Alkyl side chain substituted aromatic hydrocarbon monomer, polyarane and preparation method and application thereof

Abstract

The invention discloses an alkyl side chain substituted aromatic hydrocarbon monomer, polyarane and a preparation method and application thereof. The alkyl side chain substituted aromatic hydrocarbon monomer has a structure as shown in the following formula: # imgabs0 #, A is selected from an aromatic monomer, Y is selected from F, Cl, Br, CnH2n-1, OH, OCnH2n-1, OCnF2n-1, SH, SCnH2n-1, SCnF2n-1, N (CnH2n-1) 2 or N (CnH2n-1) 3, and n is selected from an integer from 0 to 20. The method provided by the invention has ultrahigh reaction activity, good compatibility to various functional groups, mild reaction and high yield, and can be used for preparing substituted aromatic monomers required by various ion exchange membrane materials, organic photoelectric materials and the like, and meanwhile, the prepared membrane material has the advantages of high conductivity, excellent chemical stability and the like; and the method has obvious practical application and industrialization prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of ion exchange membranes, and specifically relates to an alkyl side chain substituted aromatic hydrocarbon monomer, polyarene and a preparation method and application thereof. Background Art

[0002] In the context of energy transformation, the development of clean energy technologies, such as fuel cells, water electrolysis to produce hydrogen, and flow batteries, can achieve efficient use of intermittent renewable energy.

[0003] Ion exchange membranes play a vital role in various electrochemical processes, such as electrolysis or electrochemical devices, and these applications also place high demands on the membrane materials. First, they must have sufficient chemical stability in the operating environment. In addition, the membrane needs to withstand the swelling of the medium and the mechanical stress in the device. Another point that cannot be ignored is that the membrane materials need to have sufficient ion conductivity. These factors directly determine the operating efficiency and service life of the device.

[0004] Most of the ion exchange membrane materials currently developed belong to the category of polymers. They are synthesized from monomers through various polymerization reactions. Among them, superacid-catalyzed Friedel-Crafts hydroxyalkylation polymerization is an important method for preparing ion exchange membrane materials. In 2015, Bae et al. obtained high molecular weight polyarylalkyl polymers by polyhydroxyalkylation reaction of biphenyl and trifluoromethyl substituted ketone monomers, and then obtained a series of all-carbon skeleton anion exchange membrane materials after trimethylamine quaternization (ACS MacroLett.2015, 4, 814-8). In 2017, Jannasch et al. used N-methyl-piperidone and aromatic monomers through polyhydroxyalkylation reaction to synthesize polyaryl piperidine polymers, and then used alkyl halides of different structures for quaternization to obtain structurally rich anion exchange membrane materials (Adv.Funct.Mater.2018, 28, 1702758). In 2019, Jannasch et al. first prepared a high molecular weight polymer precursor by superacid-catalyzed polymerization of perfluoroacetophenone and biphenyl, and then sulfonated the side chain pentafluorophenyl group to obtain a perfluorophenylsulfonic acid proton exchange membrane material (ACS Macro Lett. 2019, 8, 1247-125). In principle, Friedel-Crafts hydroxyalkylation polymerization can synthesize polymers suitable for ion exchange membranes, but the comprehensive performance of the currently developed ion exchange membranes still needs to be further improved, especially in terms of chemical stability, ionic conductivity and mechanical stability. Summary of the invention

[0005] The main purpose of the present invention is to provide an alkyl side chain substituted aromatic monomer, polyarane and a preparation method and application thereof, so as to overcome the deficiencies of the prior art.

[0006] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0007] The embodiment of the present invention provides an alkyl side chain substituted aromatic monomer having a structure as shown in formula (I):

[0008]

[0009] Wherein, A is selected from aromatic monomers, and the aromatic monomer is selected from any one of the following structures:

[0010]

[0011] Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3, n is selected from an integer between 0 and 20.

[0012] The present invention also provides a method for preparing the aforementioned alkyl side chain substituted aromatic monomer, which comprises:

[0013] reacting a first mixed reaction system comprising at least an olefin monomer, 9-boranebicyclo[3,3,1]nonane, and a halogenated aromatic hydrocarbon monomer to obtain an alkyl side chain substituted aromatic hydrocarbon monomer;

[0014] The structure of the olefin monomer is Wherein Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 ) 3, n is an integer selected from 0-20; the structure of the halogenated aromatic monomer is Wherein A is selected from aromatic monomers, and X is selected from Cl, Br or I.

[0015] The embodiment of the present invention further provides a polyarene, wherein the polyarene has a structure as shown in formula (II) or formula (III):

[0016]

[0017] Wherein, A and B are independently selected from aromatic monomers, and Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; at least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0018] The present invention also provides a method for preparing the aforementioned polyarylalkane, which comprises:

[0019] A second mixed reaction system comprising at least an aromatic monomer B, an alkyl halide-substituted aromatic monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain a polyarylalkane having a structure represented by formula (II);

[0020] Wherein, the aromatic monomer B is selected from aromatic monomers; the alkyl halide substituted aromatic monomer is the aforementioned alkyl side chain substituted aromatic monomer; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0021] Alternatively, a third mixed reaction system comprising at least an aromatic monomer B, a halogenated aromatic hydrocarbon monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aromatic halide polyarylalkane precursor;

[0022] and reacting a fourth mixed reaction system comprising at least the aromatic halide polyarylalkane precursor, an olefin monomer and 9-boranebicyclo[3,3,1]nonane to obtain a polyarylalkane having a structure represented by formula (II);

[0023] Wherein, the aryl halide polyaryl alkane precursor has a structure as shown in formula (IV):

