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    • 专利摘要:
    The invention relates to novel polymers containing lithium or sodium sulphonamides, processes for their preparation and their use as electolytes in batteries.
    公开号:FR3024145A1
    申请号:FR1401709
    申请日:2014-07-23
    公开日:2016-01-29
    发明作者:Jean-Roger Desmurs；Elisabet Dunach Clinet；Philippe Knauth；Vincent MORIZUR；Sandra Olivero
    申请人:CDP INNOVATION；Aix Marseille Universite；Centre National de la Recherche Scientifique CNRS；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to novel polymers containing lithium or sodium salts of grafted sulfonamides, processes for their preparation and methods for their preparation. uses as electrolytes in lithium or sodium batteries. More specifically, the subject of the present invention is novel polymer electrolytes obtained from commercially available polymers as well as new lithium polymer or sodium polymer batteries. Lead-acid batteries have been most commonly used for many decades. However, lead technology has several disadvantages related to the weight of the batteries, the toxicity of lead and the use of a corrosive liquid. This led to the development of alkaline batteries whose electrodes are either based on nickel and cadmium (nickel-cadmium batteries) or, more recently, on nickel-based and metal hydride (nickel-hydride batteries), or on silver oxide base coupled with zinc, cadmium or iron. All these technologies use a solution of potash as electrolyte and have as a major disadvantage a relatively low specific energy density compared to the needs related to the development of portable equipment such as telephones and computers. In addition, the weight of these batteries is a disadvantage for their use in electric vehicles.
    [0002] Manufacturers have therefore developed a new lithium-battery based die using a carbon-based negative electrode, in which lithium is inserted, and a metal oxide, in particular cobalt oxide, with a high oxidation potential. as a positive electrode. The operating principle is as follows: During the electrochemical charge of the battery, the lithium ions pass through the electrolyte which is an ionic conductor and electronic insulator and intercalate in the negative electrode material generally made of graphite during the discharge of the battery, that is to say during use, it is the opposite phenomenon that takes place.
    [0003] The lithium ions are deintercalated. In batteries, the ionic conductor or electrolyte, which separates the electrodes, is a key element. On the one hand, its liquid, solid or gelled state affects the safety of the system and, on the other hand, its conductivity determines the operating temperature range. In lithium batteries, liquid electrolytes based on an organic solvent, such as dimethylenecarbonate or ethylenecarbonate, and a dissolved salt, such as lithium hexafluorophosphate Li9F6 or lithium bis (trifloromethanesulfonyl) imide (CF3SO2) 2NLi, are commonly used. However, they do not have the optimum safety conditions associated with handling a corrosive and flammable liquid. In addition, these systems have the disadvantage of being able to form dendrites during battery charges which can cause a short circuit and destruction of the battery.
    [0004] In order to overcome these major drawbacks, a new technology based on solid polymer electrolytes with lithium anode has been developed, hence the name "lithium-polymer battery". Thus, patent FR 2853320 describes electrolytes obtained by polymerization of polyorganosiloxanes by a photoinitiator in the presence of an electrolyte salt. In addition to the fact that the anion is not immobilized and migrates into the electrolyte causing polarization phenomena at the electrodes, this technique requires catalysts of the iodonium type which are particularly toxic. Thus, Chung-Bo Tsai, Yan-Ru Chen, Wen-Hsien Ho, Kuo-Feng Chiu, Shih-Hsuan Su describe in US Patent 2012/0308899 A1, the sulfonation of PEEK in SPEEK and the preparation of lithium salt. corresponding. This simple technique does not allow for a sufficient delocalization of the negative charge on the sulfonate function and the lithium ion is too coordinated with the sulfonate function to achieve very high conductivities. More recently, another approach has been described by some authors who attempted to immobilize the anion by polymerization of monomers which contained the lithium salt as electrolyte. FR 2979630 and the publication of D. Gigmes et al. in Nature Materials, 12, 452-457 (2013) describe the synthesis of block polymers containing an electrolyte whose anion is attached to the polymer. The indicated conductivities are the best obtained at this date for lithium-polymer batteries. In the synthesis of this type of electrolytes, the starting monomers are not commercial and must be prepared in several steps. In addition, the polymerization technique for preparing block polymers is expensive compared with other polymerization techniques. To overcome these drawbacks, the applicant preferred to move towards 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. (I) 15 (IV) ## STR1 ## wherein: ## STR2 ## In which: M represents a lithium or sodium atom; R represents an alkyl group having from 1 to 30 linear carbon atoms; or branched optionally substituted with a cycloalkyl, aryl moiety; A cycloalkyl group, optionally substituted with aromatic groups; an aryl or polyaryl group, optionally by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, by nitrile functions, alkylsulfonyl functions, by fluorine atoms; m represents the percentage of polymer units having an oxoaryl or dioxoaryl unit functionalized by a sulfonamide unit or unit (s). This percentage varies between 50 and 100%, preferably between 90 and 100%, n represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit not functionalized by one or more units (s) sulfonamide. This percentage varies between 0 and 50%; p represents the number of polymeric units of the polymer; p varies from 40 to 300, preferably between 60 and 200.
