JP7360856B2 - Method for producing fluorine-containing (meth)acrylic esters - Google Patents

Description

The present invention relates to a method for producing fluorine-containing (meth)acrylic esters.

Fluorine-containing (meth)acrylic esters are copolymerized with appropriate monomers to give fluorine-containing polymers, which are used as raw materials for, for example, water and oil repellents and surfactants.

Conventionally, fluorine-containing (meth)acrylic acid esters have been produced by a method in which a fluorine-containing alkyl iodide and a (meth)acrylic acid metal salt are reacted in a solvent such as tert-butanol (for example, Patent Document 1 , 2). However, this method requires a high temperature of 150° C. or higher during the reaction, and since the reaction temperature exceeds the boiling point of the solvent, it was necessary to use a pressure vessel as the reaction vessel. Furthermore, the presence of water in the system inhibits the desired reaction, so the solvent used for the reaction needs to be dehydrated and measures must be taken to prevent the contamination of water. Furthermore, filtration equipment, centrifugal separation equipment, or special evaporation equipment was required to remove metal iodide salts produced as by-products during the reaction.

Patent No. 4649689 Japanese Patent Application Publication No. 2004-359616

An object of the present invention is to provide a method for producing fluorine-containing (meth)acrylic acid esters, which allows the reaction to be carried out under mild conditions, and which is simple and industrially practicable.

The present inventors have discovered a new method for producing fluorine-containing (meth)acrylic esters that solves the above problems, and have completed the present invention.

That is, the present invention involves reacting a fluorine-containing alkyl iodide represented by the following general formula (1) with a (meth)acrylic acid metal salt in a mixed solvent of an organic solvent and water in the presence of a phase transfer catalyst. The present invention provides a method for producing fluorine-containing (meth)acrylic acid esters.

Rf-(CH ₂ ) _n -I (1)

(In formula (1), Rf is a fluorinated aliphatic hydrocarbon group having 1 to 16 carbon atoms, and n is an integer of 1 to 4)

According to the present invention, there is provided a method for producing fluorine-containing (meth)acrylic acid esters, which can be carried out under normal pressure and mild conditions, does not require dehydration treatment of solvents, allows simple purification, and is suitable for industrial production. Can be provided.

The present invention will be explained in detail below.
In the general formula (1) representing the fluorine-containing alkyl iodide according to the present invention, Rf is a linear or branched fluorinated aliphatic hydrocarbon group having 1 to 16 carbon atoms; The fluorinated aliphatic hydrocarbon group is preferred.

In the general formula (1) representing the fluorine-containing alkyl iodide according to the present invention, n is an integer of 1 to 4, preferably 2 to 4, and more preferably 2.

In the general formula (1) representing the fluorine-containing alkyl iodide according to the present invention, Rf is a fluorinated aliphatic hydrocarbon group in which 10 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably hydrogen A fluorinated aliphatic hydrocarbon group in which 50 to 100% of the number of atoms are substituted with fluorine atoms, more preferably a fluorinated aliphatic hydrocarbon group in which 70 to 100% of the number of hydrogen atoms are substituted with fluorine atoms. be.

In the general formula (1) showing the fluorine-containing alkyl iodide according to the present invention, specific structures of Rf include C ₂ F ₅ -, C ₄ F ₉ -, C ₆ F ₁₃ -, C ₈ F ₁₇ - , C ₁₀ F ₂₁ -, C ₁₂ F ₂₅ -, C ₂ F ₅ -CH=CH-C ₂ F ₄ -, C ₂ F ₅ -CH=CH-C ₄ F ₈ -, C ₂ F ₅ -CH= CH-C ₆ F ₁₂ -, C ₄ F ₉ -CH=CH-C ₂ F ₄ -, C ₄ F ₉ -CH=CH-C ₄ F ₈ -, C ₄ F ₉ -CH=CH-C ₆ F ₁₂ -, C ₆ F ₁₃ -CH=CH-C ₂ F ₄ -, C ₆ F ₁₃ -CH=CH-C ₄ F ₈ -, C ₆ F ₁₃ -CH=CH-C ₆ F ₁₂ -, (CF Examples include, but are not limited to, ₃ ) ₂ CF-, (CF ₃ ) ₂ CF-(CF ₂ ) ₂ -, (CF ₃ ) ₂ CF-(CF ₂ ) ₄ -, and the like.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, the (meth)acrylic acid metal salt may be a metal salt such as lithium, sodium, potassium, etc., and may be used in a solid form, and may be dissolved in water. It may be used in the form of an aqueous solution obtained by neutralizing (meth)acrylic acid and the corresponding metal hydroxide.

