Alkyl side chain substituted aromatic hydrocarbon monomers, polyaromatic alkyls and methods of making and using the same

Abstract

The application discloses an alkyl side chain substituted aromatic hydrocarbon monomer, a polyaromatic alkane and a preparation method and application thereof. The alkyl side chain substituted aromatic hydrocarbon monomer has the structure shown in the following formula: wherein A is selected from aromatic monomers, 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, and n is an integer selected from 0-20. The method provided by the application has super-high reaction activity, good compatibility with various functional groups, mild reaction, high yield, and can be used for preparing various ion exchange membrane materials, organic photoelectric materials and other required substituted aromatic monomers, and the prepared membrane material has the advantages of high conductivity, excellent chemical stability and the like, and has obvious practical application and industrialization prospect.

Description

Technical Field

[0001] This invention belongs to the field of ion exchange membrane technology, specifically relating to an alkyl side-chain substituted aromatic monomer, polyarylene, its preparation method and application. Background Technology

[0002] In the context of energy transition, developing clean energy technologies, such as fuel cells, water electrolysis for hydrogen production, and flow batteries, can enable the efficient utilization of intermittent renewable energy sources.

[0003] Ion exchange membranes play a crucial role in various electrochemical processes, such as electrolysis and electrochemical devices, while these applications place high demands on the membrane materials. First, they must possess sufficient chemical stability in the operating environment. Furthermore, these membranes need to withstand the swelling effects of the medium and the mechanical stresses experienced within the device. Another crucial factor is that these membrane materials must possess sufficient ion conductivity. These factors directly determine the operating efficiency and lifespan of the device.

[0004] Most currently developed ion exchange membrane materials belong to the polymer category. 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 polyarylene polymers by polyhydroxyalkylation of biphenyl with trifluoromethyl substituted ketone monomers, and then obtained a series of all-carbon framework anion exchange membrane materials by quaternization with trimethylamine (ACS MacroLett. 2015, 4, 814-8). In 2017, Jannasch et al. synthesized polyarylpiperidine polymers by polyhydroxyalkylation of N-methylpiperidinone with aromatic monomers, and then obtained structurally diverse anion exchange membrane materials by quaternization with halogenated alkanes of different structures (Adv. Funct. Mater. 2018, 28, 1702758). In 2019, Jannasch et al. first prepared a high-molecular-weight polymer precursor via superacid-catalyzed polymerization of perfluoroacetophenone and biphenyl, and then sulfonated the pentafluorophenyl groups on the side chain to obtain perfluorophenylsulfonic acid-based proton exchange membrane materials (ACS Macro Lett. 2019, 8, 1247-125). In principle, Friedel-Crafts hydroxyalkylation polymerization can synthesize polymers suitable for ion exchange membranes, but the overall performance of currently developed ion exchange membranes still needs further improvement, particularly in terms of chemical stability, ionic conductivity, and mechanical stability. Summary of the Invention

[0005] The main objective of this invention is to provide an alkyl side-chain substituted aromatic monomer, polyarylene, and their preparation method and application, so as to overcome the shortcomings of the prior art.

[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0007] This 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 monomers are selected from any 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, where n is an integer selected from 0 to 20.

[0012] This invention also provides a method for preparing the aforementioned alkyl side-chain substituted aromatic monomer, comprising:

[0013] A first mixed reaction system containing at least an olefin monomer, 9-boron bicyclic [3,3,1]nonane, and a haloaromatic monomer is reacted to prepare an alkyl side-chain substituted aromatic monomer.

[0014] The structure of the olefin monomer is as follows: Y is selected from F, Cl, Br, and 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 integers from 0 to 20; the structure of the haloaromatic monomer is Where A is selected from aromatic monomers, and X is selected from Cl, Br or I.

[0015] This invention also provides a polyarylene having a structure as shown in formula (II) or formula (III):

[0016]

[0017] In this context, A and B are independently selected from aromatic monomers, and Y is selected from F, Cl, Br, and 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 integers from 0 to 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] This invention also provides a method for preparing the aforementioned polyarylene, comprising:

[0019] A second mixed reaction system containing at least aromatic monomer B, alkyl halide-substituted aromatic monomer, ketone monomer and trifluoromethanesulfonic acid is subjected to Friedel-Crafts hydroxyalkylation polymerization to obtain a polyarylene having the structure shown in 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 as follows: At least one of R1 and R2 is a substituent containing fluorine, wherein the substituent is selected from...

[0021] Alternatively, a third mixed reaction system containing at least aromatic monomer B, haloaromatic monomer, ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aryl halopolyaryl precursor.