    [0005] Preferably, in the novel polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV: M represents a lithium-R atom represents: alkyl of 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, ethylhexyl; a 2,2-difluoroethyl, 2,2-difluoro-2- (trifluoromethyl) ethyl group; Aryl group of phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, cyanophenyl, alkylsulfonylphenyl, arylsulfonylphenyl; m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit functionalized by a sulfonamide unit. This percentage varies between 90 and 100%. n represents the percentage of polymeric units having no oxoaryl or dioxoaryl unit not functionalized by a sulfonamide unit. This percentage varies between 0 and 10%. P represents the number of polymeric units of the polymer; P varies from 40 to 300. More specifically, the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV in which: M represents a lithium or sodium atom - R represents: - an alkyl group of 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, ethylhexyl; a 2,2-difluoroethyl, 2,2-difluoro-2- (trifluoromethyl) ethyl group; aryl group of phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, cyanophenyl, alkylsulfonylphenyl, arylsulfonylphenyl, methoxyphenyl, butoxyphenyl, pentafluorophenyl, alkylsulfonylphenyl, fluorophenyl, m represents the percentage of polymeric units having a unit oxoaryl or dioxoaryl functionalized with a sulfonamide unit. This percentage varies between 90 and 100%. N represents the percentage of polymeric units having no oxoaryl or dioxoaryl unit not functionalized by a sulfonamide unit. This percentage varies between 0 and 10%. P represents the number of polymeric units of the polymer; P varies from 60 to 200. Very preferably, the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV are chosen from polymers in which: - M represents a lithium or sodium atom - R is a methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl group, (7.7 dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, ((1R) -7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, (1S) - (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis (trifluoromethyl) phenyl, 4-cyanophenyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4- ( trifluoromethyl) phenyl, 3- (trifluoromethyl) phenyl, 2 (trifluoromethyl) phenyl, 4-methylphenyl, 1-naphthyl, 1 2-Naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4-methoxyphenyl, 4-n-butylphenyl, 4-t-butylphenyl, 4- butoxyphenyl, 2-fluoro-5- (trifluoromethyl) phenyl, 4-ethylphenyl, phenoxyethyl, methoxyethyl, ethoxyethyl, 4-methoxyphenoxyethyl. M represents the percentage of polymeric units having a dioxoaryl unit functionalized by a sulfonamide. This percentage varies between 90 and 100%. n represents the percentage of polymeric units having a dioxoaryl unit which is not functionalized by a sulphonamide. This percentage varies between 0 and 10%. p represents the number of polymer unit of the polymer; P varies from 60 to 200.
    [0006] According to a first variant, the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV may be obtained: 1) by producing in a first chlorosulfonation step of a polymer of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII by a mixture of chlorosulfonic acid, thionyl chloride and a formamide according to an optimized procedure. (XVI) 20 (XVII) (XVII) (XIX) XX (XX) (XXI) 5 POP (XXII) (MID 10 in which p represents the number of polymeric units of the polymer, p varies from 40 to 300 preferably to between 60 and 200. To obtain the polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII. (XXIV) O Ln rI NJ O XX ir) O rI oo o.
    [0007] In which: m represents the percentage of polymer units having an oxoaryl or dioxoaryl unit functionalized by a chlorosulphonated group. NaN. This percentage varies between 50 and 100%, preferably between 90 and 100%, n is 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 polymeric units of the polymer; P varies from 40 to 300, preferably from 60 to 200. The starting polymers are commercial products. The polymer of formula XVI is known commercially as poly (ether ether ketone) or poly (ether ether ketone) or PEEK, (XVI). The polymer XVII is known commercially as polyetherketone ketone. or poly (ether ketone ketone) or PEKK POP (XVII) polymer XVIII is known commercially as poly (ether ether sulfone) or PEES (XVIM polymer XIX is known commercially as poly (ether sulfone) or PES 15 (XIX) the polymer XX is part of the family of poly (arene ether ketone) and is known commercially as poly (bisphenol A PAEK) (XX) XXI polymer is part of the family of poly (arene ether sulfone) and is known commercially as poly (bisphenol A PAES) 3024145 16 (XXI) the polymer XXII is known commercially as polyether ketone ether ketone ketone) or poly (ether ketone ether ketone) ketone) or PEKEKK Pop (XXII) polymer XXIII is known commercially under the name poly (ether ketone) or poly (ether ketone) or PEK () Ga II) This list of polymers is not limiting since there are a large number of other commercially available polymers or not in 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. The chlorosulfonation is carried out at a temperature between 0 ° and 80 ° C 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 solvent. The preferred solvents according to the invention are THF, methylTHF, dichloromethane, dichloroethane.
    [0008] The chlorosulfonation of certain polymers can lead to mixtures of many isomers. This is particularly true for XXII or PEKEKK polymers. 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 formula XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII are reacted with an amine of formula XXXIX in a solvent medium in the presence or absence of a lithiated or sodic base. In which: R represents a group or different groups chosen from: an alkyl or cycloalkyl group having from 1 to 30 carbon atoms, linear or branched, optionally substituted with a cycloalkyl unit, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxylated; an aryl or polyaryl group optionally substituted with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl units, by nitrile functions, alkyl- or alkylsulfonyl functions, by fluorine atoms; m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit having a grafted sulfonamide salt. This percentage varies between 50 and 100%, preferably between 90 and 100%. By way of nonlimiting example of amines that can be used in the invention, mention will be made of 4-aminoindan, 5-aminoindan and 2-isopropylsulphonylaniline. 2-propylsulfonylaniline, 1-amino-5,6,7,8-tetrahydronaphthalene, 6-aminoquinoxaline, 3-trifluoromethylaniline, 4-trifluoromethylaniline, 2,2,2-trifluoroethylamine, aniline, methylamine Ethylamine, propylamine, pentafluoroaniline, 4-fluoroaniline, methoxymethylamine, ethoxyethylamine, phenoxyethylamine, 4-methoxyphenoxyethylamine, methoxyethoxyethylamine, 2-fluorophenoxyethylamine.
    [0009] The lithium or soda-containing bases are preferably chosen from lithium hydroxide, sodium hydroxide, lithium methoxide, sodium methoxide, lithium ethoxide, sodium ethoxide, lithium isopropoxide and sodium isopropoxide. lithium tert-butylate, sodium tert-butoxide, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, lithium diisopropylamide, tert-butyllithium, methyl lithium, and the like. phenyllithium, phenylsodium, benzyllithium, benzylsodium, lithium dimsylate, sodium dimsylate. The preferred bases are those which do not form water during the reaction.
    [0010] The solvents used for the condensation reaction of the amine of formula XXXIX with the chlorosulphonated polymers of formula XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII are aprotic polar solvents. The preferred solvents are THF, methylTHF, dioxane, dichloromethane and dichloroethane, dimethylsulfoxide.
