Ion conductive compound and method for preparing same

Abstract

The present invention provides an ion conductive compound and a method for preparing same, wherein the ion conductive compound exhibits excellent ion conductivity and is useful as an ion exchange material for an anion exchange membrane, an ion conductive membrane, an electrolyte membrane, a separation membrane, a water treatment membrane, or the like.

Description

Ion-conducting compound and method for producing the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0189725, filed December 22, 2023, and Korean Patent Application No. 10-2024-0156204, filed November 6, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to an ion conductive compound and a method for producing the same.

[0004]

[0005] Ion-conducting polymers are widely used as ion-exchange materials in various electrochemical devices such as fuel cells and water electrolysis, such as anion-exchange membranes, ion-conducting membranes, electrolyte membranes, separation membranes, or water treatment membranes.

[0006] As the problem of climate change caused by global warming becomes increasingly serious, research into alternative energy sources to reduce greenhouse gas emissions is gaining traction. Among these, fuel cells are pollution-free systems that utilize the energy of the chemical reaction between hydrogen and oxygen. Their high power density and energy conversion efficiency, coupled with their miniaturization, make them ideal for a wide range of applications, including portable power sources for mobile communication equipment, transportation power sources for automobiles, and power generation systems for home and military use.

[0007] Water electrolysis technology is a technology that produces hydrogen by electrolyzing water. Depending on the characteristics of the electrolyte and the type of membrane, it is divided into alkaline water electrolysis (AWE), proton exchange membrane water electrolysis (PEMWE), and anion exchange membrane water electrolysis (AEMWE).

[0008] An anion exchange membrane electrolysis system includes an anion exchange membrane (AEM) to prevent crossover between ion redox active species of the anode and cathode, and an ion conductive polymer is mainly used in the formation of the anion exchange membrane.

[0009] Ion-conducting polymers, which are generally used to form anion exchange membranes, are composed of a polymer backbone and an ion-conducting group. Quaternary ammoniums such as benzyl ammonium, alkyl ammonium, imidazolium, piperidinium, and spiro ammonium are used as ion-conducting functional groups, and poly(aryl ether sulfone) (PES), poly(aryl ether ketone) (PAEK), poly(phenylene oxide) (PPO), polyspirobisindane, polyphenylene (PP), and styrene-ethylene-butylene-styrene copolymer (SEBS) are used as polymer backbones constituting AEMs. In particular, the polyphenylene polymer backbone with an aryl ether-free structure is highly susceptible to hydroxide ions (OH - ) has excellent chemical stability and mechanical properties, and many studies have been conducted on it recently.

[0010] In general, in the ionic conduction mechanism of AEM, water is OH -Because it acts as a conducting medium, the high ionic conductivity of AEM must be accompanied by an appropriate water uptake (WU). In addition, when AEM has a high hydration number, OH - can reduce the ionic conductivity of the material.

[0011] Polyphenylene-based AEMs have relatively low WU, i.e., low hydration number, compared to their high ion exchange capacity (IEC). Therefore, polyphenylene-based AEMs were designed to secure the required level of WU and ionic conductivity by introducing more ion-conducting groups. The ion-conducting groups with positive charges are OH-positive compared to the polymer backbone. - , which means that the stability of AEM is relatively low. In addition, the introduction of excessive ion conductors causes high WU, which induces a decrease in ionic conductivity and may have a somewhat negative effect on the long-term stability of AEM.

[0012]

[0013] The present invention aims to provide an ion-conducting compound that exhibits excellent ion conductivity and is useful as an ion-exchange material for an anion exchange membrane, an ion-conducting membrane, an electrolyte membrane, a separation membrane, or a water treatment membrane, and a method for producing the same.

[0014] The present invention also aims to provide an ion exchange material manufactured from the ion conductive polymer.

[0015]

[0016] Accordingly, according to the present invention, an ion conductive compound comprising a structure represented by the following chemical formula 1 is provided:

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1,

[0020] A 11 Inland A 17 are each independently represented by the following chemical formula 2,

[0021] B is an arylene group having 6 to 18 carbon atoms,

[0022] a1 to g1 are each independently integers of 0 or 1, but at least one of a1 to g1 is an integer of 1,

[0023] n is an integer greater than or equal to 1,

[0024] [Chemical Formula 2]

[0025]

[0026] In the above chemical formula 2,

[0027] L is a branched alkylene group having 3 to 30 carbon atoms,

[0028] Z is a quaternary ammonium cationic functional group,

[0029] Y is an anion.

[0030] In addition, according to the present invention, a method for producing an ion-conducting compound is provided, comprising: a first step of reacting a compound including a structure represented by the following chemical formula 5 with at least one compound represented by the following chemical formula 6 in the presence of a strong acid to produce a compound including a structure represented by the following chemical formula 7; and a second step of reacting the compound including the structure represented by the above chemical formula 7 with a raw material forming a quaternary ammonium-based cationic functional group.

[0031] [Chemical Formula 5]

[0032]

[0033] In the above chemical formula 5,

[0034] B is an arylene group having 6 to 18 carbon atoms,

[0035] n is an integer greater than or equal to 1,

[0036] [Chemical Formula 6]

[0037]

[0038] In the above chemical formula 6,

[0039] L is a branched alkylene group having 3 to 30 carbon atoms,

[0040] X is a halogen group,

[0041] [Chemical Formula 7]

[0042]

[0043] In the above chemical formula 7,

[0044] B is as defined in the above chemical formula 5,

[0045] X 1 Inland X 7 are each independently represented by the following chemical formula 8,

[0046] a1 to g1 are each independently integers of 0 or 1, but at least one of a1 to g1 is an integer of 1,

[0047] n is an integer greater than or equal to 1,

[0048] [Chemical Formula 8]

[0049]

[0050] In the above chemical formula 8,

[0051] L is a branched alkylene group having 3 to 30 carbon atoms,

[0052] X is a halogen group.

[0053] In addition, according to the present invention, an ion exchange material comprising the ion conductive compound is provided.

[0054] In addition, according to the present invention, an ion-conducting membrane comprising the ion-conducting compound is provided.

[0055]

[0056] The ion-conducting compound according to the present invention has an aromatic segment formed through Diels-Alder polymerization, and has a structure in which a cationic functional group is bonded to a pendant phenyl group by a branched linker, thereby exhibiting excellent ion conductivity, and is useful in manufacturing an MEA (Membrane Electrode Assembly) as a resultant ion-conducting material, particularly an anion exchange membrane, and an ionomer material.

[0057] In addition, according to the method for producing an ion-conducting compound according to the present invention, a high-purity ion-conducting compound can be produced with excellent efficiency.

[0058]

[0059] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0060] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0061] In the present invention, “pendant” means a functional group bonded to a side chain other than an element constituting the main chain skeleton, particularly an aromatic ring substituent such as a phenyl group.

[0062] In addition, in the present invention, the term "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkylthioxy group; arylthioxy group; alkylsulfoxy group; arylsulfoxy group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; alkylamino group; aralkylamino group; heteroarylamino group; arylamino group; arylphosphine group; or a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with a substituent in which two or more substituents among the above-exemplified substituents are linked. For example, a "substituent having two or more substituents connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent having two phenyl groups connected.

[0063] Also, in this specification, * in the chemical formula indicates a bonding position.

[0064] Hereinafter, the present invention will be described in detail.

[0065]

[0066] The ion conductive compound according to the present invention is a compound having a structure represented by the following chemical formula 1:

[0067] [Chemical Formula 1]

[0068]

[0069] In the above chemical formula 1,

[0070] A 11 Inland A 17 are each independently represented by the following chemical formula 2,

[0071] B is an arylene group having 6 to 18 carbon atoms,

[0072] a1 to g1 are each independently integers of 0 or 1, but at least one of a1 to g1 is an integer of 1,

[0073] n is an integer greater than or equal to 1,

[0074] [Chemical Formula 2]

[0075]

[0076] In the above chemical formula 2,

[0077] L is a branched alkylene group having 3 to 30 carbon atoms,

[0078] Z is a quaternary ammonium cationic functional group,

[0079] Y is an anion.

[0080] Specifically, the ion-conducting compound according to the present invention comprises an aromatic segment formed through Diels-Alder polymerization, as shown in the above chemical formula 1, and has a structure in which a quaternary ammonium-based cationic functional group is bonded to a pendant phenyl group via a branched linker with respect to the main chain structure. When the central skeleton of the compound is composed solely of phenyl or benzene units, it has high chemical stability and can be operated at relatively high temperatures due to its robust properties.