[0022] And, by reacting a fourth mixed reaction system comprising at least the said aryl halide polyaryl alkane precursor, olefin monomer and 9-boron bicyclo[3,3,1]nonane, to obtain a polyaryl alkane having the structure shown in formula (II);

[0023] The aryl halopolyaryl alkyl 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 as follows: A is selected from aromatic monomers, and X is selected from Cl, Br, or I; the structure of the olefin monomer is as follows: 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 to 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, wherein the substituent is selected from...

[0026] Alternatively, a fifth mixed reaction system containing at least aromatic monomer B, aryl halogenated ketone monomers, ketone monomers, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aryl halogenated polyarylene precursor.

[0027] And, by reacting a fourth mixed reaction system comprising at least the said aryl halide polyaryl alkane precursor, olefin monomer and 9-boron bicyclo[3,3,1]nonane, to obtain a polyaryl alkane having the structure shown in formula (III);

[0028] The aryl halide polyaryl alkyl 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 aryl halogenated ketone monomer is as follows: A is selected from aromatic monomers, and X is selected from Cl, Br, or I; the structure of the olefin monomer is as follows: 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 to 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, wherein the substituent is selected from...

[0031] The present invention also provides the use of the aforementioned polyarylene in the preparation of crosslinked polymers, ion exchange resins, ion exchange membranes or fuel cells.

[0032] This invention also provides a crosslinked polymer, which is prepared by reacting the aforementioned polyarylene with a first polymer; wherein the first polymer includes a polymer containing tertiary amine groups.

[0033] This invention also provides an ion exchange resin, which includes a cation exchange resin or an anion exchange resin;

[0034] The anion exchange resin is obtained by reacting the aforementioned polyarylene with tertiary amine groups; the cation exchange resin is obtained by reacting the aforementioned polyarylene with potassium thioacetate and m-chloroperoxybenzoic acid.

[0035] The present invention also 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 application of the aforementioned cross-linked polymers or ion exchange membranes in the preparation of membrane materials for fuel cells, redox flow batteries, or water electrolysis.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

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

[0039] (2) The polyarylene and the proton exchange membrane and anion exchange membrane prepared from the polyarylene provided by the present invention have the advantages of high conductivity and excellent chemical stability, and have obvious practical application and industrialization prospects. Attached Figure Description

[0040] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0041] Figure 1 This is a flowchart illustrating the preparation route of bromhexyl-substituted meta-terphenyl in Example 1 of this invention;

[0042] Figure 2 This refers to the bromhexyl-substituted meta-terphenyl in Example 1 of this invention. 1 H-NMR spectrum;

[0043] Figure 3 This is a flowchart illustrating the preparation of alkyl bromide-substituted polyaryl alkylene P1-6CBr and anion exchange resin P1-QA in Example 2 of the present invention.

[0044] Figure 4 This is the 1H NMR spectrum of the alkyl bromide-substituted polyarylene P1-6CBr in Example 2 of this invention;

[0045] Figure 5 This is the 1H NMR spectrum of the anion exchange resin P1-QA in Example 2 of this invention;

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

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

[0048] Figure 8 This is the 1H NMR spectrum of the cation exchange resin P1-SA in Example 3 of the present invention;

[0049] Figure 9 This is a flowchart illustrating the preparation of alkyl bromide-substituted polyaryl alkyl group P1-6CBr-BP-x and anion exchange resin P1-QA-BP-x in Example 4 of the present invention.

[0050] Figure 10 This is the 1H NMR spectrum of the alkyl bromide-substituted polyarylene P1-6CBr-BP-10% in Example 4 of this invention;

[0051] Figure 11 This is the 1H NMR spectrum of the double-ion substituted anion exchange resin P1-QA-BP-10% in Example 4 of the present invention.

[0052] Figure 12This is another preparation route diagram for alkyl bromide-substituted polyarylene P1-6CBr in Example 5 of the present invention;

[0053] Figure 13 This is the 1H NMR spectrum of the brominated polyarylene P1-Br in Example 5 of this invention;

[0054] Figure 14 This is the synthetic route diagram of alkyl bromide-substituted polyarylene P2-6CBr in Example 6 of the present invention;

[0055] Figure 15 These are the 1H NMR spectra of the brominated polymer P2-Br, the alkyl brominated polymer P2-6CBr, and the two cation exchange polymers P2-QA in Example 6 of this invention.