[0024]

[0025] The aromatic monomer B is selected from aromatic monomers; the structure of the halogenated aromatic monomer is A is selected from aromatic monomers, X is selected from Cl, Br or I; the structure of the olefin monomer is Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0026] Alternatively, a fifth mixed reaction system comprising at least an aromatic monomer B, an aromatic halogen-containing ketone monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aromatic halogen-containing polyarylalkane precursor;

[0027] and reacting a fourth mixed reaction system comprising at least the aromatic halide polyarylalkane precursor, an olefin monomer and 9-boranebicyclo[3,3,1]nonane to obtain a polyarylalkane having a structure represented by formula (III);

[0028] Wherein, the aryl halide polyaryl alkane precursor has a structure as shown in formula (V):

[0029]

[0030] The aromatic monomer B is selected from aromatic monomers, and the structure of the aromatic halogen ketone-containing monomer is A is selected from aromatic monomers, X is selected from Cl, Br or I; the structure of the olefin monomer is Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0031] The embodiments of the present invention also provide the use of the aforementioned polyarylalkane in preparing a cross-linked polymer, an ion exchange resin, an ion exchange membrane or a fuel cell.

[0032] The embodiment of the present invention further provides a cross-linked polymer, wherein the cross-linked polymer is obtained by reacting the aforementioned polyarylalkane with a first polymer; wherein the first polymer comprises a polymer containing a tertiary amine group.

[0033] The embodiment of the present invention further provides an ion exchange resin, wherein the ion exchange resin includes a cation exchange resin or an anion exchange resin;

[0034] The anion exchange resin is obtained by reacting the aforementioned polyarylalkane with a tertiary amine group; and the cation exchange resin is obtained by reacting the aforementioned polyarylalkane with potassium thioacetate and m-chloroperbenzoic acid.

[0035] The embodiment of the present invention further provides an ion exchange membrane, which is made of the aforementioned cross-linked polymer or ion exchange resin.

[0036] The embodiments of the present invention also provide the use of the aforementioned cross-linked polymer or ion exchange membrane in the preparation of diaphragm materials in the fields of fuel cells, redox flow batteries or water electrolysis.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] (1) The method provided by the present invention has ultra-high reactivity, good compatibility with various functional groups, mild reaction and high yield, and can be used to prepare substituted aromatic monomers required for various ion exchange membrane materials, organic optoelectronic materials, etc.

[0039] (2) The polyarylalkylene provided by the present invention and the proton exchange membrane and anion exchange membrane prepared from the polyarylalkylene have the advantages of high electrical conductivity, excellent chemical stability, etc., and have obvious practical application and industrialization prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0041] Figure 1 is a preparation route of the bromohexyl-substituted m-terphenyl in Example 1 of the present invention;

[0042] Figure 2 is the bromohexyl-substituted m-terphenyl in Example 1 of the present invention 1 H-NMR spectrum;

[0043] Figure 3 is a preparation route of the alkyl bromide substituted polyarylalkane P1-6CBr and the anion exchange resin P1-QA in Example 2 of the present invention;

[0044] Figure 4 is the H NMR spectrum of the alkyl bromide substituted polyarylalkane P1-6CBr in Example 2 of the present invention;

[0045] Figure 5 is the H NMR spectrum of the anion exchange resin P1-QA in Example 2 of the present invention;

[0046] Figure 6 is a polarization curve diagram of the hydrogen / air P1-QA anion exchange membrane fuel cell in Example 2 of the present invention;

[0047] Figure 7 is a preparation route diagram of the cation exchange resin P1-SA in Example 3 of the present invention;

[0048] Figure 8 is the H NMR spectrum of the cation exchange resin P1-SA in Example 3 of the present invention;

[0049] Fig. 9 It is a preparation route of the alkyl bromide substituted polyarylalkane P1-6CBr-BP-x and the anion exchange resin P1-QA-BP-x in Example 4 of the present invention;

[0050] Fig.10 is the H NMR spectrum of the alkyl bromide substituted polyarylalkane P1-6CBr-BP-10% in Example 4 of the present invention;

[0051] Fig.11 is the H NMR spectrum of the double ion-substituted anion exchange resin P1-QA-BP-10% in Example 4 of the present invention;

[0052] Fig.12This is another preparation route of the alkyl bromide substituted polyarylalkane P1-6CBr in Example 5 of the present invention;

[0053] Fig.13 is the H NMR spectrum of the brominated polyarylalkane P1-Br in Example 5 of the present invention;

[0054] Fig.14 is a synthetic route of the alkyl bromide substituted polyarylalkane P2-6CBr in Example 6 of the present invention;

[0055] Fig.15 It is the nuclear magnetic hydrogen spectrum of the brominated polymer P2-Br, the alkyl bromide substituted polymer P2-6CBr and the two cation exchange polymers P2-QA in Example 6 of the present invention;

[0056] Fig.16 is a preparation route of the brominated polyarylalkane P2-Br-TF, the alkyl bromide substituted polyarylalkane P2-6CBr-TF and the anion exchange resin P2-QA-TF in Example 7 of the present invention;

[0057] Fig.17 is a flow chart of the preparation of the cross-linked film in Example 8 of the present invention;

[0058] Fig.18 is a polarization curve diagram of AEMWE based on AEM-QPBP-P1-10% equipped with non-precious metal catalyst under 1M KOH conditions at 80° C. in Example 8 of the present invention;

[0059] Fig.19 This is a diagram of the method for preparing bromoalkyl-substituted m-terphenyl reported in patent WO 2024 / 046712 in comparative example 1 of the present invention. DETAILED DESCRIPTION

[0060] In view of the defects of the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0061] Specifically, as one aspect of the technical solution of the present invention, an alkyl side chain substituted aromatic hydrocarbon monomer involved has a structure as shown in formula (I):

[0062]

[0063] Wherein, A is selected from aromatic monomers, and the aromatic monomer is selected from any one of the following structures:

[0064]

[0065] Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3, n is selected from an integer between 0 and 20.