[0081] In addition, in the case of conventional DI Alder polyphenylene-based ion-conducting polymers, cationic functional groups were mainly bonded to pendant phenyls via long linear alkylene chain linkers. The long alkylene chains bonded to the pendant phenyls increased the volume around the central skeleton and also hindered the packing of polymer chains, resulting in an increase in free volume between chains. Although this increase in free volume is effective for ion transport, it has the problem of relatively lowering ion selectivity and increasing WU.

[0082] In this regard, the ion conductive compound according to the present invention can improve the chemical stability of the pendant phenyl group by bonding the quaternary ammonium-based cationic functional group to the pendant phenyl group by a branched linker. In addition, even with a high molecular weight, it exhibits excellent solubility in main solvents such as NMP and DMSO, and as a result, processability can be improved when applied to an anion exchange material. In addition, since it can have a relatively high DF (degree of functionalization) compared to the conventional one, when manufacturing an anion exchange material or anion exchange membrane using it, it can improve durability as well as improve IEC and conductivity.

[0083] The ion-conducting compound according to the present invention may be a single molecular compound containing one structure (or repeating unit structure) represented by the above chemical formula 1, i.e., n=1. In addition, the ion-conducting compound also includes ionomers and polymers containing a plurality of structures represented by the above chemical formula 1, i.e., n=2 or more.

[0084] In addition, when the ion conductive compound includes a plurality of structures represented by the chemical formula 1, it may be a homopolymer composed of only one type (or a single type) of the structures represented by the chemical formula 1, or it may be a copolymer including two or more different structures of the structures represented by the chemical formula 1.

[0085] Depending on the type and number of cationic functional groups usually bonded to the pendant phenyl group, a wide range of functions can be exhibited.

[0086] The ion conductive compound of the present invention includes a quaternary ammonium cationic functional group that is superior in terms of ionic conductivity and durability among various cationic functional groups.

[0087] The number of bonds of the above quaternary ammonium cationic functional group can be controlled by controlling the stoichiometric ratio of the precursor material used in manufacturing.

[0088] Specifically, the ion-conducting compound may be one of the compounds comprising a structure represented by the following chemical formulas 1a to 11. Among them, the compound may be one comprising a structure represented by the following chemical formula 1a:

[0089]

[0090]

[0091]

[0092] In the above chemical formulas 1a to 1l, A 11 Inland A 17 , B and n are as defined above.

[0093] In addition, in the above chemical formula 1, B may be an arylene group having 6 to 12 carbon atoms, and more specifically, may be p-phenylene, m-phenylene, or biphenylene.

[0094] Also, a1 to g1 are each independently integers of 0 or 1, but at least one of a1 to g1 may be an integer of 1.

[0095] In addition, in the above chemical formula 2, L is a branched linker to which a quaternary ammonium-based cationic functional group (Z) is bonded, and more specifically, it may be a branched alkylene group having 3 to 30 carbon atoms, represented by the following chemical formula 3:

[0096] [Chemical Formula 3]

[0097]

[0098] In the above chemical formula 3,

[0099] R 1 and R 2 At least one of them is an alkyl group having 1 to 6 carbon atoms, and the rest are hydrogen,

[0100] p is an integer from 1 to 3,

[0101] q and r are each independently integers from 0 to 10, but q and r are not both integers of 0,

[0102] s is an integer from 1 to 3.

[0103] Meanwhile, in the above chemical formula 3, p, q, r, and s are appropriately determined within the above range so that the total number of carbon atoms contained in L is 3 to 30.

[0104] More specifically, in the above chemical formula 3, R 1 and R 2 At least one of them is an alkyl group having 1 or more carbon atoms, 6 or less, or 4 or less, or 3 or less, or 2 or less carbon atoms, and the rest may be hydrogen.

[0105] More specifically, in the above chemical formula 3, R 1 and R 2 At least one of them may be a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and the rest may be hydrogen. For example, R 1 and R 2 can all be methyl groups.

[0106] Also, in the above chemical formula 3, p can be an integer of 1 or 2.

[0107] Also, q and r can each independently be integers from 0 to 6, or from 0 to 3, but q and r cannot both be integers of 0.

[0108] Also, s can be an integer of 1 or 2.

[0109] For example, in the chemical formula 3, p may be an integer of 1 or 2, r may be an integer of 0, q may be an integer of 3 to 6, and s may be an integer of 1 or 2.

[0110] More specifically, in the above chemical formula 2, L may be 1,1-dimethylhexylene, 1,1-diethylhexylene, 1,1-dimethylheptylene, or 1,1-dimethylpentylene.

[0111] In addition, in the above chemical formula 2, Z is a quaternary ammonium cationic functional group.

[0112] Specifically, Z may be represented by the following chemical formula 4-1 or chemical formula 4-2:

[0113] [Chemical Formula 4-1]

[0114]

[0115] [Chemical Formula 4-2]

[0116]

[0117] In the above chemical formulas 4-1 and 4-2,

[0118] Q is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms,

[0119] R 11 Inland R 13 , and R 21 Inland R 25 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or R 11 Inland R 13 Two adjacent units, R 21 and R 22 , or R 23 Inland R 25 Two adjacent groups can be linked to each other to form a substituted or unsubstituted N-containing heterocyclic group having 2 to 20 carbon atoms.

[0120] More specifically, the above Q may be an alkylene group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one alkyl group having 1 to 6 carbon atoms, and more specifically, may be ethylene, propylene, butylene, pentylene or hexylene.

[0121] Also, the above R11 Inland R 13 , and R 21 Inland R 25 are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a dimethylaminohexyl group, a dimethylaminopentyl group, a dimethylaminobutyl group, a dimethylaminopropyl group, or a dimethylaminoethyl group; a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, such as an adamantyl group; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, such as a phenyl group, a benzyl group, or a dimethylphenyl group; Or a heterocyclic group having 3 to 12 carbon atoms containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, such as a thiophenyl group, a furanyl group, a pyrrole group, an imidazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidyl group, a pyrrolidinyl group, a piperidinyl group, an azepanyl group; or R 11 Inland R 13 Two adjacent units, R 21 and R 22 , or R 23 Inland R 25 Two adjacent groups are connected to each other to form a heterocyclic group having 3 to 8 carbon atoms, such as a pyrrolidinyl group, a piperidinyl group, an imidazolyl group, an azepanyl group, or a 5-azoniaspiro[4,4]nonyl group, wherein the heterocyclic group may be substituted with one or more alkyl groups having 1 to 6 carbon atoms, or may be unsubstituted.

[0122] More specifically, in the above chemical formula 2, Z is trimethyl ammonium, triethyl ammonium, diethylmethylammonium, dimethylethylammonium, tripropyl ammonium, tributyl ammonium, N-methylpyrrolidinium, N-methyl piperidinium, or 6-(dimethylamino)-N,N,N-trimethylhexane-1-aminium; or 4,4'-trimethylenebis(1-methylpiperidine), N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,5-pentanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,3-propanediamine and It may be selected from the group consisting of: each derived from N,N,N',N'-tetramethyl-1,2-ethanediamine:

[0123]

[0124]

[0125] In the above formula, * is a position where it is bonded to L in the above chemical formula 2.

[0126] In addition, in the above chemical formula 2, Y is an anionic group, specifically, chloride ion, bromide ion, iodide ion, hydroxide ion (OH - ), bicarbonate ion (HCO3 - ), dihydrogen phosphate ion (H2PO4 - ), hydrogen phosphate ion (HPO4 2- ) or phosphate ion (PO4 3- ) may be.

[0127] More specifically, the above chemical formula 2 can be represented by the following chemical formula 2a.

[0128] [Chemical Formula 2a]

[0129]

[0130] In the above chemical formula 2a, R is as defined above, and (Y') - is the same as the above Y.

[0131] For example, in the above chemical formula 2a, (Y') - Go OH - In this case, chemical formula 2 may be any one of the following.

[0132]

[0133] Meanwhile, in the above chemical formula 1, n represents the number of repeating units and can be determined according to the molecular weight of the compound represented by chemical formula 1. Specifically, n may be 1 or more, or 2 or more, or 10 or more, and 1000 or less, or 500 or less.

[0134] For example, the ion-conducting compound may be a compound represented by the following chemical formula 1a-1 or 1a-2, but is not limited thereto:

[0135] [Chemical Formula 1a-1]

[0136]

[0137] [Chemical Formula 1a-2]

[0138]

[0139] In the above chemical formula 1a-1 or 1a-2, n is an integer greater than or equal to 1.

