WO2012053346A1 - Sulfolane fluoré et procédé de fabrication de sulfolane fluoré - Google Patents

Sulfolane fluoré et procédé de fabrication de sulfolane fluoré Download PDF

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WO2012053346A1
WO2012053346A1 PCT/JP2011/072802 JP2011072802W WO2012053346A1 WO 2012053346 A1 WO2012053346 A1 WO 2012053346A1 JP 2011072802 W JP2011072802 W JP 2011072802W WO 2012053346 A1 WO2012053346 A1 WO 2012053346A1
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atom
fluorine
formula
group
compound represented
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明天 高
有希 足立
葵 中園
昭佳 山内
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ダイキン工業株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to fluorine-containing sulfolane and a method for producing fluorine-containing sulfolane.
  • Sulfolane compounds are used in various applications because of their excellent high temperature characteristics and high dielectric constant characteristics.
  • energy storage devices such as lithium-ion batteries
  • digital portable electronic devices such as mobile phones, personal digital assistants and notebook computers.
  • the use of the electrolyte solution used for energy storage devices as a solvent or additive is particularly expected.
  • Patent Document 1 As a sulfolane compound known so far, for example, in Patent Document 1, sulfolane is produced by reacting sulfolane with fluorine gas.
  • Non-Patent Document 1 describes a reaction of adding fluorine gas to sulfolene.
  • Patent Document 2 a fluorinated sulfolane compound is produced by a reaction between sulfolanes and fluorine gas.
  • the sulfolane compounds have various excellent properties as described above, and various sulfolane compounds have been produced.
  • the sulfolane compounds are not particularly satisfactory in terms of oxidation resistance, and correspond to higher performance of energy storage devices. Therefore, a material with better oxidation resistance has been desired.
  • the present invention provides a novel fluorine-containing sulfolane that can be suitably used as an electrolyte for an energy storage device and a method for producing the same.
  • the present invention provides the following formula (1): (In the formula, Rf is a C 1-8 fluoroalkyl group which may contain a hetero atom.) It is related with the fluorine-containing sulfolane characterized by these.
  • Patent Document 1 and Non-Patent Document 1 do not disclose sulfolane having a fluoroalkyl group.
  • Patent Document 2 discloses a fluorinated sulfolane compound.
  • a sulfolane ring and a fluorine gas are reacted to form a sulfolane ring.
  • the hydrogen atom bonded to the carbon atom is replaced with a fluorine atom, and the fluorine-containing sulfolane of the present invention cannot be produced.
  • Rf is the following formula (2): (Wherein X 1 to X 4 each independently represents a trifluoromethyl group, a trifluoromethoxy group, a hydrogen atom, or a halogen atom, provided that at least one of X 1 to X 4 is A fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group.) It is preferable that it is the fluoroalkyl group represented by these.
  • Rf is —CF 2 CFHOCF 3 , —CH 2 CFHCF 3 , —CH 2 CH 2 CF 3 , —CFHCF 2 H, —CFHCHFCF 3 , —CF 2 CF 2 H, —CH 2 CF 2 H, and —CF It is preferably at least one group selected from the group consisting of 2 CFHCF 3 .
  • the present invention relates to an electrolytic solution containing the fluorine-containing sulfolane of the present invention.
  • the present invention provides the following formula (3): (In the formula, Rf is a C 1-8 fluoroalkyl group which may contain a hetero atom.) A compound represented by the following formula (1): (In the formula, Rf is a C 1-8 fluoroalkyl group which may contain a hetero atom.) A process for obtaining a fluorinated sulfolane represented by the formula:
  • the oxidizing agent is preferably at least one compound selected from the group consisting of peroxides, perhalogen oxides, permanganates, and chromates.
  • the compound represented by the formula (3) is obtained by reacting tetrahydrothiophene with a fluoroalkene having 2 to 8 carbon atoms:
  • Rf 1 is a fluoroalkyl group having 2 to 8 carbon atoms which may contain a hetero atom.
  • a compound represented by The fluorine-containing sulfolane represented by the formula (1) is represented by the following formula (5):
  • Rf 1 is a fluoroalkyl group having 2 to 8 carbon atoms which may contain a hetero atom.