[0056] Figure 16 This is a preparation route diagram of brominated polyarylene P2-Br-TF, alkyl brominated polyarylene P2-6CBr-TF and anion exchange resin P2-QA-TF in Example 7 of the present invention;

[0057] Figure 17 This is a flowchart illustrating the preparation of the crosslinked membrane in Example 8 of the present invention;

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

[0059] Figure 19 This is a diagram of the method for preparing bromoalkyl-substituted meta-terphenyl reported in patent WO 2024 / 046712 of Comparative Example 1 of this invention. Detailed Implementation

[0060] In view of the deficiencies of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention. The technical solution of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

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

[0062]

[0063] Wherein, A is selected from aromatic monomers, and the aromatic monomers are selected from any 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, where n is an integer selected from 0 to 20.

[0066] The alkyl side-chain substituted aromatic monomers provided by this invention have extremely 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 optoelectronic materials, etc.

[0067] Another aspect of the present invention provides a method for preparing the aforementioned alkyl side-chain substituted aromatic monomer, comprising:

[0068] A first mixed reaction system containing at least an olefin monomer, 9-boron bicyclic [3,3,1]nonane, and a haloaromatic monomer is reacted to prepare an alkyl side-chain substituted aromatic monomer.

[0069] The structure of the olefin monomer is as follows: Y is selected from F, Cl, Br, and 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 integers from 0 to 20; the structure of the haloaromatic monomer is Where 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 alkyl side-chain substituted aromatic monomers is as follows:

[0071]

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

[0073] In some preferred embodiments, the coupling reaction of the first mixed reaction system further 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, which includes a nonpolar solvent.

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

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

[0078] Furthermore, the alkaline substances include K2CO3, NaOH, KOH, CsF, Cs2CO3, NaOCH3, K3PO4, etc.

[0079] Another aspect of the present invention provides a polyarylene having a structure as shown in formula (II) or formula (III):

[0080]

[0081] In this context, A and B are independently selected from aromatic monomers, and Y is selected from F, Cl, Br, and 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-13; n is selected from integers from 0 to 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 present invention provides a method for preparing the aforementioned polyarylene, comprising:

[0083] A second mixed reaction system containing at least aromatic monomer B, alkyl halide-substituted aromatic monomer, ketone monomer and trifluoromethanesulfonic acid is subjected to Friedel-Crafts hydroxyalkylation polymerization to obtain a polyarylene having the structure shown in 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 described in claim 1; the structure of the ketone monomer is as follows: At least one of R1 and R2 is a substituent containing fluorine, wherein the substituent is selected from...

[0085] Alternatively, a third mixed reaction system containing at least aromatic monomer B, haloaromatic monomer, ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aryl halopolyaryl precursor.

[0086] And, by reacting a fourth mixed reaction system comprising at least the said aryl halide polyaryl alkane precursor, olefin monomer and 9-boron bicyclo[3,3,1]nonane, to obtain a polyaryl alkane having the structure shown in formula (II);

[0087] The aryl halopolyaryl alkyl 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 as follows: A is selected from aromatic monomers, and X is selected from Cl, Br, or I; the structure of the olefin monomer is as follows: 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 to 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, wherein the substituent is selected from...

[0091] Alternatively, a fifth mixed reaction system containing at least aromatic monomer B, aryl halogenated ketone monomers, ketone monomers, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aryl halogenated polyarylene precursor.

[0092] And, by reacting a fourth mixed reaction system comprising at least the said aryl halide polyaryl alkane precursor, olefin monomer and 9-boron bicyclo[3,3,1]nonane, to obtain a polyaryl alkane having the structure shown in formula (III);

[0093] The aryl halide polyaryl alkyl 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 aryl halogenated ketone monomer is as follows: A is selected from aromatic monomers, and X is selected from Cl, Br, or I; the structure of the olefin monomer is as follows: 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 to 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, wherein the substituent is selected from...

[0096] The aromatic monomers in this invention are selected from any of the following structures:

[0097]

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

[0099]

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

[0101]

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

[0103]

[0104] In some preferred embodiments, at least one raw material for preparing polyarylene comprises at least one type of diaryl monomer.

[0105] In some preferred embodiments, at least one starting material for preparing polyarylene contains at least one ketone group and / or carbonyl group, especially multiple different ketone groups and / or multiple different carbonyl groups.

[0106] In some preferred embodiments, the preparation of polyarylene involves Friedel-Crafts hydroxyalkylation polymerization in the presence of trifluoromethanesulfonic acid (TFSA).

[0107] In some preferred embodiments, a solvent, particularly a chlorinated solvent, is used during the Friedel-Crafts hydroxyalkylation polymerization process to prepare polyarylene.

