JP6501658B2 - Novel fluorine-containing chained ether compound, method for producing the same, and use thereof - Google Patents

Description

  The present invention relates to novel fluorine-containing chain ether compounds.

  Among halogen compounds, fluorine compounds having special functions take various forms such as resins, rubbers, organic compounds, inorganic compounds, gases, etc., and a wide range of fields such as automobiles, electric and electronics, architecture, engineering fields, medicines and pesticides It is used by

  Among these fluorine compounds, those having physical properties of liquid at normal temperature are used as solvents having high thermal and chemical stability. Among these, perfluoro compounds such as perfluoroalkanes and perfluoroalkylamines do not have any compatibility with organic compounds at all, and their applications mainly consist of a heat medium and the like. On the other hand, fluorine-containing chain-like ether compounds in which the molecule is partially fluorinated are compatible with organic compounds, and have high thermal and chemical properties while having the characteristics of ether compounds such as low viscosity and low melting point. It has excellent physical and chemical properties such as stability (oxidation resistance). Therefore, a fluorine-containing chain ether compound is used as a flash point adjustment of a solvent for fluorine oil or a flammable solvent, a cleaning agent of electronic parts and industrial products, and the like (Non-Patent Document 1).

  As such a fluorine-containing chain ether compound, for example, perfluoroalkyl ether compounds such as perfluorobutyl methyl ether and perfluorobutyl ethyl ether are known, and a hollow of a blood purifier as a specific application thereof Yarn film cleaners and vehicle cleaners have been proposed (Patent Documents 1 and 2). However, even these perfluoroalkyl ether compounds are still insufficient in terms of compatibility with a wide range of organic compounds that can be used in organic synthesis reactions, extraction and the like. Further, since the perfluoroalkyl ether compound has a low boiling point, there is also a problem that the use temperature range is limited.

In recent years, fluorine-containing chain ether compounds have also been studied as electrolyte solvents for non-aqueous secondary batteries represented by lithium ion secondary batteries (Patent Documents 3 and 4). This is because non-aqueous secondary batteries are required to improve the energy density of the battery in order to reduce the battery size and extend the driving time (Non-Patent Document 2). It is because the fluorine-containing chain | strand-shaped ether compound excellent in viscosity and oxidation resistance is effective. Patent Document 3 discloses a fluorine-containing chain ether compound having one oxygen atom in the molecule.
However, since the compounds used in Patent Documents 3 and 4 are not sufficiently compatible with other electrolytic solution components such as ethylene carbonate, there are restrictions on the composition. In addition, since the compound used in Patent Document 3 also has a low boiling point, it can not be said that the non-aqueous secondary battery for which stable operation is required in a wide temperature range has sufficient performance.

Japanese Patent Application Laid-Open No. 10-174848 JP 2008-280463 A Japanese Patent Application Laid-Open No. 11-026015 Unexamined-Japanese-Patent No. 11-307123 gazette JP 10-050343 A International Publication No. 2000/016427

"Fluorine-based materials and technology", CMC Co., Ltd.-Publishing, Hitoshi Matsuo, April 30, 2002 "Car Lithium Ion Battery" Nikkan Kogyo Shimbun (2010) p. 31 to 32

  With respect to the problems of the above-mentioned perfluoroalkyl ether compounds and fluorine-containing chained ether compounds having one oxygen atom in the molecule (hereinafter, these are also generally referred to as conventionally known perfluoroalkyl ether compounds etc.) And relatively high boiling point fluorinated ether compounds having two oxygen atoms in the molecule have been proposed (Patent Documents 5 and 6).

  The fluorine-containing chain ether compounds proposed herein have boiling points of 150 ° C. or higher and are compounds which can be used in a wide range of temperatures. However, the compound shown in Patent Document 5 has a problem that the viscosity is relatively high, and the compound shown in Patent Document 6 has a complicated synthesis method, is poor in production efficiency, and is difficult to be industrially used, etc. There was a problem.

  The present invention has been made in view of the above problems. That is, a fluorine-containing chain ether compound having a high boiling point as compared to conventionally known perfluoroalkyl ether compounds and the like, as well as being excellent in compatibility with organic compounds and capable of improving viscosity and being easily synthesizable And it aims at providing the manufacturing method.

