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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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  • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
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  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
• • H—ELECTRICITY
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  • 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
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
  • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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  • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
  • C08J2381/06—Polysulfones; Polyethersulfones
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  • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

• the present invention relates to novel polymers containing lithium or sodium salts of grafted bis (sulphonyl) imides, processes for their preparation and their use as an electrolyte in lithium or sodium batteries. * ⁇ ; More specifically, the present invention has for. object of new polymer electrolytes obtained from commercially available polymers as well as new lithium-polymer type batteries or sodium: polymers.
• Leaded batteries have been most commonly used for many decades.
• lead technology has several disadvantages related to the weight of the batteries, the toxicity of lead and the use of a corrosive liquid.
• the lithium ions pass through the electrolyte which is an ionic conductor and electronic insulator and are interposed in the negative electrode material generally constituted by graphite during the discharge of the battery, c that is to say, in use, it is the opposite phenomenon that takes place.
• Lithium ions disintercalate.
• the ionic conductor or electrolyte which separates the electrodes, is a key element.
• its liquid, solid or gelled state affects the safety of the system.
• its conductivity determines the operating temperature range.
• lithium batteries liquid electrolytes based on an organic solvent, such as dimethylenecarbonate or ethylenecarbonate, and a dissolved salt, such as lithium hexafluorophosphate LiPF 6 or lithium bis (trifloromethanesulfonyl) imide (CF 3 SO 2 ) 2NLi, are commonly used.
• organic solvent such as dimethylenecarbonate or ethylenecarbonate
• a dissolved salt such as lithium hexafluorophosphate LiPF 6 or lithium bis (trifloromethanesulfonyl) imide (CF 3 SO 2 ) 2NLi
• LiPF 6 lithium hexafluorophosphate LiPF 6 or lithium bis (trifloromethanesulfonyl) imide (CF 3 SO 2 ) 2NLi
• the applicant preferred to move to existing polymers, less expensive.
• the present invention relates to novel polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV used as electrolytes for batteries or conductive polymers.
• M represents a lithium or sodium atom
• R represents a group or different groups chosen from:
• alkyl or cycloalkyl group having from 1 to 30 linear or branched carbon atoms optionally substituted by a. cycloalkyl, aryl, perfluoroalkyl, p, pyfluoroalkyl, mono or. polyethoxylated;
• a perfluoro or polyfluoroalkyl group optionally substituted with aromatic groups, an aryl or polyaryl group optionally substituted with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl units, with nitrile functions, with alkyl or alkylsulphonyl functions, with fluorine;
• m represents the percentage of units, polymers having an oxoaryl or dioxoaryl unit having a grafted bis (sulfonyl) imide salt. This percentage varies between 50 ' and 100%, preferably between 90 and 100%,
• n represents the percentage of polymeric units having no oxoaryl or dioxoaryl unit functionalized by a bis (sulfonyl) imide unit. This percentage varies between 0 and 50%, preferably between 0 and 10%, p represents the number of polymer units of the polymer; p varies from 40 to 300, preferably between 60 and 200.
• the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI will be chosen; XII, XIII, XIV and XV in which
• M represents a lithium or sodium atom
• R represents a group or different groups chosen from:
• alkyl or cycloalkyl group having from 1 to 10 linear or branched carbon atoms optionally substituted with a cycloalkyl, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxylated unit;
• a perfluoro- or polyfluoroalkyl group optionally substituted with aromatic groups
• An aryl or polyaryl group optionally substituted with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl units, with nitrile functions, with alkyl or alkylsulphonyl functions, with fluorine atoms;
• m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit functionalized by a bis (sulfonyl) imide unit. This percentage varies between 90 and 100%.
• n represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit not functionalized by a bis (sulphonyl) imide unit. This percentage varies between 0 and 10%.
• p represents the number of polymer units of the polymer; P varies from 40 to 300.