In the production of fluorine-containing (meth)acrylic acid esters according to the present invention, the amount of (meth)acrylic acid metal salt used in the reaction is preferably 0.8 equivalent relative to the fluorine-containing alkyl iodide used in the reaction. ~5 equivalents, more preferably 1 equivalent to 3 equivalents.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, the reaction is carried out in a mixed solvent of an organic solvent and water. Carrying out the process in a mixed solvent of an organic solvent and water is effective in that it eliminates the need for dehydration of the solvent or measures to prevent water from entering.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, the organic solvent is preferably a water-insoluble organic solvent that separates from water from the viewpoints of reaction selectivity, simplification of purification, and recovery of the solvent. Water-insoluble organic solvents are effective in that water-soluble by-products and impurities containing metal iodides can be easily removed by liquid/liquid separation after the reaction. Furthermore, since it can be easily purified, it is also effective when the water-insoluble organic solvent used in the reaction is recovered by distillation or the like and reused.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, the water-insoluble organic solvent applicable to the reaction may be any solvent that is inert to the reaction related to the production of fluorine-containing (meth)acrylic esters. Although not particularly limited, specific examples include aromas such as benzene, toluene, xylene, o-xylene, m-xylene, p-xylene, ethylbenzene, cumene, mesitylene, tetralin, butylbenzene, p-cymene, and diethylbenzene. Examples include group hydrocarbon solvents, ethers such as anisole, dimethoxybenzene, and diphenyl ether, and halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, and chlorobenzene. Among these, toluene, xylene, tetralin, anisole, and chlorobenzene are preferred.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, one type of water-insoluble organic solvent may be used alone, or two or more types may be used in combination.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, a phase transfer catalyst selected from quaternary ammonium salts and quaternary phosphonium salts is preferably used as the phase transfer catalyst used in the reaction.

Specific examples of quaternary ammonium salts include tetrabutylammonium salts, tetramethylammonium salts, and tetraethylammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide (TBACl), and tetrabutylammonium iodide (TBAI). , tetrapropylammonium salt, tetrahexylammonium salt, tetraoctylammonium salt, tetradecylammonium salt, hexadecyltriethylammonium salt, dodecyltrimethylammonium salt, trioctylmethylammonium salt, octyltriethylammonium salt, benzyltrimethylammonium salt, benzyltriethyl Examples include ammonium salt, benzyltributylammonium salt, benzyldimethyloctadecylammonium salt, and phenyltrimethylammonium salt.

Specific examples of quaternary phosphonium salts include tetrabutylphosphonium salts such as tetrabutylphosphonium chloride (TBPCl), tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide, tetramethylphosphonium salts, tetraethylphosphonium salts, and tetrapropylphosphonium salts. Examples include phosphonium salt, tetrahexylphosphonium salt, tetradecylphosphonium salt, tetraoctylphosphonium salt, triethyloctadecylphosphonium salt, trioctylethylphosphonium salt, hexadecyltriethylphosphonium salt, tetraphenylphosphonium salt, methyltriphenylphosphonium salt, and the like.

Among these, tetrabutylammonium salt or tetrabutylphosphonium salt is preferably used from the viewpoint of reactivity and availability.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, one type of phase transfer catalyst may be used alone, or two or more types may be used in combination.

In the production of fluorine-containing (meth)acrylic acid esters according to the present invention, the amount of phase transfer catalyst used in the reaction is preferably 0.1 mol % to 20 mol % based on the fluorine-containing alkyl iodide used in the reaction. %, more preferably 1 mol% to 10 mol%.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, the reaction temperature is in the range of 60°C to 100°C, preferably in the range of 80°C to 100°C. Since the reaction proceeds under normal pressure and mild conditions, it is effective in that there is no need to use special reaction equipment such as a pressure vessel.