  • the fluoroalkene has the following formula (6): (Wherein X 1 to X 4 each independently represents a trifluoromethyl group, a trifluoromethoxy group, a hydrogen atom, or a halogen atom, provided that at least one of X 1 to X 4 is A fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group.) It is preferable that it is a compound represented by these.
  • the compound represented by the formula (3) is 1) 5-halogen-1-pentene (halogen: fluorine atom, chlorine atom, bromine atom or iodine atom) is substituted with Rf 2 X 5 (wherein Rf 2 represents the number of carbon atoms optionally containing a hetero atom) 1 to 7 fluoroalkyl groups, and X 5 is a chlorine atom, a bromine atom, or an iodine atom.)
  • a compound represented by the following formula (7) (Wherein Rf 2 is a fluoroalkyl group having 1 to 7 carbon atoms which may contain a hetero atom, X 6 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and X 5 Is a chlorine atom, a bromine atom, or an iodine atom.) 2)
  • the compound represented by the formula (7) is reacted with a thiolating agent to obtain
  • Rf 2 represents — (CF 2 ) n H (n is an integer of 1 to 7), — (CF 2 ) m CF 3 (m is an integer of 1 to 6), —CF (CF 3 ) 2 and at least one group selected from the group consisting of —CH (CF 3 ) 2 .
  • the fluorine-containing sulfolane of the present invention is very useful as a solvent or additive used in an electrolyte solution of an energy storage device. Moreover, the fluorine-containing sulfolane of the present invention has excellent oxidation resistance.
  • the method for producing a fluorine-containing sulfolane of the present invention can reliably produce the novel fluorine-containing sulfolane by a simple method.
  • Rf is a C 1-8 fluoroalkyl group which may contain a hetero atom. It is related with the fluorine-containing sulfolane characterized by these.
  • the fluorine-containing sulfolane of the present invention is a fluorine-containing sulfolane having a specific structure having a fluoroalkyl group, it has excellent oxidation resistance and high electrochemical stability.
  • the fluorine-containing sulfolane represented by the above formula (1) is difficult to synthesize and cannot be synthesized conventionally.
  • the synthesis was succeeded for the first time by using the production method described later, and the fluorine-containing sulfolane represented by the above formula (1) has excellent oxidation resistance and high electrochemical stability. Was found to show.
  • Rf is a fluoroalkyl group having 1 to 8 carbon atoms which may contain a hetero atom.
  • the number of carbon atoms is preferably 2 to 8, more preferably 2 to 6, and further preferably 3 to 6.
  • the “hetero atom” represents a halogen atom other than a fluorine atom, an oxygen atom, a sulfur atom, a nitrogen atom, or the like.
  • “may contain a heteroatom” means that it contains a heteroatom or does not contain a heteroatom.
  • fluoroalkyl group having 1 to 8 carbon atoms which may contain a hetero atom means a fluoroalkyl group having 1 to 8 carbon atoms or a fluoroalkyl group having 1 to 8 carbon atoms containing a hetero atom. Represents. In the present specification, “which may contain a hetero atom” has the same meaning hereinafter.
  • the fluoroalkyl group may be an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may be a perfluoroalkyl group. Further, it may be a linear fluoroalkyl group or a branched fluoroalkyl group.
  • Rf examples include fluoroalkyl groups such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, and a fluorohexyl group. These fluoroalkyl groups may be linear or branched. Further, it may be a perfluoroalkyl group.
  • Rf the following formula (2): (Wherein X 1 to X 4 each independently represents a trifluoromethyl group, a trifluoromethoxy group, a hydrogen atom, or a halogen atom, provided that at least one of X 1 to X 4 is A fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group.) Is preferably a fluoroalkyl group represented by the following formula (2-1): (In the formula, X 3 and X 4 are the same as those in the formula (2).) It is more preferable that it is the fluoroalkyl group represented by these.
  • Examples of the fluoroalkyl group represented by the formula (2) include —CF 2 CFHCF 3 , —CF 2 CF 2 H, —CF 2 CFHOCF 3 , —CFHCF 2 H, —CFHCHFHCF 3 , —CH 2 CFHCF 3 , — CH 2 CH 2 CF 3 , —CH 2 CF 2 H, —CF 2 CFClH, —CF 2 CCl 2 H, and the like can be given.