• the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV according to claim 1 in which
• M represents a lithium or sodium atom
• R represents a group or different groups chosen from:
• alkyl of 1 to 10 carbon atoms such as the methyl, ethyl, propyl, butyl, penyl, hexyl, cyclohexyl and ethylhexyl groups;
• m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit functionalized by a bis (sulfonyl) imide unit. This percentage varies between 90 and 100%.
• n represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit not functionalized by a bis (sulphonyl) imide unit. This percentage varies between 0 and 10%.
• p represents the number of polymer units of the polymer; p varies from 60 to 200.
• the group R is chosen from methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl, (7,7-dimethyl-2-oxobicyclo) groups.
• the invention furthermore relates to electrolytes formed of the abovementioned polymers for batteries, as well as batteries comprising such electrolytes.
• the abovementioned polymers according to the invention do not comprise sulphonic units - SO 3 H. These units form acidic functions whose strength, which is too limited, binds the cations and, in particular, the lithium ions, to a greater extent than .
• the bis (sulphonyl) imide units of the polymers according to the invention form acidic functions whose strength, greater than that of the sulphonic units, binds the cations and, in particular, the lithium ions, to a lesser extent, thus facilitating their migration to the within the electrolyte.
• the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV can be obtained:
• p represents the number of polymer units of the polymer; p varies from 40 to 300, preferably between 60 and 200.
• m represents the percentage of polymer units having an oxo aryl or dioxoaryl unit functionalized by a chlorosulfonated group. This percentage varies between 50 and 100%, preferably between 90 and 100%.
• n represents the percentage of polymer units having a dioxoaryl unit not functionalized by a chlorosulfonated group. This percentage varies between 0 and 50%, preferably between 0 and 10%,
• p represents the number of polymer units of the polymer; p varies from 40 to 300, preferably between 60 and 200.
• the starting polymers are commercial products.
• the polymer of formula XVI is known commercially under the name of polyether ether ketone or polyether ether ketone or PEEK
• polymer XVII is known commercially under the name of polyetherketone ketone or polyetherketone ketone or PEKK
• polymer XVIII is known commercially as polyether ether sulfone or PEES the polymer .XIX is known commercially under the name of poly (ether sulfone) OR PES
• polymer -XX is part of the poly (arene ether ketone) family and is known commercially as poly (bisphenol A PAEK)
• XXI polymer is part of the poly (arene ether sulfone) family and is known commercially as poly (bisphenol A PAES)
• polymer XXII is known commercially under the name of polyether ketone ether ketone ketone or polyether ketone ether ketone ketone) or PEKEKK
• polymer XXIII is known commercially under the name of polyether ketone or polyetherketone or PEK
• polymers are not limiting: since there are a large number of other polymers. commercially available or not in the families of poly ⁇ aryl ether ketone), poly (aryl ether sulfone). According to the invention, the preferred polymers because of their high availability are PEEK, PEK, PES, PEKK and PEKEKK.
• Chlorosulphonation is performed at a temperature between 0 th and 80 th C with 1 to 10 equivalents of chlorosulfonic acid, 1 to 30 equivalents of thionyl chloride, 1 to 10 equivalents of a preferred amide LEMENT N, N-dimethylformamide , with or without a solvent.
• the preferred solvents according to the invention are THF, methylTHF, dichloromethane, dichloroethane. Chlorosulfonation of some polymers can lead to mixtures of many isomers. This is particularly true for polymer XXII or PEKEKK.
• the chlorosulfonated polymers XXXII, XXXIII, XXXIV, XXXV and XXXVI are given by way of example. Other isomers can be formed during chlorosulfonation. 2) in a second step, the polymers of formulas XXIV, XXV, XXIV, XVII, XXVIII, XIX, XXX, XXI, XXII, XXXIII, XXXIV, XXXV, XXXVI, XXVII and XXXVIII are reacted with a sulfonamide of formula XXIX in a solvent medium.
