Polyarylene polymer

Abstract

A polyarylene polymer containing sulfonic acid functional groups, possessing high ion exchange capacity, provides films and membranes with excellent mechanical properties. This membrane is suitable for use as a proton exchange membrane and filtration membrane in electrochemical devices.

Description

[Technical Field]

[0001] Reference to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 460375 filed on 19 April 2023 and European Patent Application Publication No. 23187888.5 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 polyarylene polymer having a sulfonic acid functional group, and more particularly to a polyarylene polymer having a sulfonic acid functional group that can provide a film having high ion exchange capacity and good mechanical properties. [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 in fuel cells for 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 specifies the formula [ka] (In the formula, A represents an amino group substituted with one or two hydrocarbon groups (where 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, 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. When there are a plurality of R 1 s, R 1 s may be the same group or different groups, and two adjacent R 1 s may be bonded to form a ring, m represents 1 or 2, and k represents 4 - m, and these are obtained from the corresponding halides.) discloses a polymer containing a repeating unit of

[0006] U.S. Patent Application Publication No. 2014 / 0154610A1 discloses an aromatic copolymer containing a hydrophilic segment (A) and a hydrophobic segment (B). 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 the divalent structural unit has a benzene ring. A notable example of the structural unit having a proton-conductive group is, for example, [Chemical formula] wherein, 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 -(wherein u is an integer from 1 to 10), -C(CH3)2- or -C(CF3)2-, R 17 is, independently, a direct bond, -O(CH2) p -, -O(CF2) p -, -(CH2) p - or -(CF p ) p -(wherein p is an integer from 1 to 12), R 18 and R 19 are, independently, a hydrogen atom or a protecting group, and at least one of all R 18 and R 19 contained in the structural unit (1) is a hydrogen atom, x 1 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 formula: [Chemical formula] (wherein R 4 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and these substituents may be the same or different, r is 1 or 2, and d is 4 - r) A represents OR 5 or N(R 6 )(R 7 ), R 5 represents hydrogen, an alkali metal or an alkyl group having 1 to 20 carbon atoms, R 6 and R 7R represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and R 6 and R 7 These may be the same or different. The repeating units are obtained from the corresponding dihalide monomers. The use of polyarylene polymers in the preparation of electrolyte membranes is also disclosed. Among the exemplified polymers, the following polyarylene polymers have the phenylene units containing sulfonic acid functional groups attached to the main chain at the para position: [ka] This has been disclosed.

[0008] Polyarylene polymers in which phenylene units containing sulfonic acid functional groups are attached to the main chain at the para position, as disclosed in International Publication No. 2014 / 208714A1, are also disclosed in Japanese Patent Publication Nos. 2016207609, 2015038866, and 2015165461.

[0009] There is still a need to provide a polyarylene polymer having sulfonic acid functional groups that can be formed into a film with high ion exchange capacity and good mechanical properties.

[0010] Here, a specific polymer exhibiting high ion exchange capacity, the repeating unit of which is given by formula (1): [ka] The repeating unit and equation (2): [ka] (In the formula, R 2 (wherein is -C(O)Ar, and Ar is a C6-C20 aryl group that can be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, and a C6-C20 aryloxy group, preferably Ar is phenyl.) It has been found that a specific polymer consisting of repeating units can be obtained and that it can be formed into a film having good mechanical properties under usage conditions. Although not bound by theory, it is thought that polyarylene polymers in which the phenylene units containing sulfonic acid functional groups are attached to the main chain at the meta position may provide articles such as films with reduced brittleness. [Overview of the Initiative]

[0011] The first object of the present invention is a polyarylene polymer (hereinafter referred to as polymer (P)), wherein the repeating unit is - Formula (1): [ka] The repeating unit and - Formula (2): [ka] (In the formula, R 2 (wherein is -C(O)Ar, and Ar is a C6-C20 aryl group that can be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, and a C6-C20 aryloxy group.) The repeating unit and This polyarylene polymer is characterized by having an ion exchange capacity of 2.00 meq / g or more, comprising the following components.