  • —CF 2 CFHOCF 3 —CH 2 CFHCF 3 , —CH 2 CH 2 CF 3 , —CFHCF 2 H, —CFHCHFCF 3 , —CF 2 CF 2 H, —CH 2 CF 2 H, and — It is preferably at least one selected from the group consisting of CF 2 CFHCF 3, and at least one selected from the group consisting of —CF 2 CFHCF 3 , —CF 2 CF 2 H, and —CF 2 CFHOCF 3 It is more preferable that
  • the present invention also provides the following formula (3): (In the formula, Rf is a C 1-8 fluoroalkyl group which may contain a hetero atom.) A compound represented by the following formula (1): (In the formula, Rf is a C 1-8 fluoroalkyl group which may contain a hetero atom.) A process for obtaining a fluorinated sulfolane represented by the formula: The method for producing a fluorine-containing sulfolane of the present invention may include other steps as long as it includes the step of obtaining the fluorine-containing sulfolane.
  • a highly purified fluorine-containing sulfolane can be obtained by producing a fluorine-containing sulfolane and then performing a purification step.
  • a method usually used for purification of an organic compound such as recrystallization, filtration and rectification can be employed.
  • Rf in the above formula (3) examples include the same as Rf in the formula (1).
  • the oxidizing agent those described later can be used.
  • a method of reacting the compound represented by the formula (3) with an oxidant a method of introducing an oxidant into the liquid phase compound represented by the formula (3) and reacting the compound can be mentioned. Details of the method will be described later.
  • first production method the production method using the compound represented by the above formula (4) is referred to as “first production method”
  • second manufacturing method the production method using the compound represented by the above formula (7)
  • the first production method of the present invention comprises: Tetrahydrothiophene is reacted with a fluoroalkene having 2 to 8 carbon atoms to form the following formula (4): (In the formula, Rf 1 is a fluoroalkyl group having 2 to 8 carbon atoms which may contain a hetero atom.) A step of obtaining a compound represented by: The compound represented by the above formula (4) is reacted with an oxidizing agent to form the following formula (5): (In the formula, Rf 1 is a fluoroalkyl group having 2 to 8 carbon atoms which may contain a hetero atom.) The process of obtaining the fluorine-containing sulfolane represented by these is included.
  • the first production method of the present invention can produce the fluorine-containing sulfolane represented by the above formula (5) simply and reliably.
  • fluorine-containing sulfolane having excellent oxidation resistance and high electrochemical stability can be produced.
  • the fluoroalkene preferably has 2 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
  • Examples of the fluoroalkene include fluoroethylene, fluoropropylene, fluorobutylene, fluoropentene, and fluorohexene. These fluoroalkenes may be linear or branched. Further, the structure may contain a hetero atom, and in particular, the structure may have an ether bond. Perfluoroalkene may be used.
  • the fluoroalkene the following formula (6): (Wherein X 1 to X 4 each independently represents a trifluoromethyl group, a trifluoromethoxy group, a hydrogen atom, or a halogen atom, provided that at least one of X 1 to X 4 is A fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group.) Is preferably a compound represented by the following formula (6-1): (Wherein X 3 and X 4 are the same as those in formula (6).) It is more preferable that it is a compound represented by these.
  • Rf 1 is preferably a group represented by the above formula (2) or formula (2-1).
  • Examples of the method of reacting the fluoroalkene with tetrahydrothiophene include a method of introducing the fluoroalkene into a liquid phase tetrahydrothiophene and causing the reaction.
  • the reaction method can be any of batch method, semi-batch method, and flow method.
  • the temperature at which the fluoroalkene reacts with the tetrahydrothiophene is preferably 60 to 150 ° C., more preferably 80 to 150 ° C.
  • the reaction pressure is preferably 0.5 to 1.0 MPa.
  • the reaction time varies depending on the reaction temperature and the like, but is usually 5 to 10 hours. Further, it is preferable to carry out the reaction by adding 0.1 to 8 moles of the above fluoroalkene to 1 mole of tetrahydrothiophene.
