阅读说明：本技术 一种含耐碱解阳离子基团和氟碳侧链的离聚物及其制备方法和应用 (Ionomer containing alkali-resistant cation groups and fluorocarbon side chains and preparation method and application thereof ) 是由 魏海兵 杨雅珂 丁运生 王平 孙晓红 李学良 杨善中 于 2020-05-28 设计创作，主要内容包括：本发明公开了一种含耐碱解阳离子基团和氟碳侧链的离聚物及其制备方法和应用,该离聚物的结构单元中含有超疏水性的氟碳侧链和耐碱解的功能阳离子。基于该离聚物所制备的阴离子交换膜具有离子电导率高和化学稳定性好等优势,可作为膜材料用于燃料电池和电解水等诸多领域,同时该离聚物也可以用于燃料电池催化层的粘结剂材料。(The invention discloses an ionomer containing alkali-resistant cation groups and fluorocarbon side chains, a preparation method and application thereof. The anion exchange membrane prepared based on the ionomer has the advantages of high ionic conductivity, good chemical stability and the like, can be used as a membrane material in various fields such as fuel cells and electrolyzed water, and can also be used as a binder material of a catalyst layer of the fuel cells.)

1. An ionomer containing alkali-resistant cationic groups and fluorocarbon side chains, characterized in that: the ionomer has a structure as shown in formula (1):

in the formula: the ion-containing arylene structural unit contains alkali-soluble cation groups, and the arylene structural unit contains hydrophobic fluorocarbon side chains; the arylene structural unit containing ions is connected with the arylene structural unit through a carbon-carbon single bond, and x is 0.05-0.95; m is an integer between 10 and 1000.

2. The ionomer comprising alkali-labile cationic groups and fluorocarbon side chains of claim 1 wherein: the ionomer has a structure as shown in formula (2), formula (3) or formula (4);

formula (2) is an ionomer containing cations and fluorocarbon side chains:

wherein: each Ar is independently selected from one or more of aromatic compound residues; r¹Selected from those having 2-10 carbon atomsA meta alkylene group; r²Is alkyl, aryl or halogenated aryl; counterion A^-Selected from the group consisting of halide ions; x is 0.05-0.95, y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer between 10 and 1000;

R⁺is an organic cation and is selected from one or more of the following structures:

wherein: r⁰¹、R⁰²、R⁰³、R⁰⁴And R⁰⁵Each independently selected from a hydrocarbon group containing 1-20 carbon atoms; r⁰⁶、R⁰⁷、R⁰⁸And R⁰⁹Each independently selected from hydrogen, or alkyl or aryl with 1-20 carbon atoms, and at least one non-hydrogen substituent group;

formula (3) is an ionomer containing piperidine cations and fluorocarbon side chains:

wherein: each Ar is independently selected from one or more of aromatic compound residues, R³And R⁴Each independently selected from alkyl with 1-10 carbon atoms; r²Is alkyl, aryl or halogenated aryl; counterion A^-Selected from halide ions or methyl sulfate ions; x is 0.05-0.95, y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer between 10 and 1000;

formula (4) is a crosslinked ionomer containing piperidine cations and fluorocarbon side chains:

wherein: each Ar is independently selected from aromatic compound residuesOr a plurality of, each R³And R⁴Each independently selected from alkyl with 1-10 carbon atoms; r⁵Selected from alkylene with 2-20 carbon atoms; each R²Each independently selected from alkyl, aryl or halogenated aryl; each counterion A^-Each independently selected from halide ions or methyl sulfate ions; x1 is 0-0.94, x2 is 0.01-0.95, x1+ x2 is x, and x is more than or equal to 0.05 and less than or equal to 0.95; y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer of 10 to 1000.

3. The ionomer comprising alkali-labile cationic groups and fluorocarbon side chains of claim 2 wherein: the aromatic compound residue is:

4. the ionomer comprising alkali-labile cationic groups and fluorocarbon side chains of claim 2 wherein: r²One or more selected from the following structures:

wherein p is an integer of 1-20.

5. A method for preparing the ionomer containing alkali-disintegrable cationic group and fluorocarbon side chain as claimed in any one of claims 1 to 4, characterized in that:

1) the ionomer shown in the formula (2) is obtained by reacting a halogen-terminated polymer containing a fluorocarbon side chain with tertiary amine, N-substituted pyrrolidine, N-substituted piperidine, quinine or substituted imidazole;

the structural general formula of the fluorine-containing carbon side chain halogen-terminated polymer is shown as the formula (5):

in formula (5): x is a halogen atom; each Ar is one or more independently selected from aromatic compound residues; r¹Selected from alkylene with 2-10 carbon atoms; r²Is alkyl, aryl or halogenated aryl; x is 0.05-0.95, y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer between 10 and 1000;

the structural general formula of the tertiary amine is shown as a formula (6):

wherein R is⁰¹、R⁰²、R⁰³Each independently selected from a hydrocarbon group containing 1-20 carbon atoms;

the structural formulas of the N-substituted pyrrolidine, the N-substituted piperidine and the quinine are shown as a formula (7):

wherein R is⁰⁴And R⁰⁵Each independently selected from hydrocarbyl with 1-20 carbon atoms;

the structural formula of the substituted imidazole is shown as a formula (8):

wherein R is⁰⁶、R⁰⁷、R⁰⁸And R⁰⁹Each independently selected from hydrogen, or alkyl or aryl with 1-20 carbon atoms, and at least one non-hydrogen substituent group;