In the production of fluorine-containing (meth)acrylic esters according to the present invention, the reaction time is in the range of 1 hour to 96 hours, preferably in the range of 6 hours to 48 hours.

In the production of fluorine-containing (meth)acrylic acid esters according to the present invention, purification operations include, for example, separating the separated aqueous phase after the reaction in the above step to obtain water-soluble water-soluble metal iodide-containing esters. By-products and impurities can be easily removed. The desired product can be obtained by applying known purification methods such as distillation, concentration, recrystallization, filtration, and column chromatography to the obtained organic phase.

Examples of the present invention are shown below, but the present invention is not limited to these examples.

The following equipment was used for the analysis.
¹ H-NMR, ¹⁹ F-NMR: AVANCE II 400 manufactured by Bruker
Gas chromatography: Shimadzu GC-2014
GC-MS: Shimadzu GCMS-QP2010 Ultra

Reference example 1
1-Iodo-3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16, Synthesis of 16,16-pentacosafluoro-9-hexadecene (a ₂ )

1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,13,13, in a 150mL SUS autoclave. 14,14,14-pentacosafluoro-1-iodo-7-tetradecene (a ₁ ) 100.00 g (manufactured by Tosoh Finechem, 0.130 mol) and ditertiary butyl peroxide 0.13 g (manufactured by NOF, 0.003 mol) ), and after sealing, the inside was purged with nitrogen. Thereafter, the temperature was raised to 115° C., and 2.00 g of ethylene (manufactured by Air Water, 0.142 mol) was added while maintaining a pressure of 0.5 to 1.0 MPa. After further reacting at 115° C. for 1 hour, the reaction mixture was cooled to obtain 103.50 g of compound (a ₂ ) as a white solid. The yield was 99.9%.

The analysis results of the product are shown below.
¹ H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, C ₆ F ₁₃ CH=CH C ₆ F ₁₂ ), 3.17 (m, 2H , CH ₂ I), 2.65 (m, 2H, CH ₂ CF ₂ )
¹⁹ F-NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ (ppm): -81.41 (t, J = 9.8Hz, 3F, CF ₃ ), -114.39 (m, 4F , CF ₂ CH), -115.50 (m, 2F, CF ₂ CH ₂ ), -122.08 (m, 6F, CF ₂ CF ₂ CF ₂ ), -123.33 (m, 2F, CF ₂ ) , -123.89 (m, 6F, CF ₂ CF ₂ CF ₂ ), -126.69 (m, 2F, CF ₂ )

Example 1
2-Methylpropenoic acid 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16 ,16,16-pentacosafluoro-9-heptadecenyl (compound (A))

1-iodo-3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12, in a 100 mL four-neck eggplant flask equipped with a reflux condenser. 13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecene (a ₂ ) 15.00 g (18.75 mmol), o-xylene 45 g (manufactured by Fuji Film Wako Pure Chemical Industries) and 0.28 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.94 mmol) of tetrabutylphosphonium chloride, and the temperature was raised to 95° C. with stirring. Then, an aqueous solution in which 2.23 g of sodium methacrylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 20.60 mmol) was dissolved in 8.9 g of water was added dropwise, and the mixture was stirred at 95° C. for 12 hours. As a result of analysis by gas chromatography, the conversion rate was 96% and the selectivity of compound (A) was 71%. The results obtained are shown in Table 1.

Stirring was stopped and the separated aqueous phase was removed. After concentrating the organic layer and eluting impurities by filtration with silica gel using hexane as a developing solvent, the target product was eluted with hexane/ethyl acetate = 4/1 and concentrated under reduced pressure to obtain 8.50 g of compound (A) ( 11.2 mmol) was obtained as a colorless oil. The yield was 59.8% (on a molar basis, the same applies hereinafter).