The present inventors diligently studied to solve the above problems. As a result, the novel fluorine-containing chain-like ether compound obtained by the addition reaction of fluorine-containing alkoxyethanol and fluoroalkene has a high boiling point as compared with conventionally known perfluoroalkyl ether compounds and the like and a phase with an organic compound It has been found that the solubility is excellent. The inventors have also found that the compound can also be improved in viscosity and can be easily synthesized. Furthermore, the inventors have found that the compounds have improved physical properties with regard to oxidation resistance.
Thus, the inventor has completed the present invention.

That is, the present invention relates to the following gist.
(I)
General formula (1):
(Wherein, R ¹ represents an alkyl group having 1 to 2 carbon atoms which is substituted by at least one fluorine atom, X represents a hydrogen atom or a trifluoromethyl group, and Y represents a hydrogen atom, a fluorine atom or trifluoro A fluorine-containing chain ether compound represented by: methyl group, and Z represents a hydrogen atom or a fluorine atom.

(II)
The fluorine-containing chain ether compound represented by the above general formula (1) is 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane The fluorine-containing chain ether compound as described in (I).

(III)
A cleaning agent comprising the fluorinated chained ether compound of (I) or (II).

(IV)
An electrolytic solution for a non-aqueous secondary battery, comprising a non-aqueous solvent, an electrolyte salt, and a fluorinated chain ether compound of (I) or (II).

(V)
General formula (2):

(Wherein, R ¹ represents an alkyl group having 1 to 2 carbon atoms which is substituted by at least one fluorine atom, and X represents a hydrogen atom or a trifluoromethyl group). And general formula (3):
(Wherein Y represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and Z represents a hydrogen atom or a fluorine atom), which is reacted with a fluoroalkene compound represented by the general formula (1):

(Wherein, R ¹ , X, Y and Z are as defined above).

  According to the present invention, a fluorine-containing fluorine compound having a high boiling point as compared to conventionally known perfluoroalkyl ether compounds and the like, as well as being excellent in compatibility with organic compounds and capable of improving viscosity and being easily synthesizable A chain ether compound and a method for producing the same can be provided. Moreover, the cleaning agent containing this fluorine-containing chain | strand-shaped ether compound and the electrolyte solution for non-aqueous secondary batteries can be provided.

It is a LSV graph of an Example and a comparative example. The solid line is a LSV graph of the electrolyte solution of Example 1a containing 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane. The broken line is a LSV graph of the electrolyte solution of Comparative Example 1a containing bis (2,2,2-trifluoroethoxy) ethane. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the outline | summary of the structure of the electrochemical cell which combined the platinum electrode used for the ion conductivity measurement in the Example.

Hereinafter, one embodiment of the present invention will be described in detail.
The present embodiment relates to a novel fluorine-containing chained ether compound (hereinafter also referred to as fluorine-containing chained ether compound (1)) represented by the general formula (1).

The definition of R ¹ in the general formula (1) representing the structure of the fluorine-containing chain ether compound (1) of the present embodiment will be described. R ¹ represents a C ¹ or C 2 alkyl group substituted by at least one fluorine atom. Specifically, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2 And 2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,2-pentafluoroethyl group etc. can be mentioned. Among these, since the compound has a high fluorine content and a higher boiling point and is more excellent in oxidation resistance and safety, it is possible to use difluoromethyl group, trifluoromethyl group, 1,1,2 as R ^1. , 2-tetrafluoroethyl group and 1,1,2,2,2-pentafluoroethyl group are preferable. Among them, a trifluoromethyl group is particularly preferable as R ¹ because the compound can be expected to have lower viscosity and further high oxidation resistance.

  In the general formula (1), X represents a hydrogen atom or a trifluoromethyl group, Y represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and Z represents a hydrogen atom or a fluorine atom.

  Although the following compounds are specifically illustrated as a fluorine-containing chain | strand-shaped ether compound of General formula (1), This invention is not limited to this.

Next, the manufacturing method of the fluorine-containing chain | strand-shaped ether compound (1) of this embodiment is demonstrated.
The fluorine-containing chain ether compound (1) of the present embodiment is obtained, for example, by the reaction of a fluorine-containing alkoxyethanol compound represented by the following general formula (2) with a fluoroalkene compound represented by the following general formula (3) It can be synthesized. ^R 1, X, and Y and Z contained in the general formula (3) contained in the general formula (2) is, ^R 1 in the formula (1), X, is synonymous with Y and Z.