  • the input amount of the fluoroalkene is more preferably 0.2 to 6 mol, and still more preferably 0.2 to 5 mol, relative to 1 mol of tetrahydrothiophene.
  • the fluoroalkene When the fluoroalkene is introduced into the liquid phase tetrahydrothiophene, the fluoroalkene may be reacted with the tetrahydrothiophene in the presence of a solvent inert to the tetrahydrothiophene and the fluoroalkene.
  • reaction initiator it is preferable to add a reaction initiator to the reaction system and react tetrafluorothiophene with a fluoroalkene having 2 to 8 carbon atoms.
  • the reaction initiator is preferably added in an amount of 10 to 50 mol% with respect to the fluoroalkene.
  • the reaction initiator may be added in a reaction vessel in which tetrahydrothiophene is reacted with the fluoroalkene.
  • the reaction initiator is not particularly limited as long as it can perform the step of obtaining a compound represented by the formula (4) by reacting the tetrahydrothiophene with a fluoroalkene having 2 to 8 carbon atoms.
  • the reaction initiator is preferably at least one compound selected from the group consisting of organic peroxide initiators, radical polymerization initiators, and redox initiators.
  • organic peroxide initiator examples include ditert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ -bis (tert-butylperoxy) -p-diisopropylbenzene, 2,5- Dialkyl peroxides such as dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane-3, 1,1-di (tert-butyl) Peroxy) -3,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, benzoyl peroxide, tert-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) Hexane, tert-butylperoxymaleic acid, Examples thereof include
  • the radical polymerization initiator is preferably a water-soluble initiator, and specific examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, disuccinic acid peroxide, azobisisobutylamidine dihydrochloride, and the like. Organic initiators and the like. Among these, persulfates such as ammonium persulfate are preferable.
  • redox initiators examples include organic initiators such as disuccinic acid peroxide and azobisisobutylamidine dihydrochloride, inorganic initiators such as persulfates and hydrogen peroxide, persulfates or hydrogen peroxide and hydroxy
  • organic initiators such as disuccinic acid peroxide and azobisisobutylamidine dihydrochloride
  • inorganic initiators such as persulfates and hydrogen peroxide, persulfates or hydrogen peroxide and hydroxy
  • a redox initiator consisting of a combination with a reducing agent such as sodium methanesulfinate, sodium hydrogen sulfite, sodium thiosulfate, etc., and an inorganic start in which a small amount of iron, ferrous salt, silver sulfate, etc. coexist with these initiators Agents and the like.
  • an ammonium persulfate / sodium hydroxymethanesulfinate / ferrous sulfate system is preferable, and it is more preferable to add ethylenediaminetetraacetic acid disodium salt as a chelating agent to this system.
  • ethylenediaminetetraacetic acid disodium salt as a chelating agent to this system.
  • a redox-type initiator it is preferable to use a pH buffer together.
  • inorganic salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen carbonate, sodium carbonate and the like can be used.
  • Disodium hydrogen phosphate dihydrate, disodium hydrogen phosphate 12 A hydrate etc. are mentioned.
  • the step of reacting the compound represented by the above formula (4) with an oxidizing agent to obtain the fluorine-containing sulfolane represented by the formula (5) comprises reacting the compound represented by the above formula (4) with the oxidizing agent. It is preferable to carry out. For example, a method of introducing an oxidant into the compound represented by the above formula (4) in the liquid phase and reacting it may be mentioned.
  • the reaction method can be any of batch method, semi-batch method, and flow method.
  • the oxidizing agent is not particularly limited as long as it is normally used as an oxidizing agent.
  • the oxidizing agent is preferably at least one compound selected from the group consisting of peroxides, perhalogen oxides, permanganates, and chromates.
  • the oxidizing agent is preferably added in an amount of 100 to 500 mol% with respect to the compound represented by the formula (4).
  • the oxidizing agent include organic peroxides (for example, m-chloroperbenzoic acid), organic peracids, hydrogen peroxide, xylene dioxide, chromic acids, manganese dioxide, hypochlorous acids, and periodic acids. , Carolic acids, ceric ammonium nitrate (CAN), iodosobenzenes, and the like.
