Polymers containing sulfonamide sodium or lithium salts, methods for production thereof and uses of same as electrolytes for batteries

Abstract

The invention relates to novel polymers containing grafted sodium or lithium sulphonamides, production methods thereof and uses of same as electrolytes in batteries.

Claims

1. A polymer selected from the group consisting of polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV ##STR00044## ##STR00045## ##STR00046## wherein: M represents a lithium or sodium atom R represents an alkyl group having 1 to 30 linear or branched carbon atoms optionally substituted by a cycloalkyl, aryl motif; a cycloalkyl group, optionally substituted by aromatic groups; an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, nitrile functions, alkylsulfonyl functions, fluorine atoms; m represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif functionalized by a sulfonamide motif(s), this percentage varying between 50 and 100%, n represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif non-functionalized by one or more sulfonamide motif(s), this percentage varying between 0 and 50%, p represents the number of polymer units of the polymer, p varying from 40 to 300.

2. The polymer according to claim 1, wherein: M represents a lithium or sodium atom, R represents: an alkyl with 1 to 10 carbon atoms; a 2,2-difluoroethyl, 2,2-difluro-2-(trifluoromethyl)ethyl group; an aryl group of the phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, cyanophenyl, alkylsulfonylphenyl, aryl sulfonylphenyl, methoxyphenyl, butoxyphenyl, pentafluorophenyl, alkylsulfonylphenyl or fluorophenyl type; m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a sulfonamide motif, this percentage varying between 90 and 100%; n represents the percentage of polymer units having no oxoaryl or dioxoaryl motif non-functionalized by a sulfonamide motif, this percentage varying between 0 and 10%; p represents the number of polymer units of the polymer, p varying from 40 to 300.

3. The polymer according to claim 2, wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and ethylhexyl groups.

4. The polymer according to claim 1, wherein: M represents a lithium or sodium atom, R is a 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-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 group; m represents the percentage of polymer units having a dioxoaryl motif functionalized by a sulfonamide, this percentage varying between 90 and 100%; n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a sulfonamide, this percentage varying between 0 and 10%; p represents the number of polymer units of the polymer, p varying from 60 to 200.

5. A method for synthesis of a polymer according to claim 1, comprising: in a first step, performing chlorosulfonation of a polymer selected from the group consisting of polymers of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII, and XXIII by a mixture of chlorosulfonic acid, thionyl chloride and a formamide ##STR00047## wherein: p represents the number of polymer units of the polymer, p varying from 40 to 300, in order to obtain a polymer selected from the group consisting of the polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII ##STR00048## ##STR00049## ##STR00050## wherein: m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a chlorosulfonated group, this percentage varying between 50 and 100%, n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a chlorosulfonated group, this percentage varying between 0 and 50%, p represents the number of polymer units of the polymer, p varying from 40 to 300, in a second step, producing a reaction on the polymer selected from the group consisting of polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII with an amine of formula XXXIX in a solvent medium
RNH.sub.2(XXXIX) wherein R represents a group or different groups chosen from: an alkyl or cycloalkyl group having 1 to 30 linear or branched carbon atoms, optionally substituted by a cycloalkyl, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxyl motif; an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl, motifs, by nitrile functions, by alkyl- or alkylsulfonyl functions, by fluorine atoms; for obtaining a polymer selected from the group consisting of polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV ##STR00051## ##STR00052## ##STR00053## wherein m represents the percentage of polymer units having a functionalized oxoaryl or dioxoaryl motif having a sulfonamide function, this percentage varying between 50 and 100%, n represents the percentage of polymer units having an oxoaryl or dioxoaryl motif non-functionalized by a sulfonamide function, this percentage varying between 0 and 50%, p represents the number of polymer units of the polymer, p varying from 40 to 300, in a third step, producing a reaction on the polymer selected from the group consisting of polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV with a lithium or sodium base at a temperature of between 0 and 80 C. in a solvent medium.