The fluorine-containing alkoxyethanol compound represented by the general formula (2) can be produced according to a general synthesis method well known to those skilled in the art, for example, by reacting a fluorine-containing alcohol with ethylene carbonate or ethylene oxide. Alternatively, commercially available products may be used.
Specific examples of the fluorine-containing alkoxyethanol compound represented by the general formula (2) include the following compounds, but the present invention is not limited thereto.

The fluoroalkene compounds represented by the general formula (3) can also be produced according to general synthetic methods well known to those skilled in the art.
Examples of the fluoroalkene compound represented by the general formula (3) include tetrafluoroethylene, trifluoroethylene, 1,1-difluoroethylene, 1,1,3,3,3-pentafluoropropene and hexafluoropropylene. .

  The reaction of the fluorine-containing alkoxyethanol compound represented by the general formula (2) with the fluoroalkene compound represented by the general formula (3) can be carried out using an inorganic base and an aqueous solution thereof. As the inorganic base, for example, alkali carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate, alkali hydroxides such as sodium hydroxide and potassium hydroxide, periodic table such as magnesium hydroxide and calcium hydroxide It is possible to use hydroxides of metals belonging to These inorganic bases may be used as a solid or may be used by dissolving or suspending in water. These inorganic bases may be used alone or in combination of two or more.

  The amount of the inorganic base to be used is preferably 0.001 to 1.0 mol, more preferably 0.01 to 0.5 mol, per 1 mol of the alkoxyethanol compound represented by General Formula (2). More preferred is 02 to 0.2 mol.

  The molar ratio of the fluoroalkene compound represented by the general formula (3) to the fluorine-containing alkoxyethanol compound represented by the general formula (2) is not particularly limited, but 1:10 to 10: in terms of a good yield. A ratio appropriately selected from 1 is preferable, and a ratio appropriately selected from 1: 1 to 1: 4 is economically more preferable.

  The reaction temperature of the fluorine-containing alkoxyethanol compound represented by the general formula (2) and the fluoroalkene compound represented by the general formula (3) is not particularly limited, but for example, at a temperature appropriately selected from -20 to 200 ° C. It can be implemented. Among these, it is preferable to carry out at a temperature appropriately selected from 0 to 150 ° C. in terms of a good yield. The reaction method and reaction pressure are also not particularly limited, but it is usually preferable to carry out the reaction at a pressure of normal pressure to 5 MPa, more preferably 0.1 to 2 MPa, while continuously feeding the fluoroalkene compound. In addition, in this specification, normal pressure means the range of the pressure of 20% of upper and lower sides centering on standard atmospheric pressure 101325Pa.

  The fluorinated chain ether compound (1) obtained by the above reaction is extracted after completion of the reaction of the alkoxyethanol-containing compound represented by the general formula (2) and the fluoroalkene compound represented by the general formula (3), It can be isolated by performing ordinary treatments such as filtration. If necessary, the fluorinated chain ether compound (1) may be purified by distillation, column chromatography or the like.

Next, an example of application of the fluorine-containing chain ether compound (1) of the present embodiment will be described. The fluorinated chain ether compound (1) of the present embodiment has a high boiling point as compared with the conventionally known perfluoroalkyl ether compound etc. and is also excellent in compatibility with organic compounds. The fluorine-containing chain ether compound (1) of the present embodiment also has improved physical properties with respect to viscosity. In addition, the fluorine-containing chain ether compound (1) of the present embodiment has improved physical properties with respect to oxidation resistance.
Therefore, the fluorinated chain ether compound (1) of the present embodiment is used in various applications such as solvents for fluorine oil, detergents, solvents for organic synthesis reaction, extraction solvents, and electrolytes for non-aqueous secondary batteries. It can be used.

  Although the cleaning object is not specifically limited regarding the cleaning agent containing the fluorine-containing chain | strand-shaped ether compound (1) of this embodiment, For example, an electronic component, an industrial product, etc. can be mentioned. When the fluorine-containing chain ether compound (1) of the present embodiment is used as a detergent component, the fluorine-containing chain ether compound represented by the general formula (1) may be used alone as a detergent. The fluorine-containing chain ether compound (1) and the non-aqueous solvent may be mixed to constitute the cleaning agent. The fluorine-containing chained ether compound (1) of the present embodiment is compatible with various organic compounds, and there is no particular limitation on the non-aqueous solvent to be mixed, and it is suitable according to the solubility of the compound to be dissolved. It can be selected. Specifically, alcohols such as methanol, ethanol, isopropanol, butanol and hexanol, halogenated hydrocarbons such as chloroform and dichloromethane, hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, diethyl ether And ethers such as tetrahydrofuran, glymes such as diglyme, triglyme, tetraglyme and the like, and one or more of them may be used as the non-aqueous solvent.

