Polymer based on ionic monomers, compositions comprising the same, methods of making the same, and their use in electrochemical applications

Abstract

To provide polymers based on ionic monomers, compositions comprising the same, methods of making the same, and their use in electrochemical applications.SOLUTION: The present technology relates to an ionic polymer comprising at least one repeating unit comprising the reaction product between at least one compound comprising two or more functional groups and a metal bis(halosulfonyl)imide for use in electrochemical applications, particularly in electrochemical accumulators such as batteries, electrochromic devices, and supercapacitors. The present technology also relates to a polymer composition, a solid polymer electrolyte composition, a solid polymer electrolyte, and an electrode material comprising the ionic polymer. Their uses in electrochemical cells and electrochemical accumulators as well as their processes of manufacturing are also described.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Related Applications This application claims priority under applicable law to U.S. Provisional Patent Application No. 62 / 965,560, filed January 24, 2020, U.S. Provisional Patent Application No. 62 / 977,521, filed February 17, 2020, and European Patent Application No. 20 206 000.0, filed November 5, 2020, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Technical Field The present application relates to the field of polymers and their use in electrochemical applications. More particularly, the present application relates to the field of solid polymer electrolytes, polymer compositions, solid polymer electrolyte compositions, their manufacturing processes, and their use in electrochemical cells, electrochromic devices, supercapacitors or electrochemical accumulators, in particular in all-solid-state batteries. [Background technology]

[0003] background Solid polymer electrolytes are promising materials for many industrial applications because they enable the development of lightweight, flexible, and efficient all-solid-state electrochemical systems that are substantially safer than their counterparts based on the use of liquid electrolytes.

[0004] Despite the significant advantages of solid polymer electrolytes, their use remains limited, mainly due to their limited electrochemical stability, low transference number, and relatively low ionic conductivity. Indeed, conventional solid-state polymer electrolytes are generally used for high voltage operation (Li / Li + Since conventional solid-state polymer electrolytes do not support a voltage (≥4 V vs. 0 V), the electrochemical stability range of conventional solid-state polymer electrolytes is still relatively limited.

[0005] Furthermore, conventional solid polymer electrolytes, such as those based on poly(ethylene oxide) (PEO), face ionic conductivity problems at ambient temperatures. For example, when the polymer is in the molten state, the ionic conductivity of PEO is 10 -3 S.cm -1 (Hallinan et al., Annual review of materials research 43 (2013): 503-525). However, ionic transport occurs primarily in the amorphous phase and is reduced in the crystalline phase, resulting in a significant decrease in the ionic conductivity of PEO-based polymers. In fact, the ionic conductivity of PEO-based polymers decreases substantially at operating temperatures below their melting point (Armand, M. Solid State Ionics 9 (1983): 745-754). The degree of crosslinking of POE-based polymers is also associated with issues of electrochemical stability and low ionic conductivity, particularly due to reduced segmental mobility.

[0006] Common approaches to solving the problem of low ionic conductivity include modifying the polymer structure, for example, by using branched or block PEO-based polymers containing monomer units that lower the crystallization temperature, i.e., the glass transition temperature, or by decreasing the crystallinity of the polymer structure by increasing the ionic transport number. Another strategy used to address this problem involves incorporating nanoscale ceramic fillers, such as titanium dioxide (TiO), alumina (AlO), silicon dioxide (SiO), and lithium aluminate (LiAlO) nanoparticles, into PEO-based polymers to improve their mechanical strength. However, the presence of these fillers can contribute to the degradation of the electrochemical and / or mechanical properties of the polymer.

[0007] Therefore, there is a need for the development of a solid polymer electrolyte that eliminates one or more of the drawbacks of conventional solid polymer electrolytes. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] Hallinan et al., Annual review of materials research 43 (2013): 503-525 [Non-patent document 2] Armand, M. Solid State Ionics 9 (1983): 745-754 Summary of the Invention [Means for solving the problem]

[0009] Abstract According to one aspect, the present technology provides a method for preparing a metal bis(halosulfonyl)imide having at least one compound of Formula 1 containing at least two functional groups and a metal bis(halosulfonyl)imide having Formula 2: [ka] (In the formula, A is a linear or branched C1-C 10 Alkylene, linear or branched C1-C 10 Alkyleneoxy C1~C 10 Alkylene, linear or branched poly(C1-C 10 Alkyleneoxy)C1~C 10 a substituted or unsubstituted organic group selected from alkylene, linear or branched polyethers and linear or branched polyesters; X1 and X2 are functional groups independently and at each occurrence selected from hydroxyl groups, thiol groups and amine groups; X3 and X4 are each independently a halogen atom selected from F, Cl, Br, and I; M n+ Na + , K. + , Li + , Ca 2+ and Mg 2+ ions, which are alkali metal ions or alkaline earth metal ions selected from the group consisting of and (b) a repeat unit comprising the reaction product between

[0010] In one embodiment, the compound of Formula 1 is selected from glycerol, alkanediols, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,2-pentanediol, ethoxyhexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol, polycaprolactone diols, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, other similar glycols and diols, and combinations of at least two thereof.

[0011] In another embodiment, the compound of Formula 1 is selected from alkanediamines, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,2-propanediamine, 1,2-butanediamine, 2,3-butanediamine, 1,3-butanediamine, 1,2-pentanediamine, 2,4-diamino-2-methylpentane, ethylenediamine, 1,8-diamino-3,6-dioxaoctane, 1,11-diamino-3,6,9-trioxaundecane, 4,9-dioxa-1,12-dodecanediamine, 1,14-diamino-3,6,9,12-tetraoxatetradecane, poly(ethylene glycol) diamines, the D, ED or EDR series of products commercially available under the trade name JEFFAMINE®, other similar diamines, and combinations of at least two thereof.

[0012] In another embodiment, A is an optionally substituted linear or branched C1-C 10 alkylene, and the compound of formula 1 is a compound of formula 3: [ka] (In the formula, X1 and X2 are as defined herein; R1 and R2 are each a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a halogen atom selected from F, Cl, Br and I, and a C1-C 10 Alkyl, C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-acrylate, aminocarbonyl-C1-C 10 Alkyl-methacrylate, aminocarbonyl-C1-C 10 Alkyl-acrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate and oxycarbonylamino-C1-C 10 independently and at each occurrence selected from linear or branched substituents selected from alkyl-acrylates; l is a number ranging from 1 to 10) is a compound of

[0013] In another embodiment, A is a linear or branched optionally substituted poly(C1-C 10 Alkyleneoxy)C1~C 10 alkylene, and the compound of formula 1 is a compound of formula 4: [ka] (In the formula, X1 and X2 are as defined herein; (m is a number between 1 and 68) is a compound of

[0014] In another embodiment, A is a linear or branched optionally substituted polyether and the compound of Formula 1 has Formula 5: [ka] (In the formula, X1 and X2 are as defined herein; R3, R4 and R5 are C1 to C 10 independently and at each occurrence selected from alkyl groups, n, o, and p are selected so that the number average molecular weight of the polyether is between about 220 g / mol and about 2,000 g / mol, inclusive; n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39 is a compound of

[0015] In another embodiment, R3, R4, and R5 are methyl groups.

[0016] In another embodiment, X1 and X2 are both amine groups.

[0017] In another embodiment, A is an optionally substituted aliphatic polyester, such as polycaprolactone, and the compound of Formula 1 has Formula 7: [ka] (In the formula, t and u are numbers ranging from 1 to 10. is a compound of

[0018] According to another aspect, the present technology relates to an ionic polymer comprising at least one repeat unit of formula 8(a), or is a polymer of formula 8(b): [ka] (In the formula, A is a linear or branched C1-C 10 Alkylene, linear or branched C1-C 10 Alkyleneoxy C1~C 10Alkylene, linear or branched poly(C1-C 10 Alkyleneoxy)C1~C 10 are substituted or unsubstituted organic groups selected independently and at each occurrence from alkylene, linear or branched polyethers and linear or branched polyesters; X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; R6 is selected from a hydroxyl group, a thiol group, an amine group, and an R7-X5-A-X6- group; R7 is acrylate, methacrylate, C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, carbonyl-C1-C 10 Alkyl methacrylate carbonyl-C1~C 10 Alkyl-acrylate, carbonyloxy-C1~C 10 Alkyl-methacrylate, carbonyloxy-C1-C 10 Alkyl-acrylate, carbonylamino-C1-C 10 Alkyl-methacrylate and carbonylamino-C1-C 10 is a crosslinkable group independently selected at each occurrence from alkyl-acrylate; M n+ Na + , K. + , Li + , Ca 2+ and Mg 2+ ions, v is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

[0019] According to another aspect, the present technology provides a compound of Formula 9: [ka] (In the formula, M n+ Na+ , K. + , Li + , Ca 2+ and Mg 2+ ions, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; R1 and R2 are each a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a halogen atom selected from F, Cl, Br and I, and a C1-C 10 Alkyl, C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-acrylate, aminocarbonyl-C1-C 10 Alkyl-methacrylate, aminocarbonyl-C1-C 10 Alkyl-acrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate and oxycarbonylamino-C1-C 10 independently and at each occurrence selected from linear or branched substituents selected from alkyl-acrylates; l is a number ranging from 1 to 10, w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one repeating unit of

[0020] According to another aspect, the present technology provides a compound comprising: [ka] (In the formula, M n+ Na + , K. + , Li + , Ca 2+ and Mg2+ ions, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; m is a number ranging from 1 to 68; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one repeating unit of

[0021] According to another aspect, the present technology provides a compound of Formula 11: [ka] (In the formula, M n+ Na + , K. + , Li + , Ca 2+ and Mg 2+ ions, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; R3, R4 and R5 are C1 to C 10 independently and at each occurrence selected from alkyl groups, n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one repeating unit of

[0022] According to another aspect, the present technology provides a compound of Formula 12: [ka] (In the formula, M n+ Na + , K. + , Li + , Ca 2+ and Mg 2+ ions, t and u are numbers between 1 and 10, z is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one repeating unit of

[0023] According to another aspect, the present technology provides a compound of Formula 13: [ka] (In the formula, x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0024] According to another aspect, the present technology provides a compound of Formula 14: [ka] (In the formula, x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0025] According to another aspect, the present technology provides a compound of Formula 15: [ka] (In the formula, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0026] According to another aspect, the present technology provides a compound of Formula 16: [ka] (In the formula, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0027] According to another aspect, the present technology provides a compound of formula 17: [ka] (In the formula, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0028] According to another aspect, the present technology provides a compound of formula 18: [ka] (In the formula, X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an -NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0029] According to another aspect, the present technology provides a compound of formula 19: [ka] (In the formula, w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0030] According to another aspect, the present technology provides a compound comprising: [ka] (In the formula, w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0031] According to another aspect, the present technology provides a compound of Formula 21: [ka] (In the formula, n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0032] According to another aspect, the present technology provides a compound of Formula 22: [ka] (In the formula, n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0033] According to another aspect, the present technology provides a compound of formula 23: [ka] (In the formula, n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0034] According to another aspect, the present technology provides a compound of Formula 24: [ka] (In the formula, n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0035] According to another aspect, the present technology provides a compound of Formula 25: [ka] (In the formula, n and p are selected so that their sum (n+p) is between about 1 and about 6; o is a number between about 2 and about 39; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0036] According to another aspect, the present technology provides a compound of formula 26: [ka] (In the formula, w and x are numbers selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0037] According to another aspect, the present technology provides a compound of formula 27: [ka] (In the formula, w and x are numbers selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0038] According to another aspect, the present technology provides a compound of formula 28: [ka] (In the formula, w and x are numbers selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The present invention relates to an ionic polymer comprising at least one fragment of

[0039] According to another aspect, the present technology relates to a polymer composition comprising at least one ionic polymer as defined herein.

[0040] In one embodiment, the polymer composition further comprises at least one additional component or additive. According to one example, the additional component or additive is selected from ion conductors, inorganic particles, glass particles, ceramic particles, salts, and other similar additives, or a combination of at least two thereof. According to another example, the additional component or additive is a filler additive selected from titanium dioxide (TiO), alumina (AlO), and silicon dioxide (SiO) particles or nanoparticles.

[0041] In another embodiment, the polymer composition is used in an electrochemical cell. In another embodiment, the polymer composition is a solid polymer electrolyte composition. In another embodiment, the polymer composition is a binder for an electrode material. In another embodiment, the polymer composition is used in a supercapacitor. According to one example, the supercapacitor is a carbon-carbon supercapacitor. In another embodiment, the polymer composition is used in an electrochromic material.

[0042] According to another aspect, the present technology relates to a solid polymer electrolyte composition comprising a polymer composition as defined herein.

[0043] In another embodiment, the solid polymer electrolyte composition further comprises at least one salt. According to one example, the salt is an ionic salt selected from lithium salts, sodium salts, potassium salts, calcium salts, and magnesium salts.

[0044] In another embodiment, the solid polymer electrolyte composition further comprises at least one additional component or additive. According to one example, the additional component or additive is selected from ionically conductive materials, inorganic particles, glass particles, ceramic particles, combinations of at least two thereof, and other similar additives.

[0045] According to another aspect, the present technology relates to a solid polymer electrolyte comprising a solid polymer electrolyte composition as defined herein.

[0046] According to another aspect, the present technology relates to an electrode material comprising an electrochemically active material and a polymer composition as defined herein. In one embodiment, the polymer composition is a binder.

[0047] In another embodiment, the electrochemically active material is in the form of particles. According to one example, the electrochemically active material is selected from metal oxides, lithium metal oxides, metal phosphates, lithiated metal phosphates, titanates, and lithium titanate. According to another example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), antimony (Sb), and combinations of at least two thereof.

[0048] In another embodiment, the electrode material further comprises at least one electron-conducting material, which is selected from carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and combinations of at least two thereof.

[0049] In another embodiment, the electrode material further comprises at least one additional component or additive. According to one example, the additional component or additive is selected from ion conductors, inorganic particles, glass or ceramic particles, nanoceramics, salts, and other similar additives. According to another example, the additional component or additive is selected from Al2O3, TiO2, and SiO2.

[0050] In another embodiment, the electrode material is a positive electrode material. In another embodiment, the electrode material is a negative electrode material. According to one example, the electrochemically active material is lithium titanate or carbon-coated lithium titanate.

[0051] According to another aspect, the present technology relates to an electrode comprising an electrode material as defined herein on a current collector.

[0052] According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode, the positive electrode, and the electrolyte comprises a polymer composition as defined herein.

[0053] According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode and the positive electrode is as defined herein.

[0054] According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid polymer electrolyte as defined herein.

[0055] According to another aspect, the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein.

[0056] In one embodiment, the electrochemical accumulator is a battery selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, and a magnesium-ion battery. According to one example, the battery is a lithium battery or a lithium-ion battery.

[0057] According to another aspect, the present technology provides a method for preparing a polymer or polymer composition as defined herein, comprising: (i) preparing a metal bis(halosulfonyl)imide of formula 2; and (ii) reacting at least one compound of Formula 1 containing at least two functional groups as defined herein with said metal bis(halosulfonyl)imide of Formula 2. The present invention relates to a method, including:

[0058] In another embodiment, the method further comprises preparing a bis(halosulfonyl)imide. According to one example, the step of preparing the bis(halosulfonyl)imide is carried out by reaction between a sulfamic acid and a halosulfonic acid in the presence of at least one halogenating agent.

[0059] According to one example, the halogenating agent is selected from phosphorus trichloride, phosphorus pentachloride, thionyl chloride, thionyl fluoride, phosphorus oxychloride, and oxalyl chloride. According to one example, the halogenating agent is thionyl chloride. According to another example, the halosulfonic acid is chlorosulfonic acid.

[0060] In another embodiment, the step of preparing the bis(halosulfonyl)imide is carried out at a temperature ranging from about 60°C to about 150°C, or from about 70°C to about 145°C, or from about 80°C to about 140°C, or from about 90°C to about 100°C, or from about 110°C to about 140°C, or from about 120°C to about 140°C, or from about 125°C to about 140°C, or from about 125°C to about 135°C, inclusive.

[0061] In another embodiment, the bis(halosulfonyl)imide is a bis(chlorosulfonyl)imide.

[0062] In another embodiment, the step of preparing the metal bis(halosulfonyl)imide is carried out by a metalation reaction between a bis(halosulfonyl)imide and at least one metalating agent, optionally in the presence of a solvent.