[0012] A further object of the present invention is a method for obtaining a polymer (P), wherein formula (3): [ka] (In the formula, R 1 (These are C1-C20 alkoxy groups.) The repeating unit and - Formula (4): [ka] (In the formula, R 2(wherein is -C(O)Ar, and Ar is a C6-C20 aryl group that can be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, and a C6-C20 aryloxy group, preferably Ar is phenyl.) The repeating unit and A polymer consisting of (hereinafter referred to as polymer (PP)) is heated at a temperature of 100-200°C, and C1-C20 alkoxy groups R 1 This method includes a step of converting to an OH group.

[0013] The present invention further relates to films or membranes containing a polymer (P) or a polymer (PP), and methods for preparing such membranes. [Modes for carrying out the invention]

[0014] 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 it is said that an element or component is included in and / or selected from an enumerated list of elements or components, in the relevant embodiments expressly considered herein, it should be understood that 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, and any element or component enumerated in a list of elements or components may be omitted from such list. - In expressions such as "one repeating 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(P)" and "polymer(PP)," 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 in relation to the total number of moles of repeating units in the polymer. - The expression "weight percentage" (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. - The concentration of repeating units in "mol percent" (mol%) 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.

[0015] Polymer (P) is - Formula (1) [ka] (In the formula, R 1 (These are C1-C20 alkoxy groups.) The repeating unit and - Formula (2): [ka] (In the formula, R 2 (wherein is -C(O)Ar, and Ar is a C6-C20 aryl group that can be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, and a C6-C20 aryloxy group.) The repeating unit and It consists of.

[0016] To clarify, polymer (P) is made from repeating units and end groups. End groups are the groups at the very end of the polymer chain. Therefore, polymer (P) contains repeating units, which consist of repeating units of formula (1) and repeating units of formula (2).

[0017] In equation (2), R 2 Ar is -C(O)Ar, and Ar is a C6-C20 aryl group that can be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, and a C6-C20 aryloxy group. Preferably, Ar is phenyl, 1-naphthyl, 2-naphthyl, 3-phenanthryl, and 2-anthryl. More preferably, Ar is a phenyl group. To avoid any doubt, the expression "-C(O)Ar" specifies the ketone functional group.

[0018] The repeating units of formula (1) and formula (2) can be randomly distributed within the polymer chain.

[0019] Alternatively, polymer (P) may have a block-like structure. For example, polymer (P) may include blocks consisting of repeating units of formula (1) or (2), and blocks in which repeating units of formulas (1) and (2) are randomly distributed.

[0020] The ion exchange capacity of polymer (P) is, 1 The ion exchange capacity is 2.00 meq / g or greater when measured by 1H NMR. The ion exchange capacity is typically 2.00 to 5.50 meq / g, preferably 2.00 to 5.00 meq / g, and more preferably 2.20 to 4.40 meq / g. 1 The method for determining ion exchange capacity by 1H NMR is described in detail in the examples.

[0021] Ion exchange capacity (IEC) refers to the total number of active sites or functional groups involved in ion exchange in a polymer electrolyte membrane. In this specification, ion exchange capacity (IEC) is defined as the number of milligram equivalents of exchangeable ions per gram of dry resin.

[0022] The ion exchange capacity of polyarylene polymers can be controlled by changing the type, ratio, and combination of repeating units in the polymer. Generally, increasing the amount of repeating units of formula (1) having proton-conducting groups increases ion exchange capacity and proton conductivity, while decreasing water resistance.

[0023] The amount of repeating units in equation (1) is the amount at which the polymer exhibits an ion exchange capacity of 2.00 meq / g or more. The amount of repeating units in equation (1) is typically 20.0 to 90.0 mol% of the total amount of repeating units in the polymer.

[0024] The amounts of the repeating units in formula (1) are typically 25.0–90.0 mol%, 30.0–85.0 mol%, 35.0–85.0 mol%, and further 40.0–80.0 mol%, and 40.0–75.0 mol%. The remaining units in polymer (P) consist of one or more repeating units of formula (2).

[0025] The polymer (P) has a weight-average molecular weight Mw of 50,000 to 500,000, preferably 70,000 to 400,000, and more preferably 70,000 to 300,000. The molecular weight is measured by gel permeation chromatography using a polystyrene standard and dimethylacetamide as the eluent, as detailed in the examples.