• R represents a group or different groups chosen from:
• alkyl or cycloalkyl group having from 1 to 30 carbon atoms, linear or branched, optionally substituted with a cycloalkylalkylalkyl, alkylarea, perfluoroalkyl, p-naphthyl, or polyethoxylated copolymer;
• An aryl or polyaryl group optionally substituted with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl units, with nitrile functions, with alkyl or alkylsulphonyl functions, with fluorine atoms;
• m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit having a grafted bis (sulfonyl) imide salt. This percentage varies between 50 and 100%, preferably between 90 and 100%,
• sulphonamides which can be used in the invention, we will mention the methanesulfonamide, ethanesulfonamide, propanesulfonamide, butanesulfonamide, 1-decanesulfonamide, 1-dodecanesulfonamide / (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methanesulfonamide, ((1R ) -7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methanesulfonamide, (1S) - (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methanesulfonamide, cyclohexylmethanesulfonamide, benzenesulfonamide, toluenesulfonamide, naphthalenesulphonamides, trifluoro
• sulfonamide / nonafluorobutanesulfonamide, pentafluorobenzenesulfonamide, 2,3,5,6-tetrafluorobenzenesulfonamide, 4-fluorobenzenesulfonamide, 2,4-difluorobenzensulfonamide, 3,5-difluorobenzenesulfonamide, 2,3,4,5,6-pentafluorobenzenesulphonamide, 4- (trifluoromethyl) benzenesulfonamide, 3- (trifluoromethyl) benzenesulfonamide, 2- (trifluoromethyl) benzenesulfonamide, 4-methylbenzenesulfonamide, 1-naphthalenesulfonamide, 2-naphthalenesulfonamide, 3,5-difluorophenylmethanesulfonamide, 4-fluorophenylmethanesulfonamide, 3 trifluoromethylphenyl
• the lithiated or soda bases are preferably chosen from lithium hydroxide, sodium hydroxide, lithium methoxide, sodium methoxide, lithium ethoxide, sodium ethoxide, lithium isopropoxide, sodium isopropoxide and lithium tertiobutylate, sodium tert-butylate, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium,.
• the preferred bases are those which do not form water during the reaction.
• the solvents used for the condensation reaction of the sulfonamide of formula XXXIX with the chlorosulphonated polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII are aprotic polar solvents.
• Preferred solvents are THF, methylTHF, dioxane, dichloromethane and dichloroethane, dimethylsulfoxide.
• the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, xiii, XIV and XV can be obtained.
• p represents the number of polymer units of the polymer; p varies from 40 to 300, preferably between 60 and 200,
• m represents the percentage of polymer units having an oxoaryl or dioxoaryl unit functionalized by a chlorosulfonated group. This percentage varies between 50 and 100%, preferably between 90 and 100%.
• n represents the percentage of polymer units having a dioxoaryl unit not functionalized by a chlorosulfonated group. This percentage varies between 0 and 50%, preferably between 0 and 10%,
• p represents the number of polymer units of the polymer; p varies from 40 to 300, preferably between
• the starting polymers are commercial products.
• the polymer of formula XVI is known commercially under the name of polyether ether ketone or polyether ether ketone or PEEK
• polymer XVII is known commercially under the name of polyetherketone ketone or polyetherketone ketone or PEKK
• polymer XVIII is known commercially as polyether ether sulfone or PEES
• polymer XIX is known commercially as polyether sulphone) or PES
• polymer XX is part of the family of poly (arene ether ketone) and is known commercially as poly ⁇ bisphenol A PAEK)
• XXI is part of the poly (arene ether sulfone) family and is known commercially as poly (bisphenol A PAES)
• polymer XXII is known commercially under the name of polyether ketone ether ketone ketone or polyether ketone ether ketone ketone) or PEKEKK
• polymer XXIII is known commercially under the name polyether ketone or polyether ketone or PEK
• polymers are not limiting since there are a large number of other commercially available polymers or not in the poly (aryl ether ketone), poly (aryl ether sulfone) families.