[0063] According to one example, the metallation agent comprises an alkali metal or alkaline earth metal selected from lithium, sodium, potassium, calcium, and magnesium. According to an example, the metallation agent may be lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium hydride, lithium chloride, lithium bromide, lithium iodide, a cyclic alkyl group of the formula RCO2Li, where R is a linear or branched C1-C 10 The lithiating agent is selected from lithium carboxylates (wherein the group is an alkyl group or an aromatic hydrocarbon), lithium oxalate and metallic lithium. According to another example, the lithiating agent is lithium chloride.

[0064] In another embodiment, the solvent is selected from N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, tetrachloromethane, chloroform, acetonitrile, tetrahydrofuran, and miscible combinations of at least two thereof. According to one example, the solvent is N,N-dimethylformamide.

[0065] In another embodiment, the step of preparing the metal bis(halosulfonyl)imide of Formula 2 is carried out at a temperature ranging from about 20°C to about 150°C, or from about 30°C to about 135°C, or from about 40°C to about 130°C, or from about 50°C to about 125°C, or from about 60°C to about 120°C, or from about 70°C to about 115°C, or from about 80°C to about 110°C, or from about 90°C to about 105°C, inclusive.

[0066] In another embodiment, the step of preparing the metal bis(halosulfonyl)imide is carried out for a period of time ranging from about 10 hours to about 48 hours, or from about 10 hours to about 24 hours, or from about 12 hours to about 24 hours, inclusive.

[0067] In another embodiment, the step of reacting at least one compound of Formula 1 containing at least two functional groups with the metal bis(halosulfonyl)imide of Formula 2 is a polymerization step. According to one example, the polymerization is carried out by polycondensation. For example, the polymerization is carried out by polyesterification. According to one example, the polyesterification is carried out by Fischer esterification or Steglich esterification.

[0068] In another embodiment, the step of reacting at least one compound of Formula 1 containing at least two functional groups with the metal bis(halosulfonyl)imide of Formula 2 is carried out in the presence of a solvent. According to one example, the solvent is selected from N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, tetrachloromethane, chloroform, acetonitrile, tetrahydrofuran, and miscible combinations of at least two thereof. For example, the solvent is N,N-dimethylformamide.

[0069] In another embodiment, the polymerizing step is carried out in the presence of at least one base and optionally at least one polymerization catalyst, and / or at least one co-catalyst, and / or optionally at least one acylation catalyst.

[0070] In another embodiment, the polymerization catalyst is selected from the group consisting of acidic catalysts, nucleophilic catalysts, and boron-based catalysts.

[0071] In another embodiment, the nucleophilic catalyst is selected from the group consisting of 4-dimethylaminopyridine, pyridine and other pyridine derivatives.

[0072] In another embodiment, the boron catalyst is a boric acid catalyst, a boronic acid catalyst or a borinic acid catalyst.For example, the polymerization catalyst is selected from diarylborinic acid of formula Ar2BOH (wherein Ar is an aryl group), diphenylborinic acid, phenylboronic acid, trifluorophenylboronic acid, 9H-9-bora-10-thiaanthracen-9-ol, 10H-phenoxaborin-10-ol, boron tribromide, boron trichloride, acylfluoroborates, triethyloxonium fluoroborate, boron trifluoride etherate, boron trifluoride, tris(pentafluorophenyl)borane and other similar boron-based catalysts, or a combination of at least two of them (if suitable).

[0073] In another embodiment, the base is selected from triethylamine, N,N-diisopropylethylamine, pyridine and pyridine derivatives. According to one example, the base is triethylamine.

[0074] In another embodiment, the method further comprises a post-functionalization step or a post-polymerization modification step. According to one example, the post-functionalization step or the post-polymerization modification step is carried out to introduce at least one crosslinkable functional group. According to one example, the post-functionalization step or the post-polymerization modification step is carried out by reacting the at least one functional group with at least one precursor of the crosslinkable functional group. For example, the crosslinkable functional group can be an acrylate, a methacrylate, a C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-acrylate, aminocarbonyl-C1-C 10 Alkyl-methacrylate aminocarbonyl-C1~C 10 Alkyl-acrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate, oxycarbonylamino-C1-C 10Alkyl-acrylate, carbonyloxy-C1~C 10 Alkyl-methacrylate, carbonyloxy-C1-C 10 Alkyl-acrylate, carbonylamino-C1-C 10 Alkyl-methacrylate and carbonylamino-C1-C 10 alkyl-acrylates.

[0075] In another embodiment, the method further comprises a separation or purification step. According to one example, the separation or purification step is performed by liquid chromatography or filtration.

[0076] In another embodiment, the method further comprises coating the polymer composition. According to one example, the coating is performed by at least one method selected from doctor blade coating, comma coating, reverse-comma coating, printing, gravure coating, and slot die coating.

[0077] In another embodiment, the method further comprises drying the polymer composition to remove any residual solvent and / or water. According to one example, the steps of drying the polymer composition and coating the polymer composition are performed simultaneously.

[0078] In another embodiment, the method further comprises a crosslinking step. For example, the crosslinking step is carried out by UV irradiation, heat treatment, microwave irradiation, under electron beam irradiation, gamma ray irradiation, or X-ray irradiation. The crosslinking step may be carried out in the presence of at least one of a crosslinking agent, a thermal initiator, a photoinitiator (e.g., a UV initiator), a catalyst, a plasticizer, or a combination of at least two thereof. [Brief explanation of the drawings]

[0079] [Figure 1]FIG. 1 is a chromatogram obtained by steric exclusion chromatography (SEC) for polymer 2 described in Example 3(b).

[0080] [Figure 2] FIG. 2 is a proton nuclear magnetic resonance ( 1 H NMR) spectrum obtained for polymer 2 described in Example 3(b).

[0081] [Figure 3] FIG. 3 is a graph showing the results of a differential scanning calorimetry (DSC) analysis obtained for Polymer 2, described in Example 3(b).

[0082] [Figure 4] FIG. 4 is a chromatogram obtained by steric exclusion chromatography for polymer 4 described in Example 3(d).

[0083] [Figure 5] FIG. 5 is a proton nuclear magnetic resonance spectrum of the polymer obtained by polymerization of diethylene glycol with lithium bis(chlorosulfonyl)imide, as described in Example 3(e).

[0084] [Figure 6] FIG. 6 is a proton nuclear magnetic resonance spectrum obtained for polymer 5, described in Example 3(e).

[0085] [Figure 7] FIG. 7 is a carbon-13 nuclear magnetic resonance (.sup.13C NMR) spectrum obtained for polymer 5, described in Example 3(e).

[0086] [Figure 8] FIG. 8 is a fluorine nuclear magnetic resonance (F NMR) spectrum obtained for polymer 5, described in Example 3(e).

[0087] [Figure 9] FIG. 9 is a graph showing the results of differential scanning calorimetry analysis obtained for Polymer 5, described in Example 3(e).

[0088] [Figure 10] FIG. 10 is a graph showing the results of ionic conductivity (S.cm −1 ) as a function of temperature (1000 / T, K −1 ) for Cell 1, as described in Example 4(h).

[0089] [Figure 11] FIG. 11 is a graph showing the results of ionic conductivity (S.cm −1 ) as a function of temperature (1000 / T, K −1 ) for Cell 2, as described in Example 4(h).

[0090] [Figure 12] FIG. 12 is a graph showing the results of ionic conductivity (S.cm −1 ) as a function of temperature (1000 / T, K −1 ) for Cell 3, as described in Example 4(h).

[0091] [Figure 13] FIG. 13 is a graph showing the results of ionic conductivity (S.cm −1 ) as a function of temperature (1000 / T, K −1 ) for Cell 4, as described in Example 4(h).

[0092] [Figure 14] FIG. 14 is a graph showing the results of ionic conductivity (S.cm −1 ) as a function of temperature (1000 / T, K −1 ) for Cell 5 (Comparative Cell), as described in Example 4(h).

[0093] [Figure 15] FIG. 15 is a graph showing the results of ionic conductivity (S.cm −1 ) as a function of temperature (1000 / T, K −1 ) for Cell 6 (Comparative Cell), as described in Example 4(h).

[0094] [Figure 16]FIG. 16 shows cyclic voltammograms obtained for Cell 7 (Comparative Cell) recorded at a scan rate of 0.067 mV / s (solid line) and Cell 8 (Comparative Cell) recorded at a scan rate of 0.05 mV / s (dashed line) between 2.7 V and 4.3 V vs. Li / Li+, as described in Example 5(c).

[0095] [Figure 17] FIG. 17 shows the cyclic voltammogram obtained for Cell 7 (comparison cell) recorded at a scan rate of 0.067 mV / s between 2.5 V and 5 V vs. Li / Li+, as described in Example 5(c).

[0096] [Figure 18] FIG. 18 shows cyclic voltammograms obtained for cell 9 (solid line) and cell 10 (dashed line) recorded at a scan rate of 0.067 mV / s between 2.5 V and 5 V vs. Li / Li, as described in Example 5(c).

[0097] [Figure 19] FIG. 19 shows cyclic voltammograms obtained for Cell 7 (comparison cell) (two-dot dash line), Cell 10 (dash dot line), Cell 9 (dashed line), and Cell 11 (comparison cell) (solid line), recorded between 2.5 V and 5 V vs. Li / Li+ at a scan rate of 0.067 mV / s, as described in Example 5(c). DETAILED DESCRIPTION OF THE INVENTION

[0098] Detailed Description The following detailed description and examples are for illustrative purposes only and are not to be construed as further limiting the scope of the present invention.

[0099] All technical and scientific terms and expressions used herein have the same definitions as commonly understood by those skilled in the art. However, definitions of some terms and expressions used herein are provided below.

[0100] When the term "approximately" or its equivalent term "about" is used herein, it means to be in the approximate range or to be approximate. For example, when the terms "approximately" or "about" are used in reference to a numerical value, these words may modify the numerical value by 10% above and 10% below the apparent value. This term may also take into account experimental error, for example, due to rounding or limitations of the measuring device.

[0101] When a range of values is stated herein, the lower and upper limits of the range are always included in the definition unless otherwise specified. When ranges of values are stated in this application, all intermediate ranges and subranges, as well as individual values, contained within these ranges are included in the definition.

[0102] For further clarity, the phrase "monomer unit derived from" and equivalent phrases, as used herein, refers to a polymer repeat unit that results from the polymerization of polymerizable monomers.

[0103] The expression "repeating unit," as used herein, refers to a sequence of repeating units that form part of a polymer chain.

[0104] The term "fragment," as used herein in relation to a polymer sequence, refers to a portion of a polymer that includes repeat units and optionally end groups.

[0105] The chemical structures depicted herein are drawn in accordance with conventions in the art. Similarly, if a depicted atom, such as a carbon atom, appears to include an incomplete valence, the valence is considered to be satisfied by one or more hydrogen atoms, even if such hydrogen atoms are not explicitly depicted.

[0106] For further clarity, in this document, when a formula represents a polymer repeat unit or fragment, the end of the linkage extending beyond the bracket(s) of the formula will be defined as, for example, an OH, NH group, etc. [ka] is not necessarily a methyl group, but rather is defined as a residue of a polymer, and the definition of the group outside the brackets is left open. For example, this group may represent a group X, X, X, X, X, R, or R as defined herein, a residue of an initiator, or another polymer fragment.

[0107] As used herein, the term "alkyl" refers to a saturated hydrocarbon, including straight-chain or branched alkyl groups, having between 1 and 10 carbon atoms. Non-limiting examples of alkyl groups can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and the like. When an alkyl group is positioned between two functional groups, the term alkyl also encompasses alkylene groups such as methylene, ethylene, propylene, and the like. The term "C m ~C n Alkyl" and "C m ~C n "Alkylene" refers to an alkyl or alkylene group having the designated number "m" to the designated number "n" carbon atoms, respectively.

[0108] As used herein, the term "aryl" refers to a functional group containing a ring having aromatic character, having 6 to 14 ring atoms, preferably 6 ring atoms. The term "aryl" refers to both monocyclic and polycyclic conjugated systems. The term "aryl" also includes substituted and unsubstituted groups. Examples of aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indenyl, benzocyclooctenyl, benzocycloheptenyl, azulenyl, acenaphthylenyl, fluorenyl, phenanthrenyl, anthracenyl, perylenyl, and the like.

[0109] The present technology comprises a method for preparing a metal bis(halosulfonyl)imide having at least one compound of Formula 1 containing at least two functional groups and a metal bis(halosulfonyl)imide having Formula 2: [ka] (In the formula, A is a linear or branched C1-C 10 Alkylene, linear or branched C1-C 10 Alkyleneoxy C1~C 10 Alkylene, linear or branched poly(C1-C 10 Alkyleneoxy)C1~C 10 a substituted or unsubstituted organic group selected from alkylene, linear or branched polyethers and linear or branched polyesters; X1 and X2 are functional groups independently and at each occurrence selected from hydroxyl groups, thiol groups and amine groups; X3 and X4 are each independently a halogen atom selected from F, Cl, Br, and I; M n+ Na + , K. + , Li + , Ca 2+ and Mg 2+ ions, which are alkali metal ions or alkaline earth metal ions selected from the group consisting of and (b) a repeat unit comprising the reaction product between

[0110] According to one example, X1 and X2 can be functional groups independently and at each occurrence selected from a hydroxyl group (OH), a thiol group (SH) and a primary amine group (NH2). According to one variant of interest, X1 and X2 can be functional groups independently and at each occurrence selected from a hydroxyl group and a primary amine group.

[0111] According to another example, X1 and X2 may be the same, for example, X1 and X2 are both hydroxyl groups, or both thiol groups, or both primary amine groups. According to one variant of interest, X1 and X2 are both hydroxyl groups. According to another variant of interest, X1 and X2 are both primary amine groups.

[0112] According to another example, X3 and X4 may be the same, for example, X3 and X4 are both chlorine atoms.

[0113] According to another example, M n+ Na + , K. + and Li + ions, such as M n+ Li + It is an ion.

[0114] For example, X3 and X4 are both chlorine atoms, and M n+ Li + ion, i.e., the metal bis(halosulfonyl)imide of Formula 2 is lithium bis(chlorosulfonyl)imide.

[0115] According to another example, A is a linear or branched C2-C 10 Alkylene, linear or branched C2-C 10 Alkyleneoxy C2~C 10Alkylene, linear or branched poly(C2-C 10 Alkyleneoxy)C2~C 10 It is a substituted or unsubstituted organic group selected from alkylene, linear or branched polyethers and linear or branched polyesters.

[0116] According to another example, A is an optionally substituted linear or branched C1-C 10 alkylene, and the compound of formula 1 is a compound of formula 3: [ka] (In the formula, X1 and X2 are as defined herein; R1 and R2 are each a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a halogen atom selected from F, Cl, Br and I, and a C1-C 10 Alkyl, C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-acrylate, aminocarbonyl-C1-C 10 Alkyl-methacrylate, aminocarbonyl-C1-C 10 Alkyl-acrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate and oxycarbonylamino-C1-C 10 independently and at each occurrence selected from linear or branched substituents selected from alkyl-acrylates; l is a number ranging from 1 to 10) is a compound of

[0117] According to another example, R1 and R2 can be selected from the group consisting of a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a fluorine atom, and a C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonylamino-C1-C10 Alkyl-methacrylate and oxycarbonylamino-C1-C 10 Independently and at each occurrence, linear or branched substituents are selected from alkyl-acrylates.

[0118] According to another example, R1 and R2 can be selected from the group consisting of a hydrogen atom, a hydroxyl group, a thiol group, a primary amine group, a fluorine atom, and a C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate and oxycarbonylamino-C1-C 10 Independently and at each occurrence, linear or branched substituents are selected from alkyl-acrylates.

[0119] According to another example, l is a number in the range of 2-10.

[0120] According to another example, A is a linear or branched optionally substituted poly(C1-C 10 Alkyleneoxy)C1~C 10 alkylene, for example, the compound of formula 1 may be a compound of formula 4: [ka] (In the formula, X1 and X2 are as defined herein; m is a number ranging from 1 to 68 The compound may be:

[0121] According to one variation of interest, X1 and X2 are both hydroxyl groups or both amine groups, and the compound of formula 1 is represented by formula 4(a) or 4(b): [ka] (In the formula, m is a number ranging from 1 to 6 is a compound of

[0122] According to another variation of interest, the compound of formula 1 can be a JEFFAMINE® D series product, which compound has formula 4(c): [ka] (In the formula, m is a number ranging from 1 to 68 is a compound of

[0123] By way of example, a JEFFAMINE® D series product can be JEFFAMINE® D-230, where m is about 2.5 and the number average molecular weight of the polyether diamine is about 230 g / mol.

