WO2005073182A1 - Method for producing fluorine-containing unsaturated sulfonyl fluoride - Google Patents

Abstract

A method for producing a fluorine-containing unsaturated sulfonyl fluoride represented by the chemical formula: RfSO2F (wherein Rf is as defined below) is characterized in that a fluorine-containing unsaturated sulfonyl chloride represented by the chemical formula: RfSO2Cl (wherein Rf is a fluorine-containing hydrocarbon group having at least one unsaturated bond and may contain at least one element selected from oxygen, nitrogen and sulfur) is reacted with at least one fluorinating agent selected from alkylamine hydrofluoride, pyridine hydrofluoride and polyvinyl pyridine hydrofluoride. By this method, a fluorine-containing sulfonyl fluoride having an unsaturated bond can be commercially advantageously produced at low cost. Furthermore, this method enables to simply produce the fluorine-containing unsaturated sulfonyl fluoride with high selectivity and high yield.

Description

 Specification

 Process for producing fluorine-containing unsaturated sulfonyl fluoride

 Technical field

 The present invention relates to a method for producing a fluorinated unsaturated sulfonyl fluoride.

 Background art

 [0002] Among fluorine-containing sulfonyl fluorides having an unsaturated bond, for example, perfluorofluorosulfonylalkyl vinyl ether is a compound useful as an industrial raw material such as an ion exchange membrane material.

 [0003] As a method for producing perfluorofluorosulfonylalkylbierether, a method of reacting perfluorochlorosulfonylalkylvinylether with an alkali metal fluoride is known. For example, using NaF as a fluorinating agent, CF = CFOCF CF SO CI in a sulfolane solvent is reacted with NaF to obtain CF = CFOC

 2 2 2 2 2

 A method of using FCFSOF is known (Patent Document 1).

 2 2 2

 [0004] However, with this method, the desired sulfonyl fluoride cannot be obtained with a sufficiently high selectivity. Furthermore, since sulfolane having a low melting point and a high boiling point is used as a solvent, it is difficult to separate unreacted raw materials such as NaF and by-products such as NaCl. It becomes very complicated. Therefore, this method has a problem that it is difficult to implement industrially and a large amount of industrial waste is generated.

When a compound having a perfluoroalkyl group, for example, C F SO C1 is used as a raw material

 8 17 2

 Reports that fluorination with KF can provide C F SO F

 8 17 2

 (Patent Document 2). In this method, in order to obtain a fluorinated product in high yield, it is necessary to use sulfolane, formamide, or the like as a solvent. Even if it is fluorinated, the yield of CF SO F

 8 17 2

 Inadequate for industrial implementation.

 Patent Document 1: US Patent No. 3,560,568

 Patent Document 2: UK Patent No. 1,034,197

Disclosure of the invention Problems the invention is trying to solve

 [0006] The present invention has been made in view of the above-mentioned state of the art, and the main object of the present invention is to reduce the cost of fluorine-containing sulfonyl fluoride having an unsaturated bond by an industrially advantageous method. Is also to provide a method which can be easily produced with high selectivity and high yield.

 Means for solving the problem

 As a result of intensive studies to achieve the above object, the present inventor has found that when a fluorine-containing sulfonyl chloride having at least one unsaturated bond is used as a raw material, hydrofluoric acid of a specific amine or pyridine compound is used. It has been found that the use of a salt as a fluorinating agent makes it possible to produce a fluorinated sulfonyl fluoride with a high selectivity and a high yield by a simple method. Reached.

 [0008] That is, the present invention provides the following method for producing a fluorinated sulfonyl fluoride.

 1. Chemical formula: R SO C1 (where R is a fluorine-containing f 2 f having at least one unsaturated bond)

 A fluorine-containing unsaturated sulfonyl chloride represented by the formula: wherein the fluorine-containing hydrocarbon group may contain at least one element selected from oxygen, nitrogen and iodide. Is reacted with at least one kind of fluorinating agent selected from the following compounds (1) (m): RS〇F (where R is the same as above). 2 f

 For producing the fluorine-containing unsaturated sulfonyl fluoride to be used:

 (i) Chemical formula:

[0009] [Formula 1]

 (Wherein, R, R and R are the same or different and each represents an alkyl group or a cycloalkyl group

 one two Three

 Wherein n is an integer of 1 to 9),

(ii) Chemical formula:

(Wherein, R, R and R are the same or different and are a hydrogen atom or an alkyl group, and n is 1

 a b c

 A pyridine hydrochloride represented by the formula:

 (iii) Chemical formula:

[0013] [Formula 3]

(Wherein, R and R are the same or different and are each a hydrogen atom or an alkyl group, and n is 1

 d e is an integer of 9 and m is an integer of 2 or more).