2) the ionomer shown in the formula (3) is obtained by reacting a precursor polymer containing fluorocarbon side chains and piperidine units with a hydrocarbylating reagent;

the structural general formula of the precursor polymer containing the fluorocarbon side chain and the piperidine motif is shown as the formula (9):

in formula (9): each Ar is independently selected from one or more of aromatic compound residues; r³Selected from alkyl with 1-10 carbon atoms; r²Is alkyl, aryl or halogenated aryl; x is 0.05-0.95, y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer between 10 and 1000;

the alkylation reagent is dimethyl sulfate or monohalogenated hydrocarbon with 1-20 carbon atoms;

3) the crosslinking ionomer shown in the formula (4) is obtained by reacting a precursor polymer containing fluorocarbon side chains and piperidine units shown in the formula (9) with polyhalogenated hydrocarbon or reacting with a hydrocarbylating reagent and the polyhalogenated hydrocarbon together;

the structural general formula of the polyhalogenated hydrocarbon is shown as a formula (10):

wherein: r⁵¹、R⁵²、R⁵³And R⁵⁴Each independently selected from hydrogen, halogen, alkyl or halogenated alkyl with 1-20 carbon atoms, or aryl or halogenated aryl with 1-20 carbon atoms, and the formula (10) at least contains two halogen atoms.

6. Use of the ionomer comprising alkali-labile cationic groups and fluorocarbon side chains according to any one of claims 1 to 4, wherein: used for preparing anion exchange membranes.

7. Use according to claim 6, characterized in that:

dissolve the ionomer inObtaining an ionomer solution in an organic solvent; coating the ionomer solution on a substrate or a reinforced fabric, and removing the solvent to obtain the ionomer-based anion exchange membrane with the anion A^-；

Or: directly coating the substrate or the reinforced fabric with a reaction solution containing the ionomer, and removing the solvent and the excess hydrocarbylating agent and/or polyhalogenated hydrocarbon to obtain the ionomer-based anion exchange membrane with the anion A^-。

8. Use according to claim 6 or 7, characterized in that: the thickness of the anion exchange membrane is between 0.001 mm and 5 mm.

9. Use according to claim 6 or 7, characterized in that: anion A in the anion exchange membrane^-Can be converted into other desired anions by ion exchange, including hydroxide, carbonate, bicarbonate, hexafluorophosphate, sulfate or other anions different from A^-Other halogen ions of (1).

10. Use of the ionomer comprising alkali-labile cationic groups and fluorocarbon side chains according to any one of claims 1 to 4, wherein: a binder for a catalytic layer of a fuel cell.

Technical Field

The invention belongs to the field of ionomers and related applications thereof, and particularly relates to an ionomer containing alkali-resistant cation-decomposing groups and fluorocarbon side chains, and a preparation method and application thereof.

Background

Ionomers, also known as ion-containing polymers, generally consist of a polymer backbone, cationic groups fixed to the polymer backbone, and mobile anionic moieties. Due to its wide application in the fields of polyelectrolyte membranes, fuel cell catalyst layer binders, ion exchange resins, etc., its development and performance optimization have been receiving wide attention in the fields of chemical industry and material science. Among these, anion exchange membranes based on cation ionomer-containing anion exchange membranes are key components of anion exchange membrane fuel cells through which hydroxide ions or other anions are transported. In addition, the ionomer can also be used as a binder of a catalytic layer of an anion exchange membrane fuel cell for ion transport in the catalytic layer.

Anion exchange membranes are used in membranes and catalyst layers of fuel cells, and need to meet basic conditions of good alkali resistance, moderate water absorption, high ionic conductivity and the like. The anion exchange membrane materials reported at present are generally based on polymer frameworks such as polyether sulfone, polyphenylene oxide and polystyrene, and benzyl trialkyl ammonium is taken as a functional cationic group. However, such combinations generally suffer from poor alkali resistance and low ionic conductivity.

The preparation of ionomer materials with both excellent chemical stability and ionic conductivity is a bottleneck limiting the related applications of anion exchange membranes. The alkali resistance of ionomers depends primarily on the polymer backbone and the functional cations. In recent years, polyarylalkylene ionomers and polyarylamide cationic ionomers having no ether bonds in the main chain have attracted attention because of their outstanding alkaline hydrolysis stability (W. -H.Lee, Y.S.Kim, C.Bae, ACS Macro Lett.,2015,4,814-398; C. Pei, Liyuanheng, Chinese patent, CN 107112563B; J.Wang et al, Nat.energy,2019,4,392-398; Y.Yan et al, PCT, WO 2019/068051A 2). However, due to the inherent rigid structure of the ionomer, the prepared anion exchange membrane is difficult to form a microphase separation aggregation structure so as to improve the ionic conductivity and the ionic transmission efficiency of the membrane. On the other hand, in chinese patent application No. 201911079673.X, although it is proposed that the ion exchange capacity and ion conductivity of a polyarylalkylene ionomer can be improved by using polyquaternary ammonium cationic side chains, insufficient alkali resistance of the polyquaternary ammonium cationic side chains themselves may limit the application of such ionomers.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an ionomer simultaneously containing alkali-resistant cation-decomposing groups and fluorocarbon side chains, a preparation method and application thereof, and aims to solve the technical problem that the prepared ionomer and an anion exchange membrane based on the ionomer have excellent alkali-decomposing stability and ion conductivity.