[0140] Additionally, the ion-conducting compound may have a weight average molecular weight (Mw) of 30 to 900 kDa, more specifically, 50 to 500 kDa.

[0141] In the present invention, the weight average molecular weight of the ion conductive compound can be measured using gel permeation chromatography, and the specific measurement method and conditions are as described in the experimental examples below.

[0142] In addition, the ion exchange capacity (IEC) (meq. / g) can be controlled depending on the degree of functionalization (DF) of the side chain functional group in the ion conductive compound.

[0143] IEC is a numerical value that represents the ion transfer capacity of a single molecule. The theoretical value can be derived from the ratio of the number of functional groups to the weight of the polymer unit. Experimental methods include titrimetry and NMR analysis.

[0144] In the case of the titration method, a titration device is used for titration on a membrane doped in the form of chloride counter ion by immersing it in a 1M NaCl aqueous solution for 24 hours or according to the Mohr Titration method, and the IEC can be calculated according to the following mathematical formula 1 using the measured value of the result.

[0145] [Mathematical Formula 1]

[0146] IEC (meq.. / g) = (ΔV AgNO3 ×C AgNO3 ) / W dry

[0147] In the above mathematical formula 1,

[0148] V AgNO3 is the amount (mL) of 0.1M AgNO3 aqueous solution added to the end point,

[0149] C AgNO3 The concentration of AgNO3 aqueous solution is 0.1 mol / L,

[0150] W dry is the dry weight of the anion exchange membrane before the titration test.

[0151] one side, 1 Measurement of ICE values ​​through H-NMR analysis can be performed according to the methods disclosed in Journal of polymer science, part B: Polymer Physics 2013, 51(24), 1736-1742 and Macromolecules 2009, 42(21), 8316-8321.

[0152] The IEC of the ion conductive compound according to the present invention may be 1.0 meq. / g or more, more specifically 1.5 meq. / g or more, or 1.7 meq. / g or more, or 1.8 meq. / g or more, and 3.1 meq. / g or less, or 2.9 meq. / g or less, or 2.5 meq. / g or less. Thus, the ion conductive compound according to the present invention can exhibit superior ion conductivity because it can control the IEC over a wide range and has a relatively high IEC value compared to conventional polyphenylene-based ion conductive polymers having an equivalent level of Mw.

[0153] Meanwhile, in the present invention, the IEC of the ion conductive compound is 1 It was measured using H NMR analysis, and the specific measurement method and conditions are as described in the experimental example below.

[0154] The above ion conducting compounds are, for example,

[0155] A first step of producing a compound (hereinafter referred to as an “intermediate”) comprising a structure represented by the following chemical formula 7 by reacting a compound (hereinafter referred to as a “compound precursor”) comprising a structure represented by the following chemical formula 5 with at least one compound represented by the following chemical formula 6 in the presence of a strong acid; and

[0156] The intermediate can be manufactured by a manufacturing method including a second step of reacting the intermediate with a raw material forming a quaternary ammonium-based cationic functional group:

[0157] [Chemical Formula 5]

[0158]

[0159] In the above chemical formula 5,

[0160] B is an arylene group having 6 to 18 carbon atoms,

[0161] n is an integer greater than or equal to 1,

[0162] [Chemical Formula 6]

[0163]

[0164] In the above chemical formula 6,

[0165] L is a branched alkylene group having 3 to 30 carbon atoms,

[0166] X is a halogen group,

[0167] [Chemical Formula 7]

[0168]

[0169] In the above chemical formula 7,

[0170] B is as defined in the above chemical formula 5,

[0171] X 1 Inland X 7 are each independently represented by the following chemical formula 8,

[0172] a1 to g1 are each independently integers of 0 or 1, but at least one of a1 to g1 is an integer of 1,

[0173] n is an integer greater than or equal to 1,

[0174] [Chemical Formula 8]

[0175]

[0176] In the above chemical formula 8,

[0177] L is a branched alkylene group having 3 to 30 carbon atoms,

[0178] X is a halogen group.

[0179] In addition, the manufacturing method according to the present invention may further include, before the first step of manufacturing an intermediate, a step of manufacturing a compound precursor by reacting bistetracyclone as a dienophile with at least one ethynyl substituted aromatic compound.

[0180] Each step is explained below.

[0181] (Compound precursor synthesis step)

[0182] The compound precursor synthesis step is a step of producing a compound containing a structure represented by chemical formula 5 through a Diels-Alder reaction.

[0183] In the present invention, the compound precursor is described in Zinaida B. Shifrina, Marina S. Averina, Alexander L. Rusanov, Manfred Wagner, and Klaus Mullen, Branched Polyphenylenes by Repetitive Diels-Alder Cycloaddition, Macromolecules 2000 33 (10), 3525-3529, DOI: 10.1021 / ma991369f, and JK. Stille, FW Harris, RO Rakutis, H. Mukamal, Diels-Alder polymerizations: Polymers containing controlled aromatic segments, Journal of Polymer Science Part B: Polymer Letters, vol 4, 791-793 (1966). It can be manufactured according to the method described in https: / doi.org / 10.1002 / pol.1966.110041023, and the reaction temperature, reaction concentration, and reaction time are appropriately changed depending on the properties of the final compound precursor to be manufactured, such as the weight average molecular weight.

[0184] In the present invention, the step of preparing the compound precursor can be specifically performed by subjecting a bistetracyclone as a diene to a Diels-Alder reaction with at least one ethynyl-substituted aromatic compound as a dienophile.

[0185] By the above reaction, a compound precursor having a structure represented by chemical formula 5, for example, a Diels-Alder poly(phenylene) polymer (DAPP), is prepared.

[0186] Specifically, the above ethynyl-substituted aromatic compound may be a compound represented by the following chemical formula 9:

[0187] [Chemical Formula 9]

[0188]

[0189] In the above chemical formula 9,

[0190] B is an arylene group having 6 to 18 carbon atoms,

[0191] R a and R b are each independently hydrogen or an alkyl group having 1 to 30 carbon atoms.

[0192] Specific examples include 1,4-Diethylnylbenzene, 4,4'-Diethynylbiphenyl, and 1,3-Diethynylbenzene, and any one of these or a mixture of two or more thereof may be used.

[0193] In the above Diels-Alder reaction, the bistetracyclone and the ethynyl-substituted aromatic compound can be introduced at a molar ratio of 1.2:1 to 1:1.2, and more specifically, at a molar ratio of 1:1. In addition, the bistetracyclone and the ethynyl-substituted aromatic compound can be obtained commercially or can be manufactured directly. For example, the bistetracyclone can be manufactured by reacting 1,3-diphenyl-propane and 1,4-bisbenzyl.

[0194] Additionally, the above Diels-Alder reaction can be performed under a nitrogen atmosphere.

[0195] In addition, the above Diels-Alder reaction can be performed at a temperature of 100 to 330°C, more specifically, 110 to 220°C.

[0196] In addition, as a solvent or reaction medium in the Diels-Alder reaction, an ether compound such as diphenyl ether (Ph2O); an aromatic hydrocarbon compound such as toluene (PhMe) or xylene (PhMe2); or a mixture thereof may be used.

[0197] As a result of the above Diels-Alder reaction, DAPP is generated among the reactants, and the generated DAPP can be obtained in a solid phase through a precipitation reaction.

[0198] The above precipitation reaction can be performed according to a conventional DAPP precipitation method and is not particularly limited. For example, in the present invention, after the Diels-Alder reaction is completed, the temperature of the reactant is lowered to 100 to 120°C, a solvent such as toluene (PhMe) is added to dilute the reactant, and when the temperature of the diluted reactant is lowered to room temperature, the reactant is added dropwise to an alcohol such as methanol; or a conventional non-solvent such as hexane or acetone. As a result, the DAPP generated in the reactant is precipitated in a solid phase.

[0199] Afterwards, the precipitated DAPP can be separated and then subjected to a high purity DAPP through a typical separation and purification process such as drying, washing, and impurity separation.

[0200] (Stage 1)

[0201] Step 1 is a step of reacting the compound precursor prepared in the compound precursor synthesis step with a branched alcohol, specifically, at least one compound represented by Chemical Formula 6, in the presence of a strong acid to prepare an intermediate including a structure represented by Chemical Formula 7.