The analysis results of the product are shown below.
¹ H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ (ppm): 6.49 (m, 2H, C ₆ F ₁₃ CH=CH C ₆ F ₁₂ ), 6.14 (m, 1H , CH), 5.60 (m, 1H, CH), 4.45 (t, J=6.4Hz, 2H, CH ₂ O), 2.51 (m, 2H, CH ₂ CF ₂ ), 1. 95 (m, 3H, _CH3 )
¹⁹ F-NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ (ppm): -81.30 (t, J = 9.8Hz, 3F, CF ₃ ), -114.10 (m, 2F , CF ₂ CH ₂ ), -114.34 (m, 4F, CF ₂ CH), -122.05 (m, 6F, CF ₂ CF ₂ CF ₂ ), -123.36 (m, 2F, CF ₂ ) , -123.86 (m, 6F, CF ₂ CF ₂ CF ₂ ), -126.66 (m, 2F, CF ₂ )
GC-MS: Calculated value [C ₂₀ H ₁₁ F ₂₅ O ₂ ] ⁺ : 758, actual value: 758

Examples 2 to 9
The same reaction as in Example 1 was carried out with various changes in the (meth)acrylic acid metal salt, organic solvent, phase transfer catalyst, and reaction time. The conversion rate and selectivity of compound (A) were analyzed by gas chromatography, and the results are shown in Table 1.

Example 10
In Example 1, in the preparation of (meth)acrylic acid metal salt, 0.12 g of methacrylic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 1.4 mmol) and 0.53 g of a 10% aqueous sodium hydroxide solution were mixed, and the obtained The reaction was carried out in the same manner except that an aqueous solution was used for the reaction. The conversion rate and selectivity of compound (A) were analyzed by gas chromatography, and the results are shown in Table 1.

Example 11
Production of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylpropenoate (compound (B))

In a 100 mL four-neck eggplant flask equipped with a reflux condenser, 15.00 g of 1H,1H,2H,2H-tridecafluorooctyl iodide (a ₃ ) (manufactured by Matrix Scientific, 31.65 mmol) and 45 g of o-xylene ( Fuji Film (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.47 g (manufactured by Tokyo Chemical Industry Co., Ltd., 1.58 mmol) of tetrabutylphosphonium chloride were charged, and the temperature was raised to 95° C. with stirring. Thereafter, an aqueous solution in which 3.78 g of sodium methacrylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 34.82 mmol) was dissolved in 11.2 g of water was added dropwise, and the mixture was stirred at 100° C. for 12 hours. As a result of analysis by gas chromatography, the conversion rate was 95% and the selectivity of compound (B) was 82%. The results obtained are shown in Table 1.

Stirring was stopped and the separated aqueous phase was removed. The organic layer was distilled under reduced pressure to obtain 9.82 g (22.7 mmol) of Compound (B) as a colorless liquid at a temperature of 86 to 89° C. under 1.0 kPa. The yield was 71.8%.

Examples 12-14
In Example 11, the same reaction was performed with various changes in the (meth)acrylic acid metal salt, organic solvent, phase transfer catalyst, and reaction time. The conversion rate and selectivity of compound (B) were analyzed by gas chromatography, and the results are shown in Table 1.

Example 15
2-propenoic acid 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16, Production of 16,16-pentacosafluoro-9-heptadecenyl (compound (C))

1-Iodo-3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13 in a 10 mL test tube equipped with a reflux condenser ,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecene (a ₂ ) 1.00 g (1.25 mmol), o-xylene 3.0 g (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 17 mg of tetrabutylphosphonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 0.06 mmol) was charged, and the temperature was raised to 95° C. with stirring. Separately, in a 6 mL sample bottle, an aqueous solution obtained by mixing 0.10 g of acrylic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 1.4 mmol) and 0.53 g of a 10% aqueous sodium hydroxide solution was added dropwise, and the mixture was heated to 48 °C at 95 °C. Stir for hours. As a result of analysis by gas chromatography, the conversion rate was 95% and the selectivity of compound (C) was 70%. The results obtained are shown in Table 1.