[0124] By way of another example, the JEFFAMINE® D series product can be JEFFAMINE® D-400, where m is about 6.1 and the number average molecular weight of the polyether diamine is about 430 g / mol.

[0125] By way of another example, the JEFFAMINE® D series product can be JEFFAMINE® D-2000, where m is about 33 and the number average molecular weight of the polyether diamine is about 2,000 g / mol.

[0126] By way of another example, the JEFFAMINE® D series product can be JEFFAMINE® D-4000, where m is about 68 and the number average molecular weight of the polyether diamine is about 4,000 g / mol.

[0127] According to another example, A is a linear or branched optionally substituted polyether. According to one example, the optionally substituted polyether can be based on propylene oxide (PO), ethylene oxide (EO), or a mixture of PO / EO. For example, when A is an optionally substituted polyether based primarily on polyethylene glycol (PEG), the compound of formula 1 can be represented by formula 5: [ka] (In the formula, X1 and X2 are as defined herein; R3, R4 and R5 are C1 to C 10 independently and at each occurrence selected from alkyl groups, n, o, and p are selected so that the number average molecular weight of the polyether is between about 220 g / mol and about 2,000 g / mol, inclusive; n and p are selected so that their sum (n+p) is in the range of about 1 to about 6; o is in the range of about 2 to about 39 is a compound of

[0128] According to one variant of interest, the compound of formula 1 is a compound of formula 5, which may be a product of the JEFFAMINE® ED series, and which has formula 5(a): [ka] (In the formula, n, o, and p are selected so that the number average molecular weight of the polyether is between about 220 g / mol and about 2,000 g / mol, inclusive; n and p are selected so that their sum (n+p) is in the range of about 1 to about 6; o is a number ranging from about 2 to about 39 is a compound of

[0129] By way of example, a product of the JEFFAMINE® ED series can be JEFFAMINE® HK-511, where o is about 2, the sum (n+p) is about 1.2, and the number average molecular weight of the polyether diamine is about 220 g / mol.

[0130] By way of another example, a product of the JEFFAMINE® ED series can be JEFFAMINE® ED-2003, where o is about 39, the sum (n+p) is about 6, and the number average molecular weight of the polyether diamine is about 2,000 g / mol.

[0131] By way of another example, a product of the JEFFAMINE® ED series can be JEFFAMINE® ED-900, where o is about 12.5, the sum (n+p) is about 6, and the number average molecular weight of the polyether diamine is about 900 g / mol.

[0132] By way of another example, a product of the JEFFAMINE® ED series can be JEFFAMINE® ED-600, where o is about 9, the sum (n+p) is about 3.6, and the number average molecular weight of the polyether diamine is about 600 g / mol.

[0133] According to one variant of interest, the JEFFAMINE® ED series of products may be selected from the group consisting of JEFFAMINE® ED-600, ED-900 and ED-2003.

[0134] According to another example, A is a linear or branched optionally substituted poly(C1-C 10 Alkyleneoxy)-C1~C 10 alkylene, and the compound of formula 1 is a compound of formula 6: [ka] (In the formula, X1 and X2 are as defined herein; q and r are numbers ranging from 1 to 10. The compound may be:

[0135] According to one variant of interest, the compound of formula 1 is a compound of formula 6, formula 6(a): [ka] (In the formula, X1, X2, q and r are as defined herein. The product may be from the JEFFAMINE® EDR series of products.

[0136] By way of example, a product in the JEFFAMINE® EDR series can be JEFFAMINE® EDR-148, where q and r are about 2 and the number average molecular weight of the polyether diamine is about 148 g / mol.

[0137] By way of another example, a product in the JEFFAMINE® EDR series can be JEFFAMINE® EDR-176, where q and r are about 3 and the number average molecular weight of the polyether diamine is about 176 g / mol.

[0138] According to another example, A is an optionally substituted aliphatic polyester, such as polycaprolactone, and the compound of formula 1 may be, for example, a compound of formula 7: [ka] (In the formula, (t and u are numbers between 1 and 10) is a compound of

[0139] By way of another example, the compound of Formula 1 containing at least two functional groups can be an alcohol (or polyalcohol), glycol ether, or polyol, such as a diol (or glycol), triol, tetraol, pentol, hexol, heptol, etc., containing at least two hydroxyl groups. For example, the compound containing at least two hydroxyl groups can be a linear or branched diol (or glycol), and can be aliphatic or aromatic, for example, all diols (or glycols) are contemplated.

[0140] Non-limiting examples of compounds containing at least two hydroxyl groups include glycerol (glycerin), alkanediols, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-propanediol (or propylene glycol (PG)), 1,2-butanediol, 2,3-butanediol (or dimethylene glycol), 1,3-butanediol (or butylene glycol), 1,2-pentanediol, ethoxyhexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol, polycaprolactone diol, ethylene glycol (1,2-ethanediol), diethylene glycol (or ethylene diglycol), triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, and other similar glycols and diols, or combinations thereof. For example, the compound containing at least two hydroxyl groups may be selected from glycerol, diethylene glycol, ethylene glycol, propanediol, triethylene glycol, tetraethylene glycol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol and polycaprolactone diol.

[0141] According to one variant, the compound containing at least two hydroxyl groups may be glycerol. According to another variant, the compound containing at least two hydroxyl groups may be diethylene glycol. According to another variant, the compound containing at least two hydroxyl groups may be 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol.

[0142] According to another example, the compound containing at least two functional groups can be a polyamine containing at least two amine groups, such as a diamine or triamine. For example, the compound containing at least two amine groups can be a linear or branched diamine, and can be aliphatic or aromatic, and all diamines are contemplated. Non-limiting examples of compounds containing at least two amine groups include propane-1,2,3-triamine, alkanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,2-propanediamine, 1,2-butanediamine, 2,3-butanediamine, 1,3-butanediamine, 1,2-pentanediamine, 2,4-diamino-2-methylpentane, ethylenediamine (1,2-diaminoethane), 1,8-diamino-3,6-dioxaoctane, 1,11-diamino- Included are 3,6,9-trioxaundecane, 4,9-dioxa-1,12-dodecanediamine, 1,14-diamino-3,6,9,12-tetraoxatetradecane, poly(ethylene glycol) diamines (or PEG-diamines), JEFFAMINE® D series of products (amine-terminated polypropylene glycols), JEFFAMINE® ED series of products (primarily polyethylene glycol-based diamines), JEFFAMINE® EDR series of products and other similar polyamines, or combinations thereof.

[0143] According to one variant of interest, the compound comprising at least two amine groups has the formula HNCHCH(OCHCH) nPEG-diamine may be NH2 (wherein n is 1 or 2). According to another variant of interest, the compound comprising at least two amine groups may be a JEFFAMINE® ED series product (or O,O'-bis(2-aminopropyl)polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol). For example, the JEFFAMINE® ED series product may be selected from JEFFAMINE® ED-600, ED-900 and ED-2003.

[0144] Thus, the present technology provides a polymer comprising at least one repeat unit of formula 8(a) and / or of formula 8(b): [ka] (In the formula, A is a linear or branched C1-C 10 Alkylene, linear or branched C1-C 10 Alkyleneoxy C1~C 10 Alkylene, linear or branched poly(C1-C 10 Alkyleneoxy)C1~C 10 are substituted or unsubstituted organic groups selected independently and at each occurrence from alkylene, linear or branched polyethers and linear or branched polyesters; X5 and X6 are each independently selected from an oxygen atom, a sulfur atom, and an NH group; R6 is selected from a hydroxyl group, a thiol group, an amine group, and an R7-X5-A-X6- group; R7 is acrylate, methacrylate, C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, carbonyl-C1-C 10 Alkyl methacrylate carbonyl-C1~C 10 Alkyl-acrylate, carbonyloxy-C1~C 10 Alkyl-methacrylate, carbonyloxy-C1-C 10Alkyl-acrylate, carbonylamino-C1-C 10 Alkyl-methacrylate and carbonylamino-C1-C 10 is a crosslinkable group independently selected at each occurrence from alkyl-acrylate; M n+ Na + , K. + , Li + , Ca 2+ and Mg 2+ ions, v is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive; It relates to ionic polymers.

[0145] According to one example, X5 and X6 may be the same. For example, X5 and X6 are both oxygen atoms, or both sulfur atoms, or both NH groups. According to one variant of interest, X5 and X6 are both oxygen atoms. According to another variant of interest, X5 and X6 are both NH groups.

[0146] According to another example, the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

[0147] According to another example, the ionic polymer may be of formula 9: [ka] (In the formula, M n+ , R1, R2, 1, X5 and X6 are as defined herein; w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. It contains at least one repeating unit of

[0148] According to one example, the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

[0149] According to another example, the ionic polymer may be of formula 10: [ka] (In the formula, M n+ , m, X5 and X6 are as defined herein; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. It contains at least one repeating unit of

[0150] According to one example, the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

[0151] According to one variant of interest, X5 and X6 are both oxygen atoms or both NH groups, and the ionic polymer has formula 10(a) or 10(b): [ka] (In the formula, M n+ , m and x are as defined herein. It is an ionic polymer.

[0152] According to another example, the ionic polymer may be of formula 11: [ka] (In the formula, M n+ , R3, R4, R5, n, o, p, X5 and X6 are as defined herein; y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. It contains at least one repeating unit of

[0153] According to one example, the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

[0154] According to one variation of interest, X5 and X6 are both NH groups, R3, R4 and R5 are methyl groups, and the ionic polymer has the formula 11(a): [ka] (In the formula, M n+ , n, o, p and y are as defined herein) It is an ionic polymer.

[0155] According to another example, the ionic polymer may be of formula 12: [ka] (In the formula, M n+ , t and u are as defined herein; z is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. It contains at least one repeating unit of

[0156] According to one example, the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

[0157] By way of another example, the ionic polymer may be an ionic prepolymer. By way of another example, the ionic polymer may be an ionic copolymer.

[0158] The present technology also relates to an ionic polymer, as defined above, which is a crosslinked ionic polymer. According to one example, the ionic polymer may further comprise at least one crosslinkable functional group. According to another example, the crosslinkable functional group may be a terminal group, and may be present at at least one end of the carbon chain of the ionic polymer. According to another example, the crosslinkable functional group may be present on a side chain of the carbon chain of the ionic polymer. According to another example, the crosslinkable functional group may be present on at least one end of the carbon chain of the ionic polymer, as well as on its side chain. For example, the crosslinkable functional group may be selected from cyanate, acrylate, and methacrylate groups. According to one variant of interest, the crosslinkable functional group is a C1-C 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate, oxycarbonylamino-C1-C 10 Alkyl-acrylate, carbonylamino-C1-C 10 Alkyl-methacrylate and carbonylamino-C1-C 10 It can be selected from alkyl-acrylate groups.

[0159] According to the subject example, the ionic polymer is of formula 13: [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0160] According to another example of interest, the ionic polymer may be of formula 14: [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0161] According to another example of interest, the ionic polymer may be of formula 15: [ka] (In the formula, X5, X6 and x are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0162] According to one example, the ionic polymer may be represented by Formula 15(a): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0163] According to another example, the ionic polymer may be represented by Formula 15(b): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0164] According to another example of interest, the ionic polymer may be of formula 16: [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0165] According to one example, the ionic polymer may be represented by Formula 16(a): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0166] According to another example, the ionic polymer may be represented by Formula 16(b): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0167] According to another example of interest, the ionic polymer may be of formula 17: [ka] (In the formula, X5, X6 and x are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0168] According to one example, the ionic polymer may be represented by Formula 17(a): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0169] According to another example, the ionic polymer may be represented by Formula 17(b): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0170] According to another example of interest, the ionic polymer may be of formula 18: [ka] (In the formula, X5, X6 and x are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0171] According to one example, the ionic polymer may be represented by Formula 18(a): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0172] According to another example, the ionic polymer may be represented by Formula 18(b): [ka] (In the formula, x is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0173] According to another example of interest, the ionic polymer may be of formula 19: [ka] (In the formula, w is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0174] According to another example of interest, the ionic polymer may be of formula 20: [ka] (In the formula, w is as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0175] According to another example of interest, the ionic polymer may be of formula 21: [ka] (In the formula, n, o, p and y are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0176] According to another example of interest, the ionic polymer may be of formula 22: [ka] (In the formula, n, o, p and y are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0177] According to another example of interest, the ionic polymer may be of formula 23: [ka] (In the formula, n, o, p and y are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0178] According to another example of interest, the ionic polymer may be of formula 24: [ka] (In the formula, n, o, p and y are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0179] According to another example of interest, the ionic polymer may be of formula 25: [ka] (In the formula, n, o, p and y are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0180] According to another example of interest, the ionic polymer may be of formula 26: [ka] (In the formula, w and x are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0181] According to another example of interest, the ionic polymer may be of formula 27: [ka] (In the formula, w and x are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0182] According to another example of interest, the ionic polymer may be of formula 28: [ka] (In the formula, w and x are as defined herein. The polymer may be an ionic polymer comprising at least one fragment of

[0183] The present technology also relates to a polymer composition comprising an ionic polymer as defined above.

[0184] According to one example, the polymer composition or ionic polymer may further include at least one additional component or additive, such as an ion conductor, inorganic particles, glass particles, ceramic particles (e.g., nanoceramics), salts, and other similar additives, or combinations thereof, as needed. For example, the additional component or additive may be a filler additive and may include metal oxide particles or nanoparticles. For example, the filler additive may include titanium dioxide (TiO), alumina (AlO), and / or silicon dioxide (SiO) particles or nanoparticles.

[0185] The present technology provides a method for preparing an ionic polymer or polymer composition as defined herein, comprising: (i) preparing a metal bis(halosulfonyl)imide of formula 2; and (ii) reacting at least one compound of formula 1 containing at least two functional groups as described above with said metal bis(halosulfonyl)imide of formula 2. The present invention relates to a method, comprising:

[0186] According to one example, the method further comprises preparing a bis(halosulfonyl)imide. For example, the step of preparing the bis(halosulfonyl)imide can be carried out by reacting sulfamic acid (H3NSO3) with a halosulfonic acid of formula HSO3X3 (X3 is as defined above) in the presence of at least one halogenating agent. For example, the preparation of the bis(halosulfonyl)imide can be carried out by the method described by Beran et al., which is shown in Scheme 1 below: [ka] (wherein X3 and X4 are as defined above). (Beran et al., Zeitschrift fur anorganische und allgemeine Chemie 631.1 (2005): 55-59).

[0187] According to one variation of interest, the bis(halosulfonyl)imide is bis(chlorosulfonyl)imide (HN(SO2Cl)2).

[0188] According to one example, bis(chlorosulfonyl)imides can be prepared by reacting sulfamic acid with chlorosulfonic acid (HSO3Cl) in the presence of at least one halogenating agent.

[0189] According to another example, the step of preparing a bis(halosulfonyl)imide can further include a purification step. For example, the purification step can be performed by any known suitable purification method. For example, the purification step can be performed by distillation.

[0190] According to another example, the halogenating agent can be selected from any known compatible halogenating agent. For example, the halogenating agent may also serve as a reaction medium and / or solvent and may be selected to facilitate isolation during a subsequent purification step, if necessary. For example, the halogenating agent can be selected from phosphorus trichloride (PCl), phosphorus pentachloride (PCl), thionyl chloride (SOCl), thionyl fluoride (SOF), phosphorus oxychloride (POCl), and oxalyl chloride ((COCl)). For example, the halogenating agent is a chlorinating agent. According to one variant of interest, the halogenating agent is thionyl chloride.

[0191] Without wishing to be bound by theory, for example, thionyl chloride can react with an amine group to form a (-N=S=O) group. Thus, for example, the reaction mechanism between sulfamic acid and chlorosulfonic acid in the presence of thionyl chloride is shown in Scheme 2: [ka] It can be as illustrated in.

[0192] For example, one equivalent of sulfamic acid reacts with one equivalent of chlorosulfonic acid in the presence of two equivalents of thionyl chloride to form a bis(chlorosulfonyl)imide.