[0026] The polymer (P) may be in powder form. The term "powder" is used herein to refer to an aggregate of solid particles having individual sizes. Advantageously, the solid particles of polymer (P) have an average size of nanometers to millimeters, preferably microns to millimeters. Average particle sizes may range from 50 microns to 20 mm, 100 microns to 10 mm, and even further from 200 microns to 5 mm.

[0027] 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.

[0028] Polymer (P) powders are typically free-flowing.

[0029] The polymer (P) may be in the form of a dispersion in a suitable solvent. Examples of suitable solvents are, for example, polar organic solvents. Suitable solvents are selected from the group consisting of, for example, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone.

[0030] Polymer (P) can be prepared starting from polymer (PP), which is a precursor polymer in which the sulfonic acid functional groups in the repeating units of formula (1) are in the form of sulfonic acid ester groups.

[0031] Therefore, polymer (PP) is - Formula (3): [ka] (In the formula, R 1 (These are C1-C20 alkoxy groups.) The repeating unit and - Formula (2): [ka] (In the formula, R 2 (This is as defined for polymer (P)). The repeating unit and It includes repeating units consisting of [this].

[0032] The polymer (PP) can be prepared by copolymerizing a compound (I) that provides structural unit (3) with a compound (II) that provides structural unit (2).

[0033] A notable non-restrictive example of compound (I) is, for example, formula (I'): [ka] (In the formula, R 1 For the compound of formula (1), the above definition applies, and X 1 and X 2 (These are independently selected from the group consisting of halogens, mesylates, tosylates, or triflates.) It is a compound of X. Preferably, X 1 and X 2 It is chlorine.

[0034] Similarly, compound (II) is given by formula (II'): [ka] (In the formula, X 3 and X 4 (These are independently selected from the group consisting of halogens, mesylates, tosylates, or triflates.) It is a compound of X. Preferably, X 3 and X 4 It is chlorine.

[0035] Polymerization is preferably carried out in the presence of a catalyst. Any catalyst can be used for the polymerization of aromatic compounds.

[0036] Typically, polymers (PP) can be produced by polymerizing a monomer composition containing compounds (I) and (II) 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.

[0037] 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 can be used individually or in combination of two or more.

[0038] 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 further activated by contact with an acid such as an organic acid.

[0039] 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 can be used individually or in combination of two or more.

[0040] Methods for preparing polymers (PP) are disclosed in European Patent Application Publication No. 1935916A1, U.S. Patent Application Publication No. 20140154610A1, and International Publication Brochure No. 2014208714A1.

[0041] Polymerization is preferably carried out in the presence of a polymerization solvent.

[0042] 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.

[0043] Polymerization reactions can be carried out in an inert gas atmosphere, such as nitrogen gas.

[0044] Polymerization is preferably carried out at a temperature of 0 to 200°C, more preferably 50 to 80°C, and the polymerization time is preferably 0.5 to 100 hours, more preferably 1 to 40 hours.

[0045] After the polymerization reaction is complete, the polymer (PP) can be isolated using known polymer isolation techniques. By mixing the reaction mixture with a solvent in which the polymer (PP) is poorly soluble, the polymer (PP) can be precipitated to form a polyarylene polymer, which can then be separated from the reaction mixture by filtration. Alternatively, droplets of the reaction mixture can be added dropwise, for example, using a nozzle, to a precipitation bath containing a solvent in which the polymer (PP) is poorly soluble. Examples of solvents in which the polymer (PP) is insoluble or poorly soluble include water, acetone, methanol, ethanol, and acetonitrile. Water and acetone are preferred.

[0046] The precipitated polyarylene polymer can then be washed to remove trace amounts of catalysts and other additives, and subsequently dried.

[0047] Subsequently, the polymer (PP) can be crushed or sieved to obtain a powder containing particles having the desired particle size known to those skilled in the art.

[0048] The polymer (PP) may be in powder form. The solid particles of the polymer (PP) may have an average diameter of nanometers to millimeters, preferably micrometers to millimeters. The average particle size may range from 50 microns to 20 mm, 100 microns to 10 mm, and even further from 200 microns to 5 mm.