  • the oxidation reaction is preferably performed at 25 to 80 ° C., more preferably at 30 to 80 ° C. .
  • the reaction time varies depending on the reaction temperature and the like, but is usually 5 to 10 hours.
  • the second production method of the present invention has the following formula: (In the formula, X 6 is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) Rf 2 X 5 (wherein Rf 2 is a fluoroalkyl group having 1 to 7 carbon atoms which may contain a hetero atom, and X 5 is a chlorine atom) , Bromine atom, or iodine atom.) Is reacted with a compound represented by the following formula (7): (Wherein Rf 2 is a fluoroalkyl group having 1 to 7 carbon atoms which may contain a hetero atom, X 6 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and X 5 Is a chlorine atom, a bromine atom, or an iodine atom.) The compound represented by the above formula (7) is reacted with a thiola
  • the fluorine-containing sulfolane represented by the above formula (10) can be produced by a simple method and is not fluorinated with fluorine gas. And fluorine-containing sulfolane having high stability can be produced.
  • Halogen (X 6 ) in 5-halogen-1-pentene is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and among these, a bromine atom is preferable.
  • Rf 2 is a fluoroalkyl group having 1 to 7 carbon atoms.
  • Rf 2 is a linear or branched fluoroalkyl group.
  • Rf 2 may be an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may be a perfluoroalkyl group.
  • the hetero atom may be included.
  • Rf 2 examples include fluoroalkyl groups such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, and a fluorohexyl group. These fluoroalkyl groups may be linear or branched. Further, it may be a perfluoroalkyl group.
  • — (CF 2 ) n H (n is an integer of 1 to 7), — (CF 2 ) m CF 3 (m is an integer of 1 to 6), —CF ( CF 3 ) 2 , and —CH (CF 3 ) 2 . More preferably, it is at least one selected from —C 4 F 9 , —C 2 F 5 , —CF 3 , and —CF (CF 3 ) 2 .
  • liquid-phase 5-halogen-1- examples thereof include a method in which the compound represented by Rf 2 X 5 is introduced into pentene and reacted.
  • the reaction method can be any of batch method, semi-batch method, and flow method.
  • the reaction temperature is preferably 50 to 80 ° C, more preferably 60 to 80 ° C.
  • the compounding ratio of 5-halogen-1-pentene and the compound represented by Rf 2 X 5 is preferably 1: 1 to 1: 1.5 in molar ratio. More preferably, it is 1: 1 to 1: 1.2.
  • the reaction time varies depending on the reaction temperature and the like, but is usually 5 to 10 hours.
  • the compound represented by 5-halogen-1-pentene and the compound represented by Rf 2 X 5 is used.
  • the reaction may be carried out in the presence of an inert solvent.
  • the second production method of the present invention includes a step of reacting the compound represented by the above formula (7) with a thiolating agent to obtain the compound represented by the above formula (8).
  • a thiolating agent include thioalkoxide, thiourea, thiouric acid and the like.
  • the amount of the thiolating agent added is preferably 1 to 1.5 mol with respect to 1 mol of the compound represented by the formula (7).
  • the addition amount of the thiolating agent is more preferably 1 to 1.2 mol with respect to 1 mol of the compound represented by the formula (7).
  • the second production method of the present invention includes a step of obtaining a compound represented by the above formula (9) by cyclizing the compound represented by the above formula (8).
  • Examples of the method for carrying out the cyclization reaction include a method in which an alkali solution is added to a solution containing a compound represented by the formula (8) to carry out the reaction.
  • Examples of the method of adding the alkaline solution include a method of adding all at once, a method of intermittently adding several times before or during the reaction, and a method of continuously dropping before or during the reaction. Any method may be used, but it is preferably added by a method of continuously dropping before or during the reaction.
  • the alkaline solution examples include LiOH, NaOH, KOH, RbOH, CsOH, Be (OH) 2 , Mg (OH) 2 , Ca (OH) 2 , Sr (OH) 2 , Ba (OH) 2, and the like. Is mentioned. Among these, a solution of LiOH, NaOH, KOH is preferable. Particularly preferred are an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution.