[0202] Specifically, the first step can be performed by dissolving a compound containing a structure represented by the chemical formula 5, which is a compound precursor, and at least one compound represented by the chemical formula 6 in a solvent under a nitrogen atmosphere, and then adding a strong acid to cause a substitution reaction.

[0203] Specific examples of the compound represented by the above chemical formula 6 include 7-bromo-2-methyl-2-heptanol, 7-bromo-2-ethyl-2-heptanol, or 7-bromo-2-methyl-2-pentanol, and any one of these or a mixture of two or more thereof may be used.

[0204] The amount of the compound represented by the above chemical formula 6 can be appropriately selected in consideration of the degree of substitution of the ion-conducting group in the pendant aryl group or the backbone aryl group in the compound precursor. For example, the compound represented by the above chemical formula 6 can be introduced in a molar ratio of 1 to 10, more specifically, a molar ratio of 3 to 7, with respect to 1 mol of the compound containing the structure represented by the above chemical formula 5, which is the compound precursor.

[0205] Additionally, dichloromethane or the like can be used as a solvent for dissolving the compound precursor and the compound represented by chemical formula 6.

[0206] Additionally, the above melting process is performed at 0 to 30°C.

[0207] After the dissolution is complete, a strong acid is added dropwise to the resulting solution and mixed.

[0208] The above strong acid serves as a main catalyst for initiating the reaction. The strong acid may include trifluoromethanesulfonic acid (TFSA), methanesulfonic acid, etc., and one or a mixture of two or more thereof may be used. Alternatively, Eaton's reagent containing methanesulfonic acid (containing 7.7 wt% P2O5 in methanesulfonic acid) may be used.

[0209] Additionally, the above strong acid can be used in a molar ratio of 2 to 20, more specifically, in a molar ratio of 6 to 14, based on 1 mol of the above compound precursor.

[0210] After mixing the above strong acids, the resulting reaction mixture may be heated from 0°C to room temperature, and a stirring process may be further performed for 6 to 48 hours.

[0211] As a result of the above process, a compound represented by the above chemical formula 7 is generated among the reactants, and the generated compound can be obtained in a solid state by dropping the reactant into an alcohol such as methanol; or a common non-solvent such as hexane, acetone, etc., and subjecting the reactant to a precipitation reaction.

[0212] Afterwards, further normal separation and purification processes such as washing, separation, and drying using normal non-solvents can be performed.

[0213] In addition, after the above separation and purification process, the obtained product is redissolved in a solvent such as tetrahydrofuran (THF), dichloromethane, etc., and the resulting solution is added dropwise to an alcohol such as methanol; or a common non-solvent such as hexane, acetone, etc.; and a precipitation reaction is performed to obtain an intermediate product with high purity.

[0214] In the intermediate product resulting from the first stage reaction, X 1 Inland X 7 The degree of introduction of the branched side chain functional group can be controlled depending on the equivalence ratio of the reactants and the order of injection. In the present invention, the final result, IEC, can be determined depending on the degree of side chain functional group introduction.

[0215] (Stage 2)

[0216] The second step is a step of producing a compound having a structure represented by chemical formula 1 by reacting the intermediate produced in the first step with a raw material forming a quaternary ammonium cationic functional group.

[0217] Specifically, the second step can be performed by dissolving the intermediate in an aprotic polar solvent, and then introducing a raw material that forms a quaternary ammonium-based cationic functional group to cause a nucleophilic substitution reaction.

[0218] The raw material forming the above quaternary ammonium cationic functional group is a nucleophile that provides a quaternary ammonium cationic functional group reaction, and during the reaction, the halogen group (X) in the intermediate is replaced by the cationic group of the nucleophile.

[0219] As a raw material for forming a quaternary ammonium cationic functional group, a tertiary amine compound, a quaternary ammonium salt, or a mixture thereof can be used.

[0220] Specifically, the tertiary amine compounds include trimethylamine (TMA), triethylamine, tripropylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, 4,4'-trimethylenebis(1-methylpiperidine), N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,5-pentanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, Examples thereof include N,N,N',N'-tetramethyl-1,3-propanediamine, or N,N,N',N'-tetramethyl-1,2-ethanediamine, and one or a mixture of two or more thereof may be used.

[0221] In addition, as the above quaternary ammonium salt, specifically, 6-(dimethylamino)-N,N,N-trimethylhexan-1-aminium salt can be mentioned.

[0222] The amount of the raw material forming the quaternary ammonium-based cationic functional group may be determined depending on the degree of functionalization. For example, the raw material forming the quaternary ammonium-based cationic functional group may be added in a molar ratio of 3 to 18, or a molar ratio of 6 to 14, per 1 mole of the intermediate.

[0223] Meanwhile, when Y in the above chemical formula 2 is a hydroxide ion, the counter ion form can be changed by precipitating the product after the second-stage reaction in a strong base aqueous solution such as sodium hydroxide, potassium hydroxide, etc. In addition, when Y in the above chemical formula 2 is a bicarbonate ion, the counter ion form can be changed by precipitating in a weak base aqueous solution such as sodium bicarbonate, etc. In addition, when Y in the above chemical formula 2 is a chloride ion, the counter ion form can be changed by precipitating in an aqueous solution such as sodium chloride, etc.

[0224] In addition, in the above nucleophilic substitution reaction, examples of the aprotic polar solvent include n-methyl pyrrolidone (NMP), dimethyl acetamide, dimethyl sulfoxide, or dimethyl formamide, and one or a mixture of two or more of these may be used. The amount used is not particularly limited and may be appropriately selected taking into account reaction efficiency, etc.

[0225] As a result of the reaction between the intermediate and the raw material forming the quaternary ammonium-based cationic functional group, a compound including a structure represented by the chemical formula 1 and optionally a structure represented by the chemical formula 5 is generated in the reactant. The generated compound can be obtained in a solid state by dropping the reactant into an ether such as dimethyl ether or tetrahydrofuran; or a common non-solvent such as hexane or acetone, and performing a precipitation reaction.

[0226] Thereafter, through conventional separation and purification processes such as washing, separation, and drying, an ion-conducting compound including a structure represented by chemical formula 1 and optionally a structure represented by chemical formula 5 can be obtained with high purity and high yield.

[0227] The ion-conducting compound manufactured through the above-described manufacturing method includes an aromatic polymer segment formed through DL Alder polymerization, and has a structure in which a quaternary ammonium-based cationic functional group is bonded to a pendant phenyl group by a branched linker, and exhibits excellent ion conductivity. In addition, it can exhibit improved dimensional stability while maintaining excellent solubility. In addition, the ion-conducting polymer can exhibit improved membrane processability due to its excellent solubility compared to its relatively high molecular weight. As a result, the ion-conducting polymer can be used as various ion-exchange materials, such as an ion-conductive single membrane, an ion-conductive reinforced membrane, an ion-conductive composite membrane, an ion-conductive reinforced composite membrane, an ion-conductive cross-linked membrane, an electrolyte membrane, a separation membrane, a water treatment membrane, or an ionomer for a membrane-electrode assembly (MEA), and is particularly useful for an ion-conductive membrane. Specifically, the ion-conducting polymer can be used as an ion exchange material in a system utilizing electrochemistry, such as a water electrolysis system, a fuel cell, a redox flow battery, a carbon dioxide reduction system, an electrochemical ammonia production and decomposition system, an electrodialysis (ED) system, a reverse electrodialysis (RED) system, or a capacitive deionization (CDI) system.

[0228] Accordingly, according to another embodiment of the invention, an ion conductive film comprising the ion conductive compound is provided.

[0229] The above ion-conducting membrane can be manufactured by a conventional ion-conducting membrane manufacturing method, except that the above-mentioned ion-conducting compound is used.

[0230] For example, a resin composition is prepared by additionally including the above-mentioned ion conductive compound and, if necessary, one or more additives such as a main solvent, a co-solvent, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, an antifoaming agent, a dispersing agent, etc., and the resin composition can be prepared by extruding and spinning, rolling, casting, or any other method, and forming a molded article in the form of a fiber or film.

[0231] More specifically, an ion-conducting compound and optionally one or more additives are dissolved in a solvent such as N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide or dimethylacetamide to prepare a resin composition, and the prepared composition is applied to a plate such as a glass plate or a support for film production, dried, and a film having a thickness of several to several hundred μm, specifically 10 to 120 μm, is obtained, and then detached from the plate or support for film production to prepare the resin composition.