[0049] Polymer (PP) powders are typically free-flowing.

[0050] The polymer (PP) may be in the form of a dispersion in a suitable solvent, particularly an organic solvent. Examples of suitable solvents include, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and γ-butyrolactam, preferably selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0051] Surprisingly, it was found that the conversion of sulfonic acid ester groups in polymers (PP) to sulfonic acid groups, thereby introducing proton-conducting groups, can be favorably achieved by heat treatment. The conversion of sulfonic acid ester groups to sulfonic acid groups in polymers (PP) is carried out by heating the polymer (PP) at 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.

[0052] The step of heating the polymer (PP) to a temperature of 100-200°C includes holding the polymer (PP) at a temperature in the range of 100-200°C for a sufficient amount of time to convert the sulfonic acid ester groups to sulfonic acid groups. The heating step is typically carried out for a period of time of 0.1-20.0 hours, typically 1.0-15.0 hours, and further 1.0-10.0 hours.

[0053] This method can be conveniently carried out with polymers (PP) in powder form. The powder can be heated to a temperature of 120-200°C, more preferably 140-160°C.

[0054] Alternatively, the polymer (PP) may be dissolved in a suitable solvent and then subjected to a heat treatment process at a temperature of 100-160°C. More preferably, the polymer may be heated in solution at a temperature of 130-160°C, even more preferably 140-150°C. The solution does not contain acids, alkalis, or alkali halides, such as LiBr.

[0055] Suitable solvents include, for example, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone.

[0056] The polymer (PP) may be subjected to a heat treatment step at a temperature of 100-160°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.

[0057] The conversion is complete. 1 This can be determined using conventional analytical methods such as 1H NMR.

[0058] Due to its ion exchange capacity, polymer (P) can be conveniently used in the preparation 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, solid capacitors, and the like.

[0059] Surprisingly, polymer (P) was found to exhibit good mechanical properties, particularly excellent elongation at break.

[0060] Therefore, a further object of the present invention is an article comprising a polymer (PP). 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.

[0061] Another objective of the present invention is a method for converting a film containing polymer (P) into a polymer electrolyte membrane. As used herein, the term "polymer electrolyte membrane" refers to a film of polymer material characterized by ion exchange properties, i.e., the presence of ion exchange functional groups.

[0062] This method includes the steps of providing a film containing a polymer (PP) and heating the film at a temperature in the range of 100 to 200°C to convert the sulfonic acid ester groups in the polymer (PP) into sulfonic acid groups.

[0063] The heating of polymer (PP) 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 may be carried out in the presence of vacuum or superheated steam.

[0064] In an advantageous alternative embodiment, this method involves preparing a solution of the polymer (PP) in an 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 (PP) to sulfonic acid groups.

[0065] At the end of the above method, the polymer (PP) is completely converted to polymer (P), and the film contains polymer (P).

[0066] In another method for preparing a polymer electrolyte membrane containing polymer (P), the polymer (PP) is first subjected to a heat treatment process at a temperature in the range of 100-200°C to convert sulfonic acid ester groups to sulfonic acid groups, and then it is formed into a film. This conversion is achieved by heat treatment without chemical treatment such as hydrolysis with acid or alkali or reaction with alkali halides.

[0067] A polymer electrolyte membrane containing polymer (P) or a film containing polymer (PP) can be manufactured by a method that includes the step of applying a composition prepared by mixing the polymer with a suitable solvent onto a substrate by known methods, such as die coating, spray coating, knife coating, roll coating, spin coating, and gravure coating.

[0068] 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 polymer electrolyte film of the present invention.

[0069] The substrate is not particularly limited as long as it is a substrate to which a general composition is applied, and substrates such as 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.

[0070] The electrolyte membrane of the present invention 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.

[0071] The electrolyte membrane of the present invention preferably has a hot water solubility of 0.0 to 15.0% (after 24 hours at 120°C in water). More preferably, it has a solubility of 0.0 to 5.0%, and particularly preferably, 0.0 to 1.0%.

