Polymers containing grafted bis(sulfonyl)imide 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 bis(sulfonyl)imides, to the methods for the production thereof, and to the uses of same as electrolytes in batteries.

Claims

1. A polymer of the polyaryl ether ketone family or a polyether sulfone polymer containing a grafted bis(sulfonyl)imide lithium or sodium salt selected from the group consisting of bis(sulfonyl)imide lithium or sodium salts satisfying formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV ##STR00065## ##STR00066## ##STR00067## wherein: M represents a lithium or sodium atom 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 polyethoxylated motif; a perfluoro- or polyfluoroalkyl group optionally substituted by aromatic groups; an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, nitrile functions, alkyl or alkylsulfonyl functions, fluorine atoms; m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif having a grafted bis(sulfonyl)imide salt, this percentage varying between 50 and 100%, n represents the percentage of polymer units having no oxoaryl or dioxoaryl motif functionalized by a bis(sulfonyl)imide motif, 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 one or more different groups chosen from: an alkyl group with 1 to 10 carbon atoms; a trifluoromethyl, pentafluoroethyl, nonafluorobutyl, 1,1,2,2-tetrafluoroethyl group; an aryl group of the phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, cyanophenyl, alkylsulfonylphenyl, arylsulfonylphenyl, methoxyphenyl, butoxyphenyl, pentafluorophenyl, alkylsulfonylphenyl, fluorophenyl type, m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a bis(sulfonyl)imide motif, this percentage varying between 90 and 100%; n represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif non-functionalized by a bis(sulfonyl)imide motif, this percentage varying between 0 and 10%; p represents the number of polymer units of the polymer; p varying from 60 to 200.

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, trifluoromethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, 4-cyanophenyl, 1,1,2,2,2-pentafluoroethanyl, 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, or 4-ethylphenyl group; m represents the percentage of polymer units having a dioxoaryl motif functionalized by a bis(sulfonyl)imide, this percentage varying between 90 and 100%; n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a bis(sulfonyl)imide, 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 the chlorosulfonation of a polymer selected from the group consisting of polymers of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII by a mixture of chlorosulfonic acid, thionyl chloride and a formamide ##STR00068## wherein: p represents the number of polymer units of the polymer, p varying from 40 to 300, in order to obtain 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 ##STR00069## ##STR00070## ##STR00071## 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 a sulfonamide of formula XXXIX in a solvent medium ##STR00072## 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; a perfluoro- or polyfluoroalkyl group optionally substituted by aromatic groups; 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; m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif having a grafted bis(sulfonyl)imide, this percentage varying between 50 and 100%, in the presence of a lithium or sodium base.

6. The method according to claim 5, wherein the R group of the XXXIX sulfonamide is chosen from the 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, 2,5-bis (trifluoromethyl)phenyl, 4-cyanophenyl, 1,1,2,2,2-pentafluoroethanyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 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, or 4-ethylphenyl groups.

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 reaction is performed in a solvent or a mixture of solvents.

11. 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 sulfonamide of formula XXXIX is performed at a temperature of between 20 C. and 60 C.

12. A method for synthesis of the polymer according to claim 1, wherein: in a first step, performing the chlorosulfonation of a polymer selected from the group consisting of polymers of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII and XXIII, ##STR00073## wherein: p represents the number of polymer units of the polymer, p varying from 40 to 300, in order to obtain 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, ##STR00074## ##STR00075## ##STR00076## 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 polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII in solution with ammonia gas or in an ammonia solution in order to obtain the polymer selected from polymers of formulas XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV, ##STR00077## ##STR00078## ##STR00079## 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 polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV with a sulfonyl halogenide of formula LV ##STR00080## wherein X represents a fluorine or chlorine or bromine atom or a trifluoromethanesulfonyl or alkylsulfonyl or arylsulfonyl group; 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, a cycloalkyl group having 1 to 30 linear or branched carbon atoms, optionally substituted by a cycloalkyl, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxyl motif; a perfluoro- or polyfluoroalkyl group optionally substituted by aromatic groups; 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; in the presence of a lithium or sodium base at a temperature of between 0 and 80 C. in a solvent medium.

