Polyarylene polymer

Abstract

A method for converting a polyarylene polymer containing sulfonic acid ester functional groups into a polyarylene polymer containing sulfonic acid functional groups, the method comprising a heat treatment step.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority under U.S. Provisional Patent Application No. 63 / 460374 filed on 19 April 2023 and European Patent Application Publication No. 23187892.7 filed on 26 July 2023, the entire contents of each of these applications being incorporated herein by reference for any purpose.

[0002] The present invention relates to a method for preparing a polyarylene polymer having a sulfonic acid functional group from a polyarylene polymer having a sulfonic acid functional group. [Background technology]

[0003] The use of polymer electrolyte materials as ion-conducting materials in electrochemical devices is well known. Proton-conducting polymers, i.e., polymer electrolytes, are used as membranes in electrolytic cells, redox flow batteries, and fuel cells. For example, perfluoroalkyl sulfonic acid polymers have been used as membrane materials for fuel cells for several decades.

[0004] Polyarylene polymer electrolytes containing sulfonic acid functional groups are also known. Polyarylene polymers containing sulfonic acid functional groups can be obtained starting from monomers containing sulfonic acid esters or sulfonamide functional groups.

[0005] European Patent Application Publication No. 1935916A1 discloses a polymer comprising repeating units of the following formula: [ka] (In the formula, A represents an amino group substituted with one or two hydrocarbon groups (the total number of carbon atoms of the hydrocarbon groups is 3 to 20), or a C3-C20 alkoxy group; R1 represents a hydrogen atom, a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group; the C1-C20 alkyl group, the C1-C20 alkoxy group, the C6-C20 aryl group, the C6-C20 aryloxy group, and the C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and a C6-C20 aryloxy group; when there are a plurality of R 1 s, R 1 s may be the same group or different groups; two adjacent R 1 s may be bonded to form a ring; m represents 1 or 2; k represents 4 - m; and these are obtained from the corresponding halides).

[0006] U.S. Patent Application Publication No. 2014 / 0154610A1 discloses an aromatic copolymer containing a hydrophilic segment (A) and a hydrophobic segment (B). Here, the hydrophilic segment (A) contains a structural unit having a proton-conductive group, and the hydrophobic segment (B) contains at least one structural unit selected from the group consisting of divalent structural units. This divalent structural unit has an aromatic ring, does not have a proton-conductive group, has two bonding sites at the para-position of one ring contained in the aromatic ring, and has a benzene ring. Notable examples of the structural unit having a proton-conductive group are, for example, the following: [Chemical formula] (In the formula, Ar 11 , Ar 12 , and Ar 13is, independently, an aromatic group having a benzene ring, a condensed aromatic ring, or a nitrogen-containing heterocyclic ring, which may be substituted with a halogen atom, a C1-20 monovalent hydrocarbon group, or a C1-20 monovalent halogenated hydrocarbon group, Y and Z are, independently, a direct bond, -O-, -S-, -CO-, -SO2-, -SO-, -(CH2) u -, -(CF2) u -(u is an integer from 1 to 10), -C(CH3)2-, or -C(CF3)2-, and R 17 is, independently, a direct bond, -O(CH2) p -, -O(CF2) p -, -(CH2) p -, or -(CF2) p -(p is an integer from 1 to 12), and R 18 and R 19 are, independently, a hydrogen atom or a protecting group, and at least one of all the R 18 and R 19 contained in the structural unit (1) is a hydrogen atom, x1 is independently an integer from 0 to 6, x 2 is an integer from 1 to 7, a is 0 or 1, and b is an integer from 0 to 20).

[0007] International Publication No. WO 2014 / 208714 A1 discloses a polyarylene polymer containing a repeating unit of the following formula:

Chemical formula

[0008] According to prior art disclosures, the conversion of sulfonic acid ester groups or sulfonamide groups to sulfonic acid functional groups is achieved by either hydrolysis in an acidic or alkaline environment, or by reaction with an alkali metal halide followed by ion exchange with an acid. This conversion is usually carried out before forming polyarylene polymers into articles such as films or membranes.

