WO2007142266A1

WO2007142266A1 - Method for producing fluorinated fluorosulfonylalkyl vinyl ether

Info

Publication number: WO2007142266A1
Application number: PCT/JP2007/061456
Authority: WO
Inventors: Yuuichi Hashikawa; Akinari Sugiyama; Kazuyoshi Ichihara
Original assignee: Daikin Industries, Ltd.
Priority date: 2006-06-07
Filing date: 2007-06-06
Publication date: 2007-12-13

Abstract

Disclosed is a method for producing a fluorinated fluorosulfonylalkyl vinyl ether represented by the following chemical formula: CF2=CF(CF2)aO(CF2CF(CF3)O)b(CF2)cSO2F (wherein a, b and c are as defined below) by reacting a fluorinated chlorosulfonylalkyl vinyl ether represented by the following chemical formula: CF2=CF(CF2)aO(CF2CF(CF3)O)b(CF2)cSO2Cl (wherein a represents 0 or 1, b represents an integer of 0-5 and c represents an integer of 1-10) with a fluorinating agent represented by the following chemical formula: MF•(HF)x (wherein M represents an alkali metal and x represents an integer of 0-5). This method for producing a fluorinated fluorosulfonylalkyl vinyl ether is characterized in that the reaction is carried out in the presence of 0.05-9 parts by weight of water per 100 parts by weight of the fluorinated chlorosulfonylalkyl vinyl ether as a raw material. This method enables to commercially advantageously produce a fluorinated fluorosulfonylalkyl vinyl ether with high selectivity and high yield by a simple process.

Description

Technical field of production of fluorine-containing fluorosulfonylalkyl butyl ether

[0001] The present invention relates to a method for producing a fluorine-containing fluorosulfoalkyl alkyl ether.

Background art

[0002] Chemical formula: CF = CFO (CF CF (CF) 0) CF CF SO F (where n is 0 or 1)

2 2 3 n 2 2 2

The fluorine-containing fluorosulfoalkyl alkyl ether is a useful compound as an industrial raw material such as an ion exchange membrane material.

[0003] As a method for producing a sulfonylvinyl ether such as the fluorine-containing fluorosulfoalkyl alkyl ether, for example, hexafluoropropylene oxide is prepared by FCOCF SO

twenty two

A method of thermally decomposing the resulting acid fluoride derivative after addition to F is known (see Patent Document 1 below). However, in this method, from the case where two or more molecules of hexafluoropropylene oxide are attached, CF = CFO (CF CF (CF) 0) CF CF SO F

2 2 3 n 2 2 2

It is possible to obtain Rhebubul ether. Hexafluoropropylene oxide

From the addition of one molecule, the following formula

[0004] [Chemical 1]

[0005] A cyclized product represented by the following formula is generated as a main product, and represented by the chemical formula CF = CF0CF CF SO F

2 2 2 2

Almost no fluorine-containing fluorosulfol alkyl butyl ether can be obtained ₍

[0006] Further, FC0CF (CF) 0CF CF SO F is used as a raw material, and its cyclized product

3 2 2 2

[0007] [Chemical 2] 严

ヽ严²

F2C——CF2

[0008] is formed, then the ring is opened using CH ONa to make CF = CFOCF CF SO Na,

3 2 2 2 3

The terminal SO Na group is chlorinated to CF = CFOCF CF SO CI, and further fluorinated to SO F

A method for converting to 3 2 2 2 2 2 groups is also known (see Patent Document 2 below). The fluorination step described here uses sulfolane as the solvent and NaF as the fluorinating agent. Because it uses a sulfolane having a high melting point and a high boiling point as the solvent, it is decomposed during the reaction. Generated active ingredients such as CF = CFOCF CF SO Na, unreacted raw material NaF, and by-products

2 2 2 3

Separation from certain NaCl is difficult, and the process of recovering sulfolane and the solid active ingredient becomes very complicated. For this reason, this method is difficult to implement industrially and there is a problem that a large amount of industrial waste is generated.