[0072] The electrolyte membrane of the present invention preferably has an conductivity of 100 mS / cm or more, more preferably 150 mS / cm or more, as measured in water at 80°C. The electrolyte membrane of the present invention preferably has a conductivity of up to 500 mS / cm, more preferably up to 650 mS / cm, and even more preferably up to 800 mS / cm, as measured in water at 80°C.

[0073] The electrolyte membrane of the present invention preferably has a yield stress of 10 to 400 MPa, more preferably 20 to 400 MPa, and particularly preferably 40 to 400 MPa.

[0074] The electrolyte membrane of the present invention preferably has an elongation at break of 4 to 400%, more preferably 4 to 100%, and particularly preferably 4 to 50%. Electrolyte membranes having an elongation at break within the above range exhibit excellent membrane toughness.

[0075] The electrolyte membrane of the present invention may be a single-layer membrane or a multilayer laminate membrane.

[0076] In the case of laminate films, the thickness of each layer can be determined arbitrarily. For example, the thickness may be such that one layer is thicker than another. Each layer may be identical or different from the others.

[0077] When a laminate film is formed, the surface of the electrolyte film obtained by the method described above may be further coated with a composition containing the copolymer of the present invention by known methods such as die coating, spray coating, knife coating, slot die coating, roll coating, spin coating, and gravure coating, and optionally dried after the coating process. A film formed from a composition containing the copolymer of the present invention may be superimposed on a film obtained by the method described above and hot-pressed.

[0078] When electrolyte membranes are manufactured, reinforced polymer electrolyte membranes can be produced by using porous substrates or sheet-like fibrous materials.

[0079] Examples of methods for producing a reinforced solid polymer electrolyte membrane include impregnating a porous substrate or sheet-like fibrous material with a composition containing the copolymer of the present invention, coating a porous substrate or sheet-like fibrous material with the composition, and forming a membrane from the composition beforehand, then overlapping the membrane onto a porous substrate or sheet-like fibrous material and hot-pressing them together.

[0080] A porous substrate is preferably a material having numerous pores or voids that penetrate in the thickness direction. Examples include organic porous substrates composed of various types of resins and inorganic porous substrates composed of glass, metal oxides such as alumina, or the metal itself.

[0081] The porous substrate is preferably an organic porous substrate. 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.

[0082] Polymer electrolyte membranes can be used in many electrochemical devices, including, but not limited to, fuel cells, electrolytic cells, and redox flow batteries.

[0083] Polymer electrolyte membranes can also be used in filtration devices such as microfiltration, ultrafiltration, or reverse osmosis devices.

[0084] Accordingly, an object of the present invention is a filtration device comprising the membrane of the present invention and a method for filtering at least one fluid, the method comprising bringing the fluid into contact with at least one membrane of the present invention. Non-limiting examples of suitable fluids are selected from the group consisting of biological fluids, buffers, oil / water emulsions, water, and hydrocarbons.

[0085] Polymer electrolyte membranes can also be used as gas separation membranes.

[0086] Therefore, a further object of the present invention is a gas separation device comprising a membrane of the present invention and a method for separating at least one gas from a gas stream, the method comprising bringing the gas stream into contact with at least one membrane of the present invention.

[0087] 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]

[0088] Mechanical testing: Mechanical testing was performed on a Zwick Z010 tensile testing machine equipped with a 1kN load cell and climate chamber. The tests were conducted at a constant strain rate (50 mm / min), and the engineering strain and stress were calculated from the displacement and force signals. The tests were carried out in an Espec SH-262 climate chamber, with controlled temperature and humidity during the tests (20°C, 50RH). A dogbone-shaped sample (5 mm wide, 22 mm gauge length) was cut from the film using a die cutter.

[0089] 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.

[0090] conductivity In-plane proton conductivity was measured using a linear voltage sweep method with an Ivium Vertex One potentiostat, employing a Bekktech conductivity cell. All measurements were performed in water at 80°C. Conductivity was calculated as the reciprocal of resistivity according to the following formula.

number

[0091] Ion exchange capacity The ion exchange capacity is,1 The 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.