[0009] Surprisingly, it was discovered that the conversion from sulfonic acid ester functional groups to sulfonic acid functional groups can be successfully achieved by heat treatment of polyarylene polymers, without chemical treatments such as hydrolysis using acids or alkalis or reactions with alkali halides.

[0010] Therefore, the object of the present invention is formula (A) defined below: [ka] A method for converting sulfonic acid ester groups in a polyarylene polymer containing repeating units to sulfonic acid groups, comprising heating the polyarylene polymer to a temperature of 100°C to 200°C. This conversion is achieved by heat treatment without chemical treatments such as hydrolysis with acids or alkalis or reactions with alkali halides. [Overview of the Initiative]

[0011] The first object of the present invention is formula (A) defined below: [ka] A method for converting sulfonic acid ester groups in a polyarylene polymer containing repeating units to sulfonic acid groups, comprising heating the polyarylene polymer to a temperature of 100°C to 200°C. This conversion is achieved by heat treatment without chemical treatments such as hydrolysis with acids or alkalis or reactions with alkali halides.

[0012] The present invention further relates to films containing a polyarylene polymer containing repeating units of formula (A), and to methods for manufacturing these films and further processing them to form ion exchange membranes. [Modes for carrying out the invention]

[0013] In this application: - Any description, even if it is described in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; - Where an element or component is to be included in and / or selected from an enumerated list of elements or components, in the relevant embodiments expressly considered herein, the element or component may be any one of the individual enumerated elements or components, or may be selected from any group of two or more of the expressly enumerated elements or components; it should be understood that any element or component enumerated in a list of elements or components may be omitted from such list; - In expressions such as "a recurring unit," the indefinite article "a" is intended to mean "one or more" or "at least one" unless otherwise specified; - The use of parentheses "( )" before and after the names, symbols, or numbers of compounds, such as "polymer (GP)" and "polymer (GPA)," is solely for the purpose of better distinguishing those names, symbols, or numbers from the rest of the text; therefore, such parentheses may be omitted. - Any enumeration of numerical ranges by endpoints in this specification includes all numbers contained within the enumerated range, as well as the endpoints and equivalents of the range; - The proportion of repeating units in the polymer is expressed relative to the total number of moles of repeating units in the polymer; - The expression "weight percent" (weight%) indicates the content of a particular component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture; and as used herein, the concentration of repeating units in "mol percent" (mol%) units refers to the concentration of a given type of repeating unit relative to the total number of repeating units in the polymer, unless otherwise specified; - The term "(Cn~Cm)" used herein for organic groups (where n and m are integers) indicates that the group may contain n to m carbon atoms per group.

[0014] The object of the present invention is formula (A): [ka] (In the formula, R 1 is a C1-C20 alkoxy group which may be optionally substituted, and each R x Each of the following R groups is independently selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group, and the C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, and C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and a C6-C20 aryloxy group, and there may be multiple R groups. x If such a thing exists, then two adjacent R x (These may be joined to form a ring, and p represents 1 or 2.) A method for converting sulfonic acid ester groups to sulfonic acid groups in a polyarylene polymer (hereinafter referred to as [polymer (GP)]) containing repeating units, The method involves heating a polyarylene polymer [polymer (GP)] to a temperature of 100°C to 200°C.

[0015] This conversion is achieved by heat treatment without chemical treatment such as hydrolysis with acids or alkalis, or reaction with alkali halides. The term "chemical treatment" refers to hydrolysis with acids or alkalis, or reaction with alkali halides.

[0016] In equation (A), p is preferably 1.

[0017] C1-C20 alkoxy group R in formula (A) 1 Examples include linear, branched, or cyclic C1-C20 alkoxy groups. Notable examples include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-methylpropoxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, 2-methylpentyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy group. Alkoxy group R 1 The alkoxy group R is preferably isobutoxy, 2,2-dimethylpropoxy, or cyclohexyloxy. 1 It is more preferably 2,2-dimethylpropoxy.

[0018] Each R x These are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group. x It is preferably hydrogen.

[0019] The polymer (GP) may consist of one or more repeating units of formula (A), or it may contain other repeating units.