6. The method according to claim 5, wherein the R group of the XXXIX amine is a 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, 3,5difluorobenzyl, 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 group.

7. the method according to claim 5, wherein the chlorosulfonation is performed at a temperature of between 0 and 80 C. by a mixture of 1 to 10 equivalents of chlorosulfonic acid, 1 to 30 equivalents of thionyl chloride in the presence of 1 to 10 equivalents of an amide.

8. The method according to claim 5, wherein the base is chosen from lithine, soda, lithium methylate, sodium methylate, lithium ethylate, sodium ethylate, lithium isopropylate, sodium isopropylate, lithium tertiobutylate, sodium tertiobutylate, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, lithium diisopropylamidure, tert-butyllithium, methyllithium, phenyllithium, phenylsodium, benzyllithium, benzylsodium, lithium dimsylate, sodium dimsylate.

9. The method according to claim 5, wherein the chlorosulfonation is performed in the presence of N,N-dimethylformamide.

10. The method according to claim 5, wherein the chlorosulfonation is performed in a solvent or a mixture of solvents.

11. The method according to claim 5, wherein the amination reaction of the chlorosulfonated polymer selected from the group consisting of polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII, in order to form the sulfonamide polymer selected from the group consisting of polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV is performed in a solvent medium in the presence of the XXXIX amine in a solvent.

12. The method according to claim 5, wherein the amination reaction of the polymer selected from the group consisting of polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII with the amine of formula XXXIX is performed at a temperature of between-20 C. and 60 C.

13. The method according to claim 5, wherein m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a chlorosulfonated group, this percentage varying between 90 and 100%.

14. A method of preparing a film, comprising using filmogenic polymers according to claim 1, wherein the film has a thickness of between 10m and 200m.

15. A method for preparing a film adapted for serving as electrolyte for batteries, comprising, in a medium in the absence of traces of water and moisture, solubilizing the polymer according to claim 1 in an anhydrous solvent to obtain a polymer solution, depositing the polymer solution on a solid support, and then evaporating the solvent by heating at a temperature comprised between 20 and 80 C., inert gas sweeping or by applying reduced pressure.

16. The method according to claim 15 wherein the solvent is DMSO.

17. An electrolyte for batteries, comprising films made from polymers according to claim 1, wherein the electrolyte has a conductivity on the order of 10.sup.6 S/cm in a solvent medium and without solvent.

18. An electrolyte for batteries, comprising films made from polymers according to claim 1, wherein the electrolytes are used in a temperature range of between 20 and 100 C.

19. A polymer selected from the group consisting of polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV ##STR00054## ##STR00055## ##STR00056## wherein: m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a sulfonamide motif(s), this percentage varying between 50 and 100%, n represents the percentage of polymer units having an oxoaryl or dioxoaryl motif non-functionalized by one or more sulfonamide motif(s), this percentage varying between 0 and 50%, p represents the number of polymer units of the polymer, p varying from 40 to 300.

20. A synthesis method comprising preparing a polymer selected from the group consisting of polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV ##STR00057## ##STR00058## ##STR00059## wherein: M represents a lithium or sodium atom R represents an alkyl group having 1 to 30 linear or branched carbon atoms optionally substituted by a cycloalkyl, aryl motif; a cycloalkyl group, optionally substituted by aromatic groups: an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polvfluoro- or perfluoroalkyl chains, nitrile functions, alkylsulfonyl functions, fluorine atoms; m represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif functionalized by a sulfonamide motif(s), this percentage varying between 50 and 100%, n represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif non-functionalized by one or more sulfonamide motif(s), this percentage varying between 0 and 50%, p represents the number of polymer units of the polymer, p varying from 40 to 300, by using a polymer selected from the group consisting of polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV as synthesis intermediate ##STR00060## ##STR00061## ##STR00062## wherein: m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a sulfonamide motif(s) this percentage varying between 50 and 100%, n represents the percentage of polymer units having an oxoaryl or dioxoaryl motif non-functionalized by one or more sulfonamide motif(s), this percentage varying between 0 and 50%, p represents the number of polymer units of the polymer, p varying from 40 to 300.

