CN112979926A - Polyelectrolyte material, preparation method thereof and acidic polyelectrolyte membrane - Google Patents

Polyelectrolyte material, preparation method thereof and acidic polyelectrolyte membrane Download PDF

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CN112979926A
CN112979926A CN202110142438.3A CN202110142438A CN112979926A CN 112979926 A CN112979926 A CN 112979926A CN 202110142438 A CN202110142438 A CN 202110142438A CN 112979926 A CN112979926 A CN 112979926A
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polyelectrolyte
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徐铜文
吴亮
葛晓琳
宋晚杰
葛亮
杨正金
汪耀明
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University of Science and Technology of China USTC
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Abstract

The invention provides a polyelectrolyte material comprising a group shown as a formula (I) or a group shown as a formula (II), and also provides a preparation method of the polyelectrolyte material and an acidic polyelectrolyte membrane formed by the polyelectrolyte material. The polyelectrolyte material provided by the application adopts a super-acid catalysis Friedel-Crafts polymerization method to prepare a homopolymer or copolymer main chain, and the polymer main chain can be grafted with a plurality of side chains with different structures after halomethylation, so that the side chain ionization type cation exchange membrane is finally obtained. The acidic polyelectrolyte membrane prepared by the method has excellent mechanical strength, swelling resistance, ionic conductivity and chemical stability. The membrane can be used for electrochemical application in various acidic environments such as proton exchange membrane fuel cells, electrodialysis, divalent ion separation, water electrolysis and the like.