• the preferred polymers because of their high availability are PEEK, PEK, PES, PEKK and PEKEKK.
• Chlorosulfonation is carried out at a temperature between 0 ° and 80 ° C.
• or chlorosulfonated dioxoryls are introduced with 1 to 10 equivalents of chlorosulfonic acid, 1 to 30 equivalents of thionyl chloride, 1 to 10 equivalents of an amide, preferably N, N-dimethylformamide, with or without a solvent.
• the preferred solvents according to the invention are THF, methylTHF, dichloromethane, dichloroethane. Chlorosulfonation of some polymers can lead to mixtures of many isomers. This is particularly true for polymer XXII or PEKEKK.
• chlorosulfonated polymers XXXI, XXXII, XXXIII, XXXIV, XXXV and XXXVI are given in as an example. Other isomers can be formed during chlorosulfonation.
• m represents the percentage of polymeric units having a functionalized oxoaryl or dioxoaryl unit having a sulfonamide function. This percentage varies between 50 and 100%,
• n represents the percentage of polymeric units having an oxoaryl or nonfunctional dioxoaryl unit by a sulfonamide function. This percentage varies between 0 and 50%,
• p represents the number of polymer units of the polymer; p varies from 40 to 300, preferably between 60 and 200.
• the polymers are solubilized in a solvent such as an ether, a haloalkane, an aromatic.
• Ammonia is introduced as a gas or solution in an ether solvent, a haloalkane, an aromatic.
• the preferred solvents are dichloromethane, 1,2-dichloroethane, THF, methylTHF, diisopropyl ether, diethyl ether, anisole, methanol, dioxane, isopropanol.
• the amination of the polymers with ammonia is carried out at a temperature between -20 and 60 ° C.
• X represents a fluorine or chlorine or bromine atom or a trifluoromethanesulphonyl or alkylsulphonyl or arylsulphonyl group;
• R represents a group or different groups chosen from:
• alkyl or cycloalkyl group having from 1 to 30 linear or branched carbon atoms optionally substituted with a cycloalkyl, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxylated unit;
• a perfluoro or polyfluoroalkyl group optionally substituted with aromatic groups
• An aryl or polyaryl group optionally substituted with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl units, with nitrile functions, with alkyl or alkylsulphonyl functions, with fluorine atoms;
• a lithiated or sodate base at a temperature between 0 and 80 ° C, preferably between 20 and 60 ° C in a solvent medium.
• the R group of the sulfonyl halide (LV) will be an alkyl group having 1 to 10 carbon atoms linear or branched optionally substituted with a cycloalkyl, aryl; a cycloalkyl group; a perfluoro or polyfluoroalkyl group optionally substituted with aromatic groups; a group aryl or polyaryl optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, by alkoxy, nitrile or alkylsulphonyl functional groups, with one or more fluorine atoms.
• the halide is chosen from chlorides, bromides and fluorides of methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl,
• the lithiated or soda bases are preferably chosen from lithium hydroxide, sodium hydroxide, lithium methoxide, sodium methoxide, lithium ethoxide, sodium ethoxide, lithium isopropoxide, sodium isopropoxide and lithium tertiobutylate, sodium tert-butylate, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, diisopropylamide, lithium, tert-butyllithium, methyl lithium phenyl lithium, phenylsodium, benzyllithium, benzylsodium, lithium dimethylate, sodium dimesylate, lithium carbonate, sodium carbonate, lithium acetate, sodium acetate.
• the preferred bases are those which do not form water during the reaction. ;
• the preferred solvents are dichloromethane, 1,2-dichloroethane, THF, methylTHF, diisopropyl ether, DMSO.
• sulphonylation agents that may be used in the invention, mention may be made of 4-biphenylsulfonyl chloride, 4-chlorobenzenesulfonyl chloride and methanesulfonyl chloride.