[0020] It may be advantageous for the polymer (GP) to include not only the repeating unit of formula (A) but also the repeating unit of formula (B): [ka] (In the formula, each R y Each of the following R groups is independently selected from the group consisting of a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group, and each of the C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, and C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and a C6-C20 aryloxy group, and multiple R groups may be substituted. y If such a thing exists, then two adjacent R y The elements may be joined to form a ring, and q is an integer between 1 and 4.

[0021] The polymer (GP) may contain one or more different repeating units of formula (B).

[0022] The polymer (GP) may further contain repeating units of formula (C): [ka] (In the formula, R z1 and R z2Each of the following R groups is independently selected from the group consisting of a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group, and each of the C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, and C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and a C6-C20 aryloxy group, and multiple R groups may be substituted. z1 and R z2 If present, adjacent elements may be bonded together to form a ring, r and s are independent integers from 1 to 4, and Z is selected from the group consisting of oxygen atoms, sulfur atoms, carbonyl groups, sulfonyl groups, 2,2-isopropylidene groups, and 2,2-hexafluoroisopropylidene groups).

[0023] In polymers (GP), the amount of repeating units of formula (A) is 0.1 to 90.0 mol% of the total amount of repeating units in the polymer. The amount of repeating units of formula (A) is typically 5.0 to 70.0 mol%, 10.0 to 65.0 mol%, and even 25.0 to 60.0 mol%, or 35.0 to 55.0 mol%. The remaining units in polymers (GP) may consist of one or more repeating units of formula (B), or one or more repeating units of formulas (B) and (C).

[0024] The bonds linking the repeating units represented by formulas (A) and / or (B) and / or (C) in the polymer (GP) may have ortho, meta, or para configurations. Preferably, they have a meta and / or para configuration.

[0025] The polymer (GP) can be synthesized by known methods, such as those disclosed in European Patent Application Publication No. 1935916A1, U.S. Patent Application Publication No. 20140154610A1, and International Publication Brochure No. 2014208714A1.

[0026] The polymer (GP) can be prepared by polymerizing a dihalo compound (I) that gives structural unit (A), an optional compound (II) that gives structural unit (B), and / or an optional compound (III) that gives structural unit (C): [ka] (In the formula, R x , R 1 , p, R y , q, R z1 and R z2 Z is as defined above, and each X is independently selected from the group consisting of halogens, mesylates, tosylates, or triflates. Preferably, X is chlorine.

[0027] Polymerization is preferably carried out in the presence of a catalyst. Any catalyst for the polymerization of aromatic dihalide compounds can be used.

[0028] Typically, polymers (GP) can be produced by polymerizing a monomer composition comprising compound (I) and optionally (II) and / or (III) in the presence of a nickel compound. Examples of nickel compounds include zero-valent nickel compounds, such as bis(cyclooctadiene)nickel(O), (ethylene)bis(triphenylphosphine)nickel(O), and tetrakis(triphenylphosphine)nickel(O), and divalent nickel compounds, such as nickel halides (e.g., nickel fluoride, nickel chloride, nickel bromide, nickel iodide, etc.), bis(triphenylphosphine)nickel chloride, nickel carboxylates (e.g., nickel formate, nickel acetate, etc.), nickel sulfate, nickel carbonate, nickel nitrate, nickel acetylacetone, and nickel (dimethoxyethane) chloride. Nickel chloride and nickel bromide are preferred.

[0029] The polymerization reaction is preferably carried out in the presence of a nickel compound and a nitrogen-containing or phosphorus-containing ligand. Examples of nitrogen-containing ligands include 1,10-phenanthroline, methylenebisoxazoline, and N,N'-tetramethylethylenediamine. Examples of phosphorus-containing ligands include triphenylphosphine, tri(2-methyl)phenylphosphine, tri(3-methyl)phenylphosphine, tri(4-methyl)phenylphosphine, 1,5-cyclooctadiene, and 1,3-bis(diphenylphosphino)propane. Triphenylphosphine and tri(2-methyl)phenylphosphine are preferred. These ligand compounds may be used individually or in combination of two or more.