  Specific applications of the cleaning agent include grease, oil, ink, wax, removing agents such as flux, vehicle cleaning agents such as car window washer fluid, cleaning agents such as resist and electronic parts, drainage agents, etc. be able to.

  The fluorine-containing chain ether compound (1) of the present embodiment can also be used as a diluting solvent for fluorine oil, fluorine-based paint and the like.

When using fluorine-containing chain | strand-shaped ether compound (1) of this embodiment as a component of the solvent for organic synthesis reaction, you may use independently. Further, as in the case of the detergent, depending on the reaction, the fluorine chain ether compound (1) and various non-aqueous solvents may be mixed to constitute a solvent for organic synthesis reaction. The fluorine-containing chain ether compound (1) of the present embodiment has excellent chemical stability (oxidation resistance) as described above, and can be used as a solvent for various organic synthesis reactions.
Examples of reactions using a solvent for organic synthesis reaction containing a fluorinated chain ether compound (1) include, for example, esterification reaction, amidification reaction, amination reaction, hydrolysis reaction, cross coupling reaction, oxidation reaction , Reduction reaction, halogenation reaction, polymerization reaction and the like can be mentioned.
The fluorine-containing chain ether compound (1) of the present embodiment has a high boiling point as described above. In addition, the fluorine-containing chain ether compound (1) of the present embodiment has a melting point lower than conventionally known perfluoroalkyl ether compounds and the like. Therefore, the fluorine-containing chain ether compound (1) of the present embodiment is superior in thermal stability to conventionally known perfluoroalkyl ether compounds and the like, and is not particularly limited. The reaction can be carried out in a wide temperature range of

  The fluorine-containing chain ether compound (1) of the present embodiment can also be used as an extraction solvent. When used as an extraction solvent, the extraction layer is a lower layer with a specific gravity of greater than 1 and, therefore, when extracting the desired product from the aqueous solution, especially when the extraction rate is low and the number of extractions increases have.

  The fluorine-containing chain ether compound (1) of the present embodiment can also be used in an electrolyte solution for non-aqueous secondary batteries. The said electrolyte solution for non-aqueous secondary batteries is comprised including the fluorine-containing chain | strand-shaped ether compound of this embodiment, a non-aqueous solvent, and electrolyte salt, for example, it can prepare by mixing these. it can. The fluorine-containing chain ether compound (1) of the present embodiment has high oxidation resistance as described above, and is particularly suitable as an electrolyte solution for high energy density devices such as high voltage lithium ion batteries.

In addition, the fluorinated chain ether compound (1) of the present embodiment is sufficiently compatible with high dielectric constant solvents such as ethylene carbonate and propylene carbonate. Therefore, the fluorine-containing chain-like ether compound (1) of the present embodiment can be mixed with various non-aqueous solvents to constitute an electrolyte solution for non-aqueous secondary batteries.
In addition, although not particularly limited, the content of the fluorine-containing chain ether compound (1) is preferably in the range of 0.1 to 70% by volume with respect to the non-aqueous solvent from the viewpoint of electrolyte performance. It is particularly preferable to contain in the range of 5 to 50% by volume.

  As a non-aqueous solvent mixed in the electrolyte solution for non-aqueous secondary batteries other than fluorine-containing chain | strand-shaped ether compound (1), various aprotic polar solvents can be used, for example. Specific examples of the aprotic polar solvent include ethylene carbonate, propylene carbonate, butylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, cyclic carbonates such as difluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diphenyl carbonate, Chain carbonates such as bis (2,2,2-trifluoroethyl) carbonate, cyclic esters such as γ-butyrolactone, γ-valerolactone, propiolactone, chains such as methyl acetate, methyl butyrate and ethyl trifluoroacetate Ethers such as ester, diisopropyl ether, tetrahydrofuran, dioxolane, dimethoxyethane, diethoxyethane, methoxyethoxyethane and the like and acetonitrile Examples thereof include nitriles such as ryl and benzonitrile, phosphate esters such as trimethyl phosphate and triethyl phosphate, and fluorine-containing phosphate esters such as tris (2,2,2-trifluoroethyl) phosphate. These may be used alone or in combination of two or more.