[0009] In addition, as a method for fluorinating a fluorine-containing sulfonic acid chloride, when C F SO C1, which is a compound having a perfluoroalkyl group, is used as a raw material, fluorination is performed using KF.

8 17 2

It has been reported that C 2 F 3 SO F can be obtained (see Non-Patent Document 1 below).

8 17 2

In this method, it is necessary to use sulfolane, formamide, or the like as a solvent in order to obtain a fluorinated product in a high yield. When water is used as a solvent, which can be expected to be a simple reaction system, the solvent is used at 100 ° C. Even with fluorination, the yield of CF SO F is only about 25%.

8 17 2

Unsuitable for application.

[0010] Further, CF = CFO (CF CF (CF) 0) CF CF SO CI (where n is 0 or 1)

2 2 3 n 2 2 2

It has been reported that a fluorine-containing fluorosulfoalkyl alkyl ether can be obtained by reacting with a fluorine-containing agent using water as a solvent when the fluorine-containing chlorosulfoalkyl alkyl ether is used as a starting material (see below). (See Patent Document 3). According to this method, the target fluorine-containing fluorosulfoalkyl alkyl ether can be obtained in a relatively high yield, but HF adducts and hydrolysates are produced as by-products. In addition, a method capable of producing a target fluorine-containing fluorosulfoalkyl vinyl ether with higher selectivity and good yield is desired. Patent Document 1: British Patent 1, 034, 197

Patent Document 2: U.S. Pat.No. 3,560,568

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-244401

Non-Patent Document 1: S. Benefice—Malouet, H. Blancou, R. Teissedre and A. Commeyras, J. Fluorine Chem. 31 (1986) 319—332

Disclosure of the Invention Problems to be Solved by the Invention

[0011] The present invention has been made in view of the current state of the prior art described above, and the main object of the present invention is to easily and highly select fluorine-containing fluorosulfoalkyl alkyl ethers in an industrially advantageous manner. It is to provide a method that can be manufactured at a high yield with a high yield.

Means for solving the problem

[0012] The inventor has conducted extensive research in view of the above-described problems. As a result, when a specific fluorine-containing chlorosulfoalkylalkyl ether was used as a raw material and reacted with a fluorinating agent, it was very limited to 0.05 to 9 parts by weight per 100 parts by weight of the raw material. Surprisingly, when a small amount of water is present, the selectivity is significantly improved and by-products are much less pure and highly pure than when water is used as a solvent or without water. The inventors have found that it is possible to obtain a fluorinated fluorosulfoalkyl alkyl ether, and have completed the present invention.

That is, the present invention provides the following method for producing a fluorine-containing fluorosulfoalkyl alkyl ether.

1. Formulas: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO Cl (where a is 0 or 1, b is 0

2 2 a 2 3 b 2 c 2

Fluorine-containing chlorosulfoalkyl alkyl butyl ether represented by the following formula: MF '(HF) (wherein M is an alkali metal and X is 0 to 5) The chemical formula: CF = CF (CF) 0 (CF CF (C

2 2 a 2

F) 0) (CF) SO F (wherein a, b and c are the same as above)

3 b 2 c 2

A method for producing hole alkyl butyl ether, comprising reacting in the presence of 0.05 to 9 parts by weight of water per 100 parts by weight of fluorine-containing chloroalkyl sulfone ether used as a raw material. A method characterized by. 2. Key formula: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO CI! /, A force ^ 0, b force or

2 2 a 2 3 b 2 c 2

2. The method according to item 1, wherein fluorinated chlorosulfoalkyl alkyl butyl ether in which 1, c is an integer of 1 to 4 is used as a raw material.

3. Fluorinating agent power The method according to item 1 or 2, which is at least one selected from the group force consisting of a compound in which M is K and M is a compound in MF- (HF).