• Tetrafluorobenzenesulfonyl 4-fluorobenzenesulfonyl chloride, 3,5-difluorobenzenesulfonyl, 2,3,4,5,6-pentafluorobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, 4-
• Pentaethanesulfonyl nonafluorobutanesulfonyl fluoride, methanesulfonyl bromide, triflic anhydride, anhydride methanesulfonic acid, 4-methylbenzenesulfonyl bromide.
• Anhydrous atmosphere is understood to mean an atmosphere under a stream of nitrogen or argon.
• polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIII and XV are particularly film-forming which is a clear advantage for the intended application. They can be used to form films with a thickness of between 10 ⁇ m and 200 ⁇ m, which have good mechanical strength. In practice, these films can be manipulated by an operator without being torn. It will be noted that polymers I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII,
• XIV and XV are not crosslinked in the films obtained.
• These polymers according to the invention are indeed rigid enough to obtain mechanically resistant films without crosslinking.
• the films are prepared in anhydrous solvents, preferably DMSO.
• XV can be easily obtained by evaporation of a polymer solution deposited on a surface of a material such as glass, Teflon, plastic.
• the evaporation is carried out at a temperature between 20 and 80 ° C.
• the evaporation of the solvent is carried out by heating, by scanning an inert gas or by placing under reduced pressure.
• Example 1 Chlorosulfonation of PEEK. Preparation of the polymer XXIV
• the chlorosulfonic acid (3.24 g, 8 equivalents relative to the number of polymer units of PEEK (XVI)) is introduced, using a syringe (1.85 mL): taking care to handle under nitrogen flow.
• the reaction mixture is stirred at 20 ° C for 5 h. In the course of reaction, the formation of a viscous orange compound is observed. The supernatant is removed by taking care to handle under a stream of nitrogen.
• the weight yield of polymer EPOSO 2 Cl (XXIV) is 98% relative to the PEEK (XVI) engaged.
• the chlorosulfonic acid (2.88 g, 8 equivalents relative to the number of polymer units of the PEES (XVIII)) is introduced using a syringe (1.64 ml) taking care of handling under a flow of 'nitrogen.
• the reaction mixture is stirred at 0 ° C for 5 h. At the end of the reaction, the formation of a brown viscous compound is observed. The supernatant is removed by taking care to handle under a stream of nitrogen.
• the brown solution is precipitated in propan-2-ol (250 mL), a white precipitate is formed.
• the solid is filtered, then washed twice with 50 ml of propan-2-ol and twice with 50 ml of acetonitrile and then dried overnight under vacuum (1.10 -2 mbar).
• Chlorosulphonic acid (0.527 g, 2.1 equivalents relative to the number of polymeric units of the PES (XIX)) is introduced using a syringe (0.30 ml), taking care to manipulate under a flow of 'nitrogen.
• the mixture The reaction mixture is stirred at 42 ° C. for 18 h. At the end of the reaction, the formation of a viscous yellow compound is observed. The supernatant is removed by taking care to handle under a stream of nitrogen.
• Thionyl chloride (2.03 g, 8 equivalents relative to the number of polymer units of the PES (XIX)) is then introduced using a syringe (1.24 ml), taking care to handle under flow. nitrogen. Then N, N-dimethylformamide (0.47 g, 3 equivalents relative to the number of polymeric units of the PES (XIX)) is added using a syringe (0.50 ml), taking care to handle under nitrogen flow. The reaction mixture is again stirred at 20 ° C for 5 h, then 15 mL of distilled CH 2 C1 2 is added . At the end of the reaction, a yellow solution is observed.
• the yellow solution is precipitated in propan-2-ol (80 mL), a white precipitate is formed.
• the solid is filtered, then washed with 2 times 20 ml of propan-2-ol and 3 times 20 ml of acetonitrile, and then dried overnight under vacuum (1.10 -2 mbar).
• reaction mixture is filtered and the solid is washed with twice 10 ml of tetrahydrofuran.
• the solvent of the filtrate is evaporated on a rotary evaporator and the product obtained is dried overnight under vacuum (1.10 -2 mbar).