As the electrolyte salt, for _{example, LiBF 4, LiPF 6, LiPF} 5 (CF 3), LiAsF 6, LiSbF 6, LiClO 4, LiCF 3 SO 3, LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2 , Li salts such as LiN (SO ₂ C ₂ F ₅ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , Mg salts such as Mg (PF 6) 2, Mg (N (SO ₂ C ₂ F ₅ ) ₂ ) ₂ etc. Can be mentioned. These may be used alone or in combination of two or more. Among these electrolyte salts, LiPF ₆ , LiN (SO ₂ F) ₂ , and LiN (CF ₃ SO ₂ ) ₂ are preferable in that they have excellent dissociativeness and high ion conductivity.

  The concentration of the lithium salt in the non-aqueous secondary battery electrolyte according to the present embodiment is not particularly limited, but is preferably in the range of 0.1 to 2.5 mol / L. The lithium salt has a lower ion conductivity than when it is in the range if the concentration is lower than the following range, and a viscosity compared to when it is in the range when the concentration is higher than the following range 0.5 to 2.0 mol / L is more preferable, and 0.7 to 1.7 mol / L is even more preferable.

  The present invention will be described in more detail using the following examples, but the present invention is not limited by these examples.

Example 1: Synthesis of 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane (TeFTFEE)

After 205.0 g of 2- (2,2,2-trifluoroethoxy) ethanol and 8.2 g of a 48% aqueous solution of KOH were charged into the autoclave, the temperature was raised until the internal temperature reached 30 ° C. In this autoclave, tetrafluoroethylene was introduced into the autoclave at a pressure of 0.4 to 1.5 MPa while maintaining the internal temperature at 30 to 40 ° C. under stirring conditions. After allowing to cool, the autoclave was opened, water was added, and the organic layer was separated. After washing with the same amount of water, purification by distillation (89.5 ° C./15 kPa) gives 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoro 331.7 g of ethoxy) ethane (hereinafter abbreviated as TeFTFEE) was obtained (yield 95.5%).

  The boiling point of the obtained TeFTFEE was 156 ° C. in terms of normal pressure, and the freezing point measured according to JIS K 0065 “Method of measuring freezing point of chemical product” was −50 ° C. or less. For this reason, it was confirmed that the said compound of Example 1 is a liquid which can be handled in a wide temperature range compared with the conventionally known perfluoro alkyl ether compound etc.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.73 (tt, J = 53.4 Hz, 2.8 Hz, 1 H), δ 4.14 (m, 2 H), δ 3.90 (q, J = 8.6 Hz , 2H), δ 3.88 (m, 2H),
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-74.9 (t, J = 8.6 Hz, 3 F), δ-92.3 (td, J = 5.3 Hz, 2.8 Hz, 1 H), δ -137.3 (dt, J = 53.4 Hz, 5.3 Hz, 1 H)

[Test Example 1: Oxidation Decomposition Potential of Fluorine-Containing Chain-Like Ether Compound]
The electrochemical stability of the compounds was assessed by linear sweep voltammetry (LSV) measurements. The measurement of LSV was performed using multichannel potentiostat / galvanostat (Biologic, VMP-3).
In an argon atmosphere, 0.30 g of lithium hexafluorophosphate (LiPF ₆ ) was added to 0.24 g of TeFTFEE obtained in Example 1 as a fluorine-containing chain ether compound. An ethylene carbonate / ethyl methyl carbonate mixed solution (volume ratio: 3/7) was added to the obtained mixture to prepare 10 ml of an electrolytic solution of Example 1a. The TeFTFEE concentration and the LiPF 6 concentration in the electrolytic solution of Example 1a were 0.1 mol / L and 0.2 mol / L, respectively.

  Into the electrolytic solution of Example 1a, platinum as a working electrode, lithium foil as a counter electrode and lithium foil as a reference electrode were inserted and swept toward the noble side at a scanning speed of 5 mV / sec to measure the oxidation decomposition potential. The results are shown in FIG. Further, from the graph of LSV obtained, a voltage at which a current of 1 mA / cm 2 was observed is shown in Table 1 as a decomposition potential. In addition, all the measurement of LSV was implemented in the glove box filled with argon atmosphere.