[0232] Since the above ion conductive membrane includes the above ion conductive polymer, it can exhibit excellent ion conductivity as well as low WU and swelling ratio.

[0233] Specifically, the ion-conducting membrane has an ion exchange capacity (IEC) of 1.0 meq. / g or more, more specifically, 1.8 meq. / g or more, or 1.8 to 3.0 meq. / g, as measured after doping in the form of a chloride counter ion by immersion in a 1 M NaCl aqueous solution for 24 hours.

[0234] The ion exchange capacity of the above ion-conducting membrane can be measured by the Mohr Titration method, and the specific measurement method and conditions are as described in the experimental examples below.

[0235] In addition, the ion conductive membrane is doped in the form of a hydroxide counter ion by immersing it in a 1 M KOH aqueous solution for 24 hours, and then the resistance value at 60°C is measured using a 4-probe electrode, and the ion conductivity (IC) (σ) calculated according to the following mathematical formula 2 using the value is 70 mS / cm or more, more specifically, 80 to 130 mS / cm.

[0236] [Equation 2]

[0237] Ion Conductivity (σ, mS / cm) = L / (R x W x T)

[0238] In the above mathematical expression 2,

[0239] L is the distance (cm) between the Pt probes inside the measurement cell,

[0240] R is the measured resistance value of the membrane (Ω),

[0241] W is the width of the membrane doped with hydroxide ions (width, cm),

[0242] T is the thickness (cm) of the membrane doped with hydroxide ions.

[0243] In addition, the ion conductive membrane is doped in the form of a hydroxide counter ion by immersing it in a 1 M KOH aqueous solution for 24 hours, and then dried at 80°C for 15 hours. The water content (Water Uptake, WU) calculated according to the following mathematical formula 3 is 50 to 85 wt%.

[0244] [Equation 3]

[0245] WU (wt%) = (Wwet -W dry )×100 / W dry

[0246] (In the above mathematical formula 3,

[0247] W wet is the weight (g) of the ion-conducting membrane measured after doping in the form of hydroxide counter ion by immersion in a 1M KOH aqueous solution for 24 hours,

[0248] W dry Silver is the above W wet The weight (g) of the ion-conducting membrane measured after drying it in a vacuum oven at 80°C for 15 hours)

[0249] In addition, the above ion conductive membrane is doped in the form of hydroxide counter ions by immersing it in a 1M KOH aqueous solution for 24 hours, and then dried at 80°C for 15 hours. The swelling ratio calculated according to the following mathematical formula 4 is 8 to 15%.

[0250] [Equation 4]

[0251] Swelling Ratio (%) = (L wet -L dry )×100 / L dry

[0252] (In the above mathematical formula 4,

[0253] L wet is the length (mm) of the ion-conducting membrane measured after doping in the form of hydroxide counter ions by immersion in a 1M KOH aqueous solution for 24 hours.

[0254] L dry Silver is the above L wet The ion-conducting membrane was dried in a vacuum oven at 60 to 80°C for 15 hours, and then the length (mm) of the ion-conducting membrane was measured at room temperature.

[0255]

[0256] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0257] Meanwhile, unless otherwise stated herein, ordinary temperature means a typical laboratory temperature of 20 to 25°C, and ordinary pressure means a typical laboratory pressure of 0.95 to 1.05 atm.

[0258] NMR analysis of the compounds prepared in the synthetic examples and examples was performed using a Bruker AVANCE III HD 600MHz device (Bruker) at room temperature and spin 20Hz.

[0259] In addition, the molecular weight of the compound manufactured in the synthetic example is the weight average molecular weight (g / mol), and was measured through gel permeation chromatography analysis. Specifically, it was measured under the conditions of Column: PLgel 500Å+100Å+50Å (Agilent) and Standard: Polystyrene at various Mw by molecular weight using an Agilent 1260 / Malvern TDA305 device (Agilent).

[0260] Sample preparation conditions (solvent): Use THF solvent and use after 0.1 um PTFE filter, sample concentration 2.0 mg / ml

[0261] Column Conditions: Column GMHxl,

[0262] Solvent THF,

[0263] Sample injection volume 200 ul,

[0264] Flow rate 1.0 ml / min

[0265] Analysis temperature: room temperature

[0266] Refractive index analysis

[0267]

[0268] <Manufacture of compound precursors>

[0269] The compound precursor (iv) used in the examples and comparative examples is Zinaida B. Shifrina, Marina S. Averina, Alexander L. Rusanov, Manfred Wagner, and Klaus Mullen, Branched Polyphenylenes by Repetitive Diels-Alder Cycloaddition, Macromolecules 2000 33 (10), 3525-3529, DOI: 10.1021 / ma991369f and JK Stille, FW Harris, RO Rakutis, H. Mukamal, Diels-Alder polymerizations: Polymers containing controlled aromatic segments, Journal of Polymer Science Part B: Polymer Letters, vol 4, 791-793 (1966). It was manufactured according to the method described in https: / doi.org / 10.1002 / pol.1966.110041023, and the reaction temperature, reaction concentration, and reaction time were appropriately changed depending on the molecular weight of the compound precursor to be manufactured.

[0270]

[0271] For example, the compound precursor (iv) (Mw: 39 kDa) used in Example 1 was prepared as in Synthetic Example 1 below.

[0272] Synthesis Example 1: Preparation of compound precursor

[0273] Step 1: Bistetracyclone Synthesis

[0274]

[0275] In a 1000 mL round bottom flask, 1,4-bisbenzil (ii) (20.0 g, 58.421 mmol), 1,3-diphenyl-propanone (i) (25.798 g, 122.684 mmol), and anhydrous EtOH (540 mL) were added and stirred under reflux conditions for 30 minutes while maintaining a nitrogen atmosphere. After confirming that the opaque yellow reaction mixture turned transparent fluorescent yellow, a solution prepared by adding KOH (6.555 g, 116.842 mmol, 2.0 eq.) and anhydrous EtOH (60 mL) to a 100 mL round bottom flask in advance and stirring at room temperature was added to the reaction mixture, and the mixture was stirred under reflux conditions for 5 hours. After lowering the temperature of the resulting reaction product to room temperature, it was filtered to isolate the precipitate. The precipitate was washed with EtOH and dried to obtain bistetracyclone (iii) as a black solid. In addition, the filtrate separated as a result of the filtration was also evaporated of the solvent, dissolved in dichloromethane (DCM) with heating, and recrystallized. The obtained bistetracyclone (iii) 1 Purity was confirmed through H-NMR (total yield: 26.305 g, purity: 98%).

[0276] 1 H-NMR (CDCl 3, 600MHz): δ 6.773 (s, 4H), 6.91 (d, J= 7.8Hz, 4H), 7.17-7.28 (26H)

[0277]

[0278] Step 2: Synthesis of compound precursor (iv)

[0279]

[0280] In a 500 mL round bottom flask, bistetracyclone (iii) (27.0 g, 39.083 mmol), 1,4-diethynylbenzene (4.931 g, 39.083 mmol), and Ph2O (216 mL) prepared in step 1 were added, purged under a nitrogen stream for 1 hour, and stirred at 180°C for 24 hours, maintaining a constant temperature.

[0281] After heating was stopped, when the temperature of the reactant dropped to 100℃, toluene (260 mL) was added to dilute the reactant. When the temperature of the diluted reactant dropped to room temperature, the reactant was injected dropwise into hexane (2500 mL) with stirring. After 2 to 3 hours, stirring was stopped, and the solid produced as a result of the reaction was separated and dried. The dried solid was dissolved in THF (430 mL) and then injected dropwise into acetone (2500 mL) with stirring. The solid portion was separated and dried under reduced pressure to obtain poly(phenylene) (iv) as a compound precursor as a yellowish-white solid (yield: 29.98 g, purity: 99% excluding residual solvent).

[0282] 1 H-NMR (CDCl 3, 600MHz): δ 6.20-6.35 (4H), 6.61-6.68 (8H), 6.82-6.96 (16H), 7.06-7.26 (10H), 7.43 (s, 2H)

[0283]

[0284] Example 1

[0285] Step 1: Synthesis of Brominated Poly(phenylene)

[0286]

[0287] In a 250 mL round bottom flask, the compound precursor prepared in Synthesis Example 1, poly(phenylene) (iv) (10.0 g, 13.14 mmol) and the branched alcohol, 7-bromo-2-methyl-2-heptanol (BMH) (14.565 g, 69.65 mmol), were placed, and under a nitrogen atmosphere, dichloromethane (200 mL) was injected to dissolve poly(phenylene), followed by stirring at 0°C. Trifluoromethane sulfonic acid (TFSA, 12.30 mL, 139.29 mmol) was added dropwise to the resulting mixed solution.