[0092] Example 1 - Preparation of polymer (PP) In a 250 mL three-necked round-bottom flask, bis(triphenylphosphine)nickel chloride (1.447 g, 2.21 mmol), potassium iodide (2.204 g, 13.28 mmol), triphenylphosphine (3.483 g, 13.28 mmol), activated zinc powder (10.85 g, 166 mmol), neopentyl-3,5-dichlorobenzenesulfonate (17.54 g, 59.04 mmol) with a solid content of 37.02% in NMP, and anhydrous N-methylpyrrolidinone (72 mL) were placed under a nitrogen atmosphere. The mixture was heated to 50°C and maintained at that temperature for 30 minutes, after which 2,5-dichlorobenzophenone (14.825 g, 59.04 mmol) with a solid content of 31.7% in N-methylpyrrolidone (46.6 g) was added. The mixture was then heated to 70°C and maintained at that temperature for a further 3 hours. The reaction medium was diluted with 116 mL of N-methylpyrrolidone, and the mixture was filtered using Celite as a filter aid. The mixture was then coagulated in 1230 g of methanol and 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 material was then dried under reduced pressure (40 kPa) at 80°C for 18 hours to obtain 21.875 g (yield 91.15%) of the polymer (PP) as a beige powder.

[0093] Example 2 - Polymer (PP) film Next, 5.07 g of the polymer (PP) from Example 1 was dissolved in 5.2 g of NMP at 80°C. A portion of the prepared solution was cast onto a glass substrate using a doctor blade, then dried at 80°C for 1 hour, and subsequently dried in an oven at 80°C under nitrogen 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.

[0094] Example 3 - Conversion of polymer (PP) in powder form to polymer (P) and casting to film The polymer (PP) from Example 1 was placed in an oven at 160°C for 30 minutes. After heating, the sample was removed from the oven and subsequently dissolved in N-methylpyrrolidone to obtain a solution with a polymer solids content of 7%. The solution was then cast onto a glass plate at 80°C using a doctor blade, dried at 80°C for 1 hour, and then dried in an oven at 120°C under nitrogen for 18 hours. The film was immersed in deionized water for 5 minutes five times, dried at room temperature, and then its conductivity was measured. The conversion from sulfonic acid ester groups to sulfonic acid groups was, 1 Monitoring is performed using 1H NMR (in deuterated DMSO).

[0095] Example 4 - Preparation of polymer (P) from polymer (PP) in solution and casting of polymer (P) onto a film A portion of the polymer solution from Example 2 was taken and heated at 140°C for 3 hours. The solution was then cast onto a glass plate at 80°C using a doctor blade, dried at 80°C for 1 hour, and then dried in an oven at 120°C under nitrogen for 18 hours. The film was immersed in deionized water for 5 minutes five times, dried at room temperature, and then its conductivity was measured. The conversion from sulfonic acid ester groups to sulfonic acid groups was: 1 Monitoring is performed using 1H NMR (in deuterated DMSO).

[0096] Example 5 - Conversion of polymer (P) to polymer (PP) during casting to film A portion of the polymer solution from Example 2 was taken and then cast onto a glass plate at 80°C using a doctor blade, then placed in an oven at 120°C under nitrogen, heated to 150°C, and held 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 conversion from sulfonic acid ester groups to sulfonic acid groups was, 1 Monitoring is performed using 1H NMR (in deuterated DMSO).

[0097] Table 1 reports the ion exchange capacity (IEC) values ​​and conductivity values ​​measured at 80°C for the polymer (P) films of Examples 3-5. For reference, Table 1 also shows the IEC and conductivity values ​​for Nafion® 212 perfluorosulfonic acid film.

[0098] [Table 1]

[0099] The results in Table 1 for Example 3 show that the polymer (PP) in powder form can be converted to polymer (P) by heating. The polymer (PA) can then be formed into a film characterized by high conductivity.

[0100] The conversion from polymer (PP) to polymer (P) can be easily carried out even in solution (Example 4). The film obtained by casting this solution also exhibits high conductivity and IEC.

[0101] Advantageously, as shown in Example 5, the polymer (PP) can be converted to polymer (PA) during the film manufacturing process, particularly during the drying of the casting solution.