[0108] Another aspect of the present invention provides the use of the aforementioned polyarylene in the preparation of crosslinked polymers, ion exchange resins, ion exchange membranes or fuel cells.

[0109] Another aspect of the present invention provides a crosslinked polymer, which is prepared by reacting the aforementioned polyarylene with a first polymer; wherein the first polymer includes a polymer containing tertiary amine groups.

[0110] In some preferred embodiments, the polyarylene forms a network of ionic and / or covalent bonds with the first polymer.

[0111] In some preferred embodiments, the crosslinked polymer is prepared by reacting the aforementioned polyarylene, the first polymer, and the dopant.

[0112] Furthermore, the dopant includes mineral acids and / or compounds containing long-chain alkyl sulfonic acid groups.

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

[0114] Furthermore, the compounds containing long-chain alkyl sulfonic acid groups include compounds containing long-chain alkyl acidic substituents of sulfonic acid or phosphoric acid.

[0115] In some more specific embodiments, the method for preparing the crosslinked polymer includes: blending polyarylene with another polymer containing tertiary amine groups, heating, and obtaining the crosslinked polymer.

[0116] Furthermore, the crosslinked polymer is subjected to a doping treatment of the mixture. Mineral acids, particularly sulfuric acid, phosphoric acid, or phosphoric acid, are incorporated into the polymer mixture, or other long-chain alkyl sulfonic acid groups are introduced, especially long-chain alkyl acidic substituents containing sulfonic acid groups or phosphoric acid groups.

[0117] Another aspect of the present invention provides the application of the aforementioned crosslinked polymer in the preparation of membrane materials for alkaline water electrolysis or high-temperature proton exchange membrane fuel cells.

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

[0119] The anion exchange resin is obtained by reacting the aforementioned polyarylene with tertiary amine groups; the cation exchange resin is obtained by reacting the aforementioned polyarylene with potassium thioacetate and m-chloroperoxybenzoic acid.

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

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

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

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

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

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

[0126] In membrane preparation, the material prepared by the above method can be dissolved in a suitable solvent and then coated onto a corresponding substrate to obtain a membrane of the appropriate thickness. Ideally, it could be a cation (proton) exchange membrane or anion exchange membrane.

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

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

[0129] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

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

[0131] Example 1

[0132] Figure 1 This paper describes a method for synthesizing alkyl brominated m-terphenyl. Under a nitrogen atmosphere and at room temperature, 7.0 g of 9BBN and 100 mL of THF were added to a 100 mL Shrek flask, followed by 3.2 mL of 6-bromo-1-hexene. After thorough mixing, the mixture was reacted at 50 °C for 4–5 h. Subsequently, under a nitrogen atmosphere, 7.42 g of 1-bromo-3,5-diphenylbenzene and 1.30 g of KOH were added to 30 mL of toluene and 27 mL of water. After dissolving with stirring at room temperature, the product from the first step was slowly added dropwise, followed by 50 mg of Pd(PPh3)4. The reaction was then carried out at 80 °C for 12 h. After the reaction was complete, the mixture was extracted with diethyl ether. The extracted solution was poured into anhydrous sodium sulfate and evaporated to dryness, followed by column chromatography purification, yielding 99.5%. Figure 2 This shows the bromhexyl-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 the reaction flow for preparing membrane materials using an inventive process is shown. The first step of this process uses two raw materials: bromhexyl-substituted m-terphenyl (the first raw material) prepared in the above examples and trifluoroacetone (the second raw material). These two raw materials can be directly synthesized into an alkylbromosubstituted polyarylene, P1-6CBr, via Friedel-Crafts hydroxyalkylation polymerization. Figure 4 The 1H NMR spectrum of the alkyl bromide-substituted polyarylene P1-6CBr is shown. The integral value of the introduced alkyl bromide side chain is consistent with the expected number of protons. In a further quaternization reaction, the above polymer can be converted into the organic cationic functionalized anion exchange resin P1-QA. Figure 5 The 1H NMR spectrum of anion exchange resin P1-QA prepared from polymer P1-6CBr is shown. During the quaternization process, any other tertiary amine compound can be used to quaternize the polymer. For example, these compounds can be trimethylamine, quinine ring, N-methylpiperidine, tetramethylimidazolium, N-methylpiperazine, triphenylphosphine, 3-methyl-3,6-dimethylenebicyclo[5.5.0]undecane-6-one, etc.