4. The method according to any one of the above items 1 to 3, wherein the reaction is carried out in the presence of 0.1 to 6 parts by weight of water with respect to 100 parts by weight of the fluorine-containing chlorosulfuralkylalkyl ether used as a raw material.

[0014] The method for producing a fluorine-containing fluorosulfol alkyl butyl ether of the present invention has the following chemical formula: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO Cl (where a is 0 or 1, b is 0-5

2 2 a 2 3 b 2 c 2

Fluorine-containing chlorosulfuralkylalkyl ether represented by an integer, c is an integer of 1 to 10, and a chemical formula: MF- (HF) (wherein M is an alkali metal and X is an integer of 0 to 5) Is expressed by the following formula: CF = CF (CF) 0 (CF CF (CF) 0) (

2 2 a 2 3 b

CF 3) SO F (wherein a, b and c are the same as above)

2 c 2

This is a method for producing an alkyl vinyl ether.

[0015] Chemical formula as a raw material: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO CI (where a, b and c

2 2 a 2 3 b 2 c 2

Is the same as the above) and is a known substance. For example, in the above chemical formula, for a compound in which a is 0, by the method described in JP-A-2004-18427, A general formula CFX (CF) X (where X

twenty two

Is I or Br, and c is an integer of 1-10. ) Is a fluorine-containing compound represented by SO, CIS

Three

After reacting with 0 H, fuming sulfuric acid, etc. to make FOC (CF) X (where c and X are the same as above),

3 2 c

Oxymeric reaction with hexafluoropropylene oxide, followed by neutralization and decarboxylation reaction, CF = CF0 (CF CF (CF) 0) (CF) X (where b, c and X are the above And the same)

2 2 3 b 2 c

It can be obtained by a method of reacting with an alkali metal dithionite and a neutralizing agent to form butyl ether sulfinate, and chlorinating the obtained butyl ether sulfinate. The fluorine-containing chlorosulfoalkyl alkyl ether obtained by this method may be isolated or purified, or the crude reaction product obtained by the above reaction may be used as it is. In the present invention, the chemical formula is represented by the formula: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO CI

2 2 a 2 3 b 2 c 2

Among the fluorine-containing chlorosulfoalkyl alkyl ethers, compounds in which _a is 0, b is 0 or 1, and c is an integer of 1 to 4 are used as raw materials for producing monomer components for fuel cell electrolyte polymers. It is highly useful.

In the present invention, a compound represented by the chemical formula: MF ′ (HF) (wherein M is an alkali metal and X is an integer of 0 to 5) is used as the fluorinating agent. As the fluorinating agent, an alkali metal fluoride, an acid alkali metal fluoride or the like, which is a compound in which M is K or a compound in which M is Na in the above chemical formula, is preferable. In particular, KF is preferable. Fluorinating agents can be used alone or in combination of two or more.

[0018] The amount of the fluorinating agent used is usually about 0.5 to 10 mol, preferably about 1 to 5 mol, relative to 1 mol of the fluorinated chlorosulfuralkylalkyl ether.

[0019] The production method of the present invention comprises the use of the above-mentioned fluorine-containing chlorosulfoalkyl alkyl ether by reacting the fluorine-containing chlorosulfoalkyl alkyl ether with a fluorinating agent. An important feature is the presence of a specific amount of water of 0.05 to 9 parts by weight per 100 parts by weight of rualkyl butyl ether.

[0020] In this manner, the reaction proceeds in the presence of a specific proportion of water, which is a small amount relative to the raw material, thereby suppressing the formation of by-products and high yield with high selectivity. This makes it possible to obtain the target fluorine-containing fluorosulfoalkyl alkyl ether. If the presence of water exceeds the above range, the by-product will increase!] And the selectivity will decrease, and if below, the reaction time will be significantly longer.

[0021] In particular, the amount of water is preferably about 0.1 to 6 parts by weight with respect to 100 parts by weight of the fluorine-containing chlorosulfoalkyl alkyl butyl ether. More preferably.

