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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
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  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/54—Quaternary phosphonium compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
  • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
• • 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
  • H01M10/0568—Liquid materials characterised by the solutes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
  • H01G11/60—Liquid electrolytes characterised by the solvent
• • 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
  • H01M10/052—Li-accumulators
• • 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
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to a process for the preparation of compounds containing perfluoroalkanesulfonic acid residues, in particular the preparation of perfluoroalkanesulfonic acid esters and their further conversion to salts, and the use of the compounds prepared in electrolytes and in batteries, capacitors, supercapacitors and galvanic cells.
• Lithium-ion batteries and double-layer capacitors with very high capacities represent the current state of the art.
• LiPF ⁇ and N (C 2 H 5 ) 4 BF 4 are currently hydrolysis-sensitive and thermally unstable Substances used as conductive salt.
• HF can quickly develop in contact with moist air or with residual water from the solvents. In addition to the toxic properties, HF has a very negative effect on the cycle behavior and thus on the performance of the electrochemical cells.
• imides such as the bis (trifluoromethylsulfonyl) irid or the bis (pentafluoroethylsulfonyl) imide or methanides such as the tris (trifluoromethylsulfonyl) methanide and their derivatives have been presented.
• Quaternary ammonium and phosphonium salts with perfluoroalkanesulfonate anions have also been developed as conductive salts for galvanic cells.
• the synthesis of these salts is relatively complex since an intermediate product, the trifluoromethanesulfonic acid methyl ester (methyl triflate), is difficult to prepare.
• the object of the present invention is therefore to overcome the disadvantages of the prior art and to provide a simple and economically effective process for the synthesis of alkyl perfluoroalkanesulfonic acid and conductive salts which can be prepared therefrom.
• the invention is characterized in that perfluoroalkanesulfonic acid is reacted directly with dialkyl carbonate to give perfluoroalkanesulfonic acid alkyl ester.
• perfluoroalkanesulfonic acid is reacted directly with dialkyl carbonate to give perfluoroalkanesulfonic acid alkyl ester.
• trifluoromethanesulfonic acid can be reacted directly with dimethyl carbonate.
• the methyl triflate is formed only in low yields (cf. Example 1).
• perfluoroalkanesulfonic acid with dialkyl carbonate in the presence of a water or alcohol-consuming reagent such as e.g. a carboxylic acid derivative whose organic residue is stable to perfluoroalkanesulfonic acid, e.g.
• a carboxylic acid derivative in the sense of the present invention is a compound in which the hydroxyl group of a carboxylic acid is replaced by another functional group, for example a halide, a carboxylic acid residue or a sulfonic acid residue. In principle, all are according to the invention
• Carboxylic acid derivatives can be used if their alkyl or aryl radicals - including those containing protons - are stable against perfluoroalkanesulfonic acid.
• the alkylation of the mixture of perfluoroalkanesulfonic acid and carboxylic acid derivative is easy and leads to good ones Yields of alkylated perfluoroalkanesulfonic acid and carboxylic acid esters.
• the person skilled in the art can easily isolate both compounds by conventional methods, generally by fractional distillation.
• carboxylic acid halides in particular chlorides, carboxylic acid anhydrides or mixed carboxylic acid / sulfonic acid anhydrides, are used as carboxylic acid derivatives for the process according to the invention.
• carboxylic acid halides in particular chlorides, carboxylic acid anhydrides or mixed carboxylic acid / sulfonic acid anhydrides.
• the carboxylic acid chloride is particularly preferably selected from the group: benzoyl chloride, p-nitrobenzoyl chloride, 2,6-difluorobenzoyl chloride, pentafluorobenzoyl chloride, 2-chlorobenzoyl chloride, 3-chlorobenzoyl chloride, 4-chlorobenzoyl chloride, 2-bromobenzoyl chloride, 3-bromobenzoyl chloride, 4-bromobenzoyl chloride 3-dichlorobenzoyl chloride, 2,4-dichlorobenzoyl chloride, 2,6-dichlorobenzoyl chloride, 3,4-dichlorobenzoyl chloride, 3,5-dichlorobenzoyl chloride, trichloroacetyl chloride.