[0193] According to another example, the halogenating agent (e.g., thionyl chloride) may be added in excess. For example, the amount of halogenating agent can be in the range of about 2 equivalents to about 5 equivalents (including upper and lower limits) relative to sulfamic acid. For example, the amount of halogenating agent can be in the range of about 2 equivalents to about 4 equivalents, or about 2 equivalents to about 3 equivalents, or about 2 equivalents to about 2.75 equivalents, or about 2 equivalents to about 2.5 equivalents (including upper and lower limits) per equivalent of sulfamic acid. According to one variant of interest, the amount of halogenating agent is about 2.75 equivalents relative to sulfamic acid.

[0194] According to another example, the reaction between sulfamic acid and halosulfonic acid in the presence of at least one halogenating agent is carried out at a temperature high enough and for a time sufficient to allow the reaction to substantially complete. For example, the reaction between sulfamic acid and halosulfonic acid in the presence of at least one halogenating agent is carried out at a temperature ranging from about 60°C to about 150°C, inclusive. For example, the step of preparing the bis(halosulfonyl)imide can be carried out at a temperature ranging from about 70°C to about 145°C, or from about 80°C to about 140°C, or from about 90°C to about 100°C, or from about 110°C to about 140°C, or from about 120°C to about 140°C, or from about 125°C to about 140°C, or from about 125°C to about 135°C, inclusive. According to one preferred embodiment, the step of preparing the bis(halosulfonyl)imide can be carried out at a temperature of about 130°C, for example, for about 24 hours.

[0195] According to another example, a metal bis(halosulfonyl)imide is prepared by a metalation reaction of a bis(halosulfonyl)imide. For example, the step of preparing a metal bis(halosulfonyl)imide or the metalation step can be carried out by a reaction between a bis(halosulfonyl)imide and at least one metalation agent in the presence of a solvent. For example, the step of preparing a metal bis(halosulfonyl)imide or the metalation step can be carried out as shown in Scheme 3: [ka] (Wherein X3, X4 and M n+ is as defined above) This can be done by the method exemplified in .

[0196] According to another example, the metallation agent can be selected from any known compatible metallation agent. According to one variant, the metal of the metallation agent is an alkali metal or alkaline earth metal selected from lithium, sodium, potassium, calcium, and magnesium. For example, the metal of the metallation agent is an alkali metal selected from lithium, sodium, and potassium. According to another variant, the alkali metal is lithium, the metallation agent is a lithiation agent, and the metalation step is a lithiation step. For example, the lithiation agent can be selected for its ability to easily deprotonate and lithiate bis(halosulfonyl)imide, such as bis(chlorosulfonyl)imide. According to one variant, lithium bis(halosulfonyl)imide can be prepared by the method described by Paul et al. (Paul et al., Journal of Inorganic and Nuclear Chemistry 39.3 (1977): 441-442).

[0197] Non-limiting examples of lithiation agents include lithium hydroxide (LiOH), lithium carbonate (Li2CO3), lithium bicarbonate (LiHCO3), lithium hydride (LiH), metallic lithium, lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide, lithium ions of the formula RCO2Li (where R is a linear or branched C1-C 10 Lithium carboxylates (C2Li2O4) and lithium oxalate (C2Li2O4) are included. According to one variant of interest, the lithiating agent is lithium chloride.

[0198] According to another example, the solvent used in the step of preparing the metal bis(halosulfonyl)imide or the metalation step can be an organic solvent, such as a polar aprotic solvent. For example, the solvent can be selected from the group consisting of N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), tetrachloromethane, chloroform, acetonitrile, tetrahydrofuran (THF), and miscible combinations of at least two thereof. According to one variant of interest, the solvent for the metalation reaction is N,N-dimethylformamide. For example, the solvent may also serve as an activator for the subsequent polymerization reaction. According to one example, N,N-dimethylformamide forms a complex with the metal bis(halosulfonyl)imide, which can significantly improve the yield of the subsequent step of reacting at least one compound of Formula 1 above with the metal bis(halosulfonyl)imide of Formula 2 defined herein. For example, the complex may be the complex described by Higashi et al. (Higashi et al., Journal of Polymer Science: Polymer Chemistry Edition 22, No. 7 (1984): 1653-1660).

[0199] According to another example, the metalating agent can be added in a 1:1 molar ratio of bis(halosulfonyl)imide to metalating agent. Alternatively, the metalating agent can be added in excess relative to the bis(halosulfonyl)imide. For example, the amount of metalating agent can be in the range of about 1 to about 5 equivalents (inclusive) per equivalent of bis(halosulfonyl)imide. For example, the amount of metalating agent can be in the range of about 1 to about 4 equivalents, or about 1 to about 3 equivalents, or about 1 to about 1.5 equivalents, or about 1 to about 1.3 equivalents, or about 1 to about 1.2 equivalents (inclusive) per equivalent of bis(halosulfonyl)imide. According to one variant of interest, the amount of metalating agent can be in the range of about 1 to about 1.5 equivalents (inclusive) per equivalent of bis(halosulfonyl)imide.

[0200] According to another example, the metal bis(halosulfonyl)imide preparation step, or metalation step, can be carried out at a temperature in the range of about 20°C to about 150°C, inclusive. For example, the metal bis(halosulfonyl)imide preparation step, or metalation step, can be carried out at a temperature in the range of about 30°C to about 135°C, or about 40°C to about 130°C, or about 50°C to about 125°C, or about 60°C to about 120°C, or about 70°C to about 115°C, or about 80°C to about 110°C, or about 90°C to about 105°C, inclusive. According to one preferred variation, the metal bis(halosulfonyl)imide preparation step, or metalation step, can be carried out at a temperature of about 100°C.

[0201] According to another example, the metal bis(halosulfonyl)imide preparing step or metalation step may be carried out at a sufficiently elevated temperature and for a sufficient period of time to allow the metalation reaction to go substantially to completion.

[0202] For example, the metalation reaction can be carried out for a period ranging from about 10 hours to about 48 hours, or from about 10 hours to about 24 hours, or from about 12 hours to about 24 hours, inclusive. According to one preferred embodiment, the metalation reaction can be carried out for a period ranging from about 12 hours to about 24 hours.

[0203] According to another example, the step of reacting at least one compound of Formula 1 containing at least two of the above functional groups with a metal bis(halosulfonyl)imide of Formula 2 as defined herein is a polymerization step. For example, any compatible polymerization method is contemplated. According to one variant of interest, the polymerization of the metal bis(halosulfonyl)imide of Formula 2 with at least one compound of Formula 1 may be carried out by polycondensation or polyesterification, for example, Fischer esterification (or Fischer-Speier esterification), or modified Steglich esterification. For example, the polycondensation may be thermal polycondensation. According to one variant of interest, the polycondensation may be carried out by the method described by Slavko et al. (Slavko et al., Chemical Science 8.10 (2017): 7106-7111).

[0204] According to another example, the reaction of at least one compound of the above formula 1 with the metal bis(halosulfonyl)imide of formula 2 may be carried out in the presence of a solvent, for example, an organic solvent. For example, the solvent can be selected from the group consisting of N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, tetrachloromethane, chloroform, acetonitrile, tetrahydrofuran, and a miscible combination of at least two thereof. According to one variant of interest, the solvent for the polymerization reaction is N,N-dimethylformamide. For example, the solvent can also act as an activator in the polymerization reaction.

[0205] According to another example, polymerization may be carried out in the presence of at least one polymerization catalyst, and optionally at least one cocatalyst, and / or optionally at least one acylation catalyst. According to another example, polymerization may also be carried out in the presence of a base and without a polymerization catalyst. For example, any compatible polymerization catalyst, cocatalyst, acylation catalyst, and base are contemplated. According to one example, the polymerization catalyst may be an acid catalyst (e.g., a Lewis acid catalyst). For example, the polymerization catalyst may be a boron-based catalyst, a boric acid-based catalyst, a boronic acid-based catalyst, or a borinic acid-based catalyst as described by Slavko et al. (Slavko et al., Chemical Science 8.10 (2017): 7106-7111). Non-limiting examples of boron-based polymerization catalysts include diarylborinic acid of the formula ArBOH (where Ar is an aryl group), diphenylborinic acid, phenylboronic acid, trifluorophenylboronic acid, 9H-9-bora-10-thiaanthracen-9-ol, 10H-phenoxaborinin-10-ol, boron tribromide (BBr), boron trichloride (BCl), acylfluoroborates, triethyloxonium fluoroborate, boron trifluoride etherate, boron trifluoride (BF), tris(pentafluorophenyl)borane, and other similar boron-derived catalysts, or combinations of at least two thereof (where compatible).

[0206] According to another example, the polymerization catalyst may be a nucleophilic catalyst. For example, the polymerization may be catalyzed by bases such as pyridine, 4-dimethylaminopyridine (DMAP), and pyridine derivatives.

[0207] According to another example, the polymerization may be carried out in the presence of a base such as triethylamine (EtN), N,N-diisopropylethylamine (iPrNEt), pyridine and pyridine derivatives. According to one variant of interest, the base is triethylamine. For example, the base can be used to deprotonate the catalyst or to regenerate the catalyst. The base can also be used to neutralize the acid (e.g., hydrochloric acid (HCl)) released during the reaction.

[0208] According to one variant of interest, the polymerization may be carried out in the presence of triethylamine, diphenylborinic acid or trifluorophenylboronic acid, N,N-dimethylformamide, and 4-dimethylaminopyridine. According to another variant of interest, the polymerization may be carried out in the presence of triethylamine, diphenylborinic acid or trifluorophenylboronic acid, and N,N-dimethylformamide. Alternatively, the polymerization may be carried out in the presence of N,N-dimethylformamide and, optionally, a base, without the addition of a catalyst, cocatalyst, and / or acylation catalyst.

[0209] According to another example, the polymerization can be carried out according to Scheme 4: [ka] (In the formula, X1, X2, X3, X4, X5, X6, M n+ , A and v are as defined above) This can be carried out by the method illustrated in.

[0210] According to another example, the method further includes a post-functionalization step or a post-polymerization modification step. For example, the post-functionalization of the ionic polymer is carried out in anticipation of its crosslinking. Therefore, the post-functionalization step of the ionic polymer can be carried out as needed to functionalize the ionic polymer by introducing at least one functional group, such as a crosslinkable functional group, as defined above. The crosslinkable functional group may be present at at least one end of the carbon chain of the ionic polymer and / or on its side chain. For example, at least one end group or substituent (e.g., R1 and / or R2) in the carbon chain of the ionic polymer contains a functionality that allows the ionic polymer to be crosslinked. In some cases, the presence of such a functional group may contribute to adjusting the properties of the ionic polymer.

[0211] The optional post-functionalization or post-polymerization modification step can be carried out by reaction between at least one functional group of the ionic polymer and at least one precursor of a crosslinkable functional group. For example, the crosslinkable functional group can be an acrylate, a methacrylate, a C1-C6 10 Alkyl acrylates, C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-methacrylate, oxycarbonyl-C1-C 10 Alkyl-acrylate, aminocarbonyl-C1-C 10 Alkyl-methacrylate, aminocarbonyl-C1-C 10 Alkyl-acrylate, oxycarbonylamino-C1-C 10 Alkyl-methacrylate, oxycarbonylamino-C1-C 10 Alkyl-acrylate, carbonyloxy-C1~C 10 Alkyl-methacrylate, carbonyloxy-C1-C 10 Alkyl-acrylate, carbonylamino-C1-C 10 Alkyl-methacrylate and carbonylamino-C1-C 10 alkyl-acrylates.

[0212] According to another example, the post-functionalization reaction can be selected from esterification and amidation reactions. For example, the post-functionalization reaction can be Fisher esterification, Steglich esterification, or the reaction described in U.S. Pat. No. 7,897,674 (B2) (Zaghib et al.). According to another example, an ionic polymer having carbamate functional groups can be obtained by the reaction between 2-isocyanatoethyl methacrylate and the functional groups of an ionic polymer. According to another example, an ionic polymer having acrylate functional groups can be obtained by the reaction between the functional groups of an ionic polymer and acrylic acid (CH═CHCOOH), methacrylic acid (CHC(CH)COOH), acryloyl chloride (CH═CHCO(Cl)), methacryloyl chloride (CH═C(CH)CO(Cl)), or another suitable carboxylic acid derivative.

[0213] According to another example, the method further includes a step of substituting at least one halogen atom, e.g., a chlorine atom. For example, the substituting step may be carried out by nucleophilic substitution of the halogen atom with a nucleophilic reagent. According to one example, the nucleophilic reagent can be a salt, e.g., a lithium salt such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or a silver salt such as silver tetrafluoroborate (AgBF4). According to one variant of interest, the substituting step can be carried out by nucleophilic substitution of at least one chlorine atom with an anion (e.g., TFSI or BF4). According to one example, the ionic polymer is contacted with at least one nucleophilic reagent to react. For example, the ionic polymer can be contacted with a sufficient amount of the nucleophilic reagent at a sufficiently high temperature and for a sufficient time to ensure that the nucleophilic substitution reaction is substantially complete. For example, the ionic polymer can be contacted with about 10% by weight of LiTFSI at a temperature of about 40°C for about 2 hours to ensure that the nucleophilic substitution reaction is substantially complete. For example, the nucleophile can then be removed by filtration and precipitation in a suitable solvent, such as ethyl acetate or methanol.

[0214] According to another example, the method further comprises a separation or purification step. The separation or purification step can be performed by any known suitable separation or purification method. For example, the separation or purification step can be performed by a separation method based on molecular weight. The separation or purification step can be performed by a liquid chromatography method (e.g., steric exclusion chromatography) or a filtration method (e.g., membrane filtration or membrane separation method). For example, the separation or purification step is performed by a membrane filtration method (e.g., nanofiltration or ultrafiltration). In some embodiments, the separation or purification step can be performed by ultrafiltration. For example, ultrafiltration is performed to separate low molecular weight impurities (e.g., less than 1000 DA) from the ionic polymer, for example, by filtration of 1,000 DA (Daltons) (i.e., 1.66×10 -15 This can be done using membranes with a molecular weight cut-off (MWCO) limit of 1000 μg. According to another example, the separation or purification step can be performed before and / or after the post-functionalization or post-polymerization modification step.

[0215] According to another example, the method further comprises a step of coating (also referred to as spreading) the polymer composition or the suspension containing the ionic polymer. For example, the coating step may be performed by at least one of a doctor blade coating method, a comma coating method, a reverse comma coating method, a printing method such as gravure coating, or a slot die coating method. According to a variant of the present invention, the coating step is performed by a doctor blade coating method or a slot die coating method. According to one example, the polymer composition or the suspension containing the ionic polymer may be coated onto a substrate or a support film (e.g., a substrate made of silicone, polypropylene, or siliconized polypropylene). For example, the substrate or support film may be subsequently removed. According to another example, the polymer composition or the suspension containing the ionic polymer may be coated directly onto an electrode.

[0216] According to another example, the method further comprises a step of drying the polymer composition or ionic polymer defined above. According to one example, the drying step may be performed to remove any residual solvent. According to another example, the drying step and the coating step may be performed simultaneously and / or separately.

[0217] According to another example, the method further comprises a step of crosslinking the polymer composition or ionic polymer defined above. For example, at least one terminal group or substituent (e.g., R1 and / or R2) in the carbon chain of the ionic polymer comprises at least one functional group that allows crosslinking of the ionic polymer. According to another example, the crosslinking step can be carried out by UV irradiation, heat treatment, microwave irradiation, under electron beam irradiation, gamma ray irradiation, or X-ray irradiation. According to one target variant, the crosslinking step is carried out by UV irradiation. According to another target variant, the crosslinking step is carried out by heat treatment. According to another target variant, the crosslinking step is carried out under electron beam irradiation. According to another target variant, the crosslinking step can be carried out in the presence of a crosslinking agent, a thermal initiator, a photoinitiator, a catalyst, a plasticizer, or a combination of at least two thereof. For example, the photoinitiator is 2,2-dimethoxy-2-phenylacetophenone (Irgacure™ 651). For example, the polymer composition and the ionic polymer can be solidified after crosslinking.

[0218] The present technology also relates to the use of the polymer composition or ionic polymer defined above in electrochemical applications.

[0219] According to one example, the polymer composition or ionic polymer can be used in electrochemical cells, batteries, supercapacitors (e.g., carbon-carbon supercapacitors, hybrid supercapacitors, etc.) According to another example, the polymer composition or ionic polymer can be used in electrochromic materials, electrochromic cells, electrochromic devices (ECDs), and electrochromic sensors such as those described in U.S. Pat. No. 5,356,553.