 2. Chemical formula: In RSO C1, R is

 f 2 f

 Formula: CF = CF- (CF) -X-R-

2 2 p g

 (In the formula, X is 0, S or NH, and R is a group which may have a fluorine atom as a substituent.

 2. The method according to the above item 1, wherein the group is a divalent hydrocarbon group, and P is an integer of 0-4.

 3. Chemical formula: In RSO C1, R is

 f 2 f

 Formula: CF = CF-〇 一 [CF CF (CF) 0] CF CF-

2 2 3 q 2 2

 (Where q is an integer of 0-3). The method according to the above item 2, which is a group represented by the formula:

4. The fluorinating agent has the chemical formula: [0015] [Formula 4]

R— N '(HF) _n

(Wherein, R, R and R are the same or different and are a lower alkyl group, and n is 3)

 one two Three

 14. The method according to any one of the above items 13 to 13, which is an alkylamine hydrochloride represented by the formula: 5. After producing the fluorinated unsaturated sulfonyl fluoride by any one of the above-mentioned items 1-4, the fluorinated unsaturated sulfonyl fluoride is separated from the crude reaction product, and the remaining fluorine is removed in the next step. A method for regenerating a fluorinating agent, comprising reacting the hydrochloride of the agent with anhydrous HF to convert it to hydrofluoric acid.

In the method for producing a fluorine-containing unsaturated sulfonyl chloride of the present invention, a fluorine-containing unsaturated sulfonyl chloride represented by a chemical formula: RSOC1 is used as a raw material.

 f 2

 In the above chemical formula, R is a fluorinated hydrocarbon having at least one unsaturated bond f

 And the fluorine-containing hydrocarbon group may contain at least one element selected from oxygen, nitrogen and zeolite. The unsaturated bond may be a double bond or a triple bond, and both may be contained simultaneously. The position of the unsaturated bond is not limited. Further, in the fluorinated hydrocarbon group, all hydrogen atoms may be substituted by fluorine atoms, or only some hydrogen atoms may be substituted.

The fluorine-containing hydrocarbon group represented by R includes the following formula:

 f

 CF = CF— (CF) -X-R-

2 2 p g

 Can be exemplified. In the above formula, X is 〇, S or NH, R is a divalent hydrocarbon group which may have a fluorine atom as a substituent, and p is an integer of 0-4.

 [0020] Specific examples of R include a linear or branched alkylene group, an arylene group, and g

Examples thereof include a divalent hydrocarbon group such as a group to which these are bonded. The hydrocarbon group may further contain at least one element selected from oxygen, zeolite and nitrogen. Examples of the alkylene group include groups having about 118 carbon atoms. Examples of the arylene group include a phenylene group. These divalent hydrocarbon groups are In addition, some or all of the hydrogen atoms may be substituted or unsubstituted.

 [0021] Specific examples of the fluorine-containing hydrocarbon group represented by R include the following formula:

 f

 CF = CF—〇 一 [CF CF (CF) 〇] CF CF-

2 2 3 q 2 2

 And the group represented by In the above formula, q is an integer of 0-3.

[0022] According to the present invention, the fluorine-containing unsaturated sulfo-urquose is reacted with at least one kind of fluorinating agent selected from the compounds described in the following (i)-(iii) to obtain a fluorine-containing unsaturated sulfo-yoke. A saturated sulfonyl fluoride can be obtained.

(i) Chemical formula:

[0023] [Formula 5]

R -N-(HF) _n

R ₃

 (Wherein, R, R and R are the same or different and each represents an alkyl group or a cycloalkyl group

 one two Three

 Wherein n is an integer of 1 to 9),

 (ii) Chemical formula:

[0025]

 (Wherein, R, R and R are the same or different and are a hydrogen atom or an alkyl group, and n is 1

 a b c

 A pyridine hydrochloride represented by the formula:

(iii) Chemical formula: [0027] [Formula 7]

(Wherein, R and R are the same or different and are each a hydrogen atom or an alkyl group, and n is

 And m is an integer of 2 or more).

[0029] In the alkylamine hydrofluoride described in the above (i), R is the same or different.

 1, R and R are

 twenty three

 Is an alkyl group or a cycloalkyl group. Examples of the alkyl group include straight-chain or branched-chain alkyl groups having about 119 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-butyl and the like. A lower alkyl group having about 114 carbon atoms is preferable. Examples of the cycloalkyl group include groups having about 5 to 8 carbon atoms, such as cyclopentyl, cyclohexyl, and cyclooctyl. n is an integer from 1 to 9, preferably an integer from 2 to 9.