• carboxylic anhydride is benzoic anhydride, 2,2'-dichlorobenzoic anhydride, 3,3'-dichlorobenzoic anhydride, 4,4'-
• Dichlorobenzoic anhydride 2,2 ', 3,3, -Tetrachlorbenzoeklahydrid, 2,2', 4,4'-tetrachlorobenzoic anhydride, 2,2 ', 6,6'-TetrachIorbenzoeklahydrid, 3,3', 4,4'-tetrachlorobenzoic anhydride, 3,3 ', 5,5'-tetrachlorobenzoic anhydride, 2-bromobenzoic anhydride, 3-bromobenzoic anhydride, 4-bromobenzoic anhydride, 2,2', 6,6'-tetrafluorobenzoic anhydride.
• dialkyl carbonate used according to the invention.
• it is preferably selected from the group consisting of dimethyl carbonate, diethyicarbonate, dipropyl carbonate, dibutyl carbonate, methyl ethyl carbonate or a mixture of these dialkyl carbonates.
• the process according to the invention is preferably carried out at temperatures between room temperature and 150 ° C., in particular between 50 and 110 ° C., very particularly preferably between 70 and 100 ° C.
• the preferred reaction time is between 1 and 10 hours, in particular between 2 and 5 hours.
• the perfluoroalkanesulfonic acid esters produced according to the invention can then be further converted to the corresponding perfluoroalkanesulfonic acid salts by reaction with XR 1 R 2 R 3 , where XP or N
• R 1 , R 2 , R 3 are the same or different, optionally connected directly to one another by a single or double bond, and in each case individually or jointly the meaning
• alkyl radical with 1 to 16 carbon atoms which can be partially or completely substituted with other groups, preferably with F, CI, N (C n F ( 2 n + ⁇ -x) H ⁇ ) 2, 0 (C n F ( 2n + ⁇ -x) H ⁇ ), S0 2 (CnF (2 ⁇ + ⁇ -x) H ⁇ ), C n F (2r , + ⁇ - x ) H ⁇ with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 2n + 1 .
• optionally substituted aryl radical or optionally substituted aromatic heterocyclic radical optionally substituted
• alkylaryl radical whose alkylene group has 1 to 16 carbon atoms and which can be partially substituted with further groups, preferably with F, Cl, Br, NO 2 , CN, alkyl, aryl or heterocyclic aryl,
• An aryl radical which can be partially substituted with other groups, preferably with F, Cl, Br, NO 2 , CN, alkyl, aryl or heterocyclic aryl, or -
• An aromatic heterocyclic radical which can be partially with other groups, preferably with F , Cl, Br, N0 2 , CN, alkyl, aryl or heterocyclic aryl, can be substituted, one, two or three CH 2 groups of an alkyl radical being substituted by identical or different heteroatoms, preferably O, NH or N (alkyl) with 1 to 6 carbon atoms, and where not all three R can be perfluorinated or perchlorinated at the same time.
• the perfluoroalkanesulfonic acid salt formed precipitates or can be isolated by conventional methods.
• the unreacted perfluoroalkanesulfonic acid alkyl ester only has to be distilled off.
• a compound XR 1 R 2 R 3 is preferably used, which is selected from the group:
• R 1 , R 2 , R 3 H alkyl, preferably having 1 to 16 carbon atoms, alkylaryl,
• O, NH or N (alkyl) with 1 to 6 C atoms can be replaced and the ring and / or the alkyl radical partly with further groups, preferably with F, Cl, N (C n F (2 n + ⁇ - ⁇ ) H x) 2, 0 (C n F (2n + ⁇ - ⁇ ) H x), S ⁇ 2 (C n F (2n + ⁇ -x) H x), C n F (2n + ⁇ . ⁇ ) H x can be substituted with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 2n + 1, alkylaryl, aryl, heterocyclic aryl or heterocyclic alkylaryl.