[0220] According to another example, the polymer composition as defined herein may be a solid polymer electrolyte composition. According to another example, the polymer composition as defined herein may be used as a component of an electrode material, for example, as a binder in an electrode material.

[0221] Therefore, the present technology also relates to a solid polymer electrolyte comprising an ionic polymer as defined above or a polymer composition as defined above (i.e., comprising an ionic polymer as defined above), wherein the ionic polymer can be optionally crosslinked if crosslinkable functional groups are present in the ionic polymer.

[0222] According to one example, the solid polymer electrolyte composition or solid polymer electrolyte defined above may further comprise at least one salt, for example, the salt may be dissolved in the solid polymer electrolyte composition or solid polymer electrolyte.

[0223] The salt can be an ionic salt, such as a lithium, sodium, potassium, calcium, or magnesium salt. According to one variant of interest, the ionic salt is a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO), lithium chloride (LiCl), lithium tetra ... Lithium salts include lithium (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO), lithium hexafluoroarsenate (LiAsF), lithium trifluoromethanesulfonate (LiSOCF) (LiTf), lithium fluoroalkylphosphate Li[PF(CFCF)] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF)] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(CO)] (LiBBB), and combinations of at least two thereof. According to one targeted variation, the lithium salt can be LiPF. According to another targeted variation, the lithium salt can be LiFSI. According to another targeted variation, the lithium salt can be LiTFSI. Non-limiting examples of sodium salts include the above salts in which lithium ions are replaced by sodium ions. Non-limiting examples of potassium salts include the above salts in which the lithium ions are replaced by potassium ions. Non-limiting examples of calcium salts include the above salts in which the lithium ions are replaced by calcium ions, with the number of anions present in the salt adjusted to the charge of the calcium ions.Non-limiting examples of magnesium salts include the above salts in which the lithium ions are replaced by magnesium ions, and the number of anions present in the salt is adjusted to the charge of the magnesium ions.

[0224] According to another example, the solid polymer electrolyte composition or solid polymer electrolyte defined above may further comprise additional components or additives, such as ion-conducting materials, inorganic particles, glass particles, ceramic particles (e.g., nanoceramics), other similar additives, or a combination of at least two thereof, as needed. For example, the additional components or additives may be selected for their high ionic conductivity and may be added specifically to improve the conduction of lithium ions. According to one variant of interest, the additional components or additives may be selected from crystalline and / or amorphous forms of NASICON, LISICON, thio-LiSICON, garnet, and a combination of at least two thereof.

[0225] According to another example, the solid polymer electrolyte may be in the form of a thin film. For example, the film comprises at least one electrolyte layer comprising the solid polymer electrolyte. In some cases, additional components or additives as defined above may be included and / or substantially dispersed in the electrolyte layer or, for example, individually in an ion-conducting layer deposited on the electrolyte layer.

[0226] The present technology also relates to an electrode material comprising at least one electrochemically active material as defined above and an ionic polymer, or a polymer composition as defined herein (i.e., comprising an ionic polymer as defined herein). According to one example, the ionic polymer acts as a binder in the electrode material. According to one example, the electrode material is a positive electrode material. According to another example, the electrode material is a negative electrode material.

[0227] By way of example, the electrochemically active material may be in the form of particles. Non-limiting examples of electrochemically active materials include metal oxides, lithium metal oxides, metal phosphates, lithium metal phosphates, titanates, and lithium titanate.

[0228] For example, the metal of the electrochemically active material may be selected from the elements titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), antimony (Sb), and combinations of at least two thereof, where compatible. According to one variant of interest, the metal of the electrochemically active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), and combinations of at least two thereof, where compatible.

[0229] Non-limiting examples of electrochemically active materials also include titanates and lithium titanates (e.g., TiO, LiTiO, LiTiO 12 , H2Ti5O 11 , HTiO and combinations thereof), metal phosphates and lithiated metal phosphates (e.g., LiM'PO and M'PO (where M' can be Fe, Ni, Mn, Mg, Co and combinations thereof)), vanadium oxide and lithium vanadium oxide (e.g., LiVO, VO, LiVO, etc.), and other lithium metal oxides of the formula LiMnO, LiMO (where M'' is selected from Mn, Co, Ni and combinations thereof), Li(NiMO'')O (where M'' is selected from Mn, Co, Al, Fe, Cr, Ti, Zr, another similar metal and combinations thereof), and combinations of at least two thereof (where compatible).

[0230] According to another example, the electrochemically active material may be doped with other elements or impurities, which may be present in smaller amounts, for example, to adjust or optimize its electrochemical properties. For example, the electrochemically active material may be doped by partial substitution of the metal with other ions. For example, the electrochemically active material may be doped with a transition metal (e.g., Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, or Y) and / or a metal other than a transition metal (e.g., Mg, Al, or Sb).

[0231] According to another example, the electrochemically active material may be in the form of particles (e.g., microparticles and / or nanoparticles), which may be newly formed or commercially obtained, and may further include a coating material. The coating material may be an electronically conductive material, for example, the coating may be a carbon coating.

[0232] According to another example, the electrode material is an anode material that includes, for example, carbon coated lithium titanate (c-LTO) as the electrochemically active material.

[0233] According to another example, the electrode material may also optionally include additional components or additives, such as ionic conductors, inorganic particles, glass or ceramic particles, nanoceramics (e.g., Al2O3, TiO2, SiO2 and other similar compounds), salts (e.g., lithium salts), and other similar additives. For example, the additional components or additives can be ionic conductors selected from NASICON, LISICON, thio-LiSICON, garnet, sulfides, sulfur halides, phosphate and thio-phosphate compounds in crystalline and / or amorphous form, and combinations of at least two thereof.

[0234] According to another example, the electrode material defined herein may further comprise an electronically conductive material. Non-limiting examples of electronically conductive materials include carbon black (e.g., Ketjen™ carbon and Super P™ carbon), acetylene black (e.g., Shawinigan carbon and Denka™ carbon black), graphite, graphene, carbon fibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanofibers, carbon nanotubes (CNTs), and combinations of at least two thereof.

[0235] The present technology also relates to an electrode comprising an electrode material defined herein on a current collector (e.g., aluminum or copper). Alternatively, the electrode may be a self-supporting electrode. According to one variant, the electrode defined herein is a positive electrode. According to another variant, the electrode defined herein is a negative electrode.

[0236] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode, the positive electrode, and the electrolyte comprises an ionic polymer as defined herein, or a polymer composition as defined herein.

[0237] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode, the positive electrode, and the electrolyte is as defined herein. According to one targeted embodiment, the electrolyte is a solid polymer electrolyte as defined herein. According to another targeted embodiment, the negative electrode is as defined herein. According to another targeted variation, the positive electrode is as defined herein. According to a targeted variation, the electrolyte is a solid polymer electrolyte as defined herein, and the positive electrode is as defined herein.

[0238] The present technology also relates to a battery comprising at least one electrochemical cell defined herein.For example, the battery can be selected from lithium battery, lithium-ion battery, lithium-sulfur battery, sodium battery, sodium-ion battery, magnesium battery and magnesium-ion battery.According to one variant of interest, the battery is a lithium battery or a lithium-ion battery.For example, the battery can be an all-solid-state battery (for example, an all-solid-state lithium battery). [Example]

[0239] The following examples are for illustrative purposes and should not be construed as further limiting the scope of the invention as contemplated. These examples will be better understood with reference to the accompanying drawings. Example 1 Synthesis of bis(chlorosulfonyl)imide (Cl-SO2-NH-SO2-Cl)

[0240] The synthesis of bis(chlorosulfonyl)imide was carried out by the reaction between sulfamic acid and thionyl chloride, followed by the reaction of the product thus obtained with chlorosulfonic acid. Thus, bis(chlorosulfonyl)imide was prepared by the method illustrated in Scheme 5: [ka]

[0241] In a clean, dry flask equipped with a magnetic stir bar, 1.0 equivalent of sulfamic acid was suspended in an excess volume of thionyl chloride (2.75 equivalents). All operations were carried out under a constant flow of nitrogen. 1.0 equivalent of chlorosulfonic acid was added dropwise, and the flask was equipped with a steam trap containing saturated aqueous sodium hydroxide or lithium hydroxide solution to neutralize hydrochloric acid vapors. The resulting mixture was then heated with constant stirring in a sand bath at a temperature of approximately 130°C for approximately 24 hours.

[0242] The mixture was then purified by vacuum distillation at a temperature of about 180°C, using a heat gun to heat the mixture. The distillation was carried out using a cold trap filled with liquid nitrogen without using water circulation in the coolant. The temperature was increased at the end of the distillation to ensure completeness. The distillation was stopped before smoke formed to avoid contamination of the product.

[0243] The product thus obtained was then cooled to form bis(chlorosulfonyl)imide crystals and stored in a freezer. Example 2 Synthesis of lithium bis(chlorosulfonyl)imide Lithium bis(chlorosulfonyl)imide was prepared by the method illustrated in Scheme 6: [ka]

[0244] The synthesis of lithium bis(chlorosulfonyl)imide was carried out in a glove box under an inert nitrogen atmosphere. 1.0 equivalent of the bis(chlorosulfonyl)imide prepared in Example 1 was weighed and placed in a flask that had been pre-cleaned and dried at 120°C for 2 hours to remove any residual water. The flask was then closed with a septum. Between about 1.0 equivalent and about 1.5 equivalents of lithium chloride dissolved in anhydrous N,N-dimethylformamide was added to the flask through the septum using a needle.

[0245] The flask was then removed from the glove box and placed under a constant flow of nitrogen at a temperature of about 100°C for about 24 hours to ensure complete lithiation and activation of the mixture of lithium bis(chlorosulfonyl)imide with N,N-dimethylformamide. Example 3 polymerization (a) Polymerization of diethylene glycol with lithium bis(chlorosulfonyl)imide prepared in Example 2 (Polymer 1)

[0246] The polymerization was carried out by catalytically controlled polycondensation of diethylene glycol with lithium bis(chlorosulfonyl)imide prepared in Example 2. Thus, a polycondensation catalyst was used to control the polymerization.

[0247] The mixture containing lithium bis(chlorosulfonyl)imide prepared in Example 2 was cooled in an ice bath for 20 minutes. The septum was then removed, and the flask neck was then washed with solvent to recover as much product as possible. The flask was then closed with a new septum.

[0248] Next, 3 equivalents of triethylamine were added to the mixture. Subsequently, 25 mg of trifluorophenylboronic acid and 400 mg of 4-dimethylaminopyridine were added to the mixture. Next, 1 equivalent of diethylene glycol was added, and the reaction mixture was heated at a temperature of about 100° C. for about 72 hours.

[0249] The reaction mixture was then cooled, filtered, and precipitated into ethyl acetate. The reaction mixture was placed in an ice bath for approximately 30 minutes and then decanted.

[0250] The resulting polymer was then dissolved in a solvent mixture containing isopropanol and acetone (2:8 volume ratio) and placed in a freezer for approximately 1 hour. The mixture was then filtered to remove residual triethylamine chloride. The solvent was then evaporated using a rotary evaporator at a temperature of approximately 60°C. Finally, the polymer was dried in a vacuum oven at a temperature of approximately 60°C.

[0251] The polymer 1 thus obtained was then dissolved in 400 mL of water and filtered by ultrafiltration using a membrane with a molecular weight cut-off limit of 1,000 DA for about 7 hours.

[0252] The substitution of the chlorine atom was carried out by a nucleophilic substitution reaction using silver tetrafluoroborate as the nucleophile. The chloride ion present in polymer 1 was determined by the Mohr method to calculate the required amount of silver tetrafluoroborate. The required amount of silver tetrafluoroborate was then dissolved in a minimum amount of water and added to a solution containing 1 g of polymer 1 dissolved in 20 mL of water. The solution was then stirred at room temperature for approximately 15 minutes, then filtered and washed with methanol. The filtrate thus obtained was then evaporated to dryness. The substitution was confirmed by fluorine nuclear magnetic resonance (fluorine-19 NMR). (b) Post-functionalization of the polymer prepared in Example 3(a) (Polymer 2)

[0253] Polymer 2 was prepared by post-functionalization of polymer 1 as presented in Example 3(a) to introduce crosslinkable groups.

[0254] 4 g of the polymer prepared in Example 3(a) was dissolved in 25 ml of anhydrous N,N-dimethylformamide. 1 ml of 2-isocyanatoethyl acrylate was then added to the solution, and the resulting mixture was heated under a nitrogen atmosphere at approximately 50°C for approximately 5-12 hours. 5 ml of methanol was then added to the solution, and the solution was cooled to room temperature.

[0255] The polymer thus obtained (Polymer 2) was then dissolved in 400 mL of water and filtered by ultrafiltration using a membrane with a molecular weight cut-off limit of 1,000 DA for about 7 hours.

[0256] Polymer 2 was analyzed by steric exclusion chromatography (SEC), by proton nuclear magnetic resonance (proton NMR), by Fourier transform infrared spectroscopy (FTIR), and by differential scanning calorimetry (DSC).

[0257] Figure 1 shows the results of steric exclusion chromatography analysis obtained for polymer 2. The results were obtained to determine the average molecular weight (g / mol) of polymer 2. The steric exclusion chromatography was performed using a 0.90 ml min -1The steric exclusion chromatography results obtained with polymer 2 are presented in Tables 1 and 2. [Table 1] [Table 2]

[0258] Figure 2 shows the proton NMR spectrum obtained for polymer 2. Figure 3 shows the results of differential scanning calorimetry analysis obtained for polymer 2. As shown in Figure 3, polymer 2 exhibits a glass transition temperature (T g )=-53°C.

[0259] The lithium concentration of Polymer 2 was then determined. 30% by weight of a modified ion exchange resin, commercially available under the trade name DOWEX®, was then added to the solution. The resulting suspension was then stirred at room temperature for about 12 hours and then filtered. The filtrate was evaporated to dryness and dried in a vacuum oven at a temperature of about 65°C for about 24 hours. The lithium concentration in the polymer was determined by lithium nuclear magnetic resonance (NMR) analysis against a standard solution of lithium chloride. 7 Li NMR).

[0260] The modified ion exchange resin was obtained by the following method: 30 g of Dowex® 50WX8 (H + ) resin was packed and wetted with 2M aqueous lithium hydroxide solution. The resin was washed until a basic pH was reached at the end of the column. The modified resin was then washed with ultrapure water until a neutral pH was obtained, and then with 300 ml of methanol. The resin was then oven-dried at a temperature of about 60°C for about 12 hours. Alternatively, 30 g of Dowex® 50WX8 (H) was dissolved in 300 ml of 2M aqueous lithium hydroxide solution. +The resin was stirred for about 12 hours, and the resulting suspension was then filtered to prepare the modified ion exchange resin. The modified resin was then washed and dried as described above. (c) Polymerization of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol with lithium bis(chlorosulfonyl)imide prepared in Example 2 (Polymer 3)

[0261] The polymerization was carried out by catalytically controlled polycondensation of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol with lithium bis(chlorosulfonyl)imide prepared in Example 2.

[0262] The mixture containing lithium bis(chlorosulfonyl)imide from Example 2 was cooled in an ice bath for 20 minutes. The septum was then removed, and the flask neck was then washed with solvent to recover as much product as possible. The flask was then closed with a new septum.

[0263] Next, 3 equivalents of triethylamine were added to the mixture. Subsequently, 25 mg of trifluorophenylboronic acid and 400 mg of 4-dimethylaminopyridine were added to the mixture. Next, 1 equivalent of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol was added, and the reaction mixture was heated at a temperature of about 100° C. for about 72 hours.

[0264] The reaction mixture was then cooled, filtered, and precipitated into ethyl acetate. The reaction mixture was placed in an ice bath for approximately 30 minutes and then decanted.

[0265] The polymer was then dissolved in a solvent mixture containing isopropanol and acetone (2:8 volume ratio) and placed in a freezer for approximately 1 hour. The mixture was then filtered to remove residual triethylamine chloride. The solvent was then evaporated using a rotary evaporator at a temperature of approximately 60°C. Finally, the polymer was dried in a vacuum oven at a temperature of approximately 60°C.

[0266] The polymer thus obtained (Polymer 3) was then dissolved in 400 ml of water and filtered by ultrafiltration using a membrane with a molecular weight cut-off limit of 1,000 DA for about 7 hours.

[0267] Substitution of the chlorine atom was then carried out by the method described in Example 3(a). (d) Post-functionalization of the polymer prepared in Example 3(c) (Polymer 4)

[0268] Polymer 4 was prepared by post-functionalization of polymer 3 as presented in Example 3(c) to introduce crosslinkable groups.