13. The method according to claim 12, wherein the R group of the sulfonyl halide 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, trifluoromethyl, phenyl, tolyl, naphthyl, trifluorophenyl, 4-trifluoromethylphenyl, 3,5-bis (trifluoromethyl)phenyl, 4-cyanophenyl, 1,1,2,2,2-pentafluoroethanyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, (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, or 4-ethylphenyl group.

14. The method according to claim 12, 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 with ammonia gas or an ammonia solution in a solvent.

15. A method of preparing a film, comprising using polymers according to claim 1 to form a film having a thickness of between 10 m and 200 m.

16. A method for preparing films serving as electrolytes for batteries, comprising, in a medium in the absence of traces of water and moisture, solubilizing a polymer according to claim 1 in an anhydrous solvent, depositing the polymer solution on a solid support and then evaporating the solvent by heating, inert gas sweeping or by applying reduced pressure.

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

18. 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.8 and 210.sup.3 S/cm in a solvent medium and without solvent.

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

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the change in conductivity of the polymer described in example 7 below as a function of the temperature and in comparison with a polymer electrolyte described in the literature.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

(2) The examples below are presented as non-limiting illustrations of the subject matter of the present invention.

Example 1Chlorosulfonation of PEEK. Preparation of Polymer XXIV

(3) ##STR00032##

(4) 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.

(5) 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.

(6) 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.

(7) 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 (1.10.sup.2 mbar).

(8) 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%.

(9) The PEEKSO.sub.2C1 (XXIV) polymer weight yield is 98% with respect to the PEEK (XVI) used.

Example 2-6 Preparation of Polymer XXIV with Different Functionalization Rate

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

(11) ##STR00033##

(12) 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

(13) TABLE-US-00001 Functionalization Mass Examples m.sub.PEEK (g) t (h) rate (%) yield (%) 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 7Chlorosulfonation of PEES. Preparation of Polymer XXVI

(14) ##STR00034##

(15) 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.

(16) 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.

(17) 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 15 mL of distilled Ch.sub.2Cl.sub.2 are added. At the end of the reaction, a brown solution is observed.

(18) 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 (1.10.sup.2 mbar).

(19) The .sup.1H NMR spectrum produced in DMSO-D6 CH 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.

(20) 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%.

(21) The PEESSO.sub.2Cl XXVI polymer weight yield is 93% with respect to the PEES (XVIII) used.

Example 8Chlorosulfonation of PES. Preparation of polymer XXVII

(22) ##STR00035##

(23) 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.

(24) 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.

(25) 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 15 mL of distilled CH.sub.2Cl.sub.2 are added. At the end of the reaction, a yellow solution is observed.

(26) 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 (1.10.sup.2 mbar).

(27) 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%.

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

Example 9Preparation of Polymer XL: PEEKSO2NH2

(29) ##STR00036##

(30) In a nitrogen atmosphere, a solution of 0.300 g of PEEKSO.sub.2Cl (XXIV) prepared according to example 1 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PEEKSO.sub.2Cl (XXIV) molar concentration of 0.078 M.

(31) All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(32) This solution is slowly added to an ammonia solution (4.2 mL [C]=0.5 M in THF, 2.1 equivalents with respect to the PEEKSO.sub.2Cl (XXIV) in 10 mL of tetrahydrofuran at 0 C., then return to 20 C. The reaction mixture is agitated at 20 C. for 1 hour. At the end of the reaction, the formation of a white precipitate is observed.

(33) The reaction mixture is filtered and the solid is washed with 2 times 10 mL of tetrahydrofuran. The solvent of the filtrate is evaporated with a rotary evaporator, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(34) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 8.07-7.90 (m, 4H), 7.65-7.29 (m, 11H) and 7.29-7.13 (m, 4H) confirms the expected structure.

(35) The PEEKSO.sub.2NH.sub.2 (XL) weight yield is 96% with respect to the PEEKSO.sub.2Cl (XXIV) polymer used.