[0135] The previously described polymer P1-QA can be used to prepare membranes. For this purpose, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide, or N-methylpyrrolidone, wherein the polymer mass percentage is 1% to 30%, and an organic acid, such as trifluoroacetic acid, may be optionally added. The resulting anion exchange membranes with thicknesses of 30–100 μm exhibit very excellent hydroxide conductivity, reaching up to 175 mS / cm. -1 .

[0136] The P1-QA anion exchange membrane was applied to a hydrogen / air anion exchange membrane fuel cell. A Pt / C catalyst (60 wt% metal content) was ultrasonically mixed in a P1-QA solution (20 wt% polymer and 80 wt% catalyst). The membrane electrode assembly was prepared using a catalyst coating method: catalyst ink was sprayed onto both sides of the membrane sample. The metal loading was controlled at 0.6 mg / cm³. -2 The electrode area is 4 cm². 2 The catalyst-coated membrane was sandwiched between two sheets of carbon paper to form the MEA. Single-cell testing was conducted using an 850E Multi Range fuel cell test workstation (Scribner Associates, USA) at 80°C using the current method. Hydrogen and air with 100% humidity were simultaneously introduced to both sides of the membrane electrode at a flow rate of 400 sccm. By varying the current density and recording the corresponding voltage, the cell polarization curve was obtained, as shown in the figure. Figure 6 As shown, the battery has a maximum power density of up to 700 mW / cm². -2 .

[0137] Example 3

[0138] Figure 7 Another subsequent reaction for synthesizing the polymer is demonstrated. This is a method of sulfonation at the alkyl bromide substitution position: the bromine atom at the end of P1-6CBr is replaced with a thioacetic acid group via a nucleophilic substitution reaction. In a subsequent step, the thioacetic acid group is converted to a sulfonic acid group via oxidation. More specifically, 1 equivalent of the starting polymer P1-6CBr is dissolved in N,N-dimethylacetamide. Then, 1.12 parts of an equal amount of potassium thioacetate are added, and the mixture is stirred between 40 and 100 °C for 16 to 24 hours. The solution is then cooled to room temperature and filtered through a dialysis membrane to remove any undissolved substances. Finally, the solution is dried under vacuum to obtain a dried polymer. Next, the obtained polymer is dissolved again in N,N-dimethylacetamide, and the solution is cooled to 0 °C. Then, an equivalent amount of m-chloroperoxybenzoic acid (m-CPBA) is added in 6 portions over 10 minutes. The mixture is stirred continuously at room temperature. The polymer is then precipitated from a 1M potassium chloride solution, washed with water, and dried. Figure 8 The 1H NMR spectrum of cation exchange resin P1-SA prepared from polymer P1-6CBr is shown.

[0139] The obtained cation exchange resin P1-SA can be used to prepare both pure and mixed membranes. For pure membrane preparation, the sulfonated polymer P1-SA is dissolved in dimethyl sulfoxide, N,N-dimethylacetamide, or N-methylpyrrolidone. The resulting polymer solution is coated onto a glass plate using a doctor blade, and the solvent is then evaporated at a high temperature. For mixed acid-base membrane preparation, the 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 basic polymer such as O-PBI. The mixture is then coated and dried using the same method as for pure membrane preparation. The conductivity of the pure P1-SA proton exchange membrane is as high as 172 mS / cm. -1 It is close to the conductivity level of commercial Nafion 212 membrane.

[0140] Example 4

[0141] Figure 9 A schematic diagram of the reaction flow for preparing membrane materials using an inventive process is shown. The first step of this process uses three raw materials: bromhexyl-substituted m-terphenyl prepared in Example 1 (the first raw material), commercially available biphenyl (the second raw material), and trifluoroacetone (the third raw material). These three raw materials can be directly synthesized into an alkylbromosubstituted polyarylene, P1-6CBr-BP-x, via Friedel-Crafts hydroxyalkylation polymerization. Figure 10The 1H NMR spectrum of the alkyl bromide-substituted polyaryl alkylene oxide P1-6CBr-BP-10% is shown. Through further quaternization, the above polymer can be converted into an organic cationic functionalized anion exchange resin P1-QA-BP-x. Notably, single-ion-substituted anion exchange membranes can be constructed by selecting tertiary amine compounds as quaternizing agents, and multi-ion-substituted anion exchange resins can also be constructed by quaternizing tertiary amine monomers containing ionic groups. Figure 11 The 1H NMR spectrum of the double ion-substituted anion exchange resin P1-QA-BP-10% prepared from polymer P1-6CBr-BP-10% is shown.