[0066] The alkyl side chain substituted aromatic monomer provided by the present invention has ultra-high reactivity and good compatibility with various functional groups, and can be used to prepare substituted aromatic monomers required for various ion exchange membrane materials, organic photoelectric materials, etc.

[0067] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned alkyl side chain substituted aromatic monomer, which comprises:

[0068] reacting a first mixed reaction system comprising at least an olefin monomer, 9-boranebicyclo[3,3,1]nonane, and a halogenated aromatic hydrocarbon monomer to obtain an alkyl side chain substituted aromatic hydrocarbon monomer;

[0069] The structure of the olefin monomer is Wherein Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 ) 3, n is an integer selected from 0-20; the structure of the halogenated aromatic monomer is Wherein A is selected from aromatic monomers, and X is selected from Cl, Br or I.

[0070] In some preferred embodiments, the reaction formula for preparing the alkyl side chain substituted aromatic monomer is as follows:

[0071]

[0072] In some preferred embodiments, the preparation method specifically comprises: reacting an olefin monomer with 9-boranebicyclo[3,3,1]nonane at 30-80°C for 2-8h, and then coupling the obtained product with a halogenated aromatic monomer at 50-120°C for 10-24h to obtain an alkyl side chain substituted aromatic monomer.

[0073] In some preferred embodiments, the coupling reaction of the first mixed reaction system also includes a palladium catalyst.

[0074] Furthermore, the palladium catalyst includes any one or more combinations of Pd(OAc)2, Pd(PPh3)4, Pd(t-Bu3P)2, Pd(dppf)Cl2, and Pd2(DBA)3, and is not limited thereto.

[0075] In some preferred embodiments, the coupling reaction of the first mixed reaction system further includes a solvent, and the solvent includes a non-polar solvent.

[0076] Furthermore, the solvent includes toluene, tetrahydrofuran, dioxane, diethyl ether, DMF and the like.

[0077] In some preferred embodiments, the coupling reaction of the first mixed reaction system further includes an alkaline substance, and the alkaline substance includes an inorganic base.

[0078] Furthermore, the alkaline substance includes K2CO3, NaOH, KOH, CsF, Cs2CO3, NaOCH3, K3PO4 and the like.

[0079] Another aspect of the embodiments of the present invention further provides a polyarene, wherein the polyarene has a structure as shown in formula (II) or formula (III):

[0080]

[0081] Wherein, A and B are independently selected from aromatic monomers, and Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1)3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; at least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0082] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned polyarylalkane, which comprises:

[0083] A second mixed reaction system comprising at least an aromatic monomer B, an alkyl halide-substituted aromatic monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain a polyarylalkane having a structure represented by formula (II);

[0084] Wherein, the aromatic monomer B is selected from aromatic monomers; the alkyl halide substituted aromatic monomer is the alkyl side chain substituted aromatic monomer as claimed in claim 1; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0085] Alternatively, a third mixed reaction system comprising at least an aromatic monomer B, a halogenated aromatic hydrocarbon monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aromatic halide polyarylalkane precursor;

[0086] and reacting a fourth mixed reaction system comprising at least the aromatic halide polyarylalkane precursor, an olefin monomer and 9-boranebicyclo[3,3,1]nonane to obtain a polyarylalkane having a structure represented by formula (II);

[0087] Wherein, the aryl halide polyaryl alkane precursor has a structure as shown in formula (IV):

[0088]

[0089]

[0090] The aromatic monomer B is selected from aromatic monomers; the structure of the halogenated aromatic monomer is A is selected from aromatic monomers, X is selected from Cl, Br or I; the structure of the olefin monomer is Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1)2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0091] Alternatively, a fifth mixed reaction system comprising at least an aromatic monomer B, an aromatic halogen-containing ketone monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aromatic halogen-containing polyarylalkane precursor;

[0092] and reacting a fourth mixed reaction system comprising at least the aromatic halide polyarylalkane precursor, an olefin monomer and 9-boranebicyclo[3,3,1]nonane to obtain a polyarylalkane having a structure represented by formula (III);

[0093] Wherein, the aryl halide polyaryl alkane precursor has a structure as shown in formula (V):

[0094]

[0095] The aromatic monomer B is selected from aromatic monomers, and the structure of the aromatic halogen ketone-containing monomer is A is selected from aromatic monomers, X is selected from Cl, Br or I; the structure of the olefin monomer is Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from

[0096] The aromatic monomer in the present invention is selected from any one of the following structures:

[0097]

[0098] In some more specific embodiments, the reaction formula for preparing the polyarylalkane having the structure shown in formula (II) is as follows:

[0099]

[0100] In some more specific embodiments, the reaction formula for preparing the polyarylalkane having the structure shown in formula (II) is as follows:

[0101]

[0102] In some more specific embodiments, the reaction formula for preparing the polyarylalkane having the structure shown in formula (III) is as follows:

[0103]

[0104] In some preferred embodiments, at least one of the starting materials for preparing the polyaralkane comprises at least one type of diaryl monomer.

[0105] In some preferred embodiments, at least one starting material for preparing the polyaralkane contains at least one keto group and / or carbonyl group, in particular contains a plurality of different keto groups and / or a plurality of different carbonyl groups.