[0030] The catalyst system may also include a reducing agent. Examples of reducing agents include iron, zinc, manganese, aluminum, magnesium, sodium, and calcium. Zinc, magnesium, and manganese are preferred. These reducing agents can be made more active by contacting them with an acid such as an organic acid.

[0031] Examples of salts other than transition metal salts that can be used in the catalyst system of the present invention include sodium compounds, such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate; potassium compounds, such as potassium fluoride, potassium chloride, potassium bromide, potassium iodide, and potassium sulfate; and ammonium compounds, such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Among these, sodium bromide, sodium iodide, potassium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferred. These may be used individually or in combination of two or more.

[0032] Polymerization is preferably carried out in the presence of a polymerization solvent. Examples of polymerization solvents include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and γ-butyrolactam. Tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0033] Polymerization reactions can be carried out in an inert gas atmosphere, such as nitrogen gas.

[0034] Polymerization is preferably carried out at a temperature of 0 to 200°C, more preferably 50 to 80°C. The polymerization time is typically 0.5 to 100 hours, preferably 1 to 40 hours.

[0035] After the polymerization reaction is complete, the polymer (GP) can be isolated using known polymer isolation techniques. In one embodiment, the polymer (GP) precipitates by mixing it with the reaction mixture in a solvent in which it is poorly soluble.

[0036] The polymer (GP) precipitated from the reaction mixture is then separated by filtration. In another embodiment, droplets of the reaction mixture are dropped, for example, using a nozzle, into a precipitation bath containing a solvent in which the polymer (GP) is poorly soluble. The formed solid particles are recovered from the bath by decantation, filtration, or other known techniques.

[0037] Examples of solvents in which the polymer (GP) is insoluble or poorly soluble include water, acetone, methanol, ethanol, and acetonitrile. Water and acetone are preferred.

[0038] The precipitated polyarylene polymer can then be washed to remove trace amounts of catalysts and other additives, and subsequently dried.

[0039] The method of the present invention comprises the steps of preparing the polymer (GP) as defined above, and heating the polymer (GP) to a temperature of 100-200°C to form the sulfonic acid ester group -SO2R 1 The process includes a step of converting to a sulfonic acid group -SO3M (where M is H or a monovalent cation, preferably H). This conversion is achieved by heat treatment without chemical treatment such as hydrolysis with acid or alkali or reaction with alkali halides.

[0040] The step of heating the polymer (GP) to a temperature of 100-200°C involves holding the polyarylene polymer at a temperature in the range of 100-200°C for a sufficient time to convert the sulfonic acid ester groups to sulfonic acid groups. This conversion is achieved by heat treatment without chemical treatment. The term "chemical treatment" refers to hydrolysis with an acid or alkali, or reaction with an alkali halide. The heating step is usually carried out for a time of 0.1-20.0 hours, typically 1.0-15.0 hours, and even 1.0-10.0 hours.

[0041] The conversion is complete. 1 This can be determined using conventional analytical methods such as 1H NMR.

[0042] At the end of the process, at least 90%, preferably at least 95%, of the sulfonic acid ester groups are converted to sulfonic acid groups.

[0043] The polymer (GP) may be in powder form. As used herein, the term “powder” refers to an aggregate of solid particles having individual sizes.

[0044] Advantageously, the solid particles of the polymer (GP) have an average diameter in the range of nanometers to millimeters, preferably in the range of microns to millimeters. The average particle size may be in the range of 50 microns to 20 mm, 100 microns to 10 mm, or even 200 microns to 5 mm.

[0045] The particle size can be determined according to any method known in the art. For example, the particle size can be determined by laser diffraction of an isopropanol suspension of the particle aggregate. A MicroTrac S3500 laser diffractometer can be used according to the manufacturer's instructions or known methods.

[0046] The powder can be heated to a temperature of 120-200°C, more preferably 140-160°C.

[0047] Alternatively, the polymer (GP) may be dissolved in a solvent and then subjected to a heat treatment process at a temperature of 100-200°C, preferably 100-160°C. More preferably, the polymer (GP) can be heated in a solution at a temperature of 130-160°C, even more preferably 140-150°C.