[0142] The previously described polymer P1-QA-BP-x can be used to prepare membranes. For this purpose, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide, or N-methylpyrrolidone, wherein the polymer mass percentage is 1% to 30%, and an organic acid, such as trifluoroacetic acid, may be added optionally. The resulting anion exchange membranes with a thickness of 30-100 μm exhibit excellent alkali stability, retaining more than 90% of their conductivity after immersion in a 1M alkali solution for 10,000 hours.

[0143] Using the same method as in Example 3, the alkyl brominated polymer P1-6CBr-BP involved in the above examples 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] Figure 12 A schematic diagram of the reaction flow for preparing membrane materials using an inventive process is shown. The first step of this process uses two raw materials: 1-bromo-3,5-diphenylbenzene (the first raw material) and 1,1,1-trifluoroacetone (the second raw material). These two raw materials can be synthesized into a brominated polyarylene, P1-Br, through a polyhydroxyalkylation reaction. Figure 13 The 1H NMR spectrum of the brominated polyarylene was displayed. The integral ratio of aromatic protons perfectly matched the target structure. This polymer was then coupled with 6-bromo-1-hexene to yield the alkylbromo-substituted polymer P1-6CBr. The obtained polymer was characterized by NMR spectroscopy. The successful grafting reaction was confirmed by measuring the chemical shifts of the protons on the substituted aromatic rings.

[0146] Example 6

[0147] Figure 14A schematic diagram of the reaction flow for preparing membrane materials using an inventive process is shown. The first step of this process uses two raw materials: p-terphenyl (the first raw material) and 4′-bromo-2,2,2-trifluoroacetophenone (the second raw material). These two raw materials are synthesized into a brominated polymer, P2-Br, via a polyhydroxyalkylation reaction. Gel permeation chromatography (GPC) shows a molecular weight (Mw) of 22000 g / mol and a dispersion (D) of 1.99. This polymer is then coupled with 6-bromo-1-hexene to obtain an alkylbromosubstituted polyarylene, P2-6CBr. In a further quaternization reaction, the bromine atoms are substituted with cations, converting it 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 groups from the polymer backbone via a flexible chain provides the advantage of phase separation, thereby forming ion transport channels and improving conductivity. Figure 15 The images show the brominated polymer P2-Br, the alkyl brominated polymer P2-6CBr, and two cation exchange polymers P2-QA-1 and P2-QA-2. 1 ¹H NMR spectrum. By observing the characteristic signals of the constructed organic cation groups and integrating the characteristic groups, it can be confirmed that the quaternization reaction proceeded successfully.

[0148] The previously described polymer P2-QA can be used to prepare membranes. For this purpose, a polymer solution is formulated in dimethyl sulfoxide, N,N-dimethylacetamide, or N-methylpyrrolidone, wherein the polymer mass percentage is 1% to 30%, and optionally an organic acid, such as trifluoroacetic acid, is added. These membranes, with a thickness of 30-100 μm, exhibit very excellent hydroxide conductivity (151-175 mS / cm). -1 It also exhibits alkali stability, maintaining its chemical structure stability even after nearly 100 days of treatment with 1M alkali at 80℃.

[0149] Using the same method as in Example 3, the alkyl brominated polymer P2-6CBr involved in the above examples 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] Figure 16A schematic diagram of the reaction flow for preparing membrane materials using an inventive process is shown. The first step of this process uses three raw materials: p-terphenyl (first raw material), 2,2,2-trifluoroacetone (second raw material), and 4′-bromo-2,2,2-trifluoroacetophenone (third raw material). These three raw materials are synthesized into a brominated polymer, P2-Br-TF, via a polyhydroxyalkylation reaction. Gel permeation chromatography (GPC) shows a molecular weight (Mw) of 65,000 g / mol and a dispersion (D) of 2.68. This polymer is then coupled with 6-bromo-1-hexene to obtain an alkylbromosubstituted polyarylene, P2-6CBr-TF. In a further quaternization reaction, the bromine atoms are substituted with cations, converting it into a high-molecular-weight anion exchange resin, P2-QA-TF.

[0152] The previously described polymer P2-QA-TF can be used to prepare membranes. For this purpose, a polymer solution is prepared in dimethyl sulfoxide, N,N-dimethylacetamide, or N-methylpyrrolidone, wherein the polymer mass percentage is 1% to 30%, and an organic acid, such as trifluoroacetic acid, may be optionally added. The resulting anion exchange membranes with a thickness of 30-100 μm exhibit excellent mechanical properties, with tensile strengths of 60-80 MPa and elongation at break of 75-96%.