[0106] In some preferred embodiments, when preparing the polyarane, a Friedel-Crafts hydroxyalkylation polymerization reaction is carried out under the action of trifluoromethanesulfonic acid (TFSA).

[0107] In some preferred embodiments, a solvent, particularly a chlorinated solvent, is used during the Friedel-Crafts hydroxyalkylation polymerization process when preparing the polyaralkanes.

[0108] Another aspect of the embodiments of the present invention further provides use of the aforementioned polyarylalkane in preparing a cross-linked polymer, an ion exchange resin, an ion exchange membrane or a fuel cell.

[0109] Another aspect of the embodiments of the present invention further provides a cross-linked polymer, wherein the cross-linked polymer is obtained by reacting the aforementioned polyarylalkane with a first polymer; wherein the first polymer comprises a polymer containing a tertiary amine group.

[0110] In some preferred embodiments, the polyarylalkane forms an ionic and / or covalent bond network connection with the first polymer.

[0111] In some preferred embodiments, the cross-linked polymer is prepared by reacting the aforementioned polyarylalkane, the first polymer and a doping substance.

[0112] Furthermore, the doping substance includes a mineral acid and / or a compound containing a long-chain alkyl sulfonic acid group.

[0113] Furthermore, the mineral acid includes any one or more combinations of sulfuric acid, phosphoric acid, and phosphorosulfonic acid, but is not limited thereto.

[0114] Furthermore, the long-chain alkyl sulfonic acid group-containing compound includes a compound containing a long-chain alkyl acidic substituent group of sulfonic acid or phosphoric acid.

[0115] In some more specific embodiments, the method for preparing the cross-linked polymer comprises: blending polyarylalkane with another polymer containing a tertiary amine group, and heating to obtain the cross-linked polymer.

[0116] Furthermore, the crosslinked polymer is subjected to a doping treatment of the mixture, wherein a mineral acid, in particular sulfuric acid or phosphoric acid or phosphorus sulfonic acid, is doped into the polymer mixture, or other long-chain alkyl sulfonic acid groups, in particular long-chain alkyl acidic substituent groups containing sulfonic acid groups or phosphoric acid, are introduced.

[0117] Another aspect of the embodiments of the present invention further provides the use of the aforementioned cross-linked polymer in the preparation of a diaphragm material in the field of alkaline water electrolysis or high-temperature proton exchange membrane fuel cells.

[0118] Another aspect of the embodiments of the present invention further provides an ion exchange resin, wherein the ion exchange resin includes a cation exchange resin or an anion exchange resin;

[0119] The anion exchange resin is obtained by reacting the aforementioned polyarylalkane with a tertiary amine group; and the cation exchange resin is obtained by reacting the aforementioned polyarylalkane with potassium thioacetate and m-chloroperbenzoic acid.

[0120] Furthermore, the anion exchange resin generates stable organic cations by reacting the halomethyl groups (in the form of CH2X, where X=Cl, Br, I) present in the polyarylalkane with tertiary amine groups.

[0121] Furthermore, the cation exchange resin is produced by reacting the halomethyl groups (in the form of CH2X, wherein X=Cl, Br, I) present in the polymer with potassium thioacetate and m-chloroperbenzoic acid to generate stable organic anions.

[0122] Another aspect of the embodiments of the present invention further provides an ion exchange membrane, wherein the ion exchange membrane is made of the aforementioned cross-linked polymer or ion exchange resin.

[0123] In some preferred embodiments, the thickness of the ion exchange membrane is less than 100 μm.

[0124] Furthermore, the thickness of the ion exchange membrane is less than 75 μm.

[0125] Furthermore, the thickness of the ion exchange membrane is less than 50 μm.

[0126] When preparing a membrane, the material prepared by the above method can be dissolved in a suitable solvent and then coated on a corresponding substrate, so that a membrane of corresponding thickness can be obtained. In an ideal design, it may be a cation (proton) exchange membrane or an anion exchange membrane.

[0127] Another aspect of the embodiments of the present invention further provides the use of the aforementioned cross-linked polymer or ion exchange membrane in the preparation of diaphragm materials in the fields of fuel cells, redox flow batteries or water electrolysis.

[0128] For example, the aforementioned ion exchange membranes are used in fuel cells, in particular in low-temperature fuel cells and / or direct methanol fuel cells, or in batteries, in particular in redox flow batteries, or in electrochemical processes, in particular in electrolysis processes or electrosynthesis processes, in particular in water electrolysis processes, and as anion exchange membranes and proton exchange membranes.

[0129] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0130] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0131] Example 1

[0132] Figure 1 The method for synthesizing alkyl bromide-substituted meta-terphenyl is shown. In a nitrogen atmosphere and at room temperature, 7.0g 9BBN and 100mL THF are added to a 100mL Shrek bottle, followed by 3.2mL of the compound 6-bromo-1-hexene, mixed evenly and reacted at 50°C for 4-5h. Then, 7.42g 1-bromo-3,5-diphenylbenzene and 1.30g KOH are added to 30mL toluene and 27mL water under a nitrogen atmosphere, stirred at room temperature to dissolve, and the product of the first step is slowly added dropwise, followed by 50mg Pd(PPh3)4. After the addition, react at 80°C for 12h. After the reaction is completed, extract with ether, pour the extracted solution into anhydrous sodium sulfate and evaporate to dryness, then purify by column chromatography, with a yield of 99.5%. Figure 2 The bromohexyl-substituted m-terphenyl 1 The H-NMR spectrum verified the correctness of the target monomer structure obtained by this method.