  An electrolysis of Comparative Example 1a was performed in the same manner as in Example 1a except that bis (2,2,2-trifluoroethoxy) ethane (hereinafter abbreviated as BTFEE) was used as the fluorine-containing chain ether compound of Comparative Example 1. The solution was prepared. The oxidative decomposition potential was measured by the method of LSV of Example 1a using the electrolytic solution of Comparative Example 1a.

  The results of Example 1a and Comparative Example 1a are shown in FIG. 1 and Table 1.

TeFTFEE: 1- (1,1,2,2-tetrafluoroethoxy) -2-
(2,2,2-trifluoroethoxy) ethane BTFEE: bis (2,2,2-trifluoroethoxy) ethane

  From the results of Table 1 and FIG. 1, it became clear that TeFTFEE, which is one of the fluorine-containing chain ether compounds of the present invention, is superior in oxidation resistance to BTFEE. Although this factor is not clear, it is considered that the oxidation resistance is improved from the structural influences such as the number of fluorine atoms and the bonding of the fluorine atom to the oxygen atom adjacent carbon.

Test Example 2 Viscosity of Fluorine-Containing Chain-Like Ether Compound
The viscosity of TeFTFEE synthesized in Example 1 was measured. Specifically, the kinematic viscosity in a constant temperature bath at 20 ° C. is measured according to the method of JIS Z 8803: 1991 using a Ubbelohde viscometer, and the product of the dynamic viscosity and the density at 20 ° C. is fluorine-containing. The viscosity of the linear ether was calculated. The results are shown in Table 2.
Further, the kinematic viscosity of bis (1,1,2,2-tetrafluoroethoxy) ethane (hereinafter abbreviated as BTeFEE) used as Comparative Example 2 and the viscosity calculated from the density are also shown in Table 2.

TeFTFEE: 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane BTeFEE: bis (1,1,2,2-tetrafluoroethoxy) ethane

  It can be seen from Table 2 that TeFTFEE, which is one of the fluorine-containing chain ether compounds of the present invention, has a lower viscosity than conventionally known BTeFEE.

[Test Example 3: Compatibility of a Fluorinated Chain-like Ether Compound with an Organic Solvent]
2.0 g of each organic solvent was mixed with 2.0 g of TeFTFEE, and shaken for 1 minute. Thereafter, the mixture was allowed to stand for a while, and the state of the solution was visually confirmed. The evaluation was described in Table 3 as も の (compatible) in which the two solutions were uniform, and × (incompatible) in which the two layers were separated.

  As Comparative Example 3, the compatibility was examined in the same manner as in Example using perfluoroalkyl ether [C2F5CF (-O-CH3) C3F7, manufactured by 3M, trade name Novec 7300]. The results are shown in Table 3.

TeFTFEE: 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane Novec 7300: bis (1,1,2,2-tetrafluoroethoxy) ethane PC : Propylene carbonate

  From Table 3, it is clear that TeFTFEE, which is one of the fluorine-containing chain ether compounds of the present invention, is compatible with more nonaqueous solvents and is more excellent in compatibility than Nobec 7300.

[Test Example 4: Use as a cleaning agent]
The test piece (made of SUS-304) was immersed in mineral oil (manufactured by Matsumura Petroleum, Neovac MR-100) and heat-treated at 180 ° C. for 1 minute. The test piece was immersed in TeFTFEE and subjected to ultrasonic cleaning for 30 seconds at a temperature of 25 ° C. Subsequently, as a result of hot air drying of the test piece after ultrasonic cleaning with a drier, no remaining of mineral oil was observed, and it was confirmed that oil stains could be removed well.

[Test Example 5: Application Example of a fluorinated chain ether compound (1) as a solvent for organic synthesis (cross coupling reaction)]

  In a 100 ml Schlenk tube, 20 ml of TeFTFEE obtained in Example 1 was placed, and 4-n-propylphenylboronic acid 1.1 was added and dissolved. After nitrogen substitution, add 0.040 g of triphenylphosphine, 0.97 g of bromobenzene, 0.047 g of dichlorobis (triphenylphosphine) palladium (II) and 4.0 g of cesium carbonate under stirring, and react at 80 ° C. for 4 hours The

  After the reaction, the reaction solution was washed with 20 ml of water, and the organic layer (lower layer) was subjected to GC analysis, and it was confirmed that 4-n-propylbiphenyl which is a cross coupling product was formed in a yield of 99%. It was done.