[0153] Using the same method as in Example 3, the alkyl brominated polymer P2-6CBr-TF involved in the above examples 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] Figure 17A reaction procedure for preparing a cross-linked membrane is demonstrated, using alkyl bromide polymers (P1-6CBr or P2-6CBr) and polymers containing tertiary amine substituents as raw materials. A mixture of anion-exchange polymers linked by covalent bonds can be prepared by a Mensøe reaction between the alkyl bromide polymer and the polymer containing tertiary amine substituents. Specifically, the two polymers are mixed in a polar aprotic solvent at a desired mixing ratio. The two polymers can be mixed in any ratio from 95:5 to 5:95. Then, the solvent is evaporated in a fume hood or vacuum drying oven at a high temperature. The resulting membrane is then washed with ultrapure water. Further treatment of the membrane is possible if desired. When the alkyl bromide groups in the alkyl bromide polymer are in excess of the equivalent amount of tertiary amine groups in the tertiary amine polymer, the remaining alkyl bromide groups can be converted to an organic cationic form by reacting with any triamine. Specifically, the membrane is immersed in an aqueous solution of an amine (if liquid) or an ethanolic solution of an amine (if solid). It is best to use sterically hindered amines such as quinoline or N-methylpiperidine, or sterically hindered diamines such as DABCO. Then, rinse the membrane with ultrapure water until all residual solvent and amine are removed. Next, immerse the membrane in KOH to convert it to OH-. - The membrane is then rinsed with ultrapure water that has been pre-boiled in nitrogen. Afterward, 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 a tertiary amine polymer are in excess compared to the alkyl bromide groups in an alkyl bromide polymer, they can be doped with phosphoric acid (PA) to enable the polymer to be used in high-temperature membrane fuel cells. Alternatively, they can undergo alkylation with alkyl iodides to generate anion-exchange polymers, which can be used in alkaline applications (such as AEMWE or AEMFC) as well as in redox flow cells. In particular, the prepared AEM-QPBP-P1-10% membrane exhibits high OH- ion exchange activity at 80°C. - and Cl - The conductivity was 186.0 and 140.0 mS / cm, respectively. -1 Meanwhile, AEM-QPBP-P1-10% exhibits moderate water absorption (WU = 35.3% at 80°C), excellent dimensional stability (SR < 10% at 80°C), and superior alkali resistance (performance degradation of less than 5% after treatment with 1M NaOH solution at 80°C for 100 days), which may be attributed to its highly rigid and cross-linked structure. Furthermore, AEMWE based on AEM-QPBP-P1-10% outperforms AEMWE based on commercial PiperION at high KOH concentrations. Figure 18The polarization curves of AEMWE based on AEM-QPBP-P1-10% equipped with a non-precious metal catalyst are shown at 80 °C under 1 M KOH conditions, achieving 3000 mA cm⁻¹ at 2.0 V. -2 The current density.

[0157] Comparative Example 1

[0158] Figure 19 This invention presents a method for preparing bromoalkyl-substituted m-terphenyls reported in patent (WO 2024 / 046712). This method involves the use of the hazardous chemical reagent n-butyllithium, and the reaction conditions are harsh, requiring ultra-low temperatures (-85 to -20°C), which is unfavorable for large-scale preparation and industrialization of this type of reaction. The present invention provides a preparation method starting from aryl halogen monomers or aryl halogen polymers, through a Suzuki coupling reaction of olefins via hydroboration. The reaction conditions are mild, the substrate range is broad, applicable not only to small molecules but also showing good compatibility with various halogenated aromatic polymers. It offers high yields, no side reactions, and a yield as high as 99%, showing great promise for applications in various fields of functional modification of small organic molecules and post-polymer modification.

[0159] Comparative Example 2

[0160] The proton exchange membrane was purchased from the market as a Nafion 212.

[0161] The proton exchange membranes of different thicknesses prepared in Example 3 and Comparative Example 2 were tested for ion exchange capacity (IEC), swelling rate, water absorption rate, ionic conductivity and oxidative stability.

[0162] The IEC (International Electron Exchange Membrane) is calculated by acid-base titration to determine the hydrogen ion content in a given mass of proton exchange membrane, thus obtaining the IEC of the proton exchange membrane.

[0163] 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 in its mass and dimensions from its initial state.

[0164] Ionic conductivity was measured using the Shanghai Chenhua electrochemical testing system. The resistance of the proton exchange membrane in a fully humid state at 80℃ was measured using the two-electrode AC impedance method, and then the conductivity was calculated using a formula.

[0165] Oxidative stability was determined by completely immersing the membrane in Fenton's reagent (2 ppm Fe) at 80°C. 2+ The membrane breakage time was recorded in 3.0 wt% H2O2, and the specific results are shown in Table 1.