[0288] The resulting reaction mixture was gradually warmed from 0℃ to room temperature and stirred for 24 hours. The resulting reaction product was injected dropwise into MeOH (1000 mL) and stirred for 3 hours. After stirring was completed, the supernatant was discarded and the reaction product was obtained. The obtained reaction product was washed several times with methanol (MeOH), a nonsolvent. The solid of the washed reaction product was separated, dried, and dissolved in THF (150 mL). The resulting solution was injected dropwise into MeOH (1000 mL) and stirred for 3 hours. After stirring was completed, the solid was separated and dried under reduced pressure to obtain compound (v) of brominated poly(phenylene) (yield: 18 g).

[0289] 1 H-NMR (CDCl 3, 600MHz): δ 0.55-1.95 (m, 14H), 2.95-3.45 (2H), 6.05-7.55 (m, aromatic)

[0290]

[0291] Step 2: Aminated Poly(phenylene) Synthesis

[0292]

[0293] In a 250 mL round bottom flask, the brominated poly(phenylene)(v) (10 g, 7.38 mmol) prepared in Step 1 was dissolved in NMP (87 mL, 10 wt%). Trimethylamine (TMA, 4.2 M solution in EtOH, 21.09 mL) was added to the resulting solution and stirred for 48 hours. The resulting reaction product was dropwise injected into ethyl ether (1000 mL) and stirred for 3 hours. After stirring was completed, the supernatant was removed from the resulting reaction product, and acetone (1000 mL) as a nonsolvent was added to the remaining reaction product and washed with stirring. The washed solid was separated and dried to obtain aminated poly(phenylene) (1a-1) (yield: 11 g).

[0294] 1 H-NMR (CDCl 3, 600MHz): δ 0.60-1.75 (m, 14H), 2.80-3.10 (9H), 3.15-3.30 (m, 2H), 5.90-7.70 (m, aromatic)

[0295]

[0296] Examples 2 to 8

[0297] Compound (1a-1) was prepared by the same method as in Example 1, except that compounds (iv) having various molecular weights were used as compound precursors for preparing aminated poly(phenylene) as described in Table 1 below, and the process was performed under the described conditions.

[0298]

[0299]

[0300] The weight average molecular weight (Mw) for the final manufactured compound at each stage in Table 1 above was measured using the same method as in the weight average molecular weight measurement method (1-1) described in Experimental Example 1 below.

[0301]

[0302] Comparative Example 1

[0303] A polyphenylene ion-conducting polymer (b) was prepared according to the following reaction formula under the conditions described in Table 2 below.

[0304]

[0305] Step 1: Synthesis of Poly(phenylene)-KBr

[0306] In a 250 mL round bottom flask, the compound precursor (iv) (10.0 g, 13.14 mmol) prepared in Synthesis Example 1 and 6-Bromohexanoyl chloride (8.43 g, 39.48 mmol) were added, and dichloromethane (500 mL) was additionally added under a nitrogen atmosphere to dissolve poly(phenylene), followed by stirring at 0°C. AlCl3 (5.26 g, 39.48 mmol, 3.0 eq) was added to the resulting mixed solution, and the resulting reaction mixture was slowly warmed from 0°C to room temperature and stirred for 6 hours. The resulting reaction mixture was poured into 1 L of DI water, and a solid was precipitated by evaporating DCM at 40°C.

[0307] The precipitated solid was separated from DI water, dried, and dissolved in DCM (200 mL), then injected dropwise into 1 L of acetone and stirred. The resulting precipitated solid portion was separated and dried under reduced pressure to obtain intermediate compound (vi) (12.86 g, 76%) as a yellow solid.

[0308]

[0309] Step 2: Synthesis of Brominated Poly(phenylene) (vii)

[0310] To the intermediate compound (vi) (10 g, 7.74 mmol), Et3SiH (4.14 g, 35.6 mmol), TFA (120 mL), and 1,2-DCE (500 mL) were added, and a reduction reaction was performed by refluxing for 24 hours. After completion of the reaction, when the temperature of the reaction mixture reached room temperature, the reaction mixture was poured into MeOH (1 L), and the precipitated solid was filtered and dried. The dried solid was dissolved in DCM (100 ml) and then injected dropwise into acetone (1 L) with stirring. After washing for 3 hours, stirring was stopped, and the solid portion was separated and dried. As a result, brominated poly(phenylene) (vii) (5.59 g) was obtained.

[0311]

[0312] Step 3: Synthesis of Aminated Poly(phenylene) (b)

[0313] The brominated poly(phenylene)(vii) (10 g, 7.38 mmol) prepared above was added to a 250 mL round bottom flask and dissolved in NMP (87 mL, 10 wt%). Trimethylamine (TMA, 4.2 M solution in EtOH, 21.09 mL) was added to the resulting solution and stirred for 48 hours. The resulting reaction product was injected dropwise into ethyl ether (1000 mL) and stirred for 3 hours. After stirring was completed, the supernatant was removed from the resulting reaction product, and acetone (1000 mL) as a nonsolvent was added to the remaining reaction product and washed with stirring. The washed solid was separated and dried to obtain aminated poly(phenylene) (b) (yield: 11 g).

[0314]

[0315] Comparative Example 2

[0316] An ion conductive compound was manufactured by the same method as in Comparative Example 1, except that the conditions described in Table 1 below were changed.

[0317] However, the ion-conducting compound manufactured in Comparative Example 2 did not dissolve in the solvent. Therefore, the molecular weight was measured using some of the polymer dissolved in the solvent, and since processing into a membrane was impossible, the membrane properties could not be evaluated.

[0318]

[0319]

[0320]

[0321] The weight average molecular weight (Mw) or ion exchange capacity (IEC, meq. / g) for the final manufactured compound in each step in Table 2 above was measured using the same method as in the (1-1) weight average molecular weight and (2-2) ion exchange capacity measurement method described in Experimental Example 1 below.

[0322]

[0323] Experimental Example 1

[0324] (1) Polymer analysis

[0325] For qualitative analysis of the functional groups and structures of the polymer compounds synthesized in the above examples and comparative examples, FT-IR and NMR data were used, and for quantitative analysis of molecular weight, GPC data were used.

[0326]

[0327] (1-1) Weight average molecular weight (Mw)

[0328] Analysis was performed using gel permeation chromatography (GPC) under the following conditions. Based on a calibration curve formed using polystyrene standard foam, the Mw value (g / mol) was derived from the analysis results. However, since ionic polymers cannot be measured by GPC, GPC was measured on the precursor polymer before the quaternization reaction.

[0329] <GPC 분석 조건>

[0330] Device used: Agilent

[0331] Columns: Agilent PL Mixed D, Agilent PLgel 100Å, Agilent PLgel 50Å

[0332] Sample concentration: 1 wt / vol% in tetrahydrofuran (THF)

[0333] Carrier: THF

[0334] Detection method: RI

[0335] Flow rate: 1.0 ml / min

[0336] Column temperature: 25 ℃

[0337] Detector: Agilent RI detector

[0338] When preparing the calibration curve, polystyrene standard foams with molecular weights of 104 to 24,600 g / mol were used.

[0339]

[0340] (2) AEM evaluation

[0341] (2-1) AEM Sample Manufacturing

[0342] Step 1: Membrane Preparation

[0343] 2.0 g of the ion-conducting polymer prepared in the above examples or comparative examples was placed in a 70 ml vial and sufficiently dissolved with the solvent dimethylsulfoxide (DMSO, 35 g). The resulting polymer solution was filtered through a cotton filter to remove foreign substances contained in the polymer solution. The polymer solution from which foreign substances had been removed was spread-casted on a glass plate measuring 18 cm in length x width, and then dried in an oven at 70°C for 24 hours. After drying was complete, the glass plate was collected and a membrane was obtained.

[0344]

[0345] Step 2: Preprocessing

[0346] The membrane manufactured in step 1 above has a counter ion of the quaternary ammonium functional group of I - or Br - This membrane can change the counter ion according to the purpose, and the process is called doping. Depending on the doping solution, Cl - , HCO3 - , OH - AEM containing counter ions in the form of anions such as H2PO4 can be manufactured. - It is also possible to manufacture PEMs containing phosphate anion forms such as .