  • the concentration of the alkaline solution is preferably 20 to 40% by mass, more preferably 20 to 30% by mass.
  • the addition amount of the alkaline solution in the cyclization reaction is preferably 1.2 to 4 mol with respect to 1 mol of the compound represented by the formula (8). More preferably, it is 1.2 to 2 mol, and still more preferably 1.2 to 1.5 mol.
  • the temperature for the cyclization reaction is preferably 50 to 100 ° C., more preferably 60 to 100 ° C.
  • the reaction time varies depending on the reaction temperature and the like, but is usually 5 to 10 hours.
  • the reaction method can be any of batch method, semi-batch method, and flow method.
  • the 2nd manufacturing method of this invention includes the process of oxidizing the compound represented by the said Formula (9), and obtaining the fluorine-containing sulfolane represented by the said Formula (10).
  • the oxidation is preferably performed by reacting the compound represented by the formula (9) with an oxidizing agent.
  • an oxidizing agent for example, a method of introducing an oxidant into the compound represented by the above formula (9) in the liquid phase and reacting it may be mentioned.
  • the reaction method can be any of batch method, semi-batch method, and flow method.
  • the oxidizing agent is not particularly limited as long as it is normally used as an oxidizing agent.
  • the oxidizing agent is preferably at least one compound selected from the group consisting of peroxides, perhalogen oxides, permanganates and chromates.
  • the oxidizing agent is preferably added so as to be 2 to 4 times (molar ratio) with respect to the compound represented by the formula (9).
  • the oxidation is preferably performed at 25 to 100 ° C, more preferably 50 to 100 ° C.
  • the reaction time varies depending on the reaction temperature and the like, but is usually 5 to 10 hours.
  • the fluorine-containing sulfolane of the present invention can be used as various solvents, for example, reaction solvents for organic synthesis, extraction solvents for various inorganic and organic substances, dilution solvents for paints and inks, semiconductor resist solvents, dilution solvents for agricultural chemicals, etc. It can be used as a solvent for an electrolytic solution used in an energy storage device or the like. It can also be used as an additive for electrolytes used in energy storage devices and the like. In particular, it is useful as a solvent or additive for an electrolytic solution for an energy storage device.
  • the present invention also provides an electrolytic solution containing the above-mentioned fluorine-containing sulfolane or the fluorine-containing sulfolane obtained by the above-described production method.
  • the electrolytic solution preferably contains an electrolyte salt.
  • the electrolyte salt include LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 C 2 F 5 ) 2 .
  • Applications of the electrolytic solution using the fluorine-containing sulfolane of the present invention include, for example, an electrolytic capacitor, an electric double layer capacitor, a battery charged / discharged by charge transfer of ions, a solid display element such as electroluminescence, a current sensor and a gas Examples include sensors such as sensors.
  • a lithium ion secondary battery it is preferable to use for a lithium ion secondary battery, and the electrolytic solution of the present invention is suitably used for a lithium ion secondary battery including a positive electrode, a negative electrode, a separator, and a nonaqueous electrolytic solution containing the electrolytic solution of the present invention.
  • a lithium ion secondary battery is particularly useful as a large lithium ion secondary battery for a hybrid vehicle or a distributed power supply, but is also useful as a small lithium ion secondary battery.
  • Example 1 1) 1 step (addition reaction) The reaction was carried out in a reactor equipped with a 300 mL reflux tube. 5-Bromo-1-pentene (25 g: 168 mmol), C 4 F 9 I (65.7 g: 190 mmol), azobisisobutyronitrile (hereinafter referred to as AIBN, 551 mg: 3.4 mmol) in the reaction vessel in this order. Reagent added. Thereafter, the reaction temperature was raised to around 70-80 ° C. Although it gradually became under reflux, the reflux stopped with the progress of the reaction. After stirring for 1 hour, the reaction was completed after confirming the disappearance of the raw materials. Thereafter, only the low boiling point compound was removed under reduced pressure to proceed to the next reaction.
  • AIBN azobisisobutyronitrile
  • the NMR data of the obtained compound 1 are as follows.
  • Examples 2-4 The target product could be obtained in the same manner as in Example 1 except that the amount of compound shown in Table 1 was added.