[0133] Example 2

[0134] Figure 3A schematic diagram of a reaction process for preparing membrane materials using an inventive process is shown. The first step of the process uses two raw materials, namely, bromohexyl-substituted m-terphenyl (the first raw material) and trifluoroacetone (the second raw material) prepared in the above embodiment. These two raw materials can be directly synthesized into an alkyl bromide-substituted polyaryl alkane P1-6CBr through a Friedel-Crafts hydroxyalkylation polymerization reaction. Figure 4 The H NMR spectrum of the alkyl bromide substituted polyarene P1-6CBr is shown. The integral value of the introduced alkyl bromide side chain is consistent with the expected number of protons. In further quaternization reaction, the above polymer can be converted into an anion exchange resin P1-QA functionalized with organic cations. Figure 5 The H NMR spectrum of the anion exchange resin P1-QA prepared from the polymer P1-6CBr is shown. In the quaternization process, any other tertiary amine compounds can be used to quaternize the polymer. For example, these compounds can be trimethylamine, quinuclidine, N-methylpiperidine, tetramethylimidazole, N-methylpiperazine, triphenylphosphine, 3-methyl-3,6-dimethylenebicyclo[5.5.0]undecane-6-one, etc.

[0135] The polymer P1-QA described above can be made into a membrane. For this purpose, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide or N-methylpyrrolidone, where the polymer content is 1% to 30% by weight, and an organic acid such as trifluoroacetic acid is optionally added. The anion exchange membranes obtained with a thickness of 30-100 μm show very good hydroxide conductivity of up to 175 mS cm -1 .

[0136] The anion exchange membrane P1-QA was applied to hydrogen / air anion exchange membrane fuel cells. The Pt / C catalyst (60 wt% metal content) was ultrasonically mixed in the P1-QA solution (20 wt% polymer and 80 wt% catalyst). The membrane electrode was prepared by the catalyst coating method: the catalyst ink was sprayed on both sides of the membrane sample. The metal loading was controlled at 0.6 mg cm -2 , the electrode area is 4cm 2 The catalyst-coated membrane was sandwiched between two pieces of carbon paper to form an MEA. The single cell test was performed using an 850E Multi Range fuel cell test station (Scribner associates, USA) and an 80°C current method. Hydrogen and air with a humidity of 100% were simultaneously passed to both sides of the membrane electrode at a flow rate of 400 sccm. By changing the current density and recording the corresponding voltage, the battery polarization curve was obtained, as shown in the figure. Figure 6 The maximum power density of the battery is as high as 700 mW cm -2 .

[0137] Example 3

[0138] Figure 7 Another subsequent reaction of the synthesized polymer is shown. This is a method for sulfonation at the alkyl bromide substitution position: the bromine atom at the end of P1-6CBr is replaced by a thioacetic acid group through a nucleophilic substitution reaction. In the next step, the thioacetic acid group is converted into a sulfonic acid group through an oxidation reaction. In more detail, 1 equivalent of the starting polymer P1-6CBr is dissolved with N,N-dimethylacetamide. Subsequently, 1.12 equivalents of potassium thioacetate are added thereto and stirred at 40 to 100°C for 16 to 24 hours. Then, the solution is cooled to room temperature and filtered through a dialysis membrane to remove any undissolved material. Finally, the solution is dried under vacuum to obtain a dry polymer. Next, the obtained polymer is dissolved again in N,N-dimethylacetamide and the solution is cooled to 0°C. Then, m-chloroperbenzoic acid (m-CPBA) equivalent to the polymer is added in 6 portions within 10 minutes. The mixture is continued to be stirred at room temperature. Then, the polymer is precipitated from a 1M potassium chloride solution, washed with water and dried. Figure 8 The H NMR spectrum of the cation exchange resin P1-SA prepared from the polymer P1-6CBr is shown.

[0139] The obtained cation exchange resin P1-SA can be used to prepare both pure membranes and mixed membranes. When preparing pure membranes, the obtained sulfonated polymer P1-SA is dissolved in dimethyl sulfoxide, N,N-dimethylacetamide or N-methylpyrrolidone. The obtained polymer solution is applied to a glass plate in a layer using a scraper, and then the solvent is evaporated at a higher temperature. When preparing acid-base mixed membranes, the obtained acidic polymer is dissolved in dimethyl sulfoxide, N,N-dimethylacetamide or N-methylpyrrolidone, neutralized with a base such as triethylamine or triethanolamine, and then mixed with a dissolved alkaline polymer such as O-PBI, and scraped and dried according to the method for preparing pure membranes. The conductivity of P1-SA pure membrane proton exchange membrane is as high as 172mS cm -1 , close to the conductivity level of commercial Nafion 212 membrane.

[0140] Example 4

[0141] Fig. 9 A schematic diagram of a reaction process for preparing membrane materials using an inventive process is shown. The first step of the process uses three raw materials, namely, the bromohexyl-substituted m-terphenyl prepared in Example 1 (the first raw material), commercially purchased biphenyl (the second raw material), and trifluoroacetone (the third raw material). These three raw materials can be directly synthesized into an alkyl bromide-substituted polyaryl alkane P1-6CBr-BP-x through a Friedel-Crafts hydroxyalkylation polymerization reaction. Fig.10The H NMR spectrum of alkyl bromide substituted polyarylalkane P1-6CBr-BP-10% is shown. Through further quaternization reaction, the above polymer can be converted into anion exchange resin P1-QA-BP-x functionalized with organic cations. It is worth noting that a single ion substituted anion exchange membrane can be constructed by selecting a tertiary amine compound as a quaternization agent, and a tertiary amine monomer containing an ionic group can also be selected for quaternization reaction to construct a multi-ion substituted anion exchange resin. Fig.11 The H NMR spectrum of the doubly ion-substituted anion exchange resin P1-QA-BP-10% prepared from the polymer P1-6CBr-BP-10% is shown.