[0347]

[0348] A. Chloride Doping (for IEC measurements)

[0349] The membrane prepared in Step 1 was placed in a 1 M NaCl aqueous solution at room temperature and ion-exchanged for 24 hours. After ion-exchange was complete, the membrane was removed and thoroughly washed multiple times with distilled water. To ensure complete removal of residual NaCl, the washed membrane was stored in distilled water for 24 hours and then dried before use.

[0350]

[0351] B. Hydroxide Doping (for IC, WU measurement, MEA manufacturing)

[0352] In an environment completely blocked from CO2, such as inside a glove box with an argon atmosphere, the membrane prepared in step 1 was placed in a 1 M KOH aqueous solution and ion exchange was performed for 24 hours. After the ion exchange was completed, the membrane was taken out and thoroughly washed several times with distilled, deionized, Ar-gas bubbled water. To ensure that the residual KOH was completely removed, the washed membrane was washed several times with distilled water and then soaked in distilled water and stored for 24 hours before use. Since the membrane ion-exchanged in the form of hydroxide ions forms bicarbonate ions within a few minutes when it comes into contact with CO2 in the air, it was avoided to allow it to come into contact with CO2.

[0353]

[0354] (2-2) Ion Exchange Capacity (IEC)

[0355] For the membrane doped with the above chloride counter ion, according to the method known in Journal of polymer science, part B: Polymer Physics 2013, 51(24), 1736-1742 and Macromolecules 2009, 42(21), 8316-8321 1 IEC values ​​were measured using H-NMR analysis:

[0356] < 1 H-NMR analysis conditions>

[0357] Equipment used: 600MHz Bruker NMR

[0358] acquisition time 2.73s

[0359] delay time 1s

[0360] scan number 128

[0361] pulse 30°

[0362] solvent CDCl3

[0363] Sample concentration: 2.5 wt%

[0364]

[0365] (2-3) Ion Conductivity (IC)

[0366] For the membrane doped with the above hydroxide ions, the in-plane ion conductivity (IC) was measured using a 4-probe electrode (BekkTech Membrane Conductivity Test System). In a fuel cell system, the IC is measured by checking the resistance value according to the change in relative humidity (RH) value at a specific temperature. The difference in the water electrolysis system is that the resistance value is measured by completely immersing the measuring cell in deionized water so that the RH becomes 100% at a specific temperature.

[0367] Since the measurement was performed using a sample doped with hydroxide ions, all pretreatment procedures were performed in a CO2-free atmosphere, such as a glove box. During the IC measurement, Ar gas was continuously purged from the container containing the measurement cell to prevent the membrane from being exposed to CO2. In the glove box, a 4 cm wide and 0.7 cm long specimen (actual values ​​for each sample were applied) was mounted on the measurement cell (4-probe electrode cell) and quickly transferred to a container containing water for conductivity measurement using an Ar bag.

[0368] After sealing the container, it was connected to an IC measurement device (BekkTech Membrane Conductivity Test System) under Ar gas purge condition. The resistance value at 80℃ was measured, and the IC was calculated using the following mathematical equation 2 (BekkTech Conductivity Testing Software).

[0369] [Equation 2]

[0370] Ion Conductivity (σ, mS / cm) = L / (R x W x T)

[0371] In the above mathematical formula 2,

[0372] L is the distance (cm) between the Pt probes inside the measurement cell, which is 4.2 mm in this experimental example.

[0373] R is the measured resistance value of the membrane (Ω),

[0374] W is the width of the membrane doped with hydroxide ions (width, cm),

[0375] T is the thickness (cm) of the membrane doped with hydroxide ions.

[0376]

[0377] Additionally, the resistance values ​​at 60℃, 70℃, and 80℃ were measured, respectively, and the IC was calculated according to the above mathematical formula 2.

[0378]

[0379] (2-4) WU (Water Uptake) and Swelling Ratio

[0380] WU measures the ratio of water absorbed per unit mass. Since the weight change of an AEM sample doped with hydroxide ions was measured, the experiment was conducted in an argon-atmosphere glove box to prevent contact with CO2 as much as possible.

[0381] For the membrane doped with hydroxide ions by immersing it in the above 1M KOH aqueous solution for 24 hours, the moisture on the surface of the membrane was gently wiped off using KimWipe, and the wet state was The weight (g) of the membrane was measured (W wet ).

[0382] The membrane that completed the above measurement was dried in a vacuum oven at 80°C for 15 hours, and the weight (g) of the dry membrane was measured (W dry ) Using the measured values, WU was calculated according to the following mathematical formula 3.

[0383] [Equation 3]

[0384] WU (wt%) = (W wet -W dry )×100 / W dry

[0385]

[0386] Swelling ratio represents the rate of change in the physical size of a membrane due to water absorption. Swelling ratio can also be measured using a sample measuring water uptake.

[0387] Specifically, for the membrane doped with hydroxide ions by immersing it in a 1M KOH aqueous solution for 24 hours, the moisture on the surface of the membrane was gently wiped off using KimWipe, and the wet state was m The length of the embrane was measured and recorded accurately in mm (L wet ).

[0388] After completing the above measurement, the membrane was washed 5 times with pure water, dried in a vacuum oven at 80°C for 15 hours, and the length of the dry membrane was accurately measured in mm and recorded (L dry) After comparing with the length measured immediately after the completion of the above doping, the swelling ratio was calculated according to the following mathematical equation 4.

[0389] [Equation 4]

[0390] Swelling Ratio (%) = [(L wet -L dry )×100] / L dry

[0391] The measurement results are shown in Table 3 below.

[0392]

[0393]

[0394] In Table 3 above, NA means not measurable.

[0395] Also, a is 1 This is a measurement value measured through H-NMR analysis.

[0396] The ion-conducting compounds of the examples exhibited relatively superior conductivity, WU, and swelling characteristics at various molecular weights and DFs compared to the comparative examples.

[0397] Meanwhile, the ion-conducting compound of Comparative Example 2 was not completely dissolved in the solvent, so measurement results could not be obtained.

[0398]

[0399] Experimental Example 2

[0400] For the ion-conducting compounds prepared in Examples 1 and 7 and Comparative Examples 1 and 2, the solubility in N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO), which are solvents commonly used in the preparation of polymer membranes, was evaluated.

[0401] Specifically, 0.5 g of the polymer of the above examples or comparative examples was dissolved in 10 ml of NMP and stirred at 500 rpm for 24 hours under room temperature and pressure. The resulting reaction product was observed under a microscope, and the solubility was evaluated according to the following criteria.

[0402] The solubility evaluation was performed for DMSO using the same method as above. The results are shown in Table 4 below.

[0403] <Evaluation Criteria>

[0404] ○: All polymers are dissolved, resulting in a transparent and clean solution.

[0405] Δ: No polymer clumps are observed, but the state is relatively opaque compared to the solution state.

[0406] X: The polymer is not dissolved at all and is in a swollen state.

[0407]

[0408]

[0409] From the above experimental results, it can be seen that the ion conductive compound of the example is not only easier to manufacture a polymer membrane than the comparative example, but is also more advantageous in improving the physical properties of the manufactured polymer membrane.

Claims

1. An ion conducting compound comprising a structure represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, A 11 Inland A 17 are each independently represented by the following chemical formula 2, B is an arylene group having 6 to 18 carbon atoms, a1 to g1 are each independently an integer of 0 or 1, and at least one of a1 to g1 is an integer of 1, n is an integer greater than or equal to 1, [Chemical formula 2] In the above chemical formula 2, L is a branched alkylene group having 3 to 30 carbon atoms, Z is a quaternary ammonium cationic functional group, Y is an anion.

2. In paragraph 1, The ion conductive compound is a compound comprising any one of the structures represented by the following chemical formulas 1a to 1l: In the above chemical formulas 1a to 1l, A 11 Inland A 17 , B and n are as defined in paragraph 1.

3. In paragraph 1, The above B is an ion conducting compound which is p-phenylene, m-phenylene, or biphenylene.

4. In paragraph 1, The above L is an ion conducting compound, which is a branched alkylene group having 3 to 30 carbon atoms and represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R 1 and R 2 At least one of them is an alkyl group having 1 to 6 carbon atoms, and the others are hydrogen, p is an integer from 1 to 3, q and r are each independently an integer from 0 to 10, but q and r are not both integers of 0, s is an integer from 1 to 3.