[0166] Table 1. IEC, water absorption, swelling ratio, electrical conductivity, and oxidative stability of Example 3 and Comparative Example 1.

[0167]

[0168] Table 1 illustrates that the proton exchange membrane prepared according to this invention has comparable conductivity and oxidation stability, as well as better dimensional stability compared to commercially available products.

[0169] Comparative Example 3

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

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

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

[0173]

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

[0175] As can be seen from the above embodiments, the present invention provides a method for preparing alkyl-side-chain substituted aromatic monomers. The method provided by the present invention exhibits extremely high reactivity, mild reaction conditions, high yield, and good compatibility with various functional groups, and can be used to prepare substituted aromatic monomers required for various ion exchange membrane materials, organic optoelectronic materials, etc. The present invention also provides alkyl halide-substituted polyaryles and their preparation methods; proton exchange membranes and anion exchange membranes prepared from alkyl halide-substituted polyaryles have advantages such as high conductivity and excellent chemical stability, and have significant practical application and industrialization prospects.

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

[0177] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A polyaryl alkyl group, characterized in that, The polyarylene has a structure as shown in formula (II) or formula (III): ； In this context, A and B are independently selected from aromatic monomers, and Y is selected from F, Cl, Br, and 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 integers from 0 to 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... , , or ; The aromatic monomer is selected from any of the following structures: 。 2. The method for preparing polyarylene according to claim 1, characterized in that, include: A second mixed reaction system containing at least aromatic monomer B, alkyl halide-substituted aromatic monomer, ketone monomer and trifluoromethanesulfonic acid is subjected to Friedel-Crafts hydroxyalkylation polymerization to obtain a polyarylene having the structure shown in formula (II). Wherein, the aromatic monomer B is selected from aromatic monomers; the alkyl halide-substituted aromatic monomer has the structure shown in formula (I): ； Wherein, A is selected from aromatic monomers; 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, where n is an integer selected from 0 to 20; The structure of the ketone monomer is as follows: At least one of R1 and R2 is a substituent containing fluorine, and the substituent is selected from... , , or ; Alternatively, a third mixed reaction system containing at least aromatic monomer B, haloaromatic monomer, ketone monomer, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aryl halopolyaryl precursor. And, by reacting a fourth mixed reaction system comprising at least the said aryl halide polyaryl alkane precursor, olefin monomer and 9-boron bicyclo[3,3,1]nonane, to obtain a polyaryl alkane having the structure shown in formula (II); The aryl halide polyaryl alkyl 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 as follows: A is selected from aromatic monomers, and X is selected from Cl, Br, or I; the structure of the olefin monomer is as follows: 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 to 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... , , or ; Alternatively, a fifth mixed reaction system comprising at least p-terphenyl, 4'-bromo-2,2,2-trifluoroacetophenone, 2,2,2-trifluoroacetone, and trifluoromethanesulfonic acid is subjected to a Friedel-Crafts hydroxyalkylation polymerization reaction to obtain an aryl halide polyaryl alkyl precursor. And, by reacting a mixed reaction system comprising at least the said aryl halide polyaryl alkane precursor, 6-bromo-1-hexene and 9-boron bicyclo[3,3,1]nonane, a polyaryl alkane having the structure shown in formula (III) is obtained; The aryl halide polyaryl alkyl precursor has a structure as shown in formula (V): ； m1 is any integer greater than or equal to 1, and m2 is any integer greater than or equal to 0.

3. Use of the polyarylene according to claim 1 in the preparation of crosslinked polymers, ion exchange resins, ion exchange membranes or batteries.

4. A crosslinked polymer, characterized in that: The crosslinked polymer is prepared by reacting the polyarylene of claim 1 with a first polymer; wherein the first polymer includes a polymer containing tertiary amine groups.

5. An ion exchange resin, characterized in that: The ion exchange resin includes a cation exchange resin or an anion exchange resin; The anion exchange resin is obtained by reacting the polyarylene of claim 1 with a tertiary amine group; the cation exchange resin is obtained by reacting the polyarylene of claim 1 with potassium thioacetate and m-chloroperoxybenzoic acid.

6. An ion exchange membrane, characterized in that: The ion exchange membrane is made from the cross-linked polymer of claim 4 or the ion exchange resin of claim 5.

7. The application of the crosslinked polymer of claim 4 or the ion exchange membrane of claim 6 in the preparation of membrane materials for fuel cells, redox flow batteries or water electrolysis.

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