[0269] 4 g of the polymer prepared in Example 3(c) was dissolved in 25 ml of anhydrous N,N-dimethylformamide, 1 ml of 2-isocyanatoethyl methacrylate was added to the solution, and the resulting mixture was heated at about 50°C under a nitrogen atmosphere for about 5 to 12 hours.

[0270] The polymer thus obtained (Polymer 4) was then dissolved in 400 ml of water and filtered by ultrafiltration using a membrane with a molecular weight cut-off limit of 1,000 DA for about 7 hours.

[0271] Polymer 4 was analyzed by steric exclusion chromatography, and the results are shown in Figure 4. -1 The steric exclusion chromatography results obtained with polymer 4 are also presented in Tables 3 and 4. [Table 3] [Table 4]

[0272] The lithium concentration of Polymer 4 was also determined by the method described in Example 3(b). (e) Polymerization of Glycerol and Diethylene Glycol with Lithium Bis(chlorosulfonyl)imide Prepared in Example 2 (Polymer 5)

[0273] The polymerization was carried out by catalytically controlled polycondensation of glycerol and diethylene glycol with lithium bis(chlorosulfonyl)imide prepared in Example 2.

[0274] The mixture containing lithium bis(chlorosulfonyl)imide from Example 2 was cooled in an ice bath for 20 minutes. The septum was then removed, and the flask neck was then washed with solvent to recover as much product as possible. The flask was then closed with a new septum.

[0275] Next, 3 equivalents of triethylamine were added to the mixture. Subsequently, 25 mg of trifluorophenylboronic acid and 400 mg of 4-dimethylaminopyridine were added to the mixture. Next, 0.90 equivalents of diethylene glycol and 0.10 equivalents of glycerol were added, and the reaction mixture was heated to a temperature of about 100° C. for about 72 hours.

[0276] The reaction mixture was then cooled, filtered, and precipitated into ethyl acetate. The reaction mixture was placed in an ice bath for approximately 30 minutes and then decanted.

[0277] The polymer was then dissolved in a solvent mixture containing isopropanol and acetone (2:8 volume ratio) and placed in a freezer for approximately 1 hour. The mixture was then filtered to remove residual triethylamine chloride. The solvent was then evaporated using a rotary evaporator at a temperature of approximately 60°C. Finally, the polymer was dried in an oven under vacuum at a temperature of approximately 60°C.

[0278] The polymer thus obtained (Polymer 5) was then dissolved in 400 ml of water and filtered by ultrafiltration using a membrane with a molecular weight cut-off limit of 1,000 DA for about 7 hours.

[0279] Substitution of the chlorine atom was then carried out by the method described in Example 3(a).

[0280] Polymer 5 was analyzed by proton nuclear magnetic resonance ( 1 1H NMR) to measure carbon-13 nuclear magnetic resonance ( 13 Fluorine nuclear magnetic resonance ( 19 The compounds were analyzed by F NMR and by differential scanning calorimetry (DSC).

[0281] FIG. 5 shows the proton NMR spectrum for the polymer obtained by polymerization of diethylene glycol with the lithium bis(chlorosulfonyl)imide prepared in Example 2, for example, by the method described in Example 3(a).

[0282] 6-8 show the proton NMR spectrum, carbon-13 NMR spectrum, and fluorine NMR spectrum obtained for polymer 5, respectively.

[0283] FIG. 9 shows the results of differential scanning calorimetry analysis obtained for polymer 5, which indicates that polymer 5 exhibits a glass transition temperature (T g )=-73°C. (f) Post-functionalization of the polymer prepared in Example 3(e) (Polymer 6)

[0284] Polymer 6 was prepared by post-functionalization of polymer 5 as presented in Example 3(e) to introduce crosslinkable groups.

[0285] 4 g of the polymer prepared in Example 3(e) was dissolved in 25 ml of anhydrous N,N-dimethylformamide, 1 ml of 2-isocyanatoethyl methacrylate was then added to the solution, and the resulting mixture was heated at about 50°C under a nitrogen atmosphere for about 5-12 hours.

[0286] The polymer thus obtained (Polymer 6) was then dissolved in 400 ml of water and filtered by ultrafiltration using a membrane with a molecular weight cut-off limit of 1,000 DA for about 7 hours.

[0287] The lithium concentration of Polymer 6 was also determined by the method described in Example 3(b). A lithium concentration of 25 mol % was obtained for Polymer 6. Example 4 ionic conductivity

[0288] Examples 4(a)-4(d) relate to the preparation of polymer films for measuring the ionic conductivity of polymers defined herein by the methods described in this application, while Examples 4(e) and 4(f) are for comparative purposes. a) Preparation of polymer film containing polymer 1

[0289] Ionic conductivity results were obtained for Polymer 1 prepared in Example 3(a). 1.7 g of the polymer prepared in Example 3(a) was dissolved in 1.4 g of a solvent mixture containing water and methanol (80:20 by volume) without the addition of additional lithium salt. 10 wt. % polyvinylidene fluoride (PVdF) was added to the resulting suspension.

[0290] Next, a hotplate coating system (Erichsen Test Apparatus) with a 3 mil slit opening was used to coat the film at 15 mm.s. -1 The suspension was applied to a substrate or support membrane at a rate of 1000 rpm The polymer film thus obtained was dried directly at a temperature of 70° C. during coating.

[0291] The polymer film was then vacuum dried in an oven at a temperature of 85° C. for 48 hours to remove residual solvent.

[0292] The polymer film was then removed from the surface of the substrate or support membrane. b) Preparation of polymer film containing polymer 2

[0293] Ionic conductivity results were obtained for Polymer 2, prepared in Example 3(b). 1.7 g of the polymer prepared in Example 3(b) was dissolved in 1.4 g of a solvent mixture containing water and methanol (80:20 by volume) without the addition of any additional lithium salt.

[0294] Next, a hotplate coating system (Erichsen Test Apparatus) with a 3 mil slit opening was used to coat the film at 15 mm.s. -1 The suspension thus obtained was applied to a substrate or support membrane at a rate of 1000 rpm The polymer film thus obtained was directly dried at a temperature of 70° C. during coating.

[0295] The polymer film was then vacuum dried in an oven at a temperature of 85° C. for 48 hours to remove residual solvent.

[0296] After drying, the polymer film was placed in a polycarbonate (lexan) box under an inert helium atmosphere to reduce the presence of oxygen and moisture, and then irradiated for 5 minutes with UV light (254 nm wavelength) placed approximately 5 cm from the polymer film.

[0297] The polymer film was then removed from the surface of the substrate or support membrane. c) Preparation of polymer film containing polymer 4

[0298] Ionic conductivity results were obtained for Polymer 4, prepared in Example 3(d). 1.7 g of the polymer prepared in Example 3(d) was dissolved in 1.4 g of a solvent mixture containing water and methanol (80:20 by volume) without the addition of any additional lithium salt.

[0299] Next, a hotplate coating system (Erichsen Test Apparatus) with a 3 mil slit opening was used to coat the film at 15 mm.s. -1The suspension thus obtained was applied to a substrate or support membrane at a rate of 1000 rpm The polymer film thus obtained was directly dried at a temperature of 70° C. during coating.

[0300] The polymer film was then vacuum dried in an oven at a temperature of 85° C. for 48 hours to remove residual solvent.

[0301] After drying, the polymer film was placed in a polycarbonate (lexan) box under an inert helium atmosphere to reduce the presence of oxygen and moisture, and then irradiated for 5 minutes with UV light (254 nm wavelength) placed approximately 5 cm from the polymer film.

[0302] The polymer film was then removed from the surface of the substrate or support membrane. d) Preparation of polymer films containing polymer 6

[0303] Ionic conductivity results were obtained for polymer 6, prepared in Example 3(f). 1.7 g of the polymer prepared in Example 3(f) was dissolved in 1.4 g of a solvent mixture containing water and methanol (80:20 by volume) without the addition of any additional lithium salt.

[0304] Next, a hotplate coating system (Erichsen Test Apparatus) with a 3 mil slit opening was used to coat the film at 15 mm.s. -1 The suspension thus obtained was applied to a substrate or support membrane at a rate of 1000 rpm The polymer film thus obtained was directly dried at a temperature of 70° C. during coating.

[0305] The polymer film was then vacuum dried in an oven at a temperature of 85° C. for 48 hours to remove residual solvent.

[0306] After drying, the polymer film was placed in a polycarbonate (lexan) box under an inert helium atmosphere to reduce the presence of oxygen and moisture, and then irradiated for 5 minutes with UV light (254 nm wavelength) placed approximately 5 cm from the polymer film.

[0307] The polymer film was then removed from the surface of the substrate or support membrane. e) Preparation of polymer films containing polymer 7 (comparison)

[0308] Ionic conductivity results were obtained for the polymer described in U.S. Patent No. 7,897,674 (B2) (Zaghib et al.) (U.S. '674): 1.7 g of polymer was dissolved in 1.4 g of a solvent mixture containing water and methanol (80:20 by volume) without the addition of any additional lithium salt.

[0309] Next, a hotplate coating system (Erichsen Test Apparatus) with a 3 mil slit opening was used to coat the film at 15 mm.s. -1 The suspension thus obtained was applied to a substrate or support membrane at a rate of 1000 rpm The polymer film thus obtained was directly dried at a temperature of 70° C. during coating.

[0310] The polymer film was then vacuum dried in an oven at a temperature of 85° C. for 48 hours to remove residual solvent.

[0311] After drying, the polymer film was placed in a polycarbonate (lexan) box under an inert helium atmosphere to reduce the presence of oxygen and moisture, and then irradiated for 5 minutes with UV light (254 nm wavelength) placed approximately 5 cm from the polymer film.

[0312] The polymer film was then removed from the surface of the substrate or support membrane. f) Preparation of polymer films containing polymer 8 (comparison)

[0313] Ionic conductivity results were obtained for the polymer described in U.S. Patent No. 6,903,174 (B2) (Harvey et al.) (US '174). 1.7 g of polymer was dissolved in 1.4 g of a solvent mixture containing water and methanol (80:20 by volume) without the addition of any additional lithium salt. 0.5 wt. % of 2,2-dimethoxy-2-phenylacetophenone (Irgacure™ 651) was added to the resulting suspension.

[0314] Next, a hotplate coating system (Erichsen Test Apparatus) with a 3 mil slit opening was used to coat the film at 15 mm.s. -1 The suspension thus obtained was applied to a substrate or support membrane at a rate of 1000 rpm The polymer film thus obtained was directly dried at a temperature of 70° C. during coating.

[0315] The polymer film was then vacuum dried in an oven at a temperature of 85° C. for 48 hours to remove residual solvent.

[0316] After drying, the polymer film was placed in a polycarbonate (lexan) box under an inert helium atmosphere to reduce the presence of oxygen and moisture, and then irradiated for 5 minutes with UV light (254 nm wavelength) placed approximately 5 cm from the polymer film.

[0317] The polymer film was then removed from the surface of the substrate or support membrane. g) Preparation of a symmetric cell for ionic conductivity measurements

[0318] The entire preparation of symmetric cells containing the polymer films prepared in Examples 4(a)-4(f) was carried out in an anhydrous chamber with a dew point of about -55°C. The symmetric cells were assembled in a button cell configuration. The polymer films were placed in a 2.01 cm 2 The electrode was placed between two stainless steel blocking electrodes with an active area of 1000 Å. A symmetric cell was assembled with the configuration shown in Table 5. [Table 5] h) Measurement of the ionic conductivity of the polymer films given in Examples 4(a) to 4(f)

[0319] Ionic conductivity measurements of the symmetric cell of Example 4(g) were performed by AC electrochemical impedance spectroscopy, recorded using a VPM3 multichannel potentiostat. Electrochemical impedance spectroscopy was performed between 200 mHz and 1 MHz at temperatures ranging from 20°C to 80°C (5°C ramp-up and ramp-down).

[0320] Each electrochemical impedance measurement was taken after the oven temperature stabilized at temperature (T).

[0321] The ionic conductivity of lithium ions is given by Equation 1:

number

[0322] The graphs in Figures 10-15 show the measured ionic conductivities (S.cm) for the symmetric cells (cells 1-6) assembled in Example 4(g), respectively. -1 ) as a function of temperature (K -1 )

[0323] FIG. 10 shows the results for Cell 1 described in Example 4(g) at a temperature of 50° C., with a 1.97×10 -5 S.cm -1 This shows that an ionic conductivity value of 0.01 was obtained.

[0324] FIG. 11 shows the results for Cell 2 described in Example 4(g) at a temperature of 50° C., with a 2.65×10 -5 S.cm -1 This shows that an ionic conductivity value of 0.01 was obtained.

[0325] FIG. 12 shows the results for Cell 3 described in Example 4(g) at a temperature of 50° C., with a 5.37×10 -5 S.cm -1 This shows that an ionic conductivity value of 0.01 was obtained.

[0326] FIG. 13 shows the results for Cell 4 described in Example 4(g) at a temperature of 50° C., with a 3.25×10 -4 S.cm -1 This shows that an ionic conductivity value of 0.01 was obtained.

[0327] FIG. 14 shows the results for Cell 5 described in Example 4(g) (comparative) at a temperature of 50° C., with a 1.65×10 -4 S.cm -1 This shows that an ionic conductivity value of 0.01 was obtained.

[0328] FIG. 15 shows the results for Cell 6 described in Example 4(g) (comparative) at a temperature of 50° C., with a 1.90×10 -4 S.cm -1 This shows that an ionic conductivity value of 0.01 was obtained. Example 5 Cyclic Voltammetry a) Preparation of polymer films for cyclic voltammetry measurements

[0329] Cyclic voltammetry results were obtained for the polymers prepared in Examples 3(b) and 3(f), as well as for the polymers described in the US'674 and US'174 patents, and polyacrylonitrile (PAN) for comparison purposes.

[0330] The polymers prepared in Examples 3(b) and 3(f) and the comparative polymer were dissolved in a solvent mixture containing water and methanol (80:20 by volume).

[0331] Once the polymer was dissolved, Ketjen™ Black was added to the mixture in a polymer:Ketjen™ Black ratio of 5:1 by weight.

[0332] The resulting blend was then mixed using a ball mill to properly disperse and break up any Ketjen™ Black agglomerates.

[0333] The viscosity of the resulting mixture was adjusted using a solvent mixture containing water and methanol (80:20 by volume).

[0334] The resulting mixture was then applied to a carbon-coated aluminum current collector using a doctor blade coating system equipped with a hot plate, and the resulting polymer film was directly dried at a temperature of 70°C during coating.

[0335] The polymer film was then dried under vacuum in an oven at a temperature of 85° C. for 48 hours to remove residual solvent. b) Preparation of a symmetric cell for cyclic voltammetry measurements

[0336] The entire preparation of the symmetric cell containing the polymer film prepared in Example 5(a) was carried out in an anhydrous chamber with a dew point of about −55° C. The symmetric cell was 2.01 cm 2 The cells were assembled in a button cell configuration with an active surface area of 0.05 mm. Symmetric cells were assembled according to the configuration shown in Table 6. [Table 6] c) Cyclic voltammetry

[0337] The electrochemical stability of the oxidation of the symmetric cell described in Example 5(b) was measured using a VMP-3 model potentiostat.

[0338] Figure 16 shows the Li / Li + 1 shows the cyclic voltammetry results obtained for cell 7 (comparison cell) (solid line) recorded between 2.7 V and 4.3 V vs. Zn at a scan rate of 0.067 mV / s.

[0339] Figure 16 also shows the relationship between Li / Li + 1 shows the cyclic voltammetry results obtained for cell 8 (comparison cell) (dashed line) recorded between 2.7 V and 4.3 V vs. Zn at a scan rate of 0.05 mV / s.

[0340] Figure 17 shows the Li / Li + Figure 17 shows the cyclic voltammetry results obtained for cell 7 (comparison cell) recorded between 2.5 V and 5 V vs. Li / Li at a scan rate of 0.067 mV / s. + This indicates that oxidation of the polymer begins at a potential of about 4.37 V vs.

[0341] Figure 18 shows the Li / Li + 1 shows the cyclic voltammetry results obtained for cell 9 (solid line) and cell 10 (dashed line) recorded between 2.5 V and 5 V vs. Zn at a scan rate of 0.067 mV / s.