5. In paragraph 1, An ion conducting compound wherein L is 1,1-dimethylhexylene, 1,1-diethylhexylene, 1,1-dimethylheptylene, or 1,1-dimethylpentylene.

6. In paragraph 1, The above Z is an ion conducting compound represented by the following chemical formula 4-1 or chemical formula 4-2: [Chemical Formula 4-1] [Chemical Formula 4-2] In the above chemical formulas 4-1 and 4-2, Q is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, R 11 Inland R 13 , and R 21 Inland R 25 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or R 11 Inland R 13 Two adjacent units, R 21 And R 22 , or R 23 Inland R 25 In the above, two adjacent groups are connected to each other to form a substituted or unsubstituted N-containing heterocyclic group having 2 to 20 carbon atoms.

7. In paragraph 1, wherein Z is trimethylammonium, triethylammonium, diethylmethylammonium, dimethylethylammonium, tripropylammonium, tributylammonium, N-methylpyrrolidium, N-methylpiperidium, or 6-(dimethylamino)-N,N,N-trimethylhexan-1-aminium; or an ion conducting compound selected from the group consisting of: In the above formula, * is a position where it is bonded to L in the chemical formula 2.

8. In paragraph 1, An ion conducting compound, wherein Y is a chloride ion, a bromide ion, an iodide ion, a hydroxide ion, a bicarbonate ion, a dihydrogen phosphate ion, a hydrogen phosphate ion, or a phosphate ion.

9. In paragraph 1, The above ion conducting compound is an ion conducting compound having a structure represented by the following chemical formula 1a-1 or 1a-2: [Chemical formula 1a-1] [Chemical Formula 1a-2] In the above chemical formulas 1a-1 and 1a-2, n is as defined in clause 1.

10. In paragraph 1, The above ion-conducting compound is an ion-conducting compound having a weight average molecular weight of 30 to 900 kDa.

11. In paragraph 1, The above ion-conducting compound is an ion-conducting compound having an ion exchange capacity of 1.0 meq. / g or more.

12. A first step of producing a compound comprising a structure represented by the following chemical formula 7 by reacting a compound comprising a structure represented by the following chemical formula 5 with at least one of the compounds represented by the following chemical formula 6 in the presence of a strong acid; and A second step of reacting a compound including a structure represented by the chemical formula 7 with a raw material forming a quaternary ammonium-based cationic functional group; comprising; Method for producing an ion conductive compound according to Article 1: [Chemical Formula 5] In the above chemical formula 5, B is an arylene group having 6 to 18 carbon atoms, n is an integer greater than or equal to 1, [Chemical formula 6] In the above chemical formula 6, L is a branched alkylene group having 3 to 30 carbon atoms, X is a halogen group, [Chemical formula 7] In the above chemical formula 7, B and n are as defined in the chemical formula 5 above, X 1 Inland X 7 are each independently represented by the following chemical formula 8, a1 to g1 are each independently an integer of 0 or 1, and at least one of a1 to g1 is an integer of 1, [Chemical formula 8] In the above chemical formula 8, L and X are as defined in the chemical formula 6 above.

13. In paragraph 12, The above first step is a manufacturing method performed by dissolving a compound including a structure represented by the above chemical formula 5 and at least one compound represented by the above chemical formula 6 in a solvent under a nitrogen atmosphere, and then adding a strong acid to cause a substitution reaction.

14. In paragraph 12, A method for producing a compound represented by the above chemical formula 6, wherein the compound is 7-bromo-2-methyl-2-heptanol, 7-bromo-2-ethyl-2-heptanol, or 5-bromo-2-methyl-2-pentanol.

15. In paragraph 12, A manufacturing method wherein the compound represented by the chemical formula 6 is added in a molar ratio of 1 to 10 with respect to 1 mol of the compound including the structure represented by the chemical formula 5.

16. In paragraph 12, A manufacturing method wherein the strong acid comprises trifluoromethanesulfonic acid, methanesulfonic acid, or a mixture thereof.

17. In paragraph 12, A manufacturing method wherein the above strong acid is added in a molar ratio of 2 to 20 based on 1 mole of the compound including the structure represented by the above chemical formula 5.

18. In paragraph 12, A manufacturing method further comprising, before the first step, a step of producing a compound including a structure represented by the chemical formula 6 by subjecting a bistetracyclone to a Diels-Alder reaction with at least one ethynyl-substituted aromatic compound.

19. In paragraph 12, A method for producing the above ethynyl-substituted aromatic compound, wherein the above ethynyl-substituted aromatic compound is 1,4-diethynylbenzene, 4,4'-diethylnylbiphenyl or 1,3-diethynylbenzene.

20. In paragraph 12, The second step is a manufacturing method performed by dissolving a compound including a structure represented by the chemical formula 7 in an aprotic polar solvent, and then introducing a raw material forming a quaternary ammonium-based cationic functional group to cause a nucleophilic substitution reaction.

21. In paragraph 12, A manufacturing method wherein the raw material forming the above quaternary ammonium cationic functional group includes a tertiary amine compound, a quaternary ammonium salt, or a mixture thereof.

22. In paragraph 21, A method for producing the above tertiary amine compound, wherein the above tertiary amine compound is trimethylamine, triethylamine, tripropylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, 4,4'-trimethylenebis(1-methylpeperidine), N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,5-pentanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, or N,N,N',N'-tetramethyl-1,2-ethanediamine.

23. In paragraph 21, A method for producing the above quaternary ammonium salt, wherein the above quaternary ammonium salt is 6-(dimethylamino)-N,N,N-trimethylhexane-1-ammonium salt.

24. In paragraph 12, A manufacturing method wherein the raw material forming the above quaternary ammonium cationic functional group is added in a molar ratio of 3 to 18 per 1 mol of the compound including the structure represented by the chemical formula 7.

25. An ion exchange material comprising an ion conductive compound according to paragraph 1.

26. In paragraph 25. The above ion exchange material is an ion exchange material that is an ion-conducting single membrane, an ion-conducting reinforced membrane, an ion-conducting composite membrane, an ion-conducting reinforced composite membrane, an ion-conducting cross-linked membrane, an electrolyte membrane, a separation membrane, a water treatment membrane or an ionomer for a membrane-electrode assembly.

27. In paragraph 25. The above ion exchange material is an ion exchange material for a water electrolysis system, a fuel cell, a redox flow battery, a carbon dioxide reduction system, an electrochemical ammonia production and decomposition system, an electrodialysis system, a reverse electrodialysis system, or a capacitive desalination system.

28. An ion-conducting membrane comprising an ion-conducting compound according to paragraph 1.

29. In paragraph 28, The above ion-conducting membrane is an ion-conducting membrane having an ion exchange capacity of 1.0 meq. / g or more, measured after being doped in the form of chloride counter ions by immersion in a 1 M NaCl aqueous solution for 24 hours.

30. In paragraph 28, The above ion-conducting membrane is an ion-conducting membrane having an ion conductivity of 70 mS / cm or more when measured at 60°C after being doped in the form of hydroxide counter ions by immersion in a 1 M KOH aqueous solution for 24 hours.

31. In paragraph 28, The above ion-conducting membrane is doped in the form of hydroxide counter ions by immersing it in a 1 M KOH aqueous solution for 24 hours, and then dried at 80° C. for 15 hours, and has a WU of 50 to 85 wt% calculated according to the following mathematical formula 3: [Mathematical Formula 3] WU (wt%) = (W wet -W dry )×100 / W dry In the above mathematical expression 3, W wet is the weight of the ion-conducting membrane measured after doping in the form of hydroxide counter ions by immersion in a 1 M KOH aqueous solution for 24 hours, W dry Silver is the above W wet This is the weight of the ion-conducting membrane measured after drying it in a vacuum oven at 80°C for 15 hours.

32. In paragraph 28, The above ion-conducting membrane is doped in the form of hydroxide counter ions by immersing it in a 1 M KOH aqueous solution for 24 hours, and then dried at 80° C. for 15 hours, and has a swelling ratio of 8 to 15% calculated according to the following mathematical formula 4: [Mathematical Formula 4] Swelling ratio (%) = (L wet -L dry )×100 / L dry In the above mathematical expression 4, L wet is the length of the ion-conducting membrane measured after doping in the form of hydroxide counter ions by immersion in a 1 M KOH aqueous solution for 24 hours, L dry Silver is the above L wet This is the length of the ion-conducting membrane measured at room temperature after drying the ion-conducting membrane in a vacuum oven at 60 to 80°C for 15 hours.

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