[0048] A suitable solvent is a polar organic solvent. Suitable polar organic solvents are selected from the group consisting of, for example, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone.

[0049] Alternatively, the polymer (GP) may be subjected to a heat treatment step at a temperature of 100-200°C, preferably 130-160°C, before being isolated from the reaction mixture at the end of the polymerization process. The heat treatment step is carried out in the absence of acids, alkalis, or alkali halides.

[0050] The polymer (GP) can be molded into the form of a film or other article, which can then be subjected to a heat treatment process at a temperature of 100 to 200°C, preferably 120 to 200°C.

[0051] At the end of the process of converting the sulfonic acid ester groups of polymer (GP) to sulfonic acid groups by heating, a polymer (GPA) containing repeating units of formula (AH) is obtained: [ka] (In the formula, Rx , R 1 , and p are as defined above, and M is H or an alkali metal, preferably H). The polymer (GPA) may optionally contain repeating units of formulas (B) and / or (C) as defined above.

[0052] The polymer (GPA) may be in the form of an alkali metal salt, particularly a sodium salt or a potassium salt. The conversion of sulfonic acid groups in the polymer (PA) to alkali metal sulfonate groups can be carried out by reaction with a suitable alkali metal base such as NaOH or KOH.

[0053] Polymers containing sulfonic acid groups are generally used as ion-exchange polymers. They are also used as proton-conducting polymers.

[0054] The ion exchange capacity of polyarylene polymers can be controlled by changing the type, ratio, and combination of repeating units in the polymer. Ion exchange capacity (IEC) refers to the total number of active sites or functional groups involved in ion exchange in the polymer. In this specification, ion exchange capacity (IEC) is defined as the number of milligram equivalents of ions that can be exchanged per gram of dry resin.

[0055] The molar amounts of the repeating units of formula (A) and optionally the repeating units of formula (2) and / or (3) in the polymer (GP) are selected such that the polyarylene polymer having sulfonic acid groups, i.e., polymer (GPA), has an ion exchange capacity of 1.00 to 5.50 meq / g, preferably 1.50 to 4.50 meq / g, and more preferably 2.20 to 4.00 meq / g.

[0056] Due to its ion exchange capacity, the polymer (GPA) can be conveniently used in the manufacture of proton-conducting membranes for electrolytic cells, redox flow batteries, and fuel cells, as well as solid electrolytes for display elements, various sensors, signal transmission media, and solid capacitors. It can also be used in the manufacture of ion exchange membranes or devices.

[0057] Surprisingly, it was found that polymer (GP) can be molded into film more easily than polymer (GPA). Even more surprisingly, the present invention's method for converting polymer (GP) to polymer (GPA) was conveniently found to be applicable to polymer (GP) after molding, for example, into film.

[0058] Therefore, a further object of the present invention is an article comprising a polymer (GP). Preferably, the article is in the form of a film. The film typically has a thickness of 5 to 300 μm, preferably 10 to 150 μm, and more preferably 15 to 100 μm.

[0059] Another object of the present invention is a method for converting a film containing polymer (GP) into a polymer electrolyte membrane containing polymer (GPA). As used herein, the term "polymer electrolyte membrane" refers to a film of polymer material characterized by ion exchange properties.

[0060] In the first embodiment, the method includes the steps of preparing a film containing a polymer (GP) and heating the film at a temperature of 100 to 200°C to convert the sulfonic acid ester groups in the polymer (GP) into sulfonic acid groups.

[0061] The heating of polymer (GP) films is typically carried out at temperatures in the range of 140–160°C. The heating process is typically continued for 1.0–6.0 hours. The heating process can be carried out under vacuum or in the presence of superheated steam.

[0062] In an advantageous alternative embodiment, this method includes the steps of preparing a solution of the polymer (GP) in a polar organic solvent, coating the solution onto a substrate, and drying it at a temperature in the range of 100 to 160°C to obtain a film, while simultaneously converting the sulfonic acid ester groups in the polymer (GP) to sulfonic acid groups. Suitable polar organic solvents include, for example, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone.