• a perfluoroalkanesulfonic acid ester obtained according to the invention is furthermore preferably reacted with a compound XR 1 R 2 R 3 selected from the following group to give a salt:
• R 1 to R 4 are the same or different, optionally directly connected to one another by a single or double formation and each, individually or together, the meaning - a hydrogen
• halogen preferably fluorine, with the proviso that there is no N-halogen bond
• alkyl radical with 1 to 8 carbon atoms which is partially or completely replaced by other groups, preferably F, Cl, N (C n F ( 2 n + ⁇ -x) H x ) 2, 0 (CnF (2n + 1 - x) H x ), S0 2 (C n F (2 n + ⁇ . ⁇ ) H x ), C n F (2n + 1. x) H ⁇ with 1 ⁇ n ⁇ 6 and
• alkylaryl, aryl or heterocyclic aryl may be substituted
• the compounds prepared according to the invention with perfluoroalkanesulfonic acid residues can be used in electrolytes, galvanic cells, primary and secondary batteries, Capacitors and / or super or ultracapacitors, for example as solvents or conductive salts, can be used.
• the salts can be used both in pure form and in the form of their mixtures as conductive salts. It is also possible to use the salts together with other salts known to the person skilled in the art as the conductive salt.
• the perfluoroalkanesulfonic acid esters are strong alkylating agents and are suitable for the alkylation of organic compounds, for example in the production of medicaments and crop protection agents.
• the compounds according to the invention with perfluoroalkanesulfonic acid residues, in particular the salts, can be used in liquid, gel-like, polymeric or solid electrolytes.
• Mixtures containing the conductive salts and suitable polymers and / or suitable solvents can be used for this purpose.
• a mixture comprises pure mixtures of the components, mixtures in which the salt or salts are enclosed in a polymer or gel, and mixtures in which there are chemical and / or physical bonds between the salt or salts and a polymer or gel
• the mixture preferably contains a suitable solvent in addition to the salt or salts and the polymer.
• Aprotic solvents or mixtures thereof which are suitable for use in a primary or secondary battery, a capacitor, a supercapacitor or a galvanic cell for example carbonates, esters, ethers, sulfolanes or nitriles, are particularly preferably used as solvents for liquid or gel-like electrolytes such as, for example, dimethyl carbonate, diethyicarbonate, butylene carbonate, propylene carbonate, ethylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, methyl acetate, ⁇ -butyrolactone, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butulfoxide, dimethyl butulfoxide,
• liquid or gel-like electrolytes such as, for example, dimethyl carbonate, diethyicarbonate, butylene carbonate, propylene carbon
• Preferred polymers for polymeric or gel-like electrolytes are homopolymers or copolymers of acrylonitrile, vinylidene difluoride,
• Methyl (meth) acrylate tetrahydrofuran, ethylene oxide, siloxane, phosphazene or a mixture of at least two of the above-mentioned homopolymers and / or copolymers used, wherein the polymers can be at least partially crosslinked.
• reaction mixture is distilled at room temperature at atmospheric pressure.
• 75.05 g (89.9%) of methyl trifluoromethanesulfonate (methyl triflate) are isolated as a transparent, colorless liquid (boiling range 98-99 ° C.).
• the solid, remaining distillation residue consists mainly of p-nitrobenzoic acid methyl ester, which is obtained after crystallization from methanol as a light yellow product (25.0 g, yield: 86.0%, melting point: 93-94 ° C).
• Trifluoromethanesulfonic acid added.
• the ice bath is replaced by an oil bath and the reaction mixture is heated to 100-110 ° C. for 5 hours (temperature in the oil bath) until the gas evolution ceases.
• the mixture is cooled to room temperature and the trifluoromethanesulfonic acid ethyl ester (ethyl triflate) is distilled off under atmospheric pressure: 3.28 g (yield: 31.8%) of a transparent, colorless liquid are isolated (boiling range 114-116 ° C.).
• Trifluoromethanesulfonic acid ethyl ester (ethyl triflate) (Eur. Polym. J., Vol. 16, No. 9,

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