    [0011] According to a second variant, the polymers of formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV may be obtained: 1) by producing in a first chlorosulfonation of a polymer of formula XVI, XVII, XVII, XIX, XX, XXI, XXII and XXIII by a mixture of chlorosulfonic acid, thionyl chloride and formamide according to an optimized procedure. In which - p represents the number of polymeric units of the polymer, p varies from 40 to 300, and preferably between 60 and 200, to obtain the polymers of formulas XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII Ln d 'rI d' NJ 0 wherein m represents the percentage of polymeric units having an oxoaryl or dioxoaryl moiety functionalized by means of a moiety in which: 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 polymeric units of the polymer; P varies from 40 to 300, preferably from 60 to 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, the polymer XVII is known commercially under the name of polyetherketone ketone or poly (ether ketone ketone) or PEKK 5 POP o (XVII) the polymer XVIII is known commercially under the name of poly (ether ether sulfone) or PEES (MM polymer XIX is known commercially as poly (ether sulfone) or PES (XIX) 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) family. sulfonated ether) and is known commercially as poly (bisphenol A PAES) (XXI) polymer XXII is known commercially as polyether ketone ether ketone ketone) or polyetherketone ketone ether ketone) or PEKEKK POP (XXII) the polymer XXIII is known commercem This list of polymers is not limiting since there are a large number of other commercially available or non-commercially available polymers in the families of the polyetherketone or polyetherketone or PEK (XXIII) polymers. 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.
    [0012] The chlorosulphonation is carried out at a temperature between 0 ° and 80 ° C with 1 to 10 equivalents of chlorosulfonic acid, 1 to 30 equivalents of thionyl chloride, 1 to 10 equivalents of an amide preferentially N N, N-dimethylformamide, with or without a solvent. The preferred solvents according to the invention are THF, methylTHF, dichloromethane, dichloroethane. Chlorosulfonation of certain polymers can lead to mixtures of many isomers. This is particularly true for XXII or PEKEKK polymers. 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 formula XXIV, XXV, XXVI, XXVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII are reacted with the amine of Formula 20 (XXXIX) to obtain the polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV, (XL) 0 I (Aix) (mu) 21 (mix) S (lu) or LZ StItZOE Ln o / d 'ri of N 0 rn --IX 2 X z J 3024145 29 o (LI) 5 (LIII) in which: - m represents the percentage of polymeric units having a functionalized oxoaryl or dioxoaryl moiety having a sulfonamide function. This percentage varies between 50 and 100%, n represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit not functionalized by a sulfonamide function. This percentage varies between 0 and 50%; p represents the number of polymeric units of the polymer; p varies from 40 to 300, preferably between 60 and 200.
    [0013] To carry out this reaction with the base of formula XXXIX, the polymers are solubilized in a solvent such as an ether, a haloalkane, an aromatic or optionally in the amine of formula XXXIX if it is liquid under the conditions of the reaction. More generally, the amine of formula XXXIX is introduced as a solution in an ether solvent, a haloalkane, an aromatic. Preferred solvents are dichloromethane, 1,2-dichloroethane, THF, methylTHF, diisopropyl ether, diethyl ether, anisole. With respect to the number of chlorosulphonyl functions of the polymer of formula XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII, 2 to 12 amine equivalents are introduced of formula XXXIX, preferably 2 to 5 equivalents of amine. The tests are carried out at a temperature between -20 ° C and 60 ° C, preferably between 0 and 30 ° C. The polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV are novel intermediates for the preparation of polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV. 3) in a third step, is reacted on the polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV, a lithiated base or soda at a temperature between 30.degree. C. and 80.degree. C., preferably between 20 and 60.degree. C. in a solvent medium. Preferably, the R group of the amine XXXIX represents: an alkyl group having 1 to 10 carbon atoms linear or branched optionally substituted with a cycloalkyl, aryl; a cycloalkyl group; An aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, by alkoxy, nitrile or alkylsulfonyl functions, by one or more fluorine atoms.
    [0014] The lithium or sodium bases are chosen from lithium hydroxide, sodium hydroxide, lithium methoxide, sodium methoxide, lithium ethoxide, sodium ethoxide, lithium isopropoxide and sodium isopropoxide. lithium tertiobutylate, sodium tert-butylate, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, lithium diisopropylamide, tert-butyllithium, methyllithium and phenyllithium. , phenylsodium, benzyllithium, benzylsodium, lithium dimsylate, sodium dimsylate. The preferred bases are those which do not form water during the reaction.
    [0015] The preferred solvents are dichloromethane, 1,2-dichloroethane, THF, methylTHF, diisopropyl ether, DMSO, methanol, dioxane, isopropanol. All reactions are carried out with anhydrous solvents, preferably freshly distilled, and under anhydrous atmosphere. Anhydrous atmosphere is understood to mean an atmosphere under a stream of nitrogen or argon. The process developed by the applicant uses inexpensive products and leads to electrolytes compatible with market expectations and whose performance is greater than or equal to the best products. Surprisingly and unexpectedly, it has been found that polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV are particularly film-forming which is a distinct advantage for the intended application. Thus, films of the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV can be easily obtained by evaporation of a polymer solution. in an anhydrous solvent such as DMSO, deposited on a surface of a material such as glass, teflon, plastic. The evaporation of the solvent is carried out at a temperature between 20 and 80 ° C, by heating, by sweeping an inert gas and / or under reduced pressure. It is thus possible to obtain films having a thickness of between 10 μm and 200 μm. The films obtained have a conductivity of 10-6 S / cm in solvent medium and without solvent. The performances obtained are comparable with those of the best electrolytes. In addition, they have excellent conductivity over a wide temperature range of 20 to 100 ° C.
    [0016] The examples given below are presented as non-limiting illustrations of the subject of the present invention.
    [0017] Example 1 - Chlorosulfonation of PEEK. Preparation of Polymer XXIV Under a nitrogen atmosphere in a cylindrical glass reactor, 1.0 g of PEEK (XVI) is directly weighed, then 160 ml of distilled dichloromethane are added so as to have a molar concentration of PEEK (XVI ) All of the solvents used in these syntheses were distilled, stored and removed under a nitrogen atmosphere. 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 flow nitrogen. The reaction mixture is stirred at 20 ° C for 5 h. At the end of the reaction, the formation of an orange viscous compound is observed. The supernatant is removed by taking care to handle under a stream of nitrogen.
