-07-15 | ダイキン工業株式会社 | Method for producing fluorine-containing organic compound |
| CN114438526A (en) * | 2022-02-15 | 2022-05-06 | 万华化学集团股份有限公司 | Preparation method of epsilon-caprolactone |
| WO2023249374A1 (en) * | 2022-06-21 | 2023-12-28 | 에스케이스페셜티 주식회사 | Apparatus and method for producing pftpa by using electrochemical fluorination |
| CN119980267A (en) * | 2025-03-20 | 2025-05-13 | 国滢进出口(上海)有限公司 | A method for preparing 3-pentafluoroethyl-4-trifluoromethyl-dodecafluorohexane by electrolytic fluorination of hexafluoropropylene trimer |
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