[0022] In the production method of the present invention, other additives can be added as required. Such additives include water-soluble organic solvents that do not participate in the reaction, such as sulfolane, dimethyl sulfoxide, dimethylformamide, and other phase transfer catalysts such as C H

6 5

Quaternary ammonium salts such as CH N (CH) .C1, quaternary phosphonium salts, etc., inclusion molecules, eg For example, a cyclic ether such as 18-crown-6 can be used. The reaction rate can be improved by adding these additives.

[0023] The amount of the additive used for the aqueous organic solvent is preferably about 1 to 50 parts by weight with respect to 100 parts by weight of the fluorine-containing chlorosulfoalkyl alkyl ether used as a raw material.

[0024] The phase transfer catalyst is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorine-containing chlorosulfonylalkyl vinyl ether used as a raw material.

In the production method of the present invention, the raw material and the fluorinating agent may be reacted in the presence of the specific amount of water described above. As an example of the reaction conditions, the reaction temperature may be about 10 to 200 ° C, preferably about 15 to 100 ° C. The reaction pressure may be any of reduced pressure, atmospheric pressure and increased pressure, but is preferably atmospheric pressure. The reaction time is usually about 0.5 to 24 hours.

[0026] By the above method, the chemical formula: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO F (wherein

2 2 a 2 3 b 2 c 2 a, b and c are the same as above, and a fluorinated fluorosulfoalkyl alkyl ether can be obtained.

[0027] The obtained crude compound can be purified by a known method such as distillation or column chromatography. For example, the mixture is separated into two layers by adding water and stirring, and the lower layer becomes a fluorinated fluorosulfoalkyl alkyl ether represented by the above chemical formula and can be purified by the above method.

[0028] The fluorine-containing fluorosulfoalkyl alkyl ether obtained as described above is a substance useful as a monomer component for a fuel cell electrolyte polymer, for example.

The invention's effect

[0029] According to the production method of the present invention, it is possible to produce a fluorine-containing fluorosulfoalkyl alkyl ether with a very high selectivity and high yield by a relatively simple production method.

[0030] Therefore, according to the production method of the present invention, it is possible to reduce the cost accompanying the improvement in yield, and further, such as reduction of industrial waste, suppression of corrosion of production equipment, simplification of production process, etc. Excellent effect. Brief Description of Drawings

[0031] [Fig. 1] CF = CFO CF CF SO F selectivity and CF = CFOCF CF SO CI 100 parts by weight

2 2 2 2 2 2 2 2

The graph which shows the relationship with the amount of H 2 O.

2

BEST MODE FOR CARRYING OUT THE INVENTION

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

[0033] Example 1

Attach a stirring bar, thermometer plug, and conical tube condenser to a 200 ml four-necked flask, CF =

2

CFOCF CF SO C1 40.0g, KF 22.0g and water 0.6g (CF = CFOCF CF SO CI 100

2 2 2 2 2 2 2 1.5 parts by weight). The reactor was heated with stirring and refluxed at 95 ° C. During the reaction, the reflux temperature dropped and the reaction was stopped when it became constant at 75 ° C. The total reaction time was 2 hours.

[0034] After the reaction, water was added to dissolve the white solid to obtain a reaction solution consisting of two layers. The product was liquid-liquid separated into two layers, and the resulting organic layer was quantified by gas chromatography internal standard method. CF = CFOCF CF SO CI conversion 98.4%, selectivity 99.3%, CF = CFO CF C

2 2 2 2 2 2

It was found that F SO F was generated. The obtained aqueous layer was determined by ¹⁹ F NMR internal standard method.

twenty two

As a result, in addition to KF and KC1, CF = CF ○ CF CF SO K has a selectivity of 0.1%, CF CHFOCF C

2 2 2 3 3 2

It was confirmed that F SO F was produced with a selectivity of 0.1% and CF CHFOCF CF SO K with a selectivity of 0.5%.