In order to realize the purpose of the invention, the following technical scheme is adopted:

the invention discloses an ionomer containing alkali-resistant cationic groups and fluorocarbon side chains, which has a structure shown in a formula (1):

in the formula: the ion-containing arylene structural unit contains a cationic group with better alkali resistance, and the arylene structural unit contains a hydrophobic fluorocarbon side chain; the arylene structural unit containing ions is connected with the arylene structural unit through a carbon-carbon single bond, and x is 0.05-0.95; m is an integer between 10 and 1000.

The ionomer containing the alkali-resistant cationic group and the fluorocarbon side chain shown in the formula (1) can specifically have a structure shown in a formula (2), a formula (3) or a formula (4):

the formula (2) is an ionomer containing alkali-resistant cations and fluorocarbon side chains, the formula (3) is an ionomer containing piperidine cations and fluorocarbon side chains, and the formula (4) is a cross-linking ionomer containing piperidine cations and fluorocarbon side chains. In formula (2), formula (3) or formula (4): each Ar is independently selected from one or more of aromatic compound residues; r⁺Is an organic cation; r¹Selected from alkylene with 2-10 carbon atoms; r²Is alkyl, aryl or halogenated aryl; each R³And R⁴Each independently selected from alkyl with 1-10 carbon atoms; r⁵Selected from alkylene with 2-20 carbon atoms; each counterion A^-Each independently selected from halide ions or methyl sulfate ions; x1 is 0-0.94, x2 is 0.01-0.95, and x1+ x2 is x; x is 0.05-0.95, y is 0.05-0.90; and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer between 10 and 1000; the above groups being independently selected, i.e. different groups (e.g. R)¹、R²、R³、R⁴And R⁵) Independent of each other, also means that the same group can have multiple choices in the structural motif.

Further, the aromatic compound residue is:

further, R⁺One or more of the following structures:

wherein: r⁰¹、R⁰²、R⁰³、R⁰⁴And R⁰⁵Each independently selected from a hydrocarbon group containing 1-20 carbon atoms; r⁰⁶、R⁰⁷、R⁰⁸And R⁰⁹Are respectively and independently selected from hydrogen, alkyl or aryl with 1-20 carbon atoms, and at least contain one non-hydrogen substituent group;

further, R²One or more selected from the following structures:

wherein p is an integer between 1 and 20.

The invention also discloses a preparation method of the ionomer shown in the formula (2): is obtained by reacting a halogen end-group functionalized polymer containing a fluorocarbon side chain with tertiary amine, N-substituted pyrrolidine, N-substituted piperidine, quinine or substituted imidazole;

the fluorine carbon side chain-containing halogen-terminated polymer is prepared by condensation polymerization of aromatic compounds and omega-haloalkyl trifluoroketone, methyl perfluoroalkyl ketone, trifluoroalkyl ketone and trifluoroaryl ketone under the catalysis of strong acid, and the method is mentioned in research papers (Guzman-Gutierrez M.T.et al, Macromolecules,2011,44,194-. The structural general formula of the fluorine-containing carbon side chain halogen-terminated polymer is shown as the formula (5):

in formula (5): x is a halogen atom; each Ar is one or more independently selected from aromatic compound residues; r¹Selected from alkylene with 2-10 carbon atoms; r²Is alkyl, aryl or halogenated aryl; x is 0.05-0.95, y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer of 10 to 1000.

The structural general formula of the tertiary amine is shown as a formula (6):

wherein R is⁰¹、R⁰²、R⁰³Each independently selected from hydrocarbyl with 1-20 carbon atoms;

the structural formulas of the N-substituted pyrrolidine, the N-substituted piperidine and the quinine are shown as a formula (7):

wherein R is⁰⁴And R⁰⁵Each independently selected from hydrocarbyl with 1-20 carbon atoms;

the structural formula of the substituted imidazole is shown as a formula (8):

wherein R is⁰⁶、R⁰⁷、R⁰⁸And R⁰⁹Each independently selected from hydrogen, or alkyl or aryl with 1-20 carbon atoms, and at least one non-hydrogen substituent.