Stirring was stopped and the separated aqueous phase was removed. After concentrating the organic layer and eluting impurities by filtration with silica gel using hexane as a developing solvent, eluting the target product with hexane/ethyl acetate = 4/1 and concentrating under reduced pressure to obtain 0.57 g of compound (C) ( 0.77 mmol) was obtained as a colorless oil. The yield was 61%.

The analysis results of the product are shown below.
¹ H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ (ppm): 6.49 (m, 2H, C ₆ F ₁₃ CH=CH C ₆ F ₁₂ ), 6.44 (m, 1H , CH), 6.13 (m, 1H, CH), 5.87 (m, 1H, CH), 4.46 (t, J = 6.4Hz, 2H, CH ₂ O), 2.49 (m , 2H, CH ₂ CF ₂ )
¹⁹ F-NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ (ppm): -81.29 (t, J = 9.8Hz, 3F, CF ₃ ), -114.02 (m, 2F , CF ₂ CH ₂ ), -114.28 (m, 4F, CF ₂ CH), -121.99 (m, 6F, CF ₂ CF ₂ CF ₂ ), -123.30 (m, 2F, CF ₂ ) , -123.88 (m, 6F, CF ₂ CF ₂ CF ₂ ), -126.60 (m, 2F, CF ₂ )
GC-MS: Calculated value [C ₁₉ H ₉ F ₂₅ O ₂ ] ⁺ : 744, actual value: 744

Example 16
Production of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-propenoate (compound (D))

In a 100 mL four-neck eggplant flask, add 15.00 g of 1H,1H,2H,2H-tridecafluorooctyl iodide (a ₃ ) (manufactured by Matrix Scientific, 31.65 mmol) and 45 g of o-xylene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). ) and 0.47 g (manufactured by Tokyo Chemical Industry Co., Ltd., 1.58 mmol) of tetrabutylphosphonium chloride were added, and the temperature was raised to 95° C. with stirring. Separately, in a 6 mL sample bottle, an aqueous solution obtained by mixing 2.51 g of acrylic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 34.82 mmol) and 20.00 g of a 10% potassium hydroxide aqueous solution was added dropwise, and the mixture was heated at 95°C for 12 hours. Stir for hours. As a result of analysis by gas chromatography, the conversion rate was 96% and the selectivity of compound (D) was 77%. The results obtained are shown in Table 1.

Stirring was stopped and the separated aqueous phase was removed. The organic layer was distilled under reduced pressure, and 8.90 g (21.3 mmol) of Compound (D) was obtained as a colorless liquid at a temperature of 70 to 73° C. under 1.0 kPa. The yield was 67.3%.

Comparative example 1
When the reaction was carried out under heating and reflux conditions at 82°C using the same raw materials as in the conventional technology, the reaction did not proceed at all, making it impossible to produce fluorine-containing (meth)acrylic acid esters under normal pressure. Met.

The results obtained are shown in Table 1.
The abbreviations in Table 1 are as follows.
PMA: Potassium methacrylate SMA: Sodium methacrylate PA: Potassium acrylate SA: Sodium acrylate TBACl: Tetrabutylammonium chloride TBAI: Tetrabutylammonium iodide TBPCl: Tetrabutylphosphonium chloride

The fluorine-containing (meth)acrylic esters obtained by the production method of the present invention are useful as raw materials for functional materials such as water and oil repellents.

Claims (3)

It is characterized by reacting a fluorine-containing alkyl iodide represented by the following general formula (1) with a (meth)acrylic acid metal salt in a mixed solvent of a water-insoluble organic solvent and water in the presence of a phase transfer catalyst. A method for producing a fluorine-containing (meth)acrylic ester.
Rf-(CH ₂ ) _n -I (1)
(In formula (1), Rf is a fluorinated aliphatic hydrocarbon group having 1 to 16 carbon atoms, and n is an integer of 1 to 4) The method for producing fluorine-containing (meth)acrylic esters according to claim 1, wherein the Rf is a fluorinated aliphatic hydrocarbon group in which 10 to 100% of the hydrogen atoms are substituted with fluorine atoms. The method for producing fluorine-containing (meth)acrylic esters according to claim 1 or 2 , wherein the phase transfer catalyst is a quaternary ammonium salt or a quaternary phosphonium salt.