[0030] In the pyridine hydrochloride described in the above (ii), R R and

 a and R are the same or different b c

 A hydrogen atom or an alkyl group. Examples of the alkyl group include the same groups as the alkyl groups of the alkylamine hydrofluoride described in (i) above. n is an integer of 1 to 9, preferably an integer of 2 to 9.

[0031] In the polybutylpyridine hydrofluoride described in the above (iii), R and R are the same or de

 Is differently a hydrogen atom or an alkyl group. Examples of the phenol group include the same groups as the alkyl groups of the alkylamine hydrofluoride described in (i) above. n is an integer of 1 to 9, preferably an integer of 2 to 9. m is an integer of 2 or more, and the weight average molecular weight is in the range of about 4 000 to 160,000.

[0032] The fluorinating agent comprising the compound described in the above (i) item (iii) can be used alone or in combination of two or more. By using these fluorinating agents, the desired fluorinated unsaturated sulfonyl fluoride can be obtained with high selectivity and high yield.

[0033] Among the above fluorinating agents, regarding the alkylamine hydrofluoride described in the item (i), When n is 2—9, the compound is a liquid compound and is easy to handle.

 1, R

 2 and R 1 are lower alkyl groups having about 14 carbon atoms and n = 3 alkylamine

Three

 When the fluorinated salt is used as the fluorinating agent, the desired fluorine-containing unsaturated sulfonyl fluoride can be obtained with a high conversion and a high selectivity, and the handling can be easily performed.

[0034] The method of reacting the fluorinated unsaturated sulfourukulide used as a raw material with a fluorinating agent is not particularly limited, and both may be charged at the same time and reacted, or either one of the raw material and the fluorinating agent The other may be dropped. In particular, a method of dropping one of the raw material and the fluorinating agent with the other is advantageous in that the accumulation of reaction heat can be prevented.

 [0035] The amount of the fluorinating agent to be used is preferably about 0.1 to 10 mol, and more preferably about 115 mol, per mol of the fluorinated unsaturated sulfo-uricide used as a raw material. . In particular, when the fluorinating agent is used in an amount of about 2 to 3 moles per mole of the fluorinated unsaturated sulfo-mouth compound, the desired product can be obtained at a high conversion rate.

 [0036] The number of moles of the polyvinylpyridine hydrofluoride described in the above (m) is a structural unit represented by the following formula.

 [0037] [Formula 8]

 [0038] This is the number of moles when one of the above was converted to one molecule of bierpyridine hydrofluoric acid.

The reaction can be carried out without a solvent or in a solvent, but is preferably carried out without a solvent in terms of cost. As the solvent, a polar solvent or a non-polar solvent that does not participate in the reaction can be used. Specific examples include CH CI, CHC1, CH CN, N, N-dimethylformamide (DMF)

 2 2 3 3

 , Dimethylsulfoxide (DMSO), H〇, C F and the like. Solvent usage

 2 6 14

The amount may be, for example, about 115 parts by weight with respect to 100 parts by weight of the fluorine-containing unsaturated sulfo-mouth compound. [0040] The reaction temperature is preferably about -20 ° C to about 100 ° C, and more preferably about 10 ° C to about 40 ° C. The reaction time is generally about 0.01 hour to 48 hours, preferably about 0.5 to 24 hours.

 [0041] The reaction pressure may be any of reduced pressure, atmospheric pressure, and increased pressure, but it is preferable to carry out the reaction under atmospheric pressure.

 [0042] According to the above method, it is possible to produce the desired fluorine-containing sulfonyl fluoride with high selectivity.

 [0043] The obtained crude product is usually separated into three phases. The upper phase is the fluorinating agent, the lower phase is the desired fluorinated unsaturated sulfonyl fluoride phase, and the middle phase is the hydrofluoric acid salt of the fluorinating agent, for example, when alkylamine hydrofluoride is used as the fluorinating agent. When alkylamine hydrochloride or pyridin hydrofluoride is used as a fluorinating agent, pyridine hydrochloride is used, and when polybutylpyridine hydrofluoride is used as a fluorinating agent, polybutylpyridine hydrochloride is used.

 [0044] The desired fluorinated unsaturated sulfonyl fluoride can be purified by a known method such as filtration, distillation, column chromatography and the like. Among the fluorinated unsaturated sulfonyl fluorides thus obtained, for example, perfluoroalkylvinylsulfonyl fluoride is a substance useful as a monomer component for an electrolyte polymer.