Description

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

(1) The examples presented below are provided as a non-limiting illustration of the subject matter of the present invention.

EXAMPLE 1

Chlorosulfonation of PEEK. Preparation of Polymer XXIV

(2) ##STR00034##

(3) In 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 PEEK (XVI) molar concentration of 0.022 M. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(4) The chlorosulfonic acid (3.24 g, 8 equivalents with respect to the number of polymer units of the PEEK (XVI)) is introduced by means of a syringe (1.85 mL), taking care to work under a nitrogen flow. The reaction mixture is agitated 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 while taking care to work under a nitrogen flow.

(5) Then, thionyl chloride (12.29 g, 30 equivalents with respect to the number of polymer units of the PEEK (XVI)) is introduced by means of a syringe (7.50 mL), taking care to work under a nitrogen flow. Then, N,N-dimethylformamide (0.76 g, 3 equivalents with respect to the number of polymer units of the PEEK (XVI)) is added by means of a syringe (0.81 mL) taking care to work under a nitrogen flow. The reaction mixture is again agitated at 20 C. for 5 h, then 40 mL of distilled THF are added. At the end of the reaction, an orange solution is observed.

(6) The orange solution is precipitated in propan-2-ol (250 mL), and a white precipitate forms. The solid is filtered, then washed with 2 times 50 mL of propan-2-ol and 2 times 50 mL of acetonitrile, then dried for one night under vacuum (1.Math.10.sup.2 mbar).

(7) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H 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. The integration of the peak at 7.50 ppm in .sup.1H NMR allows us to know the chlorosulfonation rate of the PEEK (XVI). The chlorosulfonation rate of the dioxoaryl motifs is 100%.

(8) The PEEKSO.sub.2Cl (XXIV) polymer weight yield is 98% with respect to the PEEK (XVI) used.

EXAMPLE 2-6

Preparation of Polymer XXIV with Different Functionalization Rate

(9) According to the protocol described in example 1, the following polymers were prepared:

(10) ##STR00035##

(11) The differences with respect to the protocol described in example 1 are: the starting PEEK (XVI) product mass the reaction time of the first step

(12) TABLE-US-00001 m.sub.PEEK t Functionalization Mass yield Examples (g) (h) rate(%) (%) 2 1 3 72 91 3 2 4 81 93 4 2 5 93 97 5 5 15 96 96 6 10 15 99 96

EXAMPLE 7

Chlorosulfonation of PEES (XVIII). Preparation of Polymer XXVI

(13) ##STR00036##

(14) In a nitrogen atmosphere, in a cylindrical glass reactor, 1.0 g of PEES (XVIII) is directly weighed, then 160 mL of distilled dichloromethane are added so as to have a PEES (XVIII) molar concentration of 0.019 M. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(15) The chlorosulfonic acid (2.88 g, 8 equivalents with respect to the number of polymer units of the PEES (XVIII)) is introduced by means of a syringe (1.64 mL), taking care to work under a nitrogen flow. The reaction mixture is agitated 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 while taking care to work under a nitrogen flow.

(16) Then, thionyl chloride (10.93 g, 30 equivalents with respect to the number of polymer units of the PEES (XVIII)) is introduced by means of a syringe (6.6 mL), taking care to work under a nitrogen flow. Then, N,N-dimethylformamide (0.76 g, 3 equivalents with respect to the number of polymer units of the PEES (XVIII)) is added by means of a syringe (0.68 mL) taking care to work under a nitrogen flow. The reaction mixture is again agitated at 20 C. for 5 h, then 40 mL of distilled THF are added. At the end of the reaction, a brown solution is observed.

(17) The brown solution is precipitated in propan-2-ol (250 mL), and a white precipitate forms. The solid is filtered, then washed with 2 times 50 mL of propan-2-ol and 2 times 50 mL of acetonitrile, then dried for one night under vacuum (1.Math.10.sup.2 mbar).