[0342] Figure 19 shows the Li / Li + Figure 19 shows the cyclic voltammetry results obtained for cell 7 (comparison cell) (two-dot dash line), cell 10 (dash dot line), cell 9 (dashed line), and cell 11 (comparison cell) (solid line) recorded at a scan rate of 0.067 mV / s between 2.5 V and 5 V vs. V. Figure 19 shows the results obtained during the first cycle.

[0343] Several modifications can be made to any of the above embodiments without departing from the intended scope of the invention. All references, patents or scientific literature mentioned in this document are incorporated herein by reference in their entirety for all purposes.

Claims

1. at least one compound of Formula 1 containing at least two functional groups and a metal bis(halosulfonyl)imide of Formula 2: 【Chemistry 75】 [In the formula, A is a linear or branched C １ ~C １０ Alkylene, linear or branched C １ ~C １０ Alkyleneoxy C １ ~C １０ Alkylene, linear or branched poly(C １ ~C １０ alkyleneoxy)C １ ~C １０ a substituted or unsubstituted organic group selected from alkylene, linear or branched polyethers and linear or branched polyesters; X １ and X ２ is a functional group selected independently and at each occurrence from a hydroxyl group, a thiol group, and an amine group; X ３ and X ４ are halogen atoms independently selected from F, Cl, Br and I; M ｎ＋ is Na ＋ , K. ＋ , Li ＋ , Ca ２＋ and Mg ２＋ ions, and 1. An ionic polymer comprising at least one repeat unit comprising the reaction product between:

2. X ３ and X ４ and are both chlorine atoms.

3. M ｎ＋ But Na ＋ , K. ＋ and Li ＋ 3. The ionic polymer of claim 1, wherein the ionic polymer is an alkali metal ion selected from the group consisting of ions.

4. M ｎ＋ Li ＋ 4. The ionic polymer of claim 3, wherein:

5. X １ and X ２ and are both hydroxyl groups.

6. 6. The ionic polymer of claim 5, wherein the compound of Formula 1 is selected from glycerol, alkanediols, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,2-pentanediol, ethohexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol, polycaprolactone diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and combinations of at least two thereof.

7. 7. The ionic polymer of claim 6, wherein the compound of Formula 1 is a glycol.

8. 7. The ionic polymer of claim 6, wherein the compound of Formula 1 is glycerol.

9. The compound of formula 1 may be an alkanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,2-propanediamine, 1,2-butanediamine, 2,3-butanediamine, 1,3-butanediamine, 1,2-pentanediamine, 2,4-diamino-2-methylpentane, ethylenediamine, 1,8-diamino-3,6-dioxaoctane, 1, 5. The ionic polymer according to claim 1, which is selected from 11-diamino-3,6,9-trioxaundecane, 4,9-dioxa-1,12-dodecanediamine, 1,14-diamino-3,6,9,12-tetraoxatetradecane, poly(ethylene glycol) diamine, the D, ED or EDR series products sold under the trade name JEFFAMINE®, and combinations of at least two thereof.

10. 10. The ionic polymer of claim 9, wherein the compound of formula 1 is a JEFFAMINE® D series product selected from JEFFAMINE® ED-600, ED-900, and ED-2003.

11. The compound of formula 1 is represented by formula H ２ NCH ２ CH ２ (OCH ２ CH ２ ) ｎ NH ２ 10. The ionic polymer of claim 9, which is a poly(ethylene glycol) diamine of the formula: wherein n is 1 or 2.

12. A is an optionally substituted linear or branched C １ ~C １０ alkylene, and the compound of formula 1 is of formula 3: 【Chemical Formula 76】 [In the formula, X １ and X ２ is as defined in claim 1, R １ and R ２ represents a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a halogen atom selected from F, Cl, Br and I, and C １ ~C １０ Alkyl, C １ ~C １０ Alkyl-acrylate, C １ ~C １０ Alkyl-methacrylate, oxycarbonyl-C １ ~C １０ Alkyl-methacrylate, oxycarbonyl-C １ ~C １０ Alkyl-acrylate, aminocarbonyl-C １ ~C １０ Alkyl-methacrylate, aminocarbonyl-C １ ~C １０ Alkyl-acrylate, oxycarbonylamino-C １ ~C １０ Alkyl-methacrylate and oxycarbonylamino-C １ ~C １０ independently and at each occurrence selected from linear or branched substituents selected from alkyl-acrylates; and l is a number ranging from 1 to 10.

5. The ionic polymer according to claim 1, which is a compound of the formula:

13. X １ and X ２ and are both hydroxyl groups.

14. R １ and R ２ is a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a fluorine atom, and C １ ~C １０ Alkyl, C １ ~C １０ Alkyl-acrylate, C １ ~C １０ Alkyl-methacrylate, oxycarbonylamino-C １ ~C １０ Alkyl-methacrylate and oxycarbonylamino-C １ ~C １０ 14. Ionic polymer according to claim 12 or 13, selected independently and at each occurrence from linear or branched substituents selected from alkyl-acrylates.

15. A is a linear or branched optionally substituted poly(C １ ~C １０ alkyleneoxy)C １ ~C １０ alkylene, and the compound of formula 1 is of formula 4: 【Chemical 77】 [In the formula, X １ and X ２ is as defined in claim 1, m is a number ranging from 1 to 68.

5. The ionic polymer according to claim 1, which is a compound of the formula:

16. X １ and X ２ and are both hydroxyl groups.

17. 17. The ionic polymer according to claim 15 or 16, wherein m is a number in the range of 1 to 10.

18. A is a linear or branched optionally substituted polyether, and the compound of formula 1 is a compound of formula 5: 【Chemical 78】 [In the formula, X １ and X ２ is as defined in claim 1, R ３ , R ４ and R ５ is C １ ~C １０ independently and at each occurrence selected from alkyl groups, n, o, and p are selected so that the number average molecular weight of the polyether is between about 220 g / mol and about 2,000 g / mol, inclusive; n and p are selected so that their sum (n+p) is in the range of about 1 to about 6; and o is a number ranging from about 2 to about 39.

5. The ionic polymer according to claim 1, wherein the compound is

19. R ３ , R ４ and R ５ 19. The ionic polymer of claim 18, wherein is a methyl group.

20. X １ and X ２ and are both amine groups.

21. A is an optionally substituted aliphatic polyester, such as polycaprolactone, and the compound of Formula 1 is a compound of Formula 7: 【Chemical Formula 79】 [In the formula, t and u are numbers ranging from 1 to 10.

5. The ionic polymer according to claim 1, which is a compound of the formula:

22. The ionic polymer comprises at least one repeat unit of Formula 8(a) or is a polymer of Formula 8(b): 【Chemistry 80】 [In the formula, A is a linear or branched C １ ~C １０ Alkylene, linear or branched C １ ~C １０ Alkyleneoxy C １ ~C １０ Alkylene, linear or branched poly(C １ ~C １０ alkyleneoxy)C １ ~C １０ are substituted or unsubstituted organic groups selected independently and at each occurrence from alkylene, linear or branched polyethers and linear or branched polyesters; X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an NH group; R ６ represents a hydroxyl group, a thiol group, an amine group, and R ７ -X ５ -A-X ６ - is selected from the group R ７ is acrylate, methacrylate, C １ ~C １０ Alkyl-acrylate, C １ ~C １０ Alkyl-methacrylate, carbonyl-C １ ~C １０ Alkyl-methacrylate carbonyl-C １ ~C １０ Alkyl-acrylate, carbonyloxy-C １ ~C １０ Alkyl-methacrylate, carbonyloxy-C １ ~C １０ Alkyl-acrylate, carbonylamino-C １ ~C １０ Alkyl-methacrylate and carbonylamino-C １ ~C １０ is a crosslinkable group independently selected at each occurrence from alkyl-acrylate; M ｎ＋ is Na ＋ , K. ＋ , Li ＋ , Ca ２＋ and Mg ２＋ ions, v is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive. The ionic polymer of claim 1 .

23. M ｎ＋ But Na ＋ , K. ＋ and Li ＋ 23. The ionic polymer of claim 22, wherein the ionic polymer is an alkali metal ion selected from the group consisting of ions.

24. M ｎ＋ Li ＋ 24. The ionic polymer of claim 22 or 23, wherein

25. X ５ and X ６ and are both oxygen atoms.

26. X ５ and X ６ and are both sulfur atoms.

27. X ５ and X ６ and are both NH groups.

28. 28. The ionic polymer of any one of claims 22 to 27, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

29. The ionic polymer is represented by Formula 9: 【Chemistry 81】 [In the formula, M ｎ＋ is Na ＋ , K. ＋ , Li ＋ , Ca ２＋ and Mg ２＋ ions, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an NH group; R １ and R ２ represents a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a halogen atom selected from F, Cl, Br and I, and C １ ~C １０ Alkyl, C １ ~C １０ Alkyl-acrylate, C １ ~C １０ Alkyl-methacrylate, oxycarbonyl-C １ ~C １０ Alkyl-methacrylate, oxycarbonyl-C １ ~C １０ Alkyl-acrylate, aminocarbonyl-C １ ~C １０ Alkyl-methacrylate, aminocarbonyl-C １ ~C １０ Alkyl-acrylate, oxycarbonylamino-C １ ~C １０ Alkyl-methacrylate and oxycarbonylamino-C １ ~C １０ independently and at each occurrence selected from linear or branched substituents selected from alkyl-acrylates; l is a number ranging from 1 to 10; and w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one repeat unit of:

30. M ｎ＋ But Na ＋ , K. ＋ and Li ＋ 30. The ionic polymer of claim 29, wherein the ionic polymer is an alkali metal ion selected from the group consisting of ions.

31. M ｎ＋ Li ＋ 31. The ionic polymer of claim 29 or 30, wherein:

32. R １ and R ２ is a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a fluorine atom, and C １ ~C １０ Alkyl, C １ ~C １０ Alkyl-acrylate, C １ ~C １０ Alkyl-methacrylate, oxycarbonylamino-C １ ~C １０ Alkyl-methacrylate and oxycarbonylamino-C １ ~C １０ 32. An ionic polymer according to any one of claims 29 to 31, wherein the linear or branched substituents are independently and at each occurrence selected from alkyl-acrylates.

33. X ５ and X ６ and are both oxygen atoms.

34. X ５ and X ６ and are both sulfur atoms.

35. X ５ and X ６ and are both NH groups.

36. 36. The ionic polymer of any one of claims 29 to 35, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

37. The ionic polymer has Formula 10: 【Chemistry 82】 [In the formula, M ｎ＋ is Na ＋ , K. ＋ , Li ＋ , Ca ２＋ and Mg ２＋ ions, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an —NH group; m is a number ranging from 1 to 68; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one repeat unit of:

38. M ｎ＋ But Na ＋ , K. ＋ and Li ＋ 38. The ionic polymer of claim 37, wherein the ionic polymer is an alkali metal ion selected from the group consisting of ions.

39. M ｎ＋ Li ＋ 39. The ionic polymer of claim 37 or 38, wherein:

40. X ５ and X ６ and are both oxygen atoms.

41. X ５ and X ６ and are both sulfur atoms.

42. X ５ and X ６ and are both NH groups.

43. 43. The ionic polymer of any one of claims 37 to 42, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

44. The ionic polymer has the formula 11: 【Chemistry 83】 [In the formula, M ｎ＋ is Na ＋ , K. ＋ , Li ＋ , Ca ２＋ and Mg ２＋ ions, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an —NH group; R ３ , R ４ and R ５ is C １ ~C １０ independently and at each occurrence selected from alkyl groups, n and p are selected so that their sum (n+p) is in the range of from about 1 to about 6; o is a number ranging from about 2 to about 39; and y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one repeat unit of:

45. M ｎ＋ But Na ＋ , K. ＋ and Li ＋ 45. The ionic polymer of claim 44, wherein the ionic polymer is an alkali metal ion selected from the group consisting of ions.

46. M ｎ＋ Li ＋ 46. The ionic polymer of claim 44 or 45, wherein:

47. R ３ , R ４ and R ５ 47. The ionic polymer of any one of claims 44 to 46, wherein is a methyl group.

48. X ５ and X ６ and are both oxygen atoms.

49. X ５ and X ６ and are both sulfur atoms.

50. X ５ and X ６ and are both —NH groups.

51. 51. The ionic polymer of any one of claims 44 to 50, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

52. The ionic polymer has Formula 12: 【Chemistry 84】 [In the formula, M ｎ＋ is Na ＋ , K. ＋ , Li ＋ , Ca ２＋ and Mg ２＋ ions, t and u are numbers ranging from 1 to 10; z is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one repeat unit of:

53. M ｎ＋ But Na ＋ , K. ＋ and Li ＋ 53. The ionic polymer of claim 52, wherein the ionic polymer is an alkali metal ion selected from the group consisting of ions.

54. M ｎ＋ Li ＋ 54. The ionic polymer of claim 52 or 53, wherein:

55. 55. The ionic polymer of any one of claims 52 to 54, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

56. The ionic polymer has the formula 13: 【Chemistry 85】 [In the formula, x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

57. 57. The ionic polymer of claim 56, wherein the number average molecular weight of the ionic polymer is from about 8,000 g / mol to about 60,000 g / mol, inclusive.

58. The ionic polymer has Formula 14: 【Chemistry 86】 [In the formula, x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

59. 59. The ionic polymer of claim 58, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

60. The ionic polymer has the formula 15: 【Hua 87】 [In the formula, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

61. X ５ and X ６ and are both oxygen atoms.

62. X ５ and X ６ and are both sulfur atoms.

63. X ５ and X ６ and are both NH groups.

64. 64. The ionic polymer of any one of claims 60 to 63, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

65. The ionic polymer is represented by Formula 16: 【Hua 88】 [In the formula, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an —NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

66. X ５ and X ６ and are both oxygen atoms.

67. X ５ and X ６ and are both sulfur atoms.

68. X ５ and X ６ and are both —NH groups.

69. 69. The ionic polymer of any one of claims 65 to 68, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

70. The ionic polymer is represented by Formula 17: 【Chemistry 89】 [In the formula, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an —NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

71. X ５ and X ６ and are both oxygen atoms.

72. X ５ and X ６ and are both sulfur atoms.

73. X ５ and X ６ and are both —NH groups.

74. 74. The ionic polymer of any one of claims 70 to 73, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

75. The ionic polymer is represented by Formula 18: 【Chemistry 90】 [In the formula, X ５ and X ６ are each independently selected from an oxygen atom, a sulfur atom, and an —NH group; x is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

76. X ５ and X ６ and are both oxygen atoms.

77. X ５ and X ６ and are both sulfur atoms.

78. X ５ and X ６ and are both —NH groups.

79. 79. The ionic polymer of any one of claims 75 to 78, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

80. The ionic polymer has the formula 19: 【Chemistry 91】 [In the formula, and w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

81. 81. The ionic polymer of claim 80, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

82. The ionic polymer has Formula 20: 【Chemistry 92】 [In the formula, and w is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

83. 83. The ionic polymer of claim 82, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

84. The ionic polymer has the formula 21: 【Chemistry 93】 [In the formula, n and p are selected so that their sum (n+p) is in the range of from about 1 to about 6; o is a number ranging from about 2 to about 39; and y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

85. 85. The ionic polymer of claim 84, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

86. The ionic polymer is represented by Formula 22: 【Chemistry 94】 [In the formula, n and p are selected so that their sum (n+p) is in the range of from about 1 to about 6; o is a number ranging from about 2 to about 39; and y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

87. 87. The ionic polymer of claim 86, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

88. The ionic polymer has the formula 23: 【Chemistry 95】 [In the formula, n and p are selected so that their sum (n+p) is in the range of from about 1 to about 6; o is a number ranging from about 2 to about 39; and y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

89. 89. The ionic polymer of claim 88, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

90. The ionic polymer is represented by Formula 24: 【Chemistry 96】 [In the formula, n and p are selected so that their sum (n+p) is in the range of from about 1 to about 6; o is a number ranging from about 2 to about 39; and y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

91. 91. The ionic polymer of claim 90, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

92. The ionic polymer has Formula 25: 【Chemistry 97】 [In the formula, n and p are selected so that their sum (n+p) is in the range of from about 1 to about 6; o is a number ranging from about 2 to about 39; and y is a number selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

93. 93. The ionic polymer of claim 92, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

94. The ionic polymer is represented by Formula 26: 【Chemistry 98】 [In the formula, w and x are numbers selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

95. 95. The ionic polymer of claim 94, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

96. The ionic polymer is represented by Formula 27: 【Hua99】 [In the formula, w and x are numbers selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

97. 97. The ionic polymer of claim 96, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

98. The ionic polymer is represented by Formula 28: 【Chemistry 100】 [In the formula, w and x are numbers selected so that the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 150,000 g / mol, inclusive.