 Further, after producing and recovering the fluorinated unsaturated sulfonyl fluoride by the method described above, anhydrous HF is added to the remaining two-phase mixture of the fluorinating agent and the hydrochloride of the fluorinating agent. As a result, the hydrochloride of the fluorinating agent can be converted to hydrofluoric acid and regenerated as the fluorinating agent.

 In this case, the amount of anhydrous HF used may be about 0.1 to 100 moles per mol of the hydrochloride of the fluorinating agent. It is preferred to use a molar excess of anhydrous HF.

[0047] The reaction temperature is preferably in the range of about -20 ° C to about 100 ° C, and is preferably in the range of about 0 ° C to about 40 ° C. The reaction time is preferably about 0.01 to 48 hours, and preferably about 0.5 to 24 hours.

[0048] The reaction pressure may be any of reduced pressure, atmospheric pressure, and pressurized pressure, but it is preferable to carry out the reaction under atmospheric pressure or pressurized pressure up to about 5.0 MPa (gauge pressure). [0049] By the above method, the hydrochloride of the fluorinating agent can be converted to hydrofluoric acid and regenerated as the fluorinating agent.

[0050] In particular, in the formula: (CH 2) Ν · (HF) n, for a hydrofluoric acid salt in which n is about 2.5

 3 3

 Since it can be easily separated by distillation, it can be regenerated as a highly pure fluorinating agent by a simple method.

 The invention's effect

 According to the method of the present invention, it is possible to produce the desired fluorinated unsaturated sulfonyl fluoride with high selectivity and high yield by an industrially advantageous method that does not require complicated operations.

 [0052] The fluorinating agent used in the present invention can be regenerated and recycled by a simple method. Therefore, the method of the present invention can be said to be a production method with a low environmental load capable of reducing industrial waste.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1

 CF = CFOCF CF SO F

 2 2 2 2

 Prepare a 100 ml three-necked flask equipped with a dim funnel and a dropping funnel, and add 33.5 g (208. Immol) of triethylamine trifluoride (Et N: (HF)) to the flask, and add dropwise.

 3 3

 The funnel was charged with 20.0 g (67.5 mmol) of CF = CFOCF CF SO CI (the charged mole).

 2 2 2 2

 Ratio 3: 1).

 While stirring at room temperature (22 ° C.), CF = CFOCF CF SO CI was added at 1.67 g / min.

 2 2 2 2

 At a speed of. The solution began to become cloudy as the reaction progressed, and during the dropwise addition, the temperature of the solution rose from 22 ° C to 33 ° C due to heat generation. The reaction was allowed to proceed for about 1 hour with stirring after the completion of the dropwise addition.

 After completion of the reaction, the inside of the flask contains Et N: (HF) n (n = 4-6) (liquid phase) / Et N: HC1 (solid phase)

 3 3

 / CF = CFOCF CF SO F (liquid phase) in a three-phase liquid separation state. Gas chromatography

2 2 2 2

 As a result of the first and NMR measurements, the target compound CF = CF

 2

It was confirmed that CF SO F was present. CF = CF〇CF CF SO CI conversion Was 100%, and the selectivity of CF = CF〇CF CF SO F was 100%.

 2 2 2 2

 [0057] As a result of heating the reactor and distilling and recovering CF = CFOCF CF SO F by simple distillation, CF

 2 2 2 2

 = The isolation yield of CF FCF CF SO F was 96.0%.

 2 2 2 2

 [0058] Re-cattle of fluorinating agent

 Et N obtained by the above method: (HF) n (n = 46) (liquid phase) / Et N: HC1 (solid phase)

 3 3

 A 34.6 g mixture of the force and the mixture was charged into a 100 ml SUS autoclave (with a condenser (_10. Cooled to C)), and the inside of the reaction system was replaced with a vacuum. Then, 10.8 g (Et N:

 Three

(8 equivalents to HC1) and reacted.

[0059] By-product HC1 gas was trapped through the washing tower. HF to 6.lg (0.30mol) (Et N:

 Three

The pressure began to rise when charged (4.5 times the molar amount of HC1), and reached 0. IMPa (gauge pressure). At this point, HF could not be charged, so HF was charged while extracting gas in the system up to near atmospheric pressure. The final amount of HF charged was 10.3 g (0.52 mol). When the liquid in the reactor was analyzed by NMR, Et N: 7.7HF was generated.