Example 10Preparation of Polymer XLII: PEESSO2NH2

(36) ##STR00037##

(37) In a nitrogen atmosphere, a solution of 0.300 g of PEESSO.sub.2Cl (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 PEESSO.sub.2Cl (XXVI) molar concentration of 0.035 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(38) This solution is slowly added to an ammonia solution (8.7 mL [C]=0.5 M in THF, 3 equivalents with respect to the PEESSO.sub.2Cl (XXVI) in 10 mL of tetrahydrofuran at 0 C., then return to 20 C. The reaction mixture is agitated at 20 C. for 1 hour. At the end of the reaction, the formation of a white precipitate is observed.

(39) The reaction mixture is filtered and the solid is washed with 2 times 10 mL of acetonitrile, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(40) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 7.98 (dd, J=8.7, 4.2 Hz, 4H), 7.63-7.30 (m, 5H) and 7.21 (dd, J=8.4, 4.7 Hz, 4H) confirms the expected structure.

(41) The PEESSO.sub.2NH.sub.2 (XLII) polymer weight yield is 92% with respect to the PEESSO.sub.2Cl (XXVI) polymer used.

Example 11Preparation of Polymer XLIII: PESSO2NH2

(42) ##STR00038##

(43) In a nitrogen atmosphere, a solution of 0.300 g of PESSO.sub.2Cl (XXVII) prepared according to example 8 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PESSO.sub.2Cl (XXVII) molar concentration of 0.091 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(44) This solution is slowly added to an ammonia solution (10 mL [C]=0.5 M in THF, 3 equivalents with respect to the PESSO.sub.2Cl (XXVII) in 10 mL of tetrahydrofuran at 0 C., then return to 20 C. The reaction mixture is agitated at 20 C. for 1 hour. At the end of the reaction, the formation of a white precipitate is observed.

(45) The reaction mixture is filtered and the solid is washed with 2 times 10 mL of tetrahydrofuran. The solvent of the filtrate is evaporated with a rotary evaporator, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(46) The .sup.1H NMR spectrum produced in DMSO-D6 CH NMR (200 MHz) 7.79 (s, 3H) 7.58 (s, 1H), 7.50-7.35 (m, 1H), 7.33-7.02 (m, 4H) confirms the expected structure.

(47) The PESSO.sub.2NH.sub.2 (XLIII) weight yield is 98% with respect to the PESSO.sub.2Cl (XXVII) polymer used.

Example 12Preparation of Polymer Ia with R=CH3 and M=Li

(48) ##STR00039##

(49) In a nitrogen atmosphere, a solution of 0.200 g of PEEKSO.sub.2Cl (XXIV) prepared according to example 1 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PEEKSO.sub.2Cl (XXIV) molar concentration of 0.052 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(50) In a nitrogen atmosphere, in a cylindrical glass reactor, the following are added in succession: 0.054 g of methanesulfonamide (CH.sub.3SO.sub.2NH.sub.2 (XXXIX), 1.1 equivalents with respect to the SO.sub.2Cl motif number), 10 mL of distilled tetrahydrofuran so as to have a CH.sub.3SO.sub.2NH.sub.2 (XXXIX) molar concentration of 0.057 M and 0.62 mL of n-BuLi ([C]=2 M in hexane, 2.4 equivalents with respect to the PEEKSO.sub.2Cl (XXIV)) by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes. Then, the PEEKSO.sub.2Cl (XXIV) solution previously prepared is added 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 white precipitate is observed.

(51) The solvent is evaporated. The solid obtained is washed with 3 times 10 mL of tetrahydrofuran, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(52) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 7.97-7.64 (m, 4H), 7.50 (s, 1H), 7.34-6.91 (m, 6H), 2.46 (s, 4H) confirms the expected structure.

(53) The NMRH spectrum shows that there is a methylsulfonamide group with respect to the dioxoaryl motif at 2.46 ppm.

(54) The PEEKSO.sub.2N.sup.(Li.sup.+)SO.sub.2CH.sub.3 (Ia) is 97% with respect to the PEEKSO.sub.2Cl (XXIV) used.