10. The ionic polymer of claim 1, comprising at least one fragment of:

99. 99. The ionic polymer of claim 98, wherein the number average molecular weight of the ionic polymer is between about 8,000 g / mol and about 60,000 g / mol, inclusive.

100. 100. A polymer composition comprising at least one ionic polymer according to any one of claims 1 to 99.

101. 101. The polymer composition of claim 100, wherein the polymer composition further comprises at least one additional component or additive.

102. 102. The polymer composition of claim 101, wherein the additional components or additives are selected from ion conductors, inorganic particles, glass particles, ceramic particles, and combinations of at least two thereof.

103. 103. The polymer composition of claim 101 or 102, wherein the additional component or additive is a filler additive.

104. The filler additive is titanium dioxide (TiO ２ ), alumina (Al ２ O ３ ) and silicon dioxide (SiO ２ 104. The polymer composition of claim 103, wherein the polymer composition is selected from the group consisting of nanoparticles and nanoparticles.

105. 105. The polymer composition of any one of claims 100 to 104, wherein the polymer composition is a solid polymer electrolyte composition.

106. 105. The polymer composition of any one of claims 100 to 104, wherein the polymer composition is a binder for an electrode material.

107. 105. The polymer composition of any one of claims 100 to 104, wherein the polymer composition is used in an electrochemical cell.

108. 105. The polymer composition of any one of claims 100 to 104, wherein the polymer composition is used in a supercapacitor.

109. 109. The polymer composition of claim 108, wherein the supercapacitor is a carbon-carbon supercapacitor.

110. 105. The polymer composition of any one of claims 100 to 104, wherein the polymer composition is used in an electrochromic material.

111. 105. A solid polymer electrolyte composition comprising an ionic polymer according to any one of claims 1 to 99 or a polymer composition according to any one of claims 100 to 104.

112. 112. The solid polymer electrolyte composition of claim 111, wherein the solid polymer electrolyte composition further comprises at least one salt.

113. 113. The solid polymer electrolyte composition of claim 112, wherein the salt is an ionic salt.

114. 114. The solid polymer electrolyte composition of claim 113, wherein the ionic salt is selected from lithium, sodium, potassium, calcium and magnesium salts.

115. 115. The solid polymer electrolyte composition of claim 114, wherein the ionic salt is a lithium salt.

116. The lithium salt is lithium hexafluorophosphate (LiPF ６ ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF ４ ), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO ３ ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO ４ ), lithium hexafluoroarsenate (LiAsF ６ ), lithium trifluoromethanesulfonate (LiSO ３ CF ３ ) (LiTf), lithium fluoroalkyl phosphate Li[PF ３ (CF ２ CF ３ ) ３ ] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF ３ ) ４ ] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C ６ O ２ ) ２ ] (LiBBB), and combinations of at least two thereof.

117. 117. The solid polymer electrolyte composition of any one of claims 111 to 116, wherein the solid polymer electrolyte composition further comprises at least one additional component or additive.

118. 118. The solid polymer electrolyte composition of claim 117, wherein said additional components or additives are selected from ion-conducting materials, inorganic particles, glass particles, ceramic particles, and combinations of at least two thereof.

119. 119. A solid polymer electrolyte comprising an ionic polymer of any one of claims 1 to 99 or a solid polymer electrolyte composition of any one of claims 111 to 118, wherein the ionic polymer is optionally crosslinked.

120. 107. An electrode material comprising an electrochemically active material and an ionic polymer according to any one of claims 1 to 99 or a polymer composition according to any one of claims 100 to 104.

121. 121. The electrode material of claim 120, wherein the polymer or polymer composition is a binder.

122. 122. An electrode material according to claim 120 or 121, wherein the electrochemically active material is in the form of particles.

123. 123. The electrode material of any one of claims 120 to 122, wherein the electrochemically active material is selected from metal oxides, lithium metal oxides, metal phosphates, lithiated metal phosphates, titanates, and lithium titanate.

124. The metal of the electrochemically active material is titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), 124. The electrode material of claim 123, selected from aluminum (Al) and a combination of at least two thereof.

125. 125. The electrode material of any one of claims 120 to 124, wherein the electrode material further comprises at least one electronically conductive material.

126. 126. The electrode material of claim 125, wherein the electronically conductive material is selected from carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and combinations of at least two thereof.

127. 127. The electrode material of claim 126, wherein the electronically conductive material is acetylene black.

128. 128. The electrode material of any one of claims 120 to 127, wherein the electrode material further comprises at least one additional component or additive.

129. 129. The electrode material of claim 128, wherein the additional components or additives are selected from ionic conductors, inorganic particles, glass or ceramic particles, nanoceramics, and salts.

130. The additional component or additive is Al ２ O ３ , TiO ２ and SiO ２ 130. The electrode material of claim 128 or 129, selected from:

131. 131. The electrode material of any one of claims 120 to 130, wherein the electrode material is a positive electrode material.

132. 131. The electrode material of any one of claims 120 to 130, wherein the electrode material is a negative electrode material.

133. 133. The electrode material of claim 132, wherein the electrochemically active material is lithium titanate.

134. 134. The electrode material of claim 133, wherein the lithium titanate is carbon coated lithium titanate.

135. 135. An electrode comprising the electrode material of any one of claims 120 to 134 on a current collector.

136. 107. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode, the positive electrode, and the electrolyte comprises an ionic polymer according to any of claims 1 to 99 or a polymer composition according to any of claims 100 to 104.

137. 136. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode and the positive electrode is as described in claim 135.

138. 120. An electrochemical cell comprising a negative electrode, a positive electrode and the solid polymer electrolyte of claim 119.

139. 139. An electrochemical accumulator comprising at least one electrochemical cell according to any one of claims 136 to 138.

140. The electrochemical accumulator is selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, and a magnesium-ion battery.

140. The electrochemical accumulator of claim 139, wherein the battery is selected from the group consisting of:

141. 141. The electrochemical accumulator of claim 140, wherein the battery is a lithium battery or a lithium-ion battery.

142. 104. A method for preparing an ionic polymer according to any one of claims 1 to 99 or a polymer composition according to any one of claims 100 to 104, comprising the steps of: (i) preparing a metal bis(halosulfonyl)imide of formula 2; and (ii) reacting at least one compound of Formula 1 with said metal bis(halosulfonyl)imide of Formula 2 A method comprising:

143. 143. The method of claim 142, wherein the method further comprises preparing a bis(halosulfonyl)imide.

144. 144. The method of claim 143, wherein the step of preparing a bis(halosulfonyl)imide is carried out by a reaction between a sulfamic acid and a halosulfonic acid in the presence of at least one halogenating agent.

145. 145. The method of claim 144, wherein the halogenating agent is selected from phosphorus trichloride, phosphorus pentachloride, thionyl chloride, thionyl fluoride, phosphorus oxychloride and oxalyl chloride.

146. 146. The method of claim 144 or 145, wherein the halogenating agent is thionyl chloride.

147. 147. The method of any one of claims 144 to 146, wherein the halosulfonic acid is chlorosulfonic acid.

148. 148. The method of any one of claims 143 to 147, wherein the step of preparing a bis(halosulfonyl)imide is carried out at a temperature in the range of from about 60°C to about 150°C, or from about 70°C to about 145°C, or from about 80°C to about 140°C, or from about 90°C to about 100°C, or from about 110°C to about 140°C, or from about 120°C to about 140°C, or from about 125°C to about 140°C, or from about 125°C to about 135°C, inclusive.

149. 149. The method of any one of claims 143 to 148, wherein the step of preparing a bis(halosulfonyl)imide is carried out at a temperature of about 130°C for about 24 hours.

150. 150. The method of any one of claims 143 to 149, wherein the bis(halosulfonyl)imide is a bis(chlorosulfonyl)imide.

151. 151. The method of any one of claims 142 to 150, wherein the step of preparing a metal bis(halosulfonyl)imide is carried out by a metalation reaction between a bis(halosulfonyl)imide and at least one metalating agent, optionally in the presence of a solvent.

152. 152. The method of claim 151, wherein the metallation agent comprises an alkali metal selected from lithium, sodium, potassium, calcium, and magnesium.

153. 153. The method of claim 152, wherein the metallation agent comprises an alkali metal selected from lithium, sodium, and potassium.

154. 154. The method of claim 153, wherein the metallation agent is a lithiation agent.

155. The lithiation agent is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium hydride, lithium chloride, lithium bromide, lithium iodide, and compounds of the formula RCO ２ Li (wherein R is a linear or branched C １ ~C １０ 155. The method of claim 154, wherein the alkyl group is selected from the group consisting of a lithium carboxylate, a lithium oxalate, and metallic lithium.

156. 156. The method of claim 154 or 155, wherein the lithiation agent is lithium chloride (LiCl).

157. 157. The method of any one of claims 151 to 156, wherein the solvent is selected from N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, carbon tetrachloride, chloroform, acetonitrile, tetrahydrofuran, and miscible combinations of at least two thereof.

158. 158. The method of claim 157, wherein the solvent is N,N-dimethylformamide.

159. 159. The method of any one of claims 142 to 158, wherein the step of preparing a metal bis(halosulfonyl)imide is conducted at a temperature in the range of from about 20°C to about 150°C, or from about 30°C to about 135°C, or from about 40°C to about 130°C, or from about 50°C to about 125°C, or from about 60°C to about 120°C, or from about 70°C to about 115°C, or from about 80°C to about 110°C, or from about 90°C to about 105°C, inclusive of the upper and lower limits.

160. 159. The method of any one of claims 142 to 158, wherein the step of preparing a metal bis(halosulfonyl)imide is carried out at a temperature of about 100°C.

161. 160. The method of any one of claims 142 to 159, wherein the step of preparing a metal bis(halosulfonyl)imide is carried out for a period ranging from about 10 hours to about 48 hours, or from about 10 hours to about 24 hours, or from about 12 hours to about 24 hours, inclusive.

162. 162. The method of claim 161, wherein the step of preparing a metal bis(halosulfonyl)imide is carried out for a period ranging from about 12 hours to about 24 hours, inclusive.

163. 163. The method of any one of claims 142 to 162, wherein the step of reacting at least one compound of Formula 1 with the metal bis(halosulfonyl)imide of Formula 2 is a polymerization step.

164. 164. The method of claim 163, wherein the polymerization is carried out by polycondensation.

165. 164. The method of claim 163, wherein the polymerization is carried out by polyesterification.

166. 166. The method of claim 165, wherein the polyesterification is carried out by a Fischer esterification reaction.

167. 166. The method of claim 165, wherein the polyesterification is carried out by a Steglich esterification reaction.

168. 168. Any one of claims 142 to 167, wherein the step of reacting at least one compound of formula 1 with the metal bis(halosulfonyl)imide of formula 2 is carried out in the presence of a solvent. The method described in paragraph .

169. 169. The method of claim 168, wherein the solvent is selected from N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, carbon tetrachloride, chloroform, acetonitrile, tetrahydrofuran, and miscible combinations of at least two thereof.

170. 170. The method of claim 169, wherein the solvent is N,N-dimethylformamide.

171. 171. The method of any one of claims 163 to 170, wherein the polymerizing step is carried out in the presence of at least one base, and optionally at least one polymerization catalyst, and / or at least one co-catalyst, and / or optionally at least one acylation catalyst.

172. 172. The method of claim 171, wherein the polymerization catalyst is selected from the group consisting of acidic catalysts, nucleophilic catalysts, and boron-based catalysts.

173. 173. The method of claim 172, wherein the acidic catalyst is a Lewis acid catalyst.

174. 173. The method of claim 172, wherein the nucleophilic catalyst is selected from the group consisting of 4-dimethylaminopyridine, pyridine, and other pyridine derivatives.

175. 175. The method of claim 174, wherein the nucleophilic catalyst is 4-dimethylaminopyridine.

176. 173. The method of claim 172, wherein the boron-based catalyst is a boric acid-based catalyst, a boronic acid-based catalyst, or a borinic acid-based catalyst.

177. The polymerization catalyst is a compound of formula Ar ２ 173. The method of claim 172, wherein the boronic acid is selected from diarylboronic acids of 9H-9-bora-10-thiaanthracen-9-ol, 10H-phenoxaborinin-10-ol, boron tribromide, boron trichloride, acylfluoroborates, triethyloxonium fluoroborate, boron trifluoride etherate, boron trifluoride, tris(pentafluorophenyl)borane, and, where compatible, combinations of at least two thereof.

178. 178. The method of any one of claims 163 to 177, wherein the base is selected from the group consisting of triethylamine, N,N-diisopropylethylamine, pyridine and pyridine derivatives.

179. 179. The method of claim 178, wherein the base is triethylamine.

180. 179. The method of any one of claims 142 to 179, wherein the method further comprises a post-functionalization step or a post-polymerization modification step.

181. 181. The method of claim 180, wherein the post-functionalization step or the post-polymerization modification step is carried out to introduce at least one crosslinkable functional group.

182. The method of claim 181, wherein the post-functionalization step or the post-polymerization modification step is carried out by reacting at least one functional group with at least one precursor of a crosslinkable functional group.

183. The crosslinkable functional group is an acrylate, a methacrylate, a C １ ~C １０ Alkyl-acrylate, C １ ~C １０ Alkyl-methacrylate, oxycarbonyl-C １ ~C １０ Alkyl-methacrylate, oxycarbonyl-C １ ~C １０ Alkyl-acrylate, aminocarbonyl-C １ ~C １０ Alkyl-methacrylate aminocarbonyl-C １ ~C １０ Alkyl-acrylate, oxycarbonylamino-C １ ~C １０ Alkyl-methacrylate, oxycarbonylamino-C １ ~C １０ Alkyl-acrylate, carbonyloxy-C １ ~C １０ Alkyl-methacrylate, carbonyloxy-C １ ~C １０ Alkyl-acrylate, carbonylamino-C １ ~C １０ Alkyl-methacrylate and carbonylamino-C １ ~C １０ 183. The method of claim 181 or 182, wherein the alkyl acrylate is selected from alkyl acrylates.

184. 184. The method of any one of claims 142 to 183, wherein the method further comprises a separation or purification step.

185. 185. The method of claim 184, wherein the separation or purification step is carried out by liquid chromatography or filtration.

186. 186. The method of claim 185, wherein the liquid chromatography method is steric exclusion chromatography.

187. 186. The method of claim 185, wherein the filtration method is a membrane filtration method.

188. 188. The method of claim 187, wherein the membrane filtration method is membrane nanofiltration or membrane ultrafiltration.

189. The method of claim 188, wherein the membrane filtration method is membrane ultrafiltration method.

190. 190. The method of claim 189, wherein the membrane has a molecular weight cutoff limit of 1,000 DA.

191. 191. The method of any one of claims 142 to 190, wherein the method further comprises coating the polymer composition.

192. 192. The method of claim 191, wherein the coating step is performed by at least one method selected from doctor blade coating, comma coating, reverse-comma coating, printing, gravure coating, and slot die coating.

193. 193. The method of claim 192, wherein the coating step is carried out by at least one method selected from a doctor blade coating method and a slot die coating method.

194. 194. The method of any one of claims 142 to 193, wherein the method further comprises drying the polymer composition to remove any residual solvent and / or water.

195. 195. The method of claim 194, wherein the steps of drying the polymer composition and coating the polymer composition are performed simultaneously.

196. 196. The method of any one of claims 142 to 195, wherein the method further comprises a cross-linking step.

197. 197. The method of claim 196, wherein the crosslinking step is carried out by UV irradiation, by heat treatment, by microwave irradiation, under electron beam irradiation, by gamma ray irradiation, or by X-ray irradiation.

198. 200. The method of claim 197, wherein the crosslinking step is carried out by UV irradiation, heat treatment, or under electron beam irradiation.

199. 200. The method of any one of claims 196 to 198, wherein the crosslinking step is carried out in the presence of at least one of a crosslinking agent, a thermal initiator, a photoinitiator, a catalyst, a plasticizer, or a combination of at least two thereof.

200. 200. The method of claim 199, wherein the cross-linking agent is 2,2-dimethoxy-2-phenylacetophenone (Irgacure™ 651).

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