    [0018] Thionyl chloride (12.29 g, 30 equivalents relative to the number of polymer units of PEEK (XVI)) was then added using a syringe (7.50 mL), taking care to handle under nitrogen flow. Then N, N-dimethylformamide (0.76 g, 3 equivalents relative to the number of polymer units of PEEK O XVI XXIV 1) 8 eq CISO3H, 20 ° C, 5 h, CH2Cl2 2) eq SOCl2 is added. + 3 eq DMF, 20 ° C, 5 h 3024145 34 (XVI)) using a syringe (0.81 mL) taking care to handle under a stream of nitrogen. The reaction mixture was again stirred at 20 ° C for 5 h, then 40 mL of distilled THF was added. At the end of the reaction, an orange solution is observed. The orange solution is precipitated in propan-2-ol (250 mL), a white precipitate is formed. The solid is filtered and 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). NMR spectrum 111 carried out in DMSO-D6 PH NMR (200 MHz) 7.92 - 7.69 (m, 4H), 7.50 (d, J = 2.7 Hz, 1H), 7.36 - 6.83 (m, 6H)) confirms the expected structure. Integration of the peak at 7.50 ppm in 1H NMR allows us to know the level of chlorosulfonation of PEEK (XVI). The chlorosulfonation rate of the di-oxoaryl units is 100%. The weight yield of polymer PEEKSO2C1 (XXIV) is 98% compared to the PEEK (XVI) engaged.
    [0019] Example 2-6 Preparation of Polymer XXIV with Different Functionalization Levels According to the protocol described in Example 1 the following polymers were prepared: The differences with the protocol described in Example 1 are: - the mass of product starting PEEK (XVI) OOS'CI 1) 8 eq CISO3H, 20 ° C, t (h), CH2Cl2 2) eq SOCl2 + 3 eq DMF, 20 ° C, 5h n XVI XXIV OO 3024145 - the time of reaction of the first step Examples mPEEK t Rate of (g) (h) functionalization (%) 72 2 4 81 2 5 93 5 5 96 6 10 15 99 Mass yield (%) 91 93 97 96 96 Example 7 - Chlorosulfonation of PEES (XVIII).
    [0020] Preparation of Polymer XXVI Under a nitrogen atmosphere in a cylindrical glass reactor, 1.0 g of PEES (XVIII) was directly weighed, then 160 ml of distilled dichloromethane was added so as to have a molar concentration of PEES ( XVIII) of 0.019 M. All solvents used in these syntheses were distilled, stored and taken under a nitrogen atmosphere.
    [0021] 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 to handle under flow 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. O XVIII XXVI 1) 8 eq CISO3H, 0 ° C, 5 h, CH2Cl2 2) 30 eq SOCl2 + 3 eq DMF, 20 ° C, 5 h 0 = S 00 O n 3024145 36 The thionyl chloride (10 , 93 g, 30 equivalents relative to the number of polymer units of the PEES (XVIII)) using a syringe (6.6 ml), taking care to handle under a flow of nitrogen.
    [0022] Then N, N-dimethylformamide (0.76 g, 3 equivalents relative to the number of polymer units of PEES (XVIII)) was added using a syringe (0.68 mL) taking care of handle under a stream of nitrogen. The reaction mixture was again stirred at 20 ° C for 5 h, then 40 mL of distilled THF was added. At the end of the reaction, a brown solution is observed. The brown solution is precipitated in propan-2-ol (250 mL), a white precipitate is formed. The solid is filtered and 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). The 1 H NMR spectrum in DMSO-D6 PH NMR (200 MHz) δ 7.91 (ddd, J = 18.6, 8.8, 2.9 Hz, 4H), 7.44 (s, 1H). , 7.18 (d, J = 7.2 Hz, 4H), 6.99 (d, J = 7.3 Hz, 2H)) confirm the expected structure. The integration of the peak at 7.44 ppm in 1 H NMR allows us to know the level of chlorosulfonation of PEES (XVIII). The chlorosulfonation rate of the dioxoaryl units is 100%.
    [0023] The weight yield of the XXVI polymer is 84% relative to the PEES (XVIII) engaged. Example 8 - Chlorosulfonation of the PES. Preparation of the Polymer XXVII 3024145 37.0-SCI = 1) 2.1 eq CISO3H, 42 ° C, 18 h, CH2Cl2 2) 8 eq SOCl2 + 3 eq DMF, 20 ° C, 5 h XIX Under a nitrogen atmosphere, in a cylindrical glass reactor, 0.5 g of PES (XIX) is weighed directly, then 80 ml of distilled dichloromethane are added so as to have a molar concentration of PES (XIX) of 0.027 M, after stirring for 1 h. at 20 ° C, the PES (XIX) is solubilized. All the solvents used in these syntheses were distilled, stored and removed under a nitrogen atmosphere.
    [0024] The chlorosulfonic acid (0.527 g, 2.1 equivalents relative to the number of polymeric units of the PES (XIX)) is introduced with the aid of a syringe (0.30 ml), taking care to handle under flow. nitrogen. 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 polymeric units of PES (XIX)) is then introduced using a syringe (1.24 ml), taking care to handle under nitrogen flow. Then N, N-dimethylformamide (0.47 g, 3 equivalents relative to the number of polymer units of PES (XIX)) was added using a syringe (0.50 mL) taking care of 25 handle under a stream of nitrogen. The reaction mixture was again stirred at 20 ° C for 5 h, then 20 mL of distilled THF was added. At the end of the reaction, a yellow solution is observed.
    [0025] 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). The 1H NMR spectrum produced in DMSO-D6 (1H NMR (200 MHz) δ 8.29 (s, 1H), 7.92 (s, 3H), 7.19 (s, 3H)) confirms the expected structure. The integration of the peak at 8.29 ppm in 1H NMR allows us to know the chlorosulfonation rate of the PES (XIX). The chlorosulfonation rate of the oxoaryl units is 100%. The weight yield of polymer PESSO2C1 (XXVII) is 98% compared to the PES (XIX) engaged.