Examples 13 to 16Preparation of Polymers Ib-Ie with Different Sulfonamides

(55) According to the protocol described in example 12, the following polymers were prepared:

(56) ##STR00040##

(57) TABLE-US-00002 Example Sulfonamides Bases Yield (%) Products 13 NaH 98 14 n- BuLi 97 15 n- BuLi 97 16 n- BuLi 94

Example 17=Preparation of Polymer if: Bi-Functionalized (Method 1)

(58) ##STR00049##

(59) In a nitrogen atmosphere, a solution of 0.200 g of PEEKSO.sub.2Cl (XXIV) prepared according to example 1 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PEEKSO.sub.2Cl (XXIV) molar concentration of 0.052 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(60) In a nitrogen atmosphere, in a cylindrical glass reactor, the following are added in succession: 0.0197 g of methanesulfonamide (CH.sub.3SO.sub.2NH.sub.2 (XXXIX), 0.4 equivalents with respect to the SO.sub.2Cl motif number), 0.0531 g of p-toluenesulfonamide (CH.sub.3PhSO.sub.2NH.sub.2 (XXXIX), 0.6 equivalents with respect to the SO.sub.2Cl motif number), 10 mL of distilled tetrahydrofuran and 0.62 mL of n-BuLi ([C]=2 M in hexane, 2.4 equivalents with respect to the PEEKSO.sub.2Cl (XXIV)) by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes. Then, the PEEKSO.sub.2Cl (XXIV) solution previously prepared is added by means of a syringe, taking care to work under a nitrogen flow. The reaction is continued at 20 C. for 30 minutes. At the end of the reaction, a white precipitate is observed.

(61) The solvent is evaporated. The solid obtained is washed with 3 times 10 mL of tetrahydrofuran and 2 times 20 mL of CH.sub.3CN, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(62) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 7.91-7.66 (m, 4H), 7.57-7.41 (m, 2H), 7.31-6.92 (m, 7H), 2.43 (s, 0.75H), 2.27 (s, 1.5H) allows us to derive the following structure:

(63) ##STR00050##

(64) The PEEK (SO.sub.2Cl).sub.0.25n (SO.sub.2N.sup. (Li.sup.+) SO.sub.2CH.sub.3).sub.0.25n (SO.sub.2N (Li.sup.+) SO.sub.2PhCH.sub.3).sub.0.5n (If) weight yield is 91% with respect to the PEEKSO.sub.2Cl (XXIV) used.

Example 18=Preparation of Polymer Ig: Bi-Functionalized (Method 2)

(65) ##STR00051##

(66) In a nitrogen atmosphere, a solution of 0.200 g of PEEKSO.sub.2Cl (XXIV) prepared according to example 1 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PEEKSO.sub.2Cl (XXIV) molar concentration of 0.052 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(67) In a nitrogen atmosphere, in a cylindrical glass reactor, the following are added in succession: 0.0197 g of methanesulfonamide (CH.sub.3SO.sub.2NH.sub.2 (XXXIX), 0.4 equivalents with respect to the SO.sub.2Cl motif number), and 10 mL of distilled tetrahydrofuran and 0.26 mL of n-BuLi ([C]=2 M in hexane, 0.9 equivalents with respect to the PEEKSO.sub.2Cl (XXIV)) by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes. Then, the PEEKSO.sub.2Cl (XXIV) solution previously prepared is added by means of a syringe, taking care to work under a nitrogen flow. The reaction is continued at 20 C. for 30 minutes.

(68) Then, the following are added in succession: 0.0187 g of p-toluenesulfonamide (CH.sub.3PhSO.sub.2NH.sub.2 (XXXIX), 0.6 equivalents with respect to the SO.sub.2Cl motif number) and 0.36 mL of n-BuLi ([C]=2 M in hexane, 1.4 equivalents with respect to the PEEKSO.sub.2Cl (XXIV)) by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes. Then, the PEEKSO.sub.2Cl (XXIV) solution previously prepared is added 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 white precipitate is observed.