The reaction formula of the fluorine-carbon side chain-containing halogen end-group-functionalized polymer and tertiary amine, N-substituted pyrrolidine, N-substituted piperidine, quinine or substituted imidazole is shown as a formula (11):

the counterion A in the product represented by the reaction formula (11) (i.e., the structure represented by the formula (2))^-I.e. from halogen ions X into which halogen atoms X in the halo-terminated polymer containing fluorocarbon side chains are converted^-。

The invention also discloses a preparation method of the ionomer shown in the formula (3): obtained by the reaction of a precursor polymer containing fluorocarbon side chains and piperidine units and a hydrocarbylating reagent;

the precursor polymer containing fluorocarbon side chains and piperidine moieties is prepared by condensation polymerization or condensation copolymerization of an aromatic compound with an N-substituted piperidone, methyl perfluoroalkyl ketone, trifluoroalkyl ketone or trifluoroaryl ketone under catalysis of a strong acid, which polymerization methods are mentioned in research papers (J.Wang et al, Nat. energy,2019,4,392-398) and patents (Y.Yan et al, PCT, WO 2019/068051A 2). The structural general formula of the precursor polymer containing the fluorocarbon side chain and the piperidine motif is shown as the formula (9):

in formula (9): each Ar is independently selected from one or more of aromatic compound residues; r³Selected from hydrocarbon groups with 1-10 carbon atoms; r²Is alkyl, aryl or halogenated aryl; x is 0.05-0.95, y is 0.05-0.90, and x + y is more than or equal to 0.10 and less than or equal to 1.0; z is an integer between 1 and 17; m is an integer between 10 and 1000;

the structural formula of the N-substituted piperidone is shown as a formula (12):

wherein R is³Selected from alkyl containing 1-10 carbon atoms;

the alkylation reagent is dimethyl sulfate or monohalohydrocarbon with 1-20 carbon atoms, and the halogen can be Cl, Br or I;

the reaction formula of the precursor polymer containing the fluorocarbon side chain and the piperidine group and the alkylation reagent is shown as a formula (13):

in the reaction formula (13), R⁴Is the residue of a hydrocarbylating agent, and is selected from a hydrocarbyl group having 1 to 10 carbon atoms.

The counterion A in the product represented by the reaction formula (13) (i.e., the structure represented by the formula (3))^-From a hydrocarbylating reagent such as methyl sulfate ion or halogen ion.

The invention also discloses a preparation method of the crosslinking ionomer shown in the formula (4): obtained by the reaction of a precursor polymer containing fluorocarbon side chains and piperidine units shown in formula (9) and polyhalogenated hydrocarbon, or the reaction of the precursor polymer, a hydrocarbylation reagent and the polyhalogenated hydrocarbon;

the fluorocarbon-containing side chain polyarylpiperidine polymer and the alkylating agent are the same as above; the structural general formula of the polyhalogenated hydrocarbon is shown as a formula (10):

wherein: r⁵¹、R⁵²、R⁵³And R⁵⁴Independently selected from hydrogen, halogen, alkyl or halogenated alkyl with 1-20 carbon atoms, or aryl or halogenated aryl with 1-20 carbon atoms, and the formula (10) at least contains two halogen atoms, and the halogen can be Cl, Br or I.

The reaction formula of the precursor polymer containing the fluorocarbon side chain and the piperidine group, the alkylation reagent and the polyhalogenated hydrocarbon is shown as the formula (14):

in formula (14): r⁴Is the residue of a hydrocarbylating agent, which may be selected from hydrocarbyl groups having between 1 and 10 carbon atoms; r⁵Is the residue of the alkylation of polyhalogenated hydrocarbon, and can be selected from alkylene with 2-20 carbon atoms.

The counterion A in the product represented by the reaction formula (14) (i.e., the structure represented by the formula (4))^-From methyl sulfate ions or halogen ions in the hydrocarbylating agent and/or halogen ions from which halogens in the polyhalogenated hydrocarbon are converted.

Further, the synthesis method of the reaction formula shown in the formula (11) comprises the following steps: dissolving a fluorine-containing carbon side chain halogen-terminated polymer shown in formula (5) in an organic solvent S1, adding a tertiary amine, N-substituted pyrrolidine, N-substituted piperidine, quinine and/or substituted imidazole shown in formula (6) and/or formula (7) and/or formula (8) according to 1-10 times of the molar amount of the halogen-containing end group of the polymer, and reacting at 0-100 ℃ for more than 0.5 hour; after the reaction is finished, obtaining a reaction solution containing ionomer; and precipitating the reaction solution containing the ionomer in a precipitator to separate out the ionomer, and separating, washing and drying to obtain the ionomer with the structure shown in the formula (2).

Further, the synthesis method of the reaction formula shown in the formula (13) comprises the following steps: dissolving a precursor polymer containing a fluorocarbon side chain and a piperidine moiety represented by the formula (9) in an organic solvent S1, adding an alkylation reagent (dimethyl sulfate or a C1-20 monohalogenated hydrocarbon) in an amount of 1-10 times the molar amount of the piperidine group contained in the polymer, and reacting at 0-100 ℃ for 0.5 hour or more; after the reaction is finished, obtaining a reaction solution containing ionomer; and precipitating the reaction solution containing the ionomer in a precipitator to separate out the ionomer, and separating, washing and drying to obtain the ionomer with the structure shown in the formula (3).

Further, the reaction method of the reaction formula shown in formula (14) is: dissolving a precursor polymer containing a fluorocarbon side chain and a piperidine group represented by the formula (9) in an organic solvent S1, adding a polyhalogenated hydrocarbon in an amount of 0.01 to 10 times the molar amount of the piperidine group contained in the polymer, adding an alkylating agent in an amount of 0 to 10 times the molar amount of the piperidine group contained in the polymer, and reacting at 0 to 100 ℃ for 5 minutes or more; after the reaction is finished, a reaction solution containing the ionomer as shown in the formula (4) is obtained.

The ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be used for preparing an anion-exchange membrane, and the specific method comprises the following steps:

dissolving the ionomer in an organic solvent S2 to obtain an ionomer solution; coating the ionomer solution on a substrate or a reinforced fabric, and removing the solvent to obtain the ionomer-based anion exchange membrane, wherein the anions are methyl sulfate ions and/or halogen ions A^-；

Or: directly coating the reaction solution containing the ionomer on a substrate or a reinforced fabric, removing the solvent and excessive hydrocarbon alkylation reagent and/or polyhalogenated hydrocarbon to obtain the anion exchange membrane based on the ionomer, wherein the anion is methyl sulfate ion and/or halogen ion A^-。

In the preparation method of the ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains and the anion exchange membrane based on the ionomer: the organic solvents S1 and S2 are each independently preferably a polar aprotic solvent, such as dimethylsulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide; the precipitant is preferably selected from water, methanol, ethanol, acetone, diethyl ether, petroleum ether, toluene or xylene.

The preparation method of the anion exchange membrane also has the following characteristics:

the substrate is selected from a glass plate or a polytetrafluoroethylene plate; the reinforced fabric is selected from polyethylene cloth, polypropylene cloth, polyester cloth, nylon cloth or polyvinyl chloride cloth; the coating method can be solution casting film forming, rotary coating, film scraping, casting or dipping film forming; the solvent removing method can be room temperature volatilization or heating and drying at 30-200 ℃.

The anion in the anion exchange membrane, the anion of which is methyl sulfate ion and/or halogen ion, can be converted into other anions according to the need, namely A in formula (2), formula (3) or formula (4)^-Conversion from methyl sulfate ion and/or halogen ion to other desired ions, including hydroxide ion, carbonate ion, bicarbonate ion, hexafluorophosphate ion, sulfate ion or ions other than A^-Other ions of (2). During the specific operation, the film is only required to be placed in a solution (such as 0.01-10 mol L of concentration) containing corresponding ions^-1NaOH solution, KOH solution, Na₂CO₃Solution, K₂CO₃Solution, NaHCO₃Solution, KHCO₃Solution, NaPF₆Solution, KPF₆Solution, etc.) for a sufficient time, and then thoroughly washed with deionized water. For example: soaking the anion exchange membrane with the anions of halogen ions in 0.01-10 mol L^-1The NaOH aqueous solution or the concentration of the NaOH aqueous solution is 0.01 to 10mol L^-1The KOH aqueous solution is subjected to anion exchange to obtain an anion exchange membrane with hydroxide ions as anions (namely, A in the structural formula of the anion exchange membrane based on the ionomer containing alkali-resistant cation groups and fluorocarbon side chains^-Conversion to OH^-)。

The anion exchange membrane prepared from the ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be applied to the field of various diaphragms, such as fuel cells, electrolyzed water or water treatment devices, and is particularly suitable for being used as the anion exchange membrane of alkaline fuel cells.

Besides anion exchange membranes, the ionomer containing alkali-resistant cation groups and fluorocarbon side chains can also be used for preparing a binder of a catalyst layer of a fuel cell.

The invention has the beneficial effects that:

compared with the existing anion exchange membrane, the anion exchange membrane prepared based on the ionomer containing alkali-resistant cation groups and fluorocarbon side chains has excellent ionic conductivity and alkali resistance at the temperature of 80 ℃ and 2mol L^-1When the NaOH solution is subjected to alkaline hydrolysis for more than 10 days, the ionic conductivity is reduced within 5 percent, and the method has a good application prospect.

Drawings

FIG. 1 is Cl of anion exchange membrane prepared from ionomer containing alkali-resistant cation groups and fluorocarbon side chains in example 1^-Conductivity versus temperature curve.

FIG. 2 shows the anionic membranes prepared from the ionomers of examples 1 and 2 at 80 ℃ and 2mol L^-1And (3) a chloride ion conductivity change diagram at 50 ℃ after alkaline hydrolysis in NaOH aqueous solution for 300 hours.

FIG. 3 is a graph of an ionomer containing alkali-resistant cationic groups and fluorocarbon side chains as in example 3¹⁹F NMR spectrum (solvent: DMSO-d)₆)。

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has a structural formula shown in formula (15):

the preparation method comprises the following steps: will be connectedBenzene (0.30g, 1.9mmol), 7-bromo-1, 1, 1-trifluorohept-2-one (0.34g, 1.36mmol), methylpentadecafluoroheptylketone (0.36g, 0.87mmol), dichloromethane (1.9mL) and trifluoromethanesulfonic acid (1.9mL) were stirred at room temperature for 16h to give a black gelatinous material. After the reaction was completed, it was slowly added dropwise to methanol to obtain a white crude fibrous solid. It was then filtered and washed with hot methanol. After drying in vacuo, 0.90g of a white fibrous bromine-terminated precursor polymer was obtained, 500mg of which was dissolved in 10mL of DMF. Then, 2.1mL of TMA solution (4.2mol L) was added^-1Ethanol solution). The mixture was sealed in a Schlenk flask and reacted at room temperature for 3 days. After cooling to room temperature, the reaction solution was dropwise added to 200mL of ether to precipitate an ionomer, and the obtained fibrous polymer was sufficiently washed with ether and dried overnight under vacuum at 50 ℃ in vacuo (0.49g, yield: 89%).