 Three

 It was. In order to convert this Et N: 7.7HF back to Et N: 3HF, Et N (H

 3 3 3

F) was collected. Withdraw HF until it is stable at reflux temperature 70 ° C,

Three

 As a result of analyzing the liquid, it was Et N: 3.2HF.

 Example 2

 Production of CF = CFOCF CF SO F

 2 2 2 2

 Triethylamine trifluoride (Et N: (HF)) 5.4 g (33.7 mmol) and CF = CFOCF

 3 3 2 2

CF SO CI 10.Using lg (33.7 mmol) as a raw material, under the same conditions as in Example 1, CF

 twenty two

 = CFOCF CF SO F was synthesized and isolated. In this case, the charged molar ratio is 1: 1.

2 2 2 2

 The

 [0061] As a result of the reaction, the conversion of CF = CFOCF CF SO CI was 41.9%, and CF = CFOCF C

 2 2 2 2 2 2

The selectivity of FSOF is 100%, and the isolation yield of CF = CFOCF CFSOF is 38.3%.

2 2 2 2 2 2

 It was.

 Example 3

 CF = CFOCF CF SO F

 2 2 2 2

100 ml of PFA (tetrafluoroethylene and perfluoropropyl butyl ether 5.3 g (37.8 mmol) of pyridine 3-hydrofluoric acid (CHN: (HF))

 6 5 3

4.7 g (13.lmmol) of CF = CFOCF CF SO CI with a purity of 82.5 mass%

 2 2 2 2

(A molar ratio of 2.9: 1). The solution was stirred at room temperature (22 ° C) for 17 hours to allow the reaction to proceed.

 After the reaction, the PFA bottle contains C H N: (HF) n (n = 46) (liquid phase) / CF = CF〇C

 6 5 2

 It was a two-phase liquid separation state of F CF SO F (liquid phase). Gas chromatography and NMR measurement

2 2 2

As a result, the target compound CF = CFOCF CF SO F

 2 2 2 2

Was confirmed. CF = CF 〇 CF CF SO CI conversion is 80.3%, CF = CF

 2 2 2 2 2

The selectivity of OCF CF SO F was 100%.

Claims

Claims Chemical formula: R SO Cl (wherein, R is a fluorinated hydrocarbon f 2 f hydrogen group having at least one unsaturated bond, and the fluorinated hydrocarbon group is selected from oxygen, nitrogen and iodide. Fluorinated unsaturated sulfoyl chloride represented by the following formula (i), at least one element selected from the compounds shown in the following (i)-(iii): A method for producing a f 2 f-containing fluorine-containing unsaturated sulfonyl fluoride represented by a chemical formula characterized by reacting with a fluorinating agent: RS〇F (where R is the same as above): (i) Chemical formula:  [Chemical 1] R— N-(HF) _n R ₃  (In the formula, R, R and R are the same or different and each represents an alkyl group or a cycloalkyl group.  one two Three Wherein n is an integer of 1 to 9), (Π) Chemical formula: [Formula 2]

 (Wherein, R, R and R are the same or different and are a hydrogen atom or an alkyl group, and n is 1  a b c A pyridine hydrochloride represented by the formula: (iii) Chemical formula: [Formula 3]

 (Wherein, R and R are the same or different and are a hydrogen atom or an alkyl group, n is an integer of 1 de-19, and m is an integer of 2 or more) . [2] Chemical formula: R SO C1, where R is  f 2 f  Formula: CF = CF- (CF) -X-R- 2 2 p g  (In the formula, X is 0, S or NH, and R is a group which may have a fluorine atom as a substituent.  2. The method according to claim 1, wherein the group is a divalent hydrocarbon group, and P is an integer of 0-4. [3] Chemical formula: R SO C1, R,  f 2 f  Formula: CF = CF-〇 一 [CF CF (CF) 0] CF CF- 2 2 3 q 2 2  3. The method according to claim 2, wherein q is an integer of 0 to 3. [4] The fluorinating agent has the chemical formula:  [Formula 4] R— N-(HF) _n Wherein R, R and R are the same or different and are a lower alkyl group, and n is 3.  one two Three  2. The method according to claim 1, which is an alkylamine hydrochloride represented by the formula: [5] After producing the fluorinated unsaturated sulfonyl fluoride by the method according to any one of claims 14 to 14, the fluorinated unsaturated sulfonyl fluoride is separated from the crude reaction product, and then the remaining fluorinating agent is left. A method for regenerating a fluorinating agent, comprising reacting a hydrochloride of the present invention with anhydrous HF to convert it into hydrofluoric acid.