[0142] The polymer P1-QA-BP-x described previously can be made into a membrane. To this end, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide or N-methylpyrrolidone, wherein the mass percentage of the polymer is 1% to 30%, and an organic acid such as trifluoroacetic acid can be optionally added. The anion exchange membrane obtained with a thickness of 30-100 μm shows very excellent alkaline stability, and can still retain more than 90% of the conductivity after immersion in a 1M alkaline solution for 10,000 hours.

[0143] Using the same method as Example 3, the alkyl bromide polymer P1-6CBr-BP involved in the above example can be sulfonated to prepare a cation exchange resin, and its properties such as conductivity, water absorption and mechanical properties can be optimized to meet the needs of the membrane in specific application fields.

[0144] Example 5

[0145] Fig.12 A schematic diagram of the reaction process of preparing membrane materials by an inventive process is shown. The first step of the process uses two raw materials, namely 1-bromo-3,5-diphenylbenzene (the first raw material) and 1,1,1-trifluoroacetone (the second raw material). Through the polyhydroxyalkylation reaction, these two raw materials can be synthesized into a brominated polyarylalkane P1-Br. Fig.13 The H NMR spectrum of the brominated polyarene is shown. The integral ratio of the aromatic protons is completely consistent with the target structure. The polymer is then coupled with 6-bromo-1-hexene to obtain the alkyl bromide substituted polymer P1-6CBr. The obtained polymer is characterized by NMR spectroscopy. The successful grafting reaction can be confirmed by measuring the chemical shift shift of the protons on the substituted aromatic ring.

[0146] Example 6

[0147] Fig.14A schematic diagram of the reaction flow of an inventive process for preparing membrane materials is shown. The first step of the process uses two raw materials, namely, terphenyl (the first raw material) and 4′-bromo-2,2,2-trifluoroacetophenone (the second raw material). These two raw materials can be synthesized into a brominated polymer P2-Br through a polyhydroxyalkylation reaction. Gel permeation chromatography (GPC) shows that the molecular weight (Mw) is 22000 g / mol and the dispersity (D) is 1.99. Then, the polymer is coupled with 6-bromo-1-hexene to obtain an alkyl bromide-substituted polyarylalkane P2-6CBr. In a further quaternization reaction, the bromine atoms are replaced with cations, which can be converted into an anion exchange resin P2-QA with a high ion exchange capacity (2.60-2.75 mmol / g). The separation of the organic cation exchange group from the polymer backbone is separated by a flexible chain, which has the advantage of phase separation, thereby forming an ion transport channel and improving conductivity. Fig.15 The bromine-substituted polymer P2-Br, the alkyl bromide-substituted polymer P2-6CBr, and two cation exchange polymers P2-QA-1 and P2-QA-2 are shown. 1 H NMR spectrum. By observing the characteristic signals of the constructed organic cationic groups and integrating the characteristic groups, it can be determined that the quaternization reaction is successful.

[0148] The polymer P2-QA described above can be made into a membrane. For this purpose, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide or N-methylpyrrolidone, where the mass percentage of polymer is 1% to 30%, and an organic acid such as trifluoroacetic acid is optionally added. Such membranes with a thickness of 30-100 μm show very good hydroxide conductivity (151-175 mS cm -1 ) and alkali stability, and the chemical structure can still remain stable after being treated with 1M alkali at 80°C for nearly 100 days.

[0149] Using the same method as Example 3, the alkyl bromide polymer P2-6CBr involved in the above example can be sulfonated to prepare a cation exchange resin, and its properties such as conductivity, water absorption and mechanical properties can be optimized to meet the needs of the membrane in specific application fields.

[0150] Example 7

[0151] Fig.16A schematic diagram of the reaction flow of an inventive process for preparing membrane materials is shown. The first step of the process uses three raw materials, namely, terphenyl (the first raw material), 2,2,2-trifluoroacetone (the second raw material) and 4′-bromo-2,2,2-trifluoroacetophenone (the third raw material). These three raw materials can be synthesized into a brominated polymer P2-Br-TF through a polyhydroxyalkylation reaction. Gel permeation chromatography (GPC) shows that the molecular weight (Mw) is 65000 g / mol and the dispersity (D) is 2.68. Then, the polymer is coupled with 6-bromo-1-hexene to obtain an alkyl bromide-substituted polyaryl alkane P2-6CBr-TF. In a further quaternization reaction, the bromine atom is replaced by a cation, which can be converted into an anion exchange resin P2-QA-TF with a high molecular weight.

[0152] The polymer P2-QA-TF described above can be made into a membrane. For this purpose, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide or N-methylpyrrolidone, wherein the mass percentage of polymer is 1% to 30%, and an organic acid such as trifluoroacetic acid can be optionally added. The anion exchange membrane obtained with a thickness of 30-100 μm shows very excellent mechanical properties, with a tensile strength of 60-80 MP and an elongation at break of 75-96%.

[0153] Using the same method as Example 3, the alkyl bromide polymer P2-6CBr-TF involved in the above example can be sulfonated to prepare a cation exchange resin, and its properties such as conductivity, water absorption and mechanical properties can be optimized to meet the needs of the membrane in specific application fields.