• the weight yield of polymer PEEKSO 2 NH2 (XL) is 96% relative to the polymer PEEKSO 2 Cl (XXIV) engaged.
• PEESSO 2 C1 (XXVI) prepared according to Example 7 is prepared in 17 ml of distilled tetrahydrofuran and 3 ml of N, N-dimethylformamide so as to have a molar concentration. in PEESSO 2 Cl (XXVI) of 0.035 M. All the solvents used in these syntheses were distilled stored and taken under a nitrogen atmosphere.
• reaction mixture is precipitated in methanol, then after filtration, the solid obtained is washed with 2 times 10 ml of acetonitrile, and the product obtained is dried overnight under vacuum ( 1 ⁇ 10 -2 rabar).
• the weight yield of polymer PEESSO 2 NHj (XLII) is 92% relative to the polymer PEESSO 2 C1 (XXVI) engaged.
• reaction mixture is filtered and the solid is washed with twice 10 ml of tetrahydrofuran.
• the solvent of the filtrate is evaporated on a rotary evaporator, and the product obtained is dried overnight under vacuum (1.10 -2 mbar).
• the weight yield of PESSO 2 NH 2 (XLIII) is 98% relative to the PESSO 2 C1 (XXVII) engaged.
• the 1 H NMR spectrum shows that there is a methylsulfonamide group relative to the dioxoaryl moiety at 2.46 ppm.
• PEESSO 2 C1 (XXVI) prepared according to Example 7 is prepared in 9 ml of distilled tetrahydrofuran and 1 ml of distilled ⁇ , ⁇ -dimethylformamide so as to have a molar concentration. in PEESSO 2 C1 (XXVI) of 0.052 M. All the solvents used in these syntheses were distilled, stored and taken under a nitrogen atmosphere.
• the reaction mixture is stirred at 20.degree. C. for 15 minutes.
• the previously prepared PEESSO 2 CI (XXVI) solution is then introduced using a syringe, taking care to handle under a flow of nitrogen.
• the reaction is continued at 20 ° C. for 1 hour. At the end of the reaction, a white precipitate is observed.
• the NMR Ta spectrum produced in DMSO-D6 ( 1 ⁇ NMR (200 MHz) ⁇ 8.05 - 7.78 (m, 4H), 7.44 (s, 1H), 7.33 - 6.90 (m , 6H), 2.44 (s, 3H)) confirms the expected structure.
• the NMR spectrum of the 2a shows that there is a methylsulfonamide group relative to the 2,44 ppm dioxoaryl moiety.
• the PESSO 2 C1 solution (XXVII) previously prepared is then introduced using a syringe, taking care to handle under a flow of nitrogen.
• the reaction is continued at 20 ° C. for 1 hour. At the end of the reaction, a white precipitate is observed.
• the 19 F NMR spectrum shows a single peak corresponding to polymeric trifluoromethylsulfonamide.
• the NMR spectrum of the 1 ⁇ shows that there is a methylsulfonamide group with respect to the 2,46 dioxoaryl unit.
• the weight yield of PEEKSO 2 N- (Li + ) SO 2 CH 3 (la) is 35% relative to the PEEKSO 2 NH 2 (XL) engaged.
• the ionic conductivities of the polymers prepared in Examples 12-16 were determined by impedance spectroscopy.
• the results obtained with the polymer described in Example 7 are reported in Figure 1 of the drawings, which shows the evolution of the conductivity of the polymer described in Example 7 as a function of temperature and comparison with a polymer electrolyte. described in the literature (Nature Materials), these results being compared with the results obtained in the publication of D, Gigmes et al. in Nature Materials, 12, 452-457 (2013). It may be noted that at low temperature ( ⁇ 45 ° C.), the conductivities are greater than the conductivities published in patent FR 2979630 and the publication by D. Gigmes et al. in Nature Materials, 12, 452-457 (2013), even without the addition of solvent.

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