The prepared ionomer was dissolved in N-methyl-2-pyrrolidone to obtain a polymer solution with a mass fraction of 10%. After filtration, the solution was coated on a clean glass plate by a tape casting method, the glass plate was dried overnight in a forced air drying oven at 80 ℃ to remove most of the solvent, and then transferred to a vacuum drying oven at 80 ℃ to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to the room temperature, putting the glass plate into deionized water for demoulding, fully washing the glass plate with the deionized water, and then putting the film into a drying oven for drying to obtain the anion exchange membrane with the anion being bromide ion.

The anion in the anion exchange membrane prepared from the prepared ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be converted into other anions through ion exchange according to needs, for example, the membrane is soaked in 2mol/L NaCl solution for 48 hours, and then the membrane is fully washed by deionized water, so that the anion obtained is Cl^-The anion exchange membrane of (1). The film has high ionic conductivity and low water absorption, the chloride ionic conductivity at 30 ℃ is 14.9mS/cm, the chloride ionic conductivity at 50 ℃ is 24.1mS/cm, and the chloride ionic conductivity at 80 ℃ is 45.2 mS/cm. Meanwhile, the water absorption of the film at room temperature is 47 wt.%, and the water absorption at 80 ℃ is only 58 wt.%. In addition, the film was heated at 80 ℃ and 2After alkaline hydrolysis is carried out in a mol/L NaOH aqueous solution for 300h, the chloride ion conductivity at 50 ℃ can still be maintained at 23.6mS/cm, and the excellent alkali resistance is proved.

FIG. 1 shows Cl of the anion exchange membrane prepared in this example^-Conductivity versus temperature curve. The conductivity was measured in ultrapure water using an ac impedance method, and the counter ion of the anion exchange membrane tested was chloride.

FIG. 2 (left) shows the anion membrane prepared from the ionomer synthesized in this example at 80 ℃ and 2mol L^-1And (3) a chloride ion conductivity change diagram at 50 ℃ after alkaline hydrolysis in NaOH aqueous solution for 300 hours.

Example 2

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has a structural formula shown in formula (16):

the preparation method comprises the following steps: biphenyl (0.30g, 1.9mmol), 7-bromo-1, 1, 1-trifluorohept-2-one (0.37g, 1.52mmol), methylpentadecafluoroheptyl-ketone (0.21g, 0.47mmol), dichloromethane (1.9mL), and trifluoromethanesulfonic acid (1.9mL) were stirred at room temperature for 10h to give a black gelatinous material. It was then added slowly dropwise to methanol to give a white crude fibrous solid. It was then filtered and washed with hot methanol. After drying in vacuo, 0.80g of a white fibrous bromine-terminated precursor polymer was obtained, 500mg of which was dissolved in 10mL of DMF. Then, 2.4mL of TMA solution (4.2mol L) was added^-1Ethanol solution). The mixture was sealed in a Schlenk flask and reacted at room temperature for 3 days. After cooling to room temperature, the reaction solution was dropwise added to 200mL of ether to precipitate an ionomer, and the obtained fibrous polymer was sufficiently washed with ether and dried overnight under vacuum at 50 ℃ (0.48g, yield: 87%).

The prepared ionomer was dissolved in N-methyl-2-pyrrolidone to obtain a polymer solution with a mass fraction of 10%. After filtration, the solution was coated on a clean glass plate by a tape casting method, the glass plate was left to dry overnight in a drying oven at 80 ℃ to remove most of the solvent, and then transferred to a vacuum drying oven at 80 ℃ to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to the room temperature, putting the glass plate into deionized water for demoulding, fully washing the glass plate with the deionized water, and then putting the film into a drying oven for drying to obtain the anion exchange membrane with the anion being bromide ion.

Anions in the anion exchange membrane prepared from the prepared ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be converted into other anions through ion exchange according to needs, for example, the membrane is soaked in 2mol/L NaCl solution for 48 hours, and then the membrane is fully washed by deionized water, so that the anion Cl can be obtained^-The anion exchange membrane of (1). The film has high ionic conductivity, the chloride ionic conductivity at 30 ℃ is 23.3mS/cm, and the chloride ionic conductivity at 50 ℃ is 31.2 mS/cm. After the film is subjected to alkaline hydrolysis in 2mol/L NaOH aqueous solution at 80 ℃ for 300 hours, the chloride ion conductivity at 50 ℃ can still be maintained at 31.0mS/cm, and the excellent alkali resistance is proved.

FIG. 2 (right) shows the anionic membrane prepared from the ionomer synthesized in this example at 80 ℃ and 2mol L^-1And (3) a chloride ion conductivity change diagram at 50 ℃ after alkaline hydrolysis in NaOH aqueous solution for 300 hours.