Claims

1. A polyarylene polymer, the repeating unit of which is - Formula (1): 【Chemistry 1】 The repeating unit and - Formula (2): 【Chemistry 2】 (In the formula, R ２ (wherein is -C(O)Ar, and Ar is a C6-C20 aryl group that can be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group, and a C6-C20 aryloxy group.) The repeating unit and A polyarylene polymer comprising the above, characterized in that it has an ion exchange capacity of 2.00 meq / g or more.

2. R ２ The polyarylene polymer according to claim 1, wherein is -C(O)Ar, and Ar is phenyl.

3. The polyarylene polymer according to claim 1 or 2, wherein the ion exchange capacity is 2.00 meq / g to 5.50 meq / g.

4. The polyarylene polymer according to any one of claims 1 to 3, wherein the amount of repeating units of formula (1) is 20 to 90 mol%, 25 to 90 mol%, 30.0 to 85.0 mol%, 35.0 to 85.0 mol%, and further 40.0 to 80.0 mol%, and 40.0 to 75.0 mol%, based on the total amount of repeating units in the polyarylene polymer.

5. A polyarylene polymer according to any one of claims 1 to 4, having a weight-average molecular weight of 50,000 to 500,000, preferably 70,000 to 400,000, more preferably 70,000 to 300,000, as measured by gel permeation chromatography.

6. A polyarylene polymer according to any one of claims 1 to 5, in the form of a powder.

7. A dispersion comprising a polyarylene polymer according to any one of claims 1 to 5 and a solvent, preferably a polar organic solvent.

8. The dispersion according to claim 7, wherein the solvent is selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

9. A film comprising the polyarylene polymer according to any one of claims 1 to 5.

10. A polyarylene polymer, the repeating unit of which is - Formula (3): 【Transformation 3】 (In the formula, R １ (These are C1-C20 alkoxy groups.) The repeating unit and - Formula (2): 【Chemistry 4】 (In the formula, R ２ (This is as defined for polymers (P)). The repeating unit and A polyarylene polymer consisting of the repeating units of formula (3) and formula (2), in which the repeating units are randomly distributed within the polymer chain.

11. The polyarylene polymer according to claim 10, in powder form.

12. A dispersion comprising the polyarylene polymer according to claim 10 and a solvent, preferably a polar organic solvent.

13. The dispersion according to claim 12, wherein the solvent is selected from the group consisting of tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and γ-butyrolactam, preferably dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

14. A method for producing the film according to claim 9, comprising the steps of: dissolving the polyarylene polymer according to any one of claims 1 to 5 in a solvent to obtain a dispersion, or providing the dispersion according to claim 7 or 8; casting the dispersion; and drying the dispersion.

15. A method for producing the film according to claim 9, wherein the polyarylene polymer is the repeating unit thereof, - Formula (3): 【Transformation 5】 (In the formula, R １ (These are C1-C20 alkoxy groups.) The repeating unit and - Formula (2): 【Transformation 6】 (In the formula, R ２ (This is as defined for polymers (P)). The repeating unit and A step of dissolving a polyarylene polymer in an organic solvent, i) Heating the solution to a temperature of 100°C to 200°C to convert the sulfonic acid ester groups to sulfonic acid groups, casting the solution to form a film, and drying it, or ii) A step of casting the solution to form a film, and heating the cast film to a temperature of 100°C to 200°C to convert the sulfonic acid ester groups to sulfonic acid groups, and drying the film. A method that includes this.

16. A method for producing the film according to claim 9, comprising the steps of: providing a solution of the polyarylene polymer according to claim 10 in a polar organic solvent; heating the solution at a temperature of 100 to 200°C to convert sulfonic acid ester groups to sulfonic acid groups; recovering the polymer containing sulfonic acid groups; forming a solution; casting the solution; and drying the solution.

17. The method according to claim 15 or 16, wherein the heating step is performed over a period of time of 0.1 to 20.0 hours, 1.0 to 15.0 hours, and 1.0 to 10.0 hours.

18. An electrochemical device, a filtration device, or a gas separation device comprising the film described in claim 9.

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