[0154] Example 8

[0155] Fig.17A reaction process for preparing a cross-linked membrane is presented, the starting materials being an alkyl bromide polymer (P1-6CBr or P2-6CBr) and a polymer containing tertiary amine substituents. A covalently linked anion exchange polymer mixture can be prepared by a Menxiu gold reaction between the alkyl bromide polymer and the polymer containing tertiary amine substituents. Specifically, the two polymers are mixed in a polar aprotic solvent in a desired mixing ratio. The two polymers can be mixed in any mixing ratio from 95:5 to 5:95. The solvent is then evaporated at elevated temperature in a fume hood or vacuum oven. Thereafter, the formed membrane is washed with ultrapure water. If desired, the membrane can be further treated. When the alkyl bromide groups in the alkyl bromide polymer are in excess of the equivalent of the tertiary amine groups in the tertiary amine polymer, the remaining alkyl bromide groups can be converted into an organic cationic form by reaction with any triamine. Specifically, the membrane is immersed in an aqueous amine solution (if liquid) or an amine ethanol solution (if solid). It is best to use a sterically hindered amine such as quinoline or N-methylpiperidine, or a sterically hindered diamine such as DABCO. The membrane is then rinsed with ultrapure water until all residual solvent and amine are removed from the membrane. The membrane is then immersed in KOH to convert it into OH. - The membrane is then rinsed with ultrapure water that has been previously boiled in nitrogen. Afterwards, the membrane must be stored under a protective gas to prevent it from absorbing carbon dioxide from the air.

[0156] When the tertiary amine groups in the tertiary amine polymer are in excess of the equivalent of the alkyl bromide groups in the alkyl bromide polymer, on the one hand, it can be doped with phosphoric acid (PA) so that the polymer can be used in high-temperature membrane fuel cells. On the other hand, it can also be alkylated with alkyl iodides to produce anion exchange polymers, which can be used both in alkaline applications (such as AEMWE or AEMFC) and in redox flow batteries. In particular, the prepared AEM-QPBP-P1-10% membrane showed high OH at 80 °C. - and Cl - conductivity, 186.0 and 140.0 mS cm, respectively -1 Meanwhile, AEM-QPBP-P1-10% showed moderate water absorption (WU = 35.3% at 80°C), excellent dimensional stability (SR < 10% at 80°C), and superior alkaline resistance (less than 5% degradation after treatment with 1 M NaOH solution at 80°C for 100 days), which may be attributed to its highly rigid and cross-linked structure. In addition, AEMWE based on AEM-QPBP-P1-10% performed better than AEMWE based on commercial PiperION at high KOH concentrations. Fig.18The polarization curves of AEMWE based on AEM-QPBP-P1-10% equipped with non-precious metal catalysts at 80 °C in 1 M KOH were shown, and 3000 mA cm-2 was achieved at 2.0 V. -2 of current density.

[0157] Comparative Example 1

[0158] Fig.19 The method for preparing bromoalkyl-substituted meta-terphenyl reported in the patent (WO 2024 / 046712) is demonstrated. The method involves the use of the hazardous chemical reagent n-butyl lithium, and the reaction conditions are harsh and need to be carried out at ultra-low temperatures (-85 to -20°C), which is not conducive to the large-scale preparation and industrialization of such reactions. The preparation method provided by the present invention starts from an aromatic halide monomer or an aromatic halide polymer, and undergoes a Suzuki coupling reaction through the hydroboration coupling of olefins. The reaction conditions are mild and the substrate range is wide. It is not only suitable for small molecules, but also has good compatibility with various halogenated aromatic polymers, high yield, and no side reactions. The yield is as high as 99%, and it has very broad application prospects in the fields of functional modification of various organic small molecules and post-modification of polymers.

[0159] Comparative Example 2

[0160] The proton exchange membrane is Nafion 212 purchased from the market.

[0161] The proton exchange membranes of different thicknesses prepared in Example 3 and Comparative Example 2 were subjected to ion exchange capacity (IEC), swelling rate, water absorption rate, ion conductivity test and oxidation stability test.

[0162] IEC is calculated by acid-base titration to calculate the hydrogen ion content in a certain mass of proton exchange membrane, thereby obtaining the IEC of the proton exchange membrane.

[0163] The water absorption rate and swelling rate are measured by immersing the membrane in water at 80°C for 24 hours and then testing the percentage difference between its mass and size and the initial state.

[0164] The ionic conductivity was measured using the Shanghai Chenhua electrochemical test system. The two-electrode AC impedance method was used to measure the resistance of the proton exchange membrane in a fully wet state at 80°C, and then the conductivity was calculated using a formula.

[0165] Oxidative stability was measured by immersing the membrane in Fenton's reagent (2 ppm Fe 2+ at 3.0wt% H2O2), the time of film breakage was recorded, and the specific results are shown in Table 1.

[0166] Table 1 IEC, water absorption, swelling rate, conductivity and oxidation stability of Example 3 and Comparative Example 1

[0167]

[0168] Table 1 shows that the proton exchange membrane prepared by the present invention has comparable conductivity and oxidation stability and better dimensional stability than commercially available products.

[0169] Comparative Example 3

[0170] PiperION purchased from the market TM Anion exchange membrane.

[0171] The anion exchange membranes prepared in Example 2, Example 4, Example 6 and Comparative Example 3 and Comparative Example 3 were tested for ion exchange capacity (IEC), swelling ratio, hydrogen permeability, hydroxide conductivity and alkaline stability.

[0172] Table 2 IEC, swelling ratio, hydrogen permeability, hydroxide conductivity and alkaline stability of Example 2, Example 5 and Comparative Example 2

[0173]

[0174] Table 2 shows that the anion exchange membrane prepared by the present invention has comparable conductivity, dimensional stability and alkaline stability as well as better gas barrier properties compared to commercially available products.