    [0026] Example 9 - Preparation of Polymer XI, with R = NH-Ph-3-CF3 Under a nitrogen atmosphere, 0.500 g of Polymer XXIV is weighed directly into a cylindrical glass reactor and 20 ml of distilled tetrahydrofuran are then added. in order to have a molar concentration of PEEKSO 2 Cl (XXIV) of 0.065 M. All the solvents used in these syntheses were distilled, stored and taken under a nitrogen atmosphere. Under a nitrogen atmosphere in a cylindrical glass reactor, 0.624 g of 3- (trifluoromethyl) aniline (XXXIX) (3 equivalents relative to PEEKSO 2 Cl (XVI)) is directly weighed and then 20 ml of distilled tetrahydrofuran is added. in order to have a molar concentration of 0.19 M. The solution of PEEKSO2C1 (XVI) is then introduced with the aid of a syringe, taking care to handle under a stream of nitrogen. The reaction is continued at 20 ° C. for 1 hour. A clear solution is obtained which is evaporated on a rotary evaporator. After evaporation, a film-forming solid is obtained which is solubilized in 12 ml of tetrahydrofuran and then precipitated in 75 ml of acetonitrile. The precipitate is filtered and then washed with 3 times 10 ml of acetonitrile and then dried overnight under vacuum (1.10-2 mbar). The 1 H and 19 F NMR spectra are made in DMSO-D6 (11-1 NMR (200 MHz) δ 7.79 (s, 4H), 7.56 - 6.68 (m, 11H) and 19 F NMR (188 MHz). MHz) b -61,42 (s)) confirm the expected structure. The weight yield in XL with R = NH-Ph-3-CF3 is 92% relative to the polymer XXIV engaged.
    [0027] EXAMPLE 10 Preparation of Polymer I with R = NH-Ph-3CF3 and M = Li CF 3 O 0, NH, N = 0 = 8 1.1 eq Li 20 ° C, 18 h, THF XL In a cylindrical glass reactor, 0.200 g of the weight yield of XL is weighed directly with R = NH-Ph-3-CF 3 (XL), then 5 ml of distilled tetrahydrofuran CF 3 is added. 3024145 All the solvents used during these syntheses were distilled, stored and taken under a nitrogen atmosphere. Under a nitrogen atmosphere, 3 mg of lithium (1.1 equivalents relative to PEEKSO 2 NH-Ph-3-CF 3 (XL)) is added to the solution. The reaction is continued at 20 ° C. for 18 h. The solution obtained is filtered and the filtrate is evaporated. The solid obtained is dried overnight under vacuum (1.10-2 mbar). The 1H and 19F NMR spectra are carried out in DMSO-D6 (IH NMR (200 MHz) δ 8.01 - 7.69 (m, 4H), 7.68 - 7.47 (m, 2H), 7.46 - 6.67 (m, 9H) and I9F NMR (188 MHz) 5 -61.04 (s)) confirm the expected structure.
    [0028] The weight yield of PEEKSO2N- (Li +) Ph-3-CF3 (I) is 97% relative to the PEEKSO2NH-Ph-3-CF3 (XL) engaged. Example 11 - Preparation of Polymer I with R = NH-Ph-3 CF3 and M = Li Under a nitrogen atmosphere in a cylindrical glass reactor, 0.200 g of PEEKSO 2 Cl (XXIV) is weighed directly, then 10 mL of tetrahydrofuran distilled to have a molar concentration of PEEKSO 2 Cl (XXIV) of 0.052M. All solvents used in these syntheses were distilled, stored and removed under a nitrogen atmosphere. ## STR5 ## in a cylindrical glass reactor, under a nitrogen atmosphere, in a cylindrical glass reactor, directly weigh 0.100 g of 3- (trifluoromethyl) aniline (XXXIX) (1.2 equivalents relative to PEEKSO 2 Cl (XXIV)), then 10 ml of tetrahydrofuran is added. N-BuLi (0.50 ml, [C] = 2.5 M in hexane) is introduced in order to have 2.4 equivalents relative to PEEKSO2C1 (XXIV). This reagent is introduced using a syringe, taking care to handle under a stream of nitrogen. The reaction mixture is stirred at 20 ° C for 15 minutes. The solution of PEEKSO2C1 (XXIV) is then introduced with the aid of a syringe, taking care to handle under a stream of nitrogen. The reaction is continued at 20 ° C. for 1 hour. At the end of the writing, a yellow precipitate is observed.
    [0029] The precipitate is filtered and washed 3 times with 10 ml of acetonitrile. The solid obtained is dried overnight under vacuum (1.10-2 mbar). NMR spectra 111 and 19F are carried out in DMSO-D6 (1H NMR (200 MHz) δ 8.01 - 7.69 (m, 4H), 7.68-7.47 (m, 2H), 7, 46 - 6.67 (m, 9H) and 19F NMR (188 MHz) at -61.04 (s)) confirm the expected structure. The weight yield of PEEKSO 2 N- (LilPh-3-CF 3 (I) is 97% relative to the PEEKSO 2 C1 engaged Example 12 - Preparation of Polymer III with R = NH-Ph3-CF3 and M = Li CF3, CI 0 = - 00% = 0% O 2 + 1.2 2,4 eq n-BuLi H2N CF3 20 ° C, 1 h, THF XXXIX 3024145 42 Under a nitrogen atmosphere, in a cylindrical glass reactor is weighed directly 0.200 g of PEESSO2C1 (XXVI), then 10 mL of tetrahydrofuran distilled so as to have a molar concentration of PEESSO2C1 5 (XXVI) of 0.047 M. All solvents used in these syntheses were distilled, stored and removed under a nitrogen atmosphere in a cylindrical glass reactor under a nitrogen atmosphere 0.092 g of 3- (trifluoromethyl) aniline (XXXIX) (1.2 equivalents relative to PEESSO2C1 (XXVI)), then 10 mL of tetrahydrofuran are added n-BuLi (0.50 mL, [C] = 2.5 M in hexane) is introduced in order to have 2.4 equivalents relative to PEESSO 2C1 (XXVI) This reagent is introduced by syringe taking care to handle under a flow of nitrogen. The reaction mixture is stirred at 20 ° C for 15 min. The solution of PEESSO2C1 (XXVI) is then introduced with the aid of a syringe, taking care to handle under a stream of nitrogen. The reaction is continued at 20 ° C. for 1 hour. At the end of the writing, a yellow precipitate is observed. The precipitate is filtered and washed with 3 times 10 ml of acetonitrile. The solid obtained is dried overnight under vacuum (1.10-2 mbar).
    [0030] The 1 H and 19 F NMR spectra are carried out in DMSO-D6 PH NMR (200 MHz) 8.06-7.70 (m, 5H), 7.45 (s, 1H), 7.28-6, 64 (m, 9H) and 19F NMR (188 MHz) 5 -61.04 (s) confirm the expected structure.