(18) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 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) confirms the expected structure.

(19) The integration of the peak at 7.44 ppm in .sup.1H NMR allows us to know the chlorosulfonation rate of the PEES (XVIII). The chlorosulfonation rate of the dioxoaryl motifs is 100%.

(20) The XXVI polymer weight yield is 84% with respect to the PEES (XVIIII) used.

EXAMPLE 8

Chlorosulfonation of PES. Preparation of Polymer XXVII

(21) ##STR00037##

(22) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.5 g of PES (XIX) is directly weighed, then 80 mL of distilled dichloromethane are added so as to have a PES (XIX) molar concentration of 0.027 M; after 1 hour under agitation at 20 C., the PES (XIX) is solubilized. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(23) The chlorosulfonic acid (0.527 g, 2.1 equivalents with respect to the number of polymer units of the PES (XIX)) is introduced by means of a syringe (0.30 mL), taking care to work under a nitrogen flow. The reaction mixture is agitated at 42 C. for 18 h. At the end of the reaction, the formation of a yellow viscous compound is observed. The supernatant is removed while taking care to work under a nitrogen flow.

(24) Then, thionyl chloride (2.03 g, 8 equivalents with respect to the number of polymer units of the PES (XIX)) is introduced by means of a syringe (1.24 mL), taking care to work under a nitrogen flow. Then, N,N-dimethylformamide (0.47 g, 3 equivalents with respect to the number of polymer units of the PES (XIX)) is added by means of a syringe (0.50 mL) taking care to work under a nitrogen flow. The reaction mixture is again agitated at 20 C. for 5 h, then 20 mL of distilled THF are added. At the end of the reaction, a yellow solution is observed.

(25) The yellow solution is precipitated in propan-2-ol (80 mL), and a white precipitate forms. The solid is filtered, then washed with 2 times 20 mL of propan-2-ol and 3 times 20 mL of acetonitrile, then dried for one night under vacuum (1.Math.10.sup.2 mbar).

(26) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 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 .sup.1H NMR allows us to know the chlorosulfonation rate of the PES (XIX). The chlorosulfonation rate of the oxoaryl motifs is 100%.

(27) The PESSO.sub.2Cl (XXVII) polymer weight yield is 98% with respect to the PES (XIX) used.

EXAMPLE 9

Preparation of Polymer XL with RNH-Ph-3-CF3

(28) ##STR00038##

(29) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.500 g of polymer (XXIV) is directly weighed, then 20 mL of distilled tetrahydrofuran are added so as to have a PEEKSO.sub.2Cl (XXIV) molar concentration of 0.065 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(30) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.624 g of 3-(trifluoromethyl)aniline (XXXIX) (3 equivalents with respect to the PEEKSO.sub.2Cl (XV) are directly weight, then 20 mL of distilled tetrahydrofuran are added so as to have a molar concentration of 0.19 M. Then, the PEEKSO.sub.2Cl (XVI) solution is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction is continued at 20 C. for 1 hour.

(31) A limpid solution is obtained, which is evaporated with a rotary evaporator. After evaporation, a filmogenic solid is obtained, which is solubilized in 12 mL of tetrahydrofuran, then precipitated in 75 mL of acetonitrile. The precipitate is filtered, then washed with 3 times 10 mL of acetonitrile, then dried for one night under vacuum (1.Math.10.sup.2 mbar).

(32) The .sup.1H and .sup.19F NMR spectra produced in DMSO-D6 (.sup.1H NMR (200 MHz) 7.79 (s, 4H), 7.56-6.68 (m, 11H) and .sup.19F NMR (188 MHz) 61.42 (s)) confirm the expected structure.

(33) The XL weight yield with RNH-Ph-3-CF.sub.3 is 92% with respect to the polymer XXIV used.