[0063] Surprisingly, it was found that the viscosity of the solution containing polymer (GP) was more suitable for use in the film casting process than the viscosity of the solution containing polymer (GPA).

[0064] At the end of this process, the polymer (GP) is completely converted to polymer (GPA), and the film contains polymer (GPA).

[0065] Another method for producing electrolyte membranes containing polymer (GPA) involves first subjecting the polymer (GP) in powder form to a heat treatment process at a temperature in the range of 100-160°C to convert sulfonic acid ester groups to sulfonic acid groups, after which it is formed into a film.

[0066] Polymer electrolyte membranes containing polymer (GPA) or films containing polymer (GP) can be manufactured by a method comprising the step of applying a liquid composition or solution prepared by mixing the polymer with, for example, a suitable solvent, onto a substrate by a known coating method. Non-limiting examples of suitable coating methods include die coating, spray coating, knife coating, roll coating, slot die coating, spin coating, and gravure coating.

[0067] Specifically, the composition is applied to a substrate, the applied composition is dried to obtain a film, and the resulting film is optionally peeled off from the substrate. This allows us to obtain the film or electrolyte membrane of the present invention.

[0068] The substrate is not particularly limited as long as it is a substrate to which a general composition is applied, and for example, plastic substrates and metal substrates can be used. A substrate made of a thermoplastic resin such as polyethylene terephthalate (PET) film or polyimide (Kapton®) film, or a steel belt is preferred.

[0069] The electrolyte membrane containing the polymer (GPA) preferably has a dry film thickness of 10 to 100 μm, preferably 15 to 85 μm, more preferably 20 to 80 μm, and even more preferably 20 to 70 μm.

[0070] The electrolyte membrane of the present invention may be a single-layer membrane or a multilayer laminate membrane.

[0071] In the case of laminate films, the thickness of each layer can be determined arbitrarily. For example, one layer may be thicker than another. Each layer may be the same thickness as the others or different thicknesses.

[0072] The manufactured electrolyte membrane may include reinforcing materials such as porous materials or sheet-like fibrous materials.

[0073] Examples of methods for producing reinforced solid polymer electrolyte membranes include impregnating a porous material or sheet-like fibrous material with a composition containing polymer (GP); coating a porous material or sheet-like fibrous material with polymer (GP); and forming a membrane from the composition beforehand, then overlapping the membrane onto the porous material or sheet-like fibrous material and hot-pressing them together.

[0074] Porous materials are preferably materials having a large number of pores or voids that penetrate in the thickness direction. Examples include organic porous materials composed of various types of resins, and inorganic porous materials composed of glass, metal oxides such as alumina, or the metal itself.

[0075] The porous material is preferably an organic porous material. Specifically, a substrate composed of at least one selected from the group consisting of polyolefins such as polytetrafluoroethylene, high molecular weight polyethylene, crosslinked polyethylene, polyethylene, and polypropylene, polyimide, polyacrylonitrile, polyamideimide, polyetherimide, polyphenylene sulfide, polybenzamidazole, polyethersulfone, and polyetherketone is preferred.

[0076] The embodiments described above are illustrative and not limiting. Further embodiments are within the concept of the present invention. In addition, although the present invention is described in relation to specific embodiments, those skilled in the art will recognize that modifications in form and detail can be made without departing from the spirit and scope of the invention. [Examples]

[0077] Molecular weight determination method - GPC Gel permeation chromatography (GPC) analysis was performed using two PLgel 5 μm minimixed-D columns (250 × 4.6 mm) and a PLgel 5 μm MiniMIX-D guard column (50 × 4.6 mm), with dimethylacetamide (0.1 M LiBr) as the eluent, using a Waters 2695 separation module and a Waters 2487 dual-wavelength absorbance detector. A UV light detector monitoring at 270 nm was used to obtain chromatograms. A flow rate of 0.3 ml / min and an injection volume of 5 μL of 0.2 w / v% solution in the mobile phase were selected. Calibration was performed using 10 narrow molecular weight polystyrene standards (peak molecular weight range: 371,000–580 g / mol). Number average molecular weight M n and weight-average molecular weight M w I reported it.