    [0031] The weight yield of PEESSO2N- (LilPh-3-CF3 (III) is 65% relative to the PEESSO2C1 (XXVI) employed.
    [0032] Example 13 - Preparation of polymer IV with R = NH-Ph-3CF3 and M = Li 5 Under a nitrogen atmosphere, a cylindrical glass reactor is weighed directly 0.200 g PESSO2C1 (XXVII), then 10 mL of tetrahydrofuran distilled so as to have a molar concentration of PESSO 2 Cl (XXVII) of 0.076M. All the solvents used in these syntheses were distilled, stored and removed under a nitrogen atmosphere. Under a nitrogen atmosphere in a cylindrical glass reactor, 0.146 g of 3- (trifluoromethyl) aniline (XXXIX) (1.2 equivalents relative to PESSO 2 Cl (XXVII)) was directly weighed, followed by the addition of 10 ml of tetrahydrofuran. . N-BuLi (0.73 ml, [C] = 2.5 M in hexane) is introduced in order to have 2.4 equivalents relative to PESSO2C1 (XXVII). This reagent is introduced using a syringe, taking care to handle under nitrogen flow. The reaction mixture is stirred at 20 ° C for 15 min. The solution of PESSO2C1 (XXVII) is then introduced with the aid of a syringe, taking care to handle under a flow of nitrogen. The reaction is continued at 20 ° C. for 1 hour.
    [0033] At the end of the writing, a yellow precipitate is observed. The precipitate is filtered and washed with 3 times 10 ml of acetonitrile. The solid obtained is dried overnight under vacuum (1.10-2 mbar).
    [0034] ## EQU1 ## The 1 H NMR and 19 F spectra are made in DMSO-D6 (1H NMR). (200 MHz) δ 8.42 - 8.23 (m, 1H), 8.07 - 7.46 (m, 4H), 7.38 - 6.54 (m, 6H) and 19F NMR (188 MHz) b-61.03 5 (s)) confirm the expected structure. The weight yield of PESSO2N- (Li +) Ph-3-CF3 (IV) is 83% relative to the PESSO2C1 (XXVII) engaged.
    [0035] Examples 14 - Preparation of Polymer Film Under a nitrogen atmosphere in a cylindrical glass reactor, 100 mg of Polymer I, III or IV is directly weighed, then 3 ml of distilled dimethyl sulfoxide is added. All the solvents used in these syntheses were distilled, stored and removed under a nitrogen atmosphere. After complete solubilization of the polymer, the solution is introduced into a petri dish of 5 cm in diameter. The petri dish is deposited on a hot plate at 50 ° C. After one night, the solvent is completely evaporated and a cylindrical film 5 cm in diameter with a thickness of the order of 100 μm is obtained.
    [0036] Examples 15 - Conductivity measurements The ionic conductivity of the polymer prepared in Example 10 was determined by impedance spectroscopy. The results obtained with the polymer described above are reported in Table 1 and compared with the results obtained in the publication by D. Gigmes et al. in Nature Materials, 12, 452-457 (2013). Solvent DMC PC CH3CN Conductivity (Sicrn) 1,4,10-6 4,15,10-7 1,04,10-e Figure 1: Conductivity of the polymer described above at 20 ° C with different solvents It can be noticed that at room temperature achieves a conductivity of the order of 10-6 S / cm. The conductivities published in patent FR 2979630 and the publication of D. Gigmes et al. in Nature Materials, 12, 452-457 (2013) are of the same order of magnitude, but at 45 ° C. It can therefore be concluded that at room temperature very promising conductivities are obtained.
    权利要求:
    Claims (28)
    [0001]
    REVENDICATIONS1. Polymers of the Formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV (I) R o NM o 'S, I o (II) ( ## STR2 ## ## STR2 ## in which: M represents a lithium or sodium atom; R represents: an alkyl group having from 1 to 30 linear or branched carbon atoms optionally substituted with a cycloalkyl or aryl unit; a cycloalkyl group, optionally substituted with aromatic groups; An aryl or polyaryl group, optionally with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, with nitrile functions, with alkylsulfonyl functions, with fluorine atoms, m represents the percentage of polymer units having an oxoaryl unit or dioxoaryl functionalized by a sulfonamide unit. This percentage varies between 50 and 100%; n represents the percentage of polymer units having no oxoaryl or dioxoaryl unit not functionalized by one or more sulfonamide units. This percentage varies between 0 and 50%, p represents the number of polymeric units of the polymer; p varies from 40 to 300. 20
    [0002]
    2. Polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV according to claim 1, characterized in that: M represents an atom of lithium or sodium - R represents: - an alkyl of 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, ethylhexyl; a 2,2-difluoroethyl, 2,2-difluoro-2- (trifluoromethyl) ethyl group; Aryl group of phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, cyanophenyl, alkylsulfonylphenyl, arylsulfonylphenyl. m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit functionalized by a sulfonamide unit. This percentage varies between 90 and 100%. n represents the percentage of polymeric units having no oxoaryl or dioxoaryl unit not functionalized by a sulfonamide unit. This percentage varies between 0 and 10%. p represents the number of polymer unit of the polymer; P varies from 40 to 300.