  • Example 5 1 step (addition reaction) The reaction was carried out using an autoclave, which is a pressure-resistant reaction vessel. Add tetrahydrothiophene (100 g: 1.136 mol) and initiator perbutyl D (16.7 g: 114 mmol, manufactured by NOF Corporation, di-tert-butyl peroxide), fill with hexafluoropropylene to 0.3 MPa, and apply heat The reaction temperature was raised. Gradually, heat generation was confirmed at around 120 ° C., and a decrease in pressure was also confirmed. Hexafluoropropylene was continuously added up to a limit of 0.6 MPa. The reaction was terminated when it was determined that there was no pressure drop. The reaction solution was taken out and the target product was collected by distillation. The total amount of hexafluoropropylene charged was 40 g (267 mmol).
  • the NMR data of the obtained compound 5 are as follows.
  • Examples 6 and 7 The target product could be obtained in the same manner as in Example 5 except that the amount of compound shown in Table 2 was added.
  • the electrolyte solution is put in a three-electrode voltage measuring cell (working electrode: platinum, counter electrode: Li, reference electrode: Li, HS cell manufactured by Hosen Co., Ltd.), and the potential is run at 3 mV / sec with a potentiostat. The decomposition current was measured. Table 3 shows the measurement results.
  • Test (measurement of battery characteristics) A cylindrical secondary battery was produced by the following method.
  • a positive electrode active material obtained by mixing LiCoO 2 , carbon black and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd., trade name: KF-1000) at 90/3/7 (mass%) was mixed with N-methyl-2-pyrrolidone. What was dispersed and made into a slurry form was uniformly applied onto a positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) and dried to form a positive electrode mixture layer. Then, after compression-molding with a roller press machine, it cut
  • a negative electrode current collector (thickness 10 ⁇ m) was prepared by adding styrene-butadiene rubber dispersed in distilled water to artificial graphite powder to a solid content of 6% by mass and mixing with a disperser to form a slurry. On the copper foil) and dried to form a negative electrode mixture layer, and then compression molded with a roller press and cut. Then, it dried and welded the lead body and produced the strip
  • the belt-like positive electrode was overlapped with the belt-like negative electrode through a microporous polyethylene film (separator) having a thickness of 20 ⁇ m and wound in a spiral shape to obtain a laminated electrode body having a spiral winding structure. In that case, it wound so that the rough surface side of the positive electrode current collector could be the outer peripheral side. Thereafter, the electrode body was filled in a bottomed cylindrical battery case having an outer diameter of 18 mm, and the positive and negative lead bodies were welded.
  • the lithium secondary battery was examined for discharge capacity, load characteristics (high temperature storage characteristics) and cycle characteristics in the following manner. The results are shown in Table 4.
  • the battery was charged at 1.0 C at 4.5 V until the charging current became 1/10 C, discharged at a current equivalent to 0.2 C to 3.0 V, and the discharge capacity was determined. Thereafter, the battery was charged at 1.0 C and 4.5 V until the charging current became 1/10 C, and placed in a constant temperature bath at 85 ° C. for 2 days. Two days later, the battery was sufficiently placed to cool to room temperature and discharged at a current corresponding to 0.2 C until 3.0 V was reached. Thereafter, the battery was charged at 1.0 C at 4.5 V until the charging current became 1/10 C and discharged at a current equivalent to 0.2 C until 3.0 V, and the discharge capacity after storage was determined. The discharge capacity before storage and the discharge capacity charged after storage and discharged at 0.2 C were substituted into the following calculation formula to obtain high temperature storage characteristics.
  • Cycle characteristics As for the cycle characteristics, the charge / discharge cycle performed under the above charge / discharge conditions (charging at 1.0 C until the charging current becomes 1/10 C at 4.5 V and discharging to 3.0 V at a current equivalent to 1 C) is 1
  • the discharge capacity after the first cycle and the discharge capacity after 100 cycles were measured.
  • the value obtained by the following formula was used as the cycle retention rate.
  • the fluorine-containing sulfolane of the present invention is excellent in oxidation resistance and exhibits high electrochemical stability, it can be suitably used for various applications.