Example 3

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has a structural formula shown in formula (17):

the preparation method comprises the following steps: biphenyl (0.30g, 1.9mmol), 7-bromo-1, 1, 1-trifluorohept-2-one (0.28g, 1.14mmol), methylpentadecafluoroheptyl ketone (0.22g, 0.47mmol), 1,1, 1-trifluoroacetone (0.04g,0.38mmol), dichloromethane (1.9mL) and trifluoromethanesulfonic acid (1.9mL) were stirred at room temperature for 24h to give a black gel-like mass. It was then added slowly dropwise to methanol to give a white crude fibrous solid. It was then filtered and washed with hot methanol. After the vacuum drying, the mixture is dried in vacuum,0.80g of a white fibrous bromine-terminated precursor polymer was obtained, 500mg of which was dissolved in 10mL of DMF. Then, 2.1mL of TMA solution (4.2mol L) was added^-1Ethanol solution). The mixture was sealed in a Schlenk flask and reacted at room temperature for 3 days. After cooling to room temperature, the reaction solution was dropwise added to 200mL of ether to precipitate an ionomer, and the obtained fibrous polymer was sufficiently washed with ether and dried overnight under vacuum at 50 ℃ in vacuo (0.49g, yield: 90%).

The prepared ionomer was dissolved in N-methyl-2-pyrrolidone to obtain a polymer solution with a mass fraction of 10%. After filtration, the solution was coated on a clean glass plate by a tape casting method, the glass plate was left to dry overnight in a drying oven at 80 ℃ to remove most of the solvent, and then transferred to a vacuum drying oven at 80 ℃ to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to the room temperature, putting the glass plate into deionized water for demoulding, fully washing the glass plate with the deionized water, and then putting the film into a drying oven for drying to obtain the anion exchange membrane with the anion being bromide ion.

Anions in the anion exchange membrane prepared from the prepared ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be converted into other anions through ion exchange according to needs, for example, the membrane is soaked in 2mol/L NaCl solution for 48 hours, and then the membrane is fully washed by deionized water, so that the anion Cl can be obtained^-The anion exchange membrane of (1). The film has high ionic conductivity, and the chloride ionic conductivity of the film at 30 ℃ is 21.3 mS/cm.

FIG. 3 shows the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains synthesized in this example¹⁹F NMR spectrum (solvent: DMSO-d)₆)。

Example 4

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has a structural formula shown in formula (18):

the preparation method comprises the following steps: terphenyl (0.6g, 2.60mmol), methylpentadecafluoroheptyl ketone (0.18g, 0.45mmol), N-methylpiperidinone (0.25g, 2.21mmol), dichloromethane (2.2mL), trifluoroacetic acid (0.17mL), and trifluoromethanesulfonic acid (2.20mL) were stirred at room temperature for 6h to give a dark blue-colored material. After the reaction was complete, it was slowly added dropwise to 2M K₂CO₃In solution, a greenish fibrous solid was obtained. It was then filtered and hot 2M K₂CO₃And (4) washing the solution. After drying under vacuum, 1.00g of a white fibrous polymer was obtained. 850mg of this polymer was dissolved in N-methyl-2-pyrrolidone (14mL), and 0.5g of K was added₂CO₃Adding CH after 30min₃I, reacting at room temperature for 24 hours, and slowly adding the reaction system into water to obtain a large amount of white block polymer. Filtration and drying gave a piperidine cationic group-containing polymer of the structure represented by formula (18) (810mg, yield 97%).

The prepared ionomer was dissolved in N-methyl-2-pyrrolidone to obtain a polymer solution with a mass fraction of 10%. After filtration, the solution was coated on a clean glass plate by a tape casting method, the glass plate was dried overnight in a forced air drying oven at 80 ℃ to remove most of the solvent, and then transferred to a vacuum drying oven at 80 ℃ to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to the room temperature, putting the glass plate into deionized water for demoulding, fully washing the glass plate with the deionized water, and then putting the film into a drying oven for drying to obtain the anion exchange membrane with the anion being iodide.

Anions in the anion exchange membrane prepared from the prepared ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be converted into other anions through ion exchange according to needs, for example, the membrane is soaked in 2mol/L NaOH solution for 48 hours, and then the membrane is fully washed by deionized water, so that the anion OH can be obtained^-The anion exchange membrane of (1). The film has high ionic conductivity, and the hydroxyl ionic conductivity of the film at 30 ℃ is 19.2 mS/cm.

Example 5

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has the structural formula shown in formula (19):

the preparation method comprises the following steps: fluorene (0.50g, 2.57mmol), methylpentadecafluoroheptyl ketone (0.24g, 0.45mmol), N-methylpiperidinone (0.25g, 2.21mmol), dichloromethane (2.2mL), trifluoroacetic acid (0.17mL) and trifluoromethanesulfonic acid (2.20mL) were stirred at room temperature for 6h to give a deep red material. After the reaction was complete, it was slowly added dropwise to 2M K₂CO₃In solution, a greenish fibrous solid was obtained. It was then filtered and hot 2M K₂CO₃And (4) washing the solution. After drying under vacuum, 1.00g of a white fibrous polymer was obtained. 850mg of this polymer was dissolved in N-methyl-2-pyrrolidone (14mL), and 0.5g of K was added₂CO₃Adding CH after 30min₃I, reacting at room temperature for 24 hours, and slowly adding the reaction system into water to obtain a large amount of white block polymer. Filtration and drying gave a piperidine cationic group-containing polymer of the structure represented by formula (19) (810mg, yield 97%).