    [0003]
    3. Polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV according to claim 1, characterized in that: M represents an atom of lithium or sodium - R represents: - an alkyl group of 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, ethylhexyl; a 2,2-difluoroethyl, 2,2-difluoro-2- (trifluoromethyl) ethyl group; aryl group of phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, cyanophenyl, alkylsulfonylphenyl, arylsulfonylphenyl, methoxyphenyl, butoxyphenyl, pentafluorophenyl, alkylsulfonylphenyl, fluorophenyl, 30-m represents the percentage of polymeric units having a unit oxoaryl or dioxoaryl functionalized by a sulphonamide unit. This percentage varies between 90 and 100%. n represents the percentage of polymeric units having no oxoaryl or dioxoaryl unit not functionalized by a sulfonamide unit. This percentage varies between 0 and 10%. p represents the number of polymer unit of the polymer; P varies from 60 to 200. 10
    [0004]
    4. Polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV according to claim 1, characterized in that: - M represents an atom of lithium or sodium - R is methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl, (7,7-dimethyl-2-oxobicyclo [2.2.1 ] heptan-1-yl) methyl, ((1R) -7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, (1S) - (7,7-dimethyl-2-oxobicyclo) [2.2.1] heptan-1-yl) methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis (trifluoromethyl) phenyl, 4-cyanophenyl, nonafluorobutyl, pentafluorophenyl, 2,3,5, 6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4- (trifluoromethyl) phenyl, 3- (trifluoromethyl) phenyl 2- (trifluoromethyl) phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3- rifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4-methoxyphenyl, 4-nbutylphenyl, 4-t-butylphenyl, 4-butoxyphenyl, 2-fluoro-5- (trifluoromethyl) phenyl, 4-ethylphenyl, Phenoxyethyl, methoxyethyl, ethoxyethyl, 4-methoxyphenoxyethyl. m represents the percentage of polymeric units having a dioxoaryl moiety functionalized with a sulfonamide. This percentage varies between 90 and 100%. n represents the percentage of polymeric units having a dioxoaryl unit not functionalized by a sulphonamide. This percentage varies between 0 and 10%. p represents the number of polymeric units of the polymer; P varies from 60 to 200.
    [0005]
    5. Process for synthesizing polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, characterized in that: 1) in a first step, chlorosulfonation of a polymer of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII is carried out with a mixture of chlorosulfonic acid, thionyl chloride and formamide according to an optimized procedure. (XVI)) POPO (XVII) (XVII (XVIII) 3024145 53 (XIX) (XX)) (Xa) POP (XXII) (in which: p represents the number of polymeric units of the polymer; from 40 to 300, to obtain the polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII of NJ 0 wherein m represents the percentage of polymeric units having an oxoaryl or dioxoaryl moiety functionalized by means of a moiety; This percentage varies between 50 and 100%, n represents the percentage of polymer units having a non-functionalized dioxoaryl unit with a chlorosulphonated group, this percentage varies between 0 and 50%, p represents the number of chlorosulphonated groups. Polymeric units of the polymer: P varies from 40 to 300. 2) In a second step, the polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX are reacted. , XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII an amine of formula XXXIX in a solvent medium. Wherein: R represents a group or different groups selected from: - an alkyl or cycloalkyl group having 1 to 30 carbon atoms linear or branched optionally substituted by a cycloalkyl unit, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxylated; an aryl or polyaryl group optionally substituted with alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl units, with nitrile functions, with alkyl or alkylsulfonyl functions, with fluorine atoms; m represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit having a grafted sulfonamide salt. This percentage varies between 50 and 100% in the presence of a lithiated or sodic base. 20
    [0006]
    6. Process according to claim 5, characterized in that an amine of formulas XXXIX is reacted with polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV. , XXXV, XXXVI, XXXVII and XXXVIII in which: m represents the percentage of polymer units having an oxoaryl or dioxoaryl unit functionalized by a chlorosulfonated group. This percentage varies between 90 and 100%. n represents the percentage of polymer units having a dioxoaryl unit not functionalized by a chlorosulphonated group. This percentage varies between 0 and 10%, p represents the number of polymeric units of the polymer; P varies from 60 to 200, 5 in the presence of a lithiated or sodic base.
    [0007]
    7. Process according to claim 5, characterized in that the R group of the amine XXXIX is a methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl or 1-octyldecyl group. (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, ((1R) -7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, (1S) - (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 415 trifluoromethylphenyl, 3,5-bis (trifluoromethyl) phenyl, 4- cyanophenyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4- (Trifluoromethyl) phenyl, 3- (trifluoromethyl) phenyl, 2 (trifluoromethyl) phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4-methoxyphenyl 4-n-butylphenyl, 4-t-butylphenyl, 4-butoxyphenyl, 2-fluoro-5- (trifluoromethyl) phenyl, 4-ethylphenyl, phenoxyethyl, methoxyethyl, ethoxyethyl, 4-methoxyphenoxyethyl, in the presence of a base lithiated or sodic. 30
    [0008]
    8. Process for synthesizing polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV, characterized in that 3024145 59 1) in a first step chlorosulfonation of a polymer of the formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII and XXIII is carried out in which p represents the number of polymeric units of the polymer; P varies from 40 to 300 to obtain the chlorosulfonated polymers of formulas XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII in which: m represents the percentage of polymer units having a dioxoaryl unit functionalized by a chlorosulfonated group. This percentage varies between 50 and 100%; n represents the percentage of polymer units having a dioxoaryl unit which is not functionalized by a chlorosulphonated group. This percentage varies between 0 and 50%, p represents the number of polymer unit of the polymer; P varies from 40 to 300, 2) in a second stage, the polymers of formulas XXIV, XXV, XXVI, XXVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII are reacted. and XXXVIII in bulk or in solution the amine of formula XXXIX to obtain the polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV. (XL) (Aix) (Ai ix) 0T g 0, ---.....- ', ........ `, .... / .. L -----.' -, ... ',' '.. .. . ^' _,. / C) u - 1 II .... ---- "----.... nc, .. ., --...--- '0 w / III ... s., .., / * ---- 0 0 HN to 09 StItZ0E Ln d- HXJ rI l.0 J NJ X 0 M LO In which: 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 oxoaryl or dioxoaryl units which are not functionalized by a sulphonamide function, this percentage varies between 0 and 50%, p represents the number of polymer units of the polymer, p varies from 40 to 300. 3) in a third step, is reacted on the polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV, a base lithiated or soda at a temperature of between 0 and 8000 in a solvent medium.
    [0009]
    9. Process according to claim 8, characterized in that the R group represents: an alkyl group having from 1 to 10 linear or branched carbon atoms optionally substituted with a cycloalkyl or aryl unit; A cycloalkyl group; an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, by alkoxy, nitrile or alkylsulfonyl functions, by one or more fluorine atoms.
    [0010]
    10. Process according to claim 8, characterized in that the R group of the amine XXXIX is a methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl or 1-octyldecyl group. (7,7-Dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, ((1R) -7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, (1S) - (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-yl) methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 430 trifluoromethylphenyl, 3,5-bis (trifluoromethyl) phenyl, 4- cyanophenyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4- (trifluoromethyl) phenyl, 3- (trifluoromethyl) phenyl, 2- (trifluoromethyl) phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4 trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4- methoxyphenyl, 4-n-butylphenyl, 4-t-butylphenyl, 4-butoxyphenyl, 2-fluoro-5- (trifluoromethyl) phenyl, 4-ethylphenyl, phenoxyethyl, methoxyethyl, ethoxyethyl, 4-methoxyphenoxyethyl.