EXAMPLE 10

Preparation of Polymer I with RNH-Ph-3-CF3 and M=Li

(34) ##STR00039##

(35) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.200 g of

(36) The XL weight yield with RNH-Ph-3-CF.sub.3 (XL), then 5 mL of distilled tetrahydrofuran are added. All of the solvents used during these syntheses have been distilled, stored and collected in a nitrogen atmosphere.

(37) In a nitrogen atmosphere, 3 mg of lithium (1.1 equivalents with respect to PEEKSO.sub.2NH-Ph-3-CF.sub.3 (XL)) are added to the solution. The reaction is continued at 20 C. for 18 hours.

(38) The solution obtained is filtered, then the filtrate is evaporated. The solid obtained is dried for one night under vacuum (1.Math.10.sup.2 mbar).

(39) The .sup.1H and .sup.19F NMR spectra are produced in DMSO-D6 (.sup.1H NMR (200 MHz) 8.01-7.69 (m, 4H), 7.68-7.47 (m, 2H), 7.46-6.67 (m, 9H) and .sup.19F NMR (188 MHz) 61.04 (s)) confirm the expected structure.

(40) The PEEKSO.sub.2N(Li.sup.+)Ph-3-CF.sub.3 (I) is 97% with respect to the PEEKSO.sub.2NH-Ph-3-CF.sub.3 (XL) used.

EXAMPLE 11

Preparation of Polymer I with RNH-Ph-3-CF and M=Li

(41) ##STR00040##

(42) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.200 g of PEEKSO.sub.2Cl (XVIV) is directly weighed, then 10 mL of distilled tetrahydrofuran are added so as to have a PEEKSO.sub.2Cl (XVIV) molar concentration of 0.052 M. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(43) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.100 g of 3-(trifluoromethyl)aniline (XXXIX) (1.2 equivalents with respect to the PEEKSO.sub.2Cl (XVIV)) is directly weighed, then 10 mL of tetrahydrofuran are added. n-BuLi (0.50 ml, [C]=2.5 M in hexane) is introduced so as to have 2.4 equivalents with respect to the PEEKSO.sub.2Cl (XVIV). This reagent is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes.

(44) Then, the PEEKSO.sub.2Cl (XVIV) solution is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction is continued at 20 C. for 1 hour. At the end of the reaction, a yellow precipitate is observed.

(45) The precipitate is filtered and washed with 3 times 10 ml of acetonitrile. The solid obtained is dried for one night under vacuum (1.Math.10.sup.2 mbar).

(46) The NMR .sup.1H and .sup.19F spectra produced in DMSO-D6 (.sup.1H NMR (200 MHz) 8.01-7.69 (m, 4H), 7.68-7.47 (m, 2H), 7.46-6.67 (m, 9H) and .sup.19F NMR (188 MHz) 61.04 (s)) confirm the expected structure.

(47) The PEEKSO.sub.2N.sup.(Li.sup.+)Ph-3-CF.sub.3 (I) weight yield is 97% with respect to the PEEKSO.sub.2Cl used.

EXAMPLE 12

Preparation of Polymer III with RNH-Ph-3-CF3 and M=Li

(48) ##STR00041##

(49) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.200 g of PEESSO.sub.2Cl (XXVI) is directly weighed, then 10 mL of distilled tetrahydrofuran are added so as to have a PEESSO.sub.2Cl (XXVI) molar concentration of 0.047 M. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(50) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.092 g of 3-(trifluoromethyl)aniline (XXXIX) (1.2 equivalents with respect to the PEESSO.sub.2Cl (XXVI)) is directly weighed, then 10 mL of tetrahydrofuran are added. n-BuLi (0.50 ml, [C]=2.5 M in hexane) is introduced so as to have 2.4 equivalents with respect to the PEESSO.sub.2Cl (XXVI). This reagent is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes.

(51) Then, the PEESSO.sub.2Cl (XXVI) solution is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction is continued at 20 C. for 1 hour. At the end of the reaction, a yellow precipitate is observed.

(52) The precipitate is filtered and washed with 3 times 10 ml of acetonitrile. The solid obtained is dried for one night under vacuum (1.Math.10.sup.2 mbar).