[0175] As can be seen from the above examples, the present invention provides a method for preparing alkyl side chain substituted aromatic monomers. The method provided by the present invention has ultra-high reactivity, mild reaction, high yield, good compatibility with various functional groups, and can be used to prepare substituted aromatic monomers required for various ion exchange membrane materials, organic photoelectric materials, etc. The present invention also provides alkyl halide substituted polyarylalkane and a preparation method; the proton exchange membrane and anion exchange membrane prepared from the alkyl halide substituted polyarylalkane have the advantages of high conductivity, excellent chemical stability, etc., and have obvious practical application and industrialization prospects.

[0176] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0177] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. An alkyl side chain substituted aromatic monomer, characterized in that: The alkyl side chain substituted aromatic monomer has a structure as shown in formula (I): Wherein, A is selected from aromatic monomers, and the aromatic monomer is selected from any one of the following structures: Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3, n is selected from an integer between 0 and 20.

2. The method for preparing an alkyl side chain substituted aromatic hydrocarbon monomer according to claim 1, characterized in that: include: reacting a first mixed reaction system comprising at least an olefin monomer, 9-boranebicyclo[3,3,1]nonane, and a halogenated aromatic hydrocarbon monomer to obtain an alkyl side chain substituted aromatic hydrocarbon monomer; The structure of the olefin monomer is Wherein Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 ) 3, n is an integer selected from 0-20; the structure of the halogenated aromatic monomer is Wherein A is selected from aromatic monomers, and X is selected from Cl, Br or I.

3. The preparation method according to claim 2, characterized in that: Specifically include: The olefin monomer is reacted with 9-boranebicyclo[3,3,1]nonane at 30-80° C. for 2-8 hours, and then the obtained product is coupled with a halogenated aromatic monomer at 50-120° C. for 10-24 hours to obtain an alkyl side chain substituted aromatic monomer; And / or, the coupling reaction of the first mixed reaction system also includes a palladium catalyst; And / or, the coupling reaction of the first mixed reaction system further comprises a solvent, and the solvent comprises a non-polar solvent; And / or, the coupling reaction of the first mixed reaction system further includes an alkaline substance, and the alkaline substance includes an inorganic base.

4. A polyarene, characterized in that The polyarene has a structure as shown in formula (II) or formula (III): Wherein, A and B are independently selected from aromatic monomers, and Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; at least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from 5. The method for preparing polyarylene as claimed in claim 4, characterized in that: include: A second mixed reaction system comprising at least an aromatic monomer B, an alkyl halide-substituted aromatic monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain a polyarylalkane having a structure represented by formula (II); Wherein, the aromatic monomer B is selected from aromatic monomers; the alkyl halide substituted aromatic monomer is the alkyl side chain substituted aromatic monomer as claimed in claim 1; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from Alternatively, a third mixed reaction system comprising at least an aromatic monomer B, a halogenated aromatic hydrocarbon monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aromatic halide polyarylalkane precursor; and reacting a fourth mixed reaction system comprising at least the aromatic halide polyarylalkane precursor, an olefin monomer and 9-boranebicyclo[3,3,1]nonane to obtain a polyarylalkane having a structure represented by formula (II); Wherein, the aryl halide polyaryl alkane precursor has a structure as shown in formula (IV): The aromatic monomer B is selected from aromatic monomers; the structure of the halogenated aromatic monomer is A is selected from aromatic monomers, X is selected from Cl, Br or I; the structure of the olefin monomer is Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; ml is any integer ≥1, m2 is any integer ≥0; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from Alternatively, a fifth mixed reaction system comprising at least an aromatic monomer B, an aromatic halogen-containing ketone monomer, a ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aromatic halogen-containing polyarylalkane precursor; and reacting a fourth mixed reaction system comprising at least the aromatic halide polyarylalkane precursor, an olefin monomer and 9-boranebicyclo[3,3,1]nonane to obtain a polyarylalkane having a structure represented by formula (III); Wherein, the aryl halide polyaryl alkane precursor has a structure as shown in formula (V): The aromatic monomer B is selected from aromatic monomers, and the structure of the aromatic halogen ketone-containing monomer is A is selected from aromatic monomers, X is selected from Cl, Br or I; the structure of the olefin monomer is Y is selected from F, Cl, Br, C n H 2n-1 , OH, OC n H 2n-1 , OC n F 2n-1 , SH, SC n H 2n-1 , SC n F 2n-1 、N(C n H 2n-1 )2 or N(C n H 2n-1 )3; n is an integer selected from 0-20; m1 is any integer ≥1, m2 is any integer ≥0; the structure of the ketone monomer is At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from 6. Use of the polyarylalkane according to claim 4 in the preparation of cross-linked polymers, ion exchange resins, ion exchange membranes or batteries.

7. A cross-linked polymer, characterized in that: The cross-linked polymer is obtained by reacting the polyarylalkane according to claim 4 with a first polymer; wherein the first polymer comprises a polymer containing a tertiary amine group.

8. An ion exchange resin, characterized in that: The ion exchange resin includes a cation exchange resin or an anion exchange resin; Wherein, the anion exchange resin is obtained by reacting the polyarylalkane described in claim 4 with a tertiary amine group; the cation exchange resin is obtained by reacting the polyarylalkane described in claim 4 with potassium thioacetate and m-chloroperbenzoic acid.

9. An ion exchange membrane, characterized in that: The ion exchange membrane is made of the cross-linked polymer according to claim 7 or the ion exchange resin according to claim 8.

10. Use of the cross-linked polymer according to claim 7 or the ion exchange membrane according to claim 9 in preparing a diaphragm material in the field of fuel cells, redox flow batteries or water electrolysis.

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