2 2 3 2 2 3

Came.

[0035] Examples 2 to 5 and Comparative Examples 1 to 4

In the same manner as in Example 1, the amount of H 2 O with respect to CF = CFOCF CF SO CI in the raw material was determined.

2 2 2 2 2 By changing, CF = CFO CF CF SO F was synthesized with the charge shown in Table 1.

2 2 2 2

[0036] Table 1 shows the selectivity of each component in the product. Also for CF = CFOCF CF SO CI

2 2 2 2

Figure 1 shows the relationship between the amount of H 2 O and CF = CFOCF CF SO F selectivity. In Table 1 and Figure 1,

2 2 2 2 2

The amount of H 0 added is expressed in parts by weight with respect to 100 parts by weight of CF = CFOCF CF SO CI.

2 2 2 2 2

[0037] [Table 1] Examples Comparative examples

2 3 4 5 1 2 3 4 Finish H ₂ 0 (g) 0.04 1.0 3.3 5.4 9.0 20.0 63.6 100 included CF, = CF0CF ₂ CF ₂ S0 ₂ C1 (g) 67.2 66.9 66.9 66.9 66.7 66.7 67.6 20 Quantity KF (Crystalline product) ) ( _G ) 36.7 37.0 36.8 37.0 36.7 37.0 37.6 11.7

H ₂ 0 addition (part by weight) 0.05 1.5 5.0 8.0 13.5 30.0 94.1 500 selection CF ₂ = CF0 CF ₂ CF ₂ S0 ₂ F 97.8 99.3 99.2 98.5 94.4 91.1 82.8 41.4 selection CF ₃ CHF0CF ₂ CF ₂ S0 ₂ F 0.5 0.1 0.1 0.2 1.8 2.1 4.4 0.0 Ratio CF ₂ = CF0CF ₂ CF ₂ S0 ₃ K 0.3 0.1 0.2 0.4 0.8 2.3 4.7 17.5

(%) CF ₃ CHF0CF ₂ CF ₂ S0 ₃ K 1.4 0.5 0.5 0.9 2.5 4.5 3.2 41.1 From the above results, the amount of HO for 100 parts by weight of CF = CFOCF CF SO CI is 0.05 to 9

2 2 2 2 2

When it is within the range of parts by weight, the selectivity power of CF ₂ = CFO CF ₂ CF ₂ SO F is ¾7% or more, and it is clear that the selectivity is remarkably high.

Claims

The scope of the claims

[1] Chemical formula: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO Cl (where a is 0 or 1, b is 0 to 5

2 2 a 2 3 b 2 c 2

And a chemical formula: MF- (HF) (wherein M is an alkali metal and X is an integer of 0 to 5) And a chemical formula: CF = CF (CF) 0 (CF CF (CF) 0)

2 2 a 2 3

(CF) SO F (wherein a, b and c are the same as above) fluorinated fluorosulfol b 2 c 2

A method for producing an alkyl butyl ether comprising a fluorine-containing chlorosulfo as a raw material

-A method characterized in that the reaction is carried out in the presence of 0.05 to 9 parts by weight of water with respect to 100 parts by weight of rualkylbulle ether.

[2] Key equation: CF = CF (CF) 0 (CF CF (CF) 0) (CF) SO CI, a force 0, b force 0 or 1,

2 2 a 2 3 b 2 c 2

2. The method according to claim 1, wherein a fluorine-containing chlorosulfoalkyl alkyl ether whose c is an integer of 1 to 4 is used as a raw material.

[3] The method according to claim 1 or 2, wherein the fluorinating power is at least one selected from the group consisting of a compound in which M is K and M is Na in MF- (HF).

[4] 0 per 100 parts by weight of fluorine-containing chlorosulfuralkylalkyl ether as raw material

The method according to any one of claims 1 to 3, wherein the reaction is carried out in the presence of 1 to 6 parts by weight of water.