    [0011]
    11. Process according to claim 5 or 8, characterized in that the chlorosulfonation is carried out at a temperature of between 0 and 80 ° C.
    [0012]
    12. Process according to Claim 5 or 8, characterized in that the chlorosulfonation is carried out more particularly at a temperature of between 0 ° and 80 ° C. with a mixture of 1 to 10 equivalents of chlorosulphonic acid and 1 to 30 equivalents of chloride. thionyl in the presence of 1 to 10 equivalents of an amide.
    [0013]
    13. Process according to claim 5 or 8, characterized in that the base is chosen from lithium hydroxide, sodium hydroxide, lithium methoxide, sodium methoxide, lithium ethoxide, sodium ethoxide and sodium hydroxide. lithium isopropoxide, sodium isopropoxide, lithium tertiobutylate, sodium tert-butylate, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, lithium diisopropylamide , tert-butyllithium, methyllithium, phenyllithium, phenylsodium, benzyllithium, benzylsodium, lithium dimesylate, sodium dimesylate. The preferred bases are those which do not form water during the reaction. 5
    [0014]
    14. Process according to claim 5 or 8, characterized in that the chlorosulfonation is carried out in the presence of an amide such as N, N-dimethylformamide.
    [0015]
    15. Process according to claims 5 or 8, characterized in that the reaction is carried out in a solvent, preferably THF, methylTHF, dichloromethane, dichloroethane or a mixture of solvents. 15
    [0016]
    16. Process according to claim 8, characterized in that the amination reaction of the chlorosulphonated polymers of formulas XXIV, XXV, XXVI, XXVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII to form the sulfonamide polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV is carried out in a solvent medium in the presence of the amine XXXIX in a solvent such as THF, methylTHF, methanol, dioxane, isopropanol. 25
    [0017]
    17. Process according to claim 8, characterized in that the amination reaction of the polymers of formulas XXIV, XXV, XXVI, XXVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII. with the amine of formula XXXIX is carried out at a temperature between -20 and 60 ° C. 3024145 66
    [0018]
    18. Process according to claim 8, characterized in that the reaction of the lithiated or soded base with the polymers XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII. and LIV is carried out at a temperature between 0 and 80 ° C.
    [0019]
    19. Polymers of the Formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV (XL), ## STR2 ## O (XLI) 15 (XLII) (XLIII) wherein L is: ## STR2 ## wherein 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 dioxoaryl unit not functionalized by a sulfonamide function. This percentage varies between 0 and 50%, p represents the number of polymeric units of the polymer; p varies from 40 to 300. 5
    [0020]
    20. Polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV according to claim 19 in which: m represents the percentage of units polymers having a functionalized oxoaryl or dioxoaryl unit having a sulfonamide function. This percentage varies between 90 and 100%; n represents the percentage of polymeric units having an oxoaryl or dioxoaryl unit not functionalized by a sulfonamide function. This percentage varies between 0 and 10%, p represents the number of polymeric units of the polymer; p varies from 60 to 200. 20
    [0021]
    21. Use of the Polymers of Formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV as Synthesis Intermediates in the Preparation of the Polymers of Formulas I, II III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV.
    [0022]
    22. Use of the film-forming polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV to prepare films with a thickness of between 10 μm and 200 pm.
    [0023]
    23. A process for the preparation of films serving as electrolytes, characterized in that one operates in a medium in the absence of traces of water and moisture by solubilizing one of the polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV in an anhydrous solvent, depositing the polymer solution on a solid support and then evaporating the solvent.
    [0024]
    24. The method of claim 23 characterized in that the solvent is DMSO. 10
    [0025]
    25. The method of claim 23, characterized in that the evaporation of the solvent is carried out at a temperature between 20 and 80 ° C. 15
    [0026]
    26. The method of claim 23, characterized in that the evaporation of the solvent is carried out by heating, scanning an inert gas or under reduced pressure. 20
    [0027]
    27. Electrolytes characterized in that the polymer films of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV have a conductivity of the order of 10-6 S / cm in solvent medium and without solvent. 25
    [0028]
    28. Electrolytes characterized in that the polymer films of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV are used in a range of temperature between 20 and 100 ° C. 30
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1401709A|FR3024145B1|2014-07-23|2014-07-23|NOVEL POLYMERS CONTAINING SULFONAMIDE LITHIUM OR SODIUM SALTS, PROCESSES FOR THEIR PREPARATION AND USES THEREOF AS ELECTROLYTES FOR BATTERIES|FR1401709A| FR3024145B1|2014-07-23|2014-07-23|NOVEL POLYMERS CONTAINING SULFONAMIDE LITHIUM OR SODIUM SALTS, PROCESSES FOR THEIR PREPARATION AND USES THEREOF AS ELECTROLYTES FOR BATTERIES|
    KR1020177005145A| KR20170048354A|2014-07-23|2015-07-20|Novel polymers containing sulphonamide sodium or lithium salts, production methods thereof and uses of same as electrolytes for batteries|
    EP15763958.4A| EP3172259B1|2014-07-23|2015-07-20|Novel polymers containing sulphonamide sodium or lithium salts, production methods thereof and uses of same as electrolytes for batteries|
    JP2017524114A| JP6723998B2|2014-07-23|2015-07-20|Novel polymer containing sodium sulfonamide or lithium salt, process for its preparation and its use as electrolyte for batteries|
    PCT/FR2015/000153| WO2016012669A1|2014-07-23|2015-07-20|Novel polymers containing sulphonamide sodium or lithium salts, production methods thereof and uses of same as electrolytes for batteries|
    CN201580051067.0A| CN107004455B|2014-07-23|2015-07-20|New polymers, preparation method containing sulfonamide sodium or lithium salts and its purposes as cell electrolyte|
    US15/327,606| US10109883B2|2014-07-23|2015-07-20|Polymers containing sulfonamide sodium or lithium salts, methods for production thereof and uses of same as electrolytes for batteries|
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