(53) The NMR .sup.1H and .sup.19F spectra produced in DMSO-D6 (.sup.1H NMR (200 MHz) 8.06-7.70 (m, 5H), 7.45 (s, 1H), 7.28-6.64 (m, 9H) and .sup.19F NMR (188 MHz) 61.04 (s) confirm the expected structure.

(54) The PEESSO.sub.2N.sup.(Li.sup.+)Ph-3-CF.sub.3 (III) weight yield is 65% with respect to the PEESSO.sub.2Cl (XXVI) used.

EXAMPLE 13

Preparation of Polymer IV with RNH-Ph-3-Cf3 and M=Li

(55) ##STR00042##

(56) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.200 g of PESSO.sub.2Cl (XXVII) is directly weighed, then 10 mL of distilled tetrahydrofuran are added so as to have a PESSO.sub.2Cl (XXVII) molar concentration of 0.076 M. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(57) In a nitrogen atmosphere, in a cylindrical glass reactor, 0.146 g of 3-(trifluoromethyl)aniline (XXXIX) (1.2 equivalents with respect to the PESSO.sub.2Cl (XXVII)) is directly weighed, then 10 mL of tetrahydrofuran are added. n-BuLi (0.73 ml, [C]=2.5 M in hexane) is introduced so as to have 2.4 equivalents with respect to the PESSO.sub.2Cl (XXVII). This reagent is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes.

(58) Then, the PESSO.sub.2Cl (XXVII) solution is introduced by means of a syringe, taking care to work under a nitrogen flow. The reaction is continued at 20 C. for 1 hour. At the end of the reaction, a yellow precipitate is observed.

(59) The precipitate is filtered and washed with 3 times 10 ml of acetonitrile. The solid obtained is dried for one night under vacuum (1.Math.10.sup.2 mbar).

(60) The NMR .sup.1H and .sup.19F spectra produced in DMSO-D6 (.sup.1H NMR (200 MHz) 8.42-8.23 (m, 1H), 8.07-7.46 (m, 4H), 7.38-6.54 (m, 6H) and .sup.19F NMR (188 MHz) 61.03 (s)) confirm the expected structure.

(61) The PESSO.sub.2N.sup.(Li.sup.+)Ph-3-CF.sub.3 (IV) weight yield is 83% with respect to the PESSO.sub.2Cl (XXVII) used.

EXAMPLES 14

Preparation of Polymer Film

(62) In a nitrogen atmosphere, in a cylindrical glass reactor, 100 mg of polymer I, III or IV are directly weighted, then 3 mL of distilled dimethylsulfoxide are added. All of the solvents used during these syntheses were distilled, stored and collected in a nitrogen atmosphere. After complete solubilization of the polymer, the solution is introduced into a petri dish with a diameter of 5 cm. The petri dish is placed on a heating plate at 50 C. After one night, the solvent is totally evaporated and a cylindrical film having a diameter of 5 cm, and a thickness of approximately 100 m is obtained. This film is a transparent film having sufficient mechanical resistance to be extracted from the petri dish by means of a clamp and handled by an operator without tearing.

EXAMPLES 15

Conductivity Measurements

(63) ##STR00043##

(64) 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 of D. Gigmes et al. in Nature Materials, 12, 452-457 (2013).

(65) TABLE-US-00002 TABLE 1 conductivity of the polymer described above at 20 C. with different solvents Solvent DMC PC CH.sub.3CN Conductivity (S/cm) 1.4 .Math. 10.sup.6 4.15 .Math. 10.sup.7 1.04 .Math. 10.sup.6

(66) It may be noted that, at room temperature, a conductivity on the order of 10.sup.6 S/cm is obtained. The conductivities published in patent FR 2979630 and the publication of D. Gigmes et al. in Nature Materials, 12, 452-457 (2013) are on the same order of amplitude, but at 45 C. It may therefore be concluded that at room temperature, very promising conductivities are obtained.