[0078] conductivity In-plane proton conductivity was measured using a Bekktech conductivity cell and a linear voltage sweep method with an Ivium Vertex One potentiostat. All measurements were performed in water at 80°C. Conductivity was calculated as the reciprocal of resistivity according to the following formula:

number

[0079] Ion exchange capacity The ion exchange capacity is, 1The determination was made using 1H NMR (deuterated DMSO). The molar percentage of the sulfonated comonomer was calculated using the ratio of the integral values ​​for 7.8–8.2 ppm (3H) and 6.75–7.8 ppm (8H). The IEC was then calculated from this value.

[0080] Example 1: Preparation of polymer (GP-1) In a 250 mL three-necked round-bottom flask, bis(triphenylphosphine)nickel chloride (1.316 g, 20.12 mmol), potassium iodide (2.004 g, 12.07 mmol), triphenylphosphine (3.167 g, 12.07 mmol), 2,5-dichlorobenzophenone (11.58 g, 46.13 mmol), 2,6-dichlorobenzonitrile (0.883 g, 5.13 mmol), activated zinc powder (9.867 g, 150.9 mmol), and anhydrous N-methylpyrrolidone (110 mL) were placed under a nitrogen atmosphere. The mixture was heated to 70°C and held at that temperature for 30 minutes, after which neopentyl-3,5-dichlorobenzenesulfonate (14.67 g, 49.35 mmol), with a solid content of 37% in N-methylpyrrolidone (39.6 g), was added. The mixture was then held at 70°C for a further 3 hours. The reaction medium was diluted with N-methylpyrrolidone (65 mL), and the mixture was filtered using Celite as a filtration aid. The resulting reaction mixture was divided into three parts. One of the two parts was poured into methanol to solidify the polymer, and it was filtered. The resulting polymer was washed and filtered four times with methanol containing 5% HCl, and then washed and filtered four more times with methanol. The isolated substance was then dried under reduced pressure (40 kPa) at 80°C for 18 hours to obtain the polymer (GP-1) as a powder. 1 Analysis was performed by 1H NMR.

[0081] Example 1a - Conversion from polymer (GP-1) to polymer (GPA-1) and further conversion to film A portion of the reaction solution obtained in Example 1 (113 g) was placed in a 250 mL three-necked round-bottom flask and heated at 150 °C for 3 hours. The polymer was allowed to coagulate in water (2000 g) and filtered. The polymer was then washed and dried under reduced pressure (40 kPa) at 70 °C for 18 hours to obtain 6.27 g of polymer GPA-1 as a brown powder (yield 75.8%). 1 ¹H NMR confirmed that the neopentyl sulfonate ester was completely converted to -SO3H.

[0082] Next, polymer (GPA-1) (5g) was dissolved in 55g of N-methylpyrrolidone at 80°C. A portion of the prepared solution was cast onto a glass substrate using a doctor blade and dried under nitrogen at 150°C for 18 hours. The film was immersed in deionized water for 5 minutes five times, then dried at room temperature, and its conductivity was measured. The conductivity and IEC values ​​are reported in Table 1.

[0083] Comparative Example 1 - Conversion from polymer (GP-1) to polymer (GPA-1') using LiBr The second portion (113 g) of the reaction solution was placed in a 250 mL three-necked round-bottom flask with LiBr (7.5 g) and heated at 100 °C for 24 hours. The resulting reaction mixture was very viscous. The polymer was allowed to solidify in water (2000 g) and filtered. The polymer was then washed four times with acetone, seven times with 1 N aqueous sulfuric acid solution, and twice with water. The isolated substance was then dried under reduced pressure (40 kPa) at 70 °C for 18 hours to obtain 6.16 g (yield 74.5%) of the polymer (GPA-1') as a brown powder. 1 ¹H NMR confirmed that the neopentyl sulfonate ester was converted to -SO3H.