(69) The solvent is evaporated. The solid obtained is washed with 3 times 10 mL of tetrahydrofuran, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(70) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 7.91-7.69 (m, 4H), 7.60-7.43 (m, 2.2H), 7.31-6.95 (m, 7.2H), 2.44 (s, 1.2H), 2.27 (s, 1.8H) confirms the expected structure:

(71) ##STR00052##

(72) The PEEK (SO.sub.2N.sup.(Li.sup.+) SO.sub.2CH.sub.3).sub.0.4n(SO.sub.2N.sup.(Li.sup.+) SO.sub.2PhCH.sub.3).sub.0.6n (Ig) weight yield is 89% with respect to the PEEKSO.sub.2Cl (XXIV) used.

Example 19=Preparation of Polymer IIIa with R=CH3 and M=Li

(73) ##STR00053##

(74) In a nitrogen atmosphere, a solution of 0.200 g of PEESSO.sub.2Cl (XXVI) prepared according to example 7 is prepared in 9 mL of distilled tetrahydrofuran and 1 mL of distilled N,N-dimethylformamide so as to have a PEESSO.sub.2Cl (XXVI) molar concentration of 0.052 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(75) In a nitrogen atmosphere, in a cylindrical glass reactor, the following are added in succession: 0.045 g of methanesulfonamide (CH.sub.3SO.sub.2NH.sub.2 (XXXIX), 1.1 equivalents with respect to the SO.sub.2Cl motif number), 10 mL of distilled tetrahydrofuran so as to have a CH.sub.3SO.sub.2NH.sub.2 (XXXIX) molar concentration of 0.0472 M and 0.57 mL of n-BuLi ([C]=2 M in hexane, 2.4 equivalents with respect to the PEESSO.sub.2Cl (XXVI)) by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes. Then, the PEESSO.sub.2Cl (XXVI) solution previously prepared is added 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 white precipitate is observed.

(76) The solvent is evaporated. The solid obtained is washed with 3 times 10 mL of tetrahydrofuran, then dried for one night under vacuum (1.10.sup.2 mbar).

(77) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H 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 .sup.1H NMR spectrum shows that there is a methylsulfonamide group with respect to the dioxoaryl motif at 2.44 ppm.

(78) The PEESSO.sub.2N.sup.(Li.sup.+)SO.sub.2CH.sub.3 (IIIA) weight yield is 87% with respect to the PEESSO.sub.2Cl (XXVI) used.

Examples 20Preparation of Polymers IIIa-b with Different Sulfonamides

(79) According to the protocol described in example 19, the following polymers were prepared:

(80) ##STR00054##

(81) TABLE-US-00003 Example Sulfonamides Bases Yield (%) Products 14 n- BuLi 97 15 n- BuLi 98

Example 21Preparation of Polymers IV with R=CF3 and M=Li

(82) ##STR00059##

(83) In a nitrogen atmosphere, a solution of 0.200 g of PEESSO.sub.2Cl (XXVII) prepared according to example 8 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PESSO.sub.2Cl (XXVII) molar concentration of 0.060 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere.

(84) In a nitrogen atmosphere, in a cylindrical glass reactor, the following are added in succession: 0.099 g of methanesulfonamide (CH.sub.3SO.sub.2NH.sub.2 (XXXIX), 1.1 equivalents with respect to the SO.sub.2Cl motif number), 10 mL of distilled tetrahydrofuran so as to have a CH.sub.3SO.sub.2NH.sub.2 (XXXIX) molar concentration of 0.0666 M and 0.72 mL of n-BuLi ([C]=2 M in hexane, 2.4 equivalents with respect to the PESSO.sub.2Cl (XXVII)) by means of a syringe, taking care to work under a nitrogen flow. The reaction mixture is agitated at 20 C. for 15 minutes. Then, the PESSO.sub.2Cl (XXVII) solution previously prepared is added 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 white precipitate is observed.

(85) The solvent is evaporated. The solid obtained is washed with 3 times 10 mL of tetrahydrofuran, then dried for one night under vacuum (1.10.sup.2 mbar).