  From this result, it was confirmed that TeFTFEE, which is one of the fluorinated chained ether compounds of the present invention having excellent compatibility as described above, can be used as a solvent for organic synthesis.

[Test Example 6: Evaluation of ion conductivity and viscosity in non-aqueous electrolyte solution]
The ion conductivity and the viscosity of the non-aqueous electrolyte solution containing TeFTFEE, which is one obtained by Example 1, were evaluated.

The measurement of the ion conductivity (unit: mS / cm) of the non-aqueous electrolyte solution is carried out at 20 ° C. using the method described in “Electrochemical Measurement Manual, Basic edition, 2002, 45, Electrochemical Society edition, Maruzen Co., Ltd.” I went there. That is, a standard solution with known conductivity was injected in advance into the electrochemical cell 3 in which the platinum electrodes 4 shown in FIG. 2 were combined facing each other, and the cell constant was calculated. The prepared electrolyte was injected into the electrochemical cell and sealed. The solution resistance was measured by a complex impedance method using a potentiostat / galvanostat (VersaSTAT 4-400 manufactured by Toyo Corporation) after the electrochemical cell was allowed to stand in a thermostat at 20 ° C. for 1 hour. The ion conductivity of each non-aqueous electrolyte was calculated from the obtained solution resistance value.
Calculation formula: Ion conductivity (mS / cm) = solution resistance (Ω) / cell constant

  The viscosity (unit: mPa · sec) of the non-aqueous electrolyte solution was measured using a cone-plate type rotational viscometer (DV-I PRIME, manufactured by BrookField). That is, the prepared electrolytic solution was introduced into a cup of a rotational viscometer connected to a fluid-type thermostat, and it was made to flow and measured until the temperature became constant at 20 ° C.

Preparation of the non-aqueous electrolyte solution of the example was performed as follows.
Ethylene carbonate (hereinafter abbreviated as EC), tris (2,2,2-trifluoroethyl) phosphate (hereinafter abbreviated as TFEP), and TeFTFEE were mixed at a volume ratio of 50/25/25. Lithium hexafluorophosphate (hereinafter referred to as LiPF6) was added as an electrolyte to the resulting mixture to a concentration of 1.0 mol / L, and the mixture was thoroughly stirred at 20 ° C. to dissolve completely, Example 1b A non-aqueous electrolyte was prepared. The ionic conductivity and the viscosity of the non-aqueous electrolyte solution of Example 1b were measured by the above-mentioned method.

A non-aqueous electrolytic solution of Comparative Example 4 was prepared in the same manner as in Example 1b, except that EC and TFEP were mixed at a volume ratio of 50/50 without adding TeFTFEE. The ion conductivity and the viscosity of the non-aqueous electrolyte solution of Comparative Example 4 were also measured by the above-described method.
The results are shown in Table 4.

LiPF6: lithium hexafluorophosphate EC: ethylene carbonate TFEP: tris (2,2,2-trifluoroethyl) phosphate
TeFTFEE: 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane

  From the results shown in Table 4, it can be understood that the non-aqueous electrolyte of Example 1 b has high ion conductivity and low viscosity as compared to the non-aqueous electrolyte of Comparative Example 4.

  The fluorinated chain ether compound of the present invention has a high boiling point as compared with conventionally known perfluoroalkyl ether compounds and the like, and is excellent in compatibility with an organic compound and can improve the viscosity and is easy It can be synthesized. Therefore, it can be widely used as a cleaning agent for electronic parts, industrial products, etc., a solvent for organic synthesis, and an electrolyte for non-aqueous secondary batteries, and is extremely useful.

1: LSV graph of 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane (Example 1a) 2: bis (2,2,2-triethoxy) LSV graph of fluoroethoxy) ethane (Comparative Example 1a) 3: Glass electrochemical cell 4: Platinum electrode

Claims (4)

1- (1,1,2,2-tetrafluoro-ethoxy) -2- (2,2,2-trifluoroethoxy) ethanone down. A detergent comprising 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane according to claim 1 . A non-aqueous system comprising a non-aqueous solvent, an electrolyte salt, and 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane according to claim 1 Electrolyte solution for secondary battery. A process for producing 1- (1,1,2,2-tetrafluoroethoxy) -2- (2,2,2-trifluoroethoxy) ethane according to claim 1,
The above production method, which comprises reacting 2- (2,2,2-trifluoroethoxy) ethanol with tetrafluoroethylene .