The prepared ionomer was dissolved in N-methyl-2-pyrrolidone to obtain a polymer solution with a mass fraction of 10%. After filtration, the solution was coated on a clean glass plate by a tape casting method, the glass plate was dried overnight in a forced air drying oven at 80 ℃ to remove most of the solvent, and then transferred to a vacuum drying oven at 80 ℃ to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to the room temperature, putting the glass plate into deionized water for demoulding, fully washing the glass plate with the deionized water, and then putting the film into a drying oven for drying to obtain the anion exchange membrane with the anion being iodide.

Anions in the anion exchange membrane prepared from the prepared ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be converted into other anions through ion exchange according to needs, for example, the membrane is soaked in 2mol/L NaCl solution for 48 hours, and then the membrane is fully washed by deionized water, so that the anion Cl can be obtained^-Anion of (2)And (3) a proton exchange membrane. The film has high ionic conductivity, and the chloride ionic conductivity of the film at 30 ℃ is 22.9 mS/cm.

Example 6

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has a structural formula shown in formula (20):

the preparation method comprises the following steps: terphenyl (0.6g, 2.60mmol), methylpentadecafluoroheptyl ketone (0.18g, 0.45mmol), N-methylpiperidinone (0.25g, 2.21mmol), dichloromethane (2.2mL), trifluoroacetic acid (0.17mL), and trifluoromethanesulfonic acid (2.20mL) were stirred at room temperature for 6h to give a dark blue-colored material. After the reaction was complete, it was slowly added dropwise to 2M K₂CO₃In solution, a greenish fibrous solid was obtained. It was then filtered and hot 2M K₂CO₃And (4) washing the solution. After drying under vacuum, 1g of a white fibrous polymer was obtained. 850mg of this polymer was dissolved in N-methyl-2-pyrrolidone (14mL), and 0.5g of K was added₂CO₃Powdery solid, 178mg of CH are initially added₃I reaction was carried out with stirring, and after a certain period of time, 255mg of 1, 6-diiodohexane was added, and after stirring at room temperature for 0.5 hour, the reaction solution was coated on a clean glass plate, which was left to dry overnight in a 50 ℃ drying oven to remove most of the solvent, and then transferred to an 80 ℃ vacuum drying oven to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into deionized water for demoulding, then soaking the glass plate in the deionized water for 48 hours, fully washing the glass plate with the deionized water, and then placing the film in a drying oven for drying to obtain the anion exchange membrane with anions being iodine ions.

Anions in the anion exchange membrane prepared from the prepared ionomer containing the alkali-resistant cation groups and the fluorocarbon side chains can be converted into other anions through ion exchange according to needs, for example, the membrane is soaked in 2mol/L NaCl solution for 48 hours, and then the membrane is fully washed by deionized water, so that the anion Cl can be obtained^-The anion exchange membrane of (1). The film has high ionic conductivity, and the chloride ionic conductivity of the film at 30 ℃ is 20.6 mS/cm.

Example 7

In this example, the ionomer containing alkali-resistant cationic groups and fluorocarbon side chains has a structural formula shown in formula (21):

the preparation method comprises the following steps: biphenyl (0.30g, 1.9mmol), N-methylphenidate (0.13g, 1.14mmol), methylpentadecafluoroheptyl ketone (0.22g, 0.47mmol), 1,1, 1-trifluoroacetone (0.04g,0.38mmol), dichloromethane (1.9mL), and trifluoromethanesulfonic acid (1.9mL) were stirred at room temperature for 6h to give a black gel-like mass. After the reaction was completed, it was slowly added dropwise to methanol to obtain a white crude fibrous solid. It was then filtered and washed with hot methanol. After drying in vacuo, 0.6g of a white fibrous bromine-terminated precursor polymer was obtained. 500mg of this bromine-terminated precursor polymer was dissolved in N-methyl-2-pyrrolidone (10mL), and then 0.3g of K was added₂CO₃Adding CH after 30min₃I, reacting at room temperature for 24 hours, and slowly adding the reaction system into water to obtain a large amount of white block polymer. Filtration and drying gave a piperidine cationic group-containing polymer of the structure represented by formula (21) (500mg, yield 92%).

The prepared ionomer was dissolved in N-methyl-2-pyrrolidone to obtain a polymer solution with a mass fraction of 10%. After filtration, the solution was coated on a clean glass plate by a tape casting method, the glass plate was dried overnight in a forced air drying oven at 80 ℃ to remove most of the solvent, and then transferred to a vacuum drying oven at 80 ℃ to sufficiently remove the solvent. And (3) taking out the glass plate after the temperature is reduced to the room temperature, putting the glass plate into deionized water for demoulding, fully washing the glass plate with the deionized water, and then putting the film into a drying oven for drying to obtain the anion exchange membrane with the anion being iodide.

The prepared alkali-resistant cation-containing group and fluorocarbon side chain are separatedThe anion in the anion exchange membrane prepared from the polymer can be converted into other anions through ion exchange according to the requirement, for example, the membrane is placed in 2mol/L NaCl solution for soaking for 48h, and then the membrane is fully washed by deionized water, so that the anion Cl can be obtained^-The anion exchange membrane of (1). The film has high ionic conductivity, and the chloride ionic conductivity of the film at 30 ℃ is 20.7 mS/cm.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.