  • the fluorine-containing sulfolane of the present invention is particularly useful as a solvent or additive for an electrolyte solution for an energy storage device, for example.
  • the method for producing fluorine-containing sulfolane of the present invention can easily and reliably produce fluorine-containing sulfolane having excellent oxidation resistance.

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Abstract

La présente invention concerne : un nouveau sulfolane fluoré adapté à une utilisation dans une solution d'électrolyte dans un dispositif de stockage d'énergie ; et l'un de ses procédés de fabrication. La présente invention concerne un sulfolane fluoré caractérisé en ce qu'il est représenté par la formule (1) (où Rf représente un groupement fluoroalkyle en C1-8 pouvant contenir un hétéroatome).
PCT/JP2011/072802 2010-10-20 2011-10-03 Sulfolane fluoré et procédé de fabrication de sulfolane fluoré WO2012053346A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015060703A (ja) * 2013-09-18 2015-03-30 トヨタ自動車株式会社 非水電解質二次電池の製造方法
CN111066191A (zh) * 2017-08-08 2020-04-24 住友精化株式会社 非水电解液用添加剂、非水电解液及蓄电装置

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101952428B1 (ko) * 2013-01-31 2019-04-22 솔브레인 주식회사 전해액 및 이를 포함하는 리튬 이차 전지
US12074286B2 (en) 2018-03-30 2024-08-27 Sumitomo Seika Chemicals Co., Ltd. Additive for nonaqueous electrolyte solutions, nonaqueous electrolyte solution, and electricity storage device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002047286A (ja) * 2000-07-28 2002-02-12 Mitsubishi Chemicals Corp フッ化スルホラン類の製造方法
JP2003132944A (ja) * 2001-10-22 2003-05-09 Mitsubishi Chemicals Corp リチウム二次電池用非水系電解液及びそれを用いたリチウム二次電池
WO2008084846A1 (fr) * 2007-01-12 2008-07-17 Daikin Industries, Ltd. Condensateur électrique à deux couches

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002047286A (ja) * 2000-07-28 2002-02-12 Mitsubishi Chemicals Corp フッ化スルホラン類の製造方法
JP2003132944A (ja) * 2001-10-22 2003-05-09 Mitsubishi Chemicals Corp リチウム二次電池用非水系電解液及びそれを用いたリチウム二次電池
WO2008084846A1 (fr) * 2007-01-12 2008-07-17 Daikin Industries, Ltd. Condensateur électrique à deux couches

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEN, J. ET AL.: "Insertion of Fluoroalkenes into Activated C-H Bonds for the Preparation of Polyfluorinated Sulfanes, Alcohols, and Acyclic and Cyclic Ethers", INORGANIC CHEMISTRY, vol. 35, no. 23, 1996, pages 6676 - 6681 *
DMOWSKI, W. ET AL.: "Electrochemical trifluoromethylation of 3-sulfolene. Synthesis of meso-and DL-3,4-bis(trifluoromethyl) sulfolanes", JOURNAL OF FLUORINE CHEMISTRY, vol. 87, no. 2, 1998, pages 179 - 183 *
FEIRING, A.E. ET AL.: "Synthesis of partially fluorinated monomers and polymers for ion- exchange resins", JOURNAL OF FLUORINE CHEMISTRY, vol. 93, 1999, pages 93 - 101 *
SASAKI, Y. ET AL.: "Tetrabutylammonium phosphomolybdate on fluorapatite: an efficient solid catalyst for solvent-free selective oxidation of sulfides", TETRAHEDRON LETTERS, vol. 45, no. 52, 2004, pages 9513 - 9515 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015060703A (ja) * 2013-09-18 2015-03-30 トヨタ自動車株式会社 非水電解質二次電池の製造方法
US10217993B2 (en) 2013-09-18 2019-02-26 Toyota Jidosha Kabushiki Kaisha Method of manufacturing non-aqueous electrolyte secondary battery
CN111066191A (zh) * 2017-08-08 2020-04-24 住友精化株式会社 非水电解液用添加剂、非水电解液及蓄电装置
CN111066191B (zh) * 2017-08-08 2023-05-05 住友精化株式会社 非水电解液用添加剂、非水电解液及蓄电装置

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