(86) The .sup.1H and .sup.19F NMR spectra produced in DMSO-D6 (.sup.1H NMR (200 MHz) 8.40-8.22 (m, 1H), 8.11-7.83 (m, 3H), 7.40-7.01 (m, 3H. .sup.19F NMR (188 MHz) 5-77.81 (s) confirm the expected structure.

(87) The .sup.19F NMR spectrum shows a single peak corresponding to the polymeric trifluoromethylsulfonamide.

(88) The PESSO.sub.2N.sup.(Li.sup.+)SO.sub.2CH.sub.3 (IVa) weight yield is 83% with respect to the PESSO.sub.2Cl (XXVII) used.

Examples 22 to 24Preparation of Polymers IVb-d with Different Sulfonamides

(89) According to the protocol described in example 21, the following polymers were prepared:

(90) ##STR00060##

(91) TABLE-US-00004 Example x eq Yield (%) Products 22 1 eq 95 23 0.6 eq 96 24 0.2 eq 93

Examples 25Alternative Preparation of Polymer Ia with R=CH3 and M=Li

(92) ##STR00064##

(93) In a nitrogen atmosphere, a solution of 0.200 g of PEEKSO.sub.2NH.sub.2 (XL) prepared according to example 9 is prepared in 10 mL of distilled tetrahydrofuran so as to have a PEEKSO.sub.2NH.sub.2 (XL) molar concentration of 0.057 M. All of the solvents used in these syntheses were distilled, stored and collected in a nitrogen atmosphere. After solubilization of the PEEKSO.sub.2NH.sub.2, 0.68 mL of n-BuLi ([C]=2 M in hexane, 2.4 equivalents with respect to the PEEKSO.sub.2NH.sub.2 (XL)) are added by means of a syringe, taking care to work under a nitrogen flow. After 15 minutes at room temperature, 0.0783 g of methanesulfonyl chloride (CH.sub.3SO.sub.2Cl (LV), 1.2 equivalents with respect to the SO.sub.2NH.sub.2 motif number) are added. The reaction is continued at 20 C. for 1 hour. At the end of the reaction, a white precipitate is observed.

(94) The solvent is evaporated. The solid obtained is washed with 3 times 10 mL of tetrahydrofuran, then the product obtained is dried for one night under vacuum (1.10.sup.2 mbar).

(95) The .sup.1H NMR spectrum produced in DMSO-D6 (.sup.1H NMR (200 MHz) 7.97-7.64 (m, 4H), 7.50 (s, 1H), 7.34-6.91 (m, 6H), 2.46 (s, 3H) confirms the expected structure.

(96) The .sup.1H NMR spectrum shows that there is a methylsulfonamide group with respect to the dioxoaryl motif at 2.46 ppm.

(97) The PEEKSO.sub.2N.sup.(Li.sup.+)SO.sub.2CH.sub.3 (Ia) weight yield is 35% with respect to the PEEKSO.sub.2NH.sub.2 (XL) used.

Examples 26-28Preparation of Polymer Films

(98) In a nitrogen atmosphere, in a cylindrical glass reactor, 100 mg of polymer I, III or IV are directly weighed, 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 placed in a petri dish having a diameter of 5 cm. The petri dish is deposited 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 on the order of 100 m is obtained. This film is a transparent film with sufficient mechanical resistance to be extracted from the petri dish by means of a clamp and handled by an operator without tearing.

Examples 29Conductivity Measurements

(99) 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 FIG. 1 of the drawings, which shows the change in conductivity of the polymer described in example 7 as a function of the temperature and in 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).

(100) It may be noted that, at low temperature (<45), the conductivities are superior to the conductivities published in patent FR 2979630 and the publication of D. Gigmes et al. in Nature Materials, 12, 452-457 (2013), even without the addition of solvent. Moreover, the conductivities obtained in the presence of a plasticizing solvent, such as acetonitrile or dimethylcarbonate (DMC), are on the same order of amplitude of, or even superior to, the results described in patent FR 2979630 and the publication of D. Gigmes et al. in Nature Materials, 12, 452-457 (2013) for the entire temperature range studied.