[0084] Next, the polymer (GPA-1') was dissolved in 55 g of N-methylpyrrolidone at 80°C. A portion of the prepared solution was cast onto a glass substrate using a doctor blade and then dried under nitrogen at 150°C for 18 hours. The film was immersed in deionized water for 5 minutes five times, then dried at room temperature and its conductivity was measured. The conductivity and IEC values ​​are reported in Table 1.

[0085] The ion exchange capacity (IEC) values ​​measured for the films of Example 1 and Comparative Example 1, and their conductivity measured at 80°C, are reported in Table 1.

[0086] [Table 1]

[0087] The data in Table 1 demonstrates that the sulfonic acid ester groups of the polymer (GP) can be quantitatively converted to ionically conductive sulfonic acid groups by heat treatment alone, without any chemical treatment. Films obtained by casting the solution also exhibit high conductivity.

Claims

1. Formula (A): 【Chemistry 1】 (In the formula, R １ is a C1-C20 alkoxy group which may be optionally substituted, and each R ｘ Each of the following is independently selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group, and the C1-C20 alkyl group, the C1-C20 alkoxy group, the C6-C20 aryl group, the C6-C20 aryloxy group, and the C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and the C6-C20 aryloxy group, and a plurality of R ｘ If such a thing exists, then two adjacent R ｘ (These may be joined to form a ring, and p represents 1 or 2.) A method for converting sulfonic acid ester groups in a polyarylene polymer containing repeating units to sulfonic acid groups, A method comprising heating the polyarylene polymer to a temperature of 100°C to 200°C.

2. The aforementioned polyarylene polymer is of formula (B): 【Chemistry 2】 (In the formula, each R ｙ Each of the following is independently selected from the group consisting of a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group, and the C1-C20 alkyl group, the C1-C20 alkoxy group, the C6-C20 aryl group, the C6-C20 aryloxy group, and the C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and a C6-C20 aryloxy group, and a plurality of R ｙ If such a thing exists, then two adjacent R ｙ (The elements may be joined to form a ring, and q is an integer between 1 and 4.) The method according to claim 1, further comprising a repeating unit.

3. The aforementioned polyarylene polymer is of formula (C): 【Transformation 3】 (wherein, R ｚ１ and R ｚ２ are each independently selected from the group consisting of a fluorine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 acyl group, or a cyano group, and the C1-C20 alkyl group, the C1-C20 alkoxy group, the C6-C20 aryl group, the C6-C20 aryloxy group, and the C2-C20 acyl group may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, a C6-C20 aryl group, and a C6-C20 aryloxy group. When a plurality of R z１ and R ｚ２ are present, adjacent ones may be bonded to form a ring, r and s are each independently an integer of 1 to 4, and Z is selected from the group consisting of an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a 2,2-isopropylidene group, and a 2,2-hexafluoroisopropylidene group). The method according to claim 1 or 2, further comprising a repeating unit.

4. The method according to any one of claims 1 to 3, wherein the amount of repeating units of formula (A) is 0.1 to 90.0 mol% of the total amount of repeating units in the polymer.

5. The method according to any one of claims 1 to 4, wherein the polyarylene polymer comprising a repeating unit of formula (A) and optionally repeating units of formula (B) and / or (C) is in powder form.

6. The method according to claim 5, wherein the powder is an aggregate of solid particles having an average particle size in the range of 50 microns to 20 mm.

7. The method according to claim 5 or 6, wherein the polyarylene polymer powder is heated to a temperature of 120 to 200°C, preferably 140 to 160°C.

8. The method according to any one of claims 1 to 4, wherein the polyarylene polymer comprising repeating units of formula (A) and optionally repeating units of formula (B) and / or (C) is dissolved in a solvent, and then a heat treatment step is performed on the same at a temperature of 100 to 160°C, preferably 130 to 160°C.

9. The method according to claim 7, carried out in the absence of an acid, alkali, or alkali halide.

10. The method according to claim 8 or 9, wherein the solvent is selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone.

11. The method according to any one of claims 1 to 10, wherein the step of heating the polyarylene polymer is carried out for 0.1 to 20.0 hours, preferably 1.0 to 15.0 hours, and more preferably 1.0 to 10.0 hours.

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