Description

Polyelectrolyte material, preparation method thereof and acidic polyelectrolyte membrane
Technical Field
The invention relates to the technical field of ionic polymer membranes, in particular to a polyelectrolyte material, a preparation method thereof and an acidic polyelectrolyte membrane.
Background
Energy crisis and environmental pollution are two major problems in the world at present, and the technology based on the ion exchange membrane has wide application prospects in the aspects of ion separation, energy conversion, clean production, energy conservation, emission reduction and the like.
The fuel cell is a high-efficiency, safe and green energy conversion device, and is expected to become a new technology for solving the problems of environment and energy. Among them, Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of being lightweight, efficient, environmentally friendly, and the like, and are widely used in various fields. The proton exchange membrane as the core component of the PEMFC largely determines the performance of the cell, and the conventional proton exchange membrane is widely formed by using perfluorinated sulfonic acid resin, such as Nafion, which has been commercialized, but the wide application of Nafion in various fields is limited due to the disadvantages of high preparation cost, complicated preparation process, high methanol permeability, and the like. Therefore, in order to improve the performance of the proton exchange membrane and reduce the cost of the membrane material, an acidic polyelectrolyte membrane with excellent comprehensive performance needs to be prepared through reasonable structural design.
Disclosure of Invention
The invention aims to provide an acidic polyelectrolyte membrane with excellent comprehensive performance.
In view of the above, the present application provides a polyelectrolyte material comprising a group of formula (I) or a group of formula (II),
Figure BDA0002929608370000011
wherein Ar is independently selected from formula (a) or formula (b);
R1and R2Independently selected from formula (c), formula (d), formula (e), formula (f) or formula (g);
d is an ionizing group;
Figure BDA0002929608370000021
wherein R is3～R10Independently selected from hydrogen, halogen or alkyl of C1-C10;
m is an integer of 0 to 3;
r is an integer of 0 to 10;
n represents the degree of polymerization.
Preferably, D is a small molecule containing sulfonic acid group represented by formula (h);
Figure BDA0002929608370000022
wherein R' is selected from formula (h1), formula (h2) or formula (h 3);
Figure BDA0002929608370000023
n is an integer of 1 to 10.
Preferably, D is 4-hydroxy benzene sulfonic acid sodium salt, 1-naphthol-3-sodium sulfonate, 1-naphthol-3, 6-sodium disulfonate or 4-hydroxy butane-1-sulfonic acid.
The application also provides a preparation method of the polyelectrolyte material, which comprises the following steps:
A) carrying out Friedel-crafts reaction on an aryl compound shown as a formula (III) or an aryl compound shown as a formula (IV) and a ketone compound shown as a formula (V) in a catalyst and a solvent to obtain an initial polymer;
B) carrying out halogenation reaction on the initial polymer, a solvent and a halogen methylation reagent to obtain a halogenated polymer;
carrying out substitution reaction on a halogenated polymer, micromolecules with ionized groups and an acid-binding agent in a solvent to obtain a polyelectrolyte material;
or B') carrying out sulfonation reaction on the initial polymer and a sulfonation reagent to obtain a polyelectrolyte material;
Figure BDA0002929608370000031
wherein R is1And R2Independently selected from formula (c), formula (d), formula (e), formula (f) or formula (g);
R3～R10independently selected from hydrogen, halogen or alkyl of C1-C10;
m is an integer of 0 to 3;
r is an integer of 0 to 10;
Figure BDA0002929608370000041
preferably, in step a), the solvent is selected from one or more of dichloromethane, trichloromethane and 1, 2-dichloroethane; the catalyst is selected from one or two of trifluoroacetic acid and trifluoromethanesulfonic acid; the reaction temperature is-0-30 ℃; the reaction time is 0.5-24 h.
Preferably, in the step of obtaining the halogenated polymer in the step B), the solvent is one or more selected from tetrachloroethylene, chlorobenzene and carbon tetrachloride; the concentration of the initial polymer and solvent is 2-5% w/v; the halomethylation reagent is N-bromosuccinimide and chloro (methoxy) methane; the temperature of the halogenation reaction is 70-140 ℃; the halogenation reaction time is 3-6 h.
Preferably, in the step of obtaining the polyelectrolyte material in step B), the small molecule with an ionized group is selected from one or more of sodium 4-hydroxybenzenesulfonate, sodium 1-naphthol-3-sulfonate, sodium 1-naphthol-3, 6-disulfonate and 4-hydroxybutane-1-sulfonic acid; the acid-binding agent is selected from one or more of anhydrous potassium carbonate, triethylamine, pyridine and diisopropylethylamine; the solvent is selected from one or more of N, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the molar ratio of the halogenated polymer to the small molecule with the ionized group is (0.8-1): 1; the mole ratio of the acid-binding agent to the small molecules with the ionized groups is (1-4): 1; the reaction temperature is 80-120 ℃; the reaction time is 1-3 days.
Preferably, in step B'), the sulfonating agent is selected from one of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, sulfamic acid and sulfite.
The application also provides an acidic polyelectrolyte membrane which is obtained by ion exchange of the polyelectrolyte material or the polyelectrolyte material prepared by the preparation method in an acidic solution.
Preferably, the acidic solution is hydrochloric acid or sulfuric acid; the concentration of the acidic solution is 1-3 mol/L; the exchange time is 12-24 h.
The chemical structure of the main chain of the polyelectrolyte material comprises aromatic structural units, polar groups such as aryl ether bonds are avoided, C-F bonds with large aromatic ring and bond energy are not easily attacked by hydroxyl radicals and hydrogen radicals, so that the polyelectrolyte material has good main chain stability, and meanwhile, polymer chains with high molecular weight can be obtained through Friedel-Crafts polymerization due to the large rigidity of the aromatic ring and the freely rotatable C-F bonds; the aggregation of ionic groups can be realized by chemically modifying the side chain, so that the construction of an ion channel is realized, and hydrogen ions can be rapidly transmitted to achieve high ion conductivity. The acidic polyelectrolyte membrane prepared by the invention is applied to a fuel cell, and can obtain very high proton conductivity, wherein the conductivity is 126mS/cm at 30 ℃, the conductivity is 243.7mS/cm at 80 ℃, and the tensile strength is 43MPa at room temperature.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the initial polymer of example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a brominated polymer of example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the cation exchange polymer obtained in example 1;
FIG. 4 is a tensile strength test of the cation exchange polymer obtained in example 1;
FIG. 5 is a chemical stability test of the cation exchange polymer obtained in example 1;
FIG. 6 is a temperature-rising conductivity test of the acidic polyelectrolyte membrane obtained in example 1.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The embodiment of the invention discloses a polyelectrolyte material comprising a group shown as a formula (I) or a group shown as a formula (II),
Figure BDA0002929608370000061
wherein Ar is independently selected from formula (a) or formula (b);
R1and R2Independently selected from formula (c), formula (d), formula (e), formula (f) or formula (g);
d is an ionizing group;
Figure BDA0002929608370000062
wherein R is3～R10Independently selected from hydrogen, halogen or alkyl of C1-C10;
m is an integer of 0 to 3;
r is an integer of 0 to 10;
n represents the degree of polymerization.
According to the invention, said R1Specifically, it may be selected from CF3，R2Specifically, the above formula (c), formula (d), formula (e), formula (f) or formula (g) is selected.
D is specifically a small molecule containing a sulfonic acid group shown in a formula (h);
Figure BDA0002929608370000071
wherein R' is selected from formula (h1), formula (h2) or formula (h 3);
Figure BDA0002929608370000072
n is an integer of 1 to 10.
More specifically, D is 4-hydroxy benzene sulfonic acid sodium salt, 1-naphthol-3-sodium sulfonate, 1-naphthol-3, 6-sodium disulfonate or 4-hydroxy butane-1-sulfonic acid.
The application also provides a preparation method of the polyelectrolyte material, which comprises the following steps:
A) carrying out Friedel-crafts reaction on an aryl compound shown as a formula (III) or an aryl compound shown as a formula (IV) and a ketone compound shown as a formula (V) in a catalyst and a solvent to obtain an initial polymer;
B) carrying out halogenation reaction on the initial polymer, a solvent and a halogen methylation reagent to obtain a halogenated polymer;
carrying out substitution reaction on a halogenated polymer, micromolecules with ionized groups and an acid-binding agent in a solvent to obtain a polyelectrolyte material;
or B') carrying out sulfonation reaction on the initial polymer and a sulfonation reagent in a solvent to obtain a polyelectrolyte material;
Figure BDA0002929608370000073
Figure BDA0002929608370000081
wherein R is1And R2Independently selected from formula (c), formula (d), formula (e), formula (f) or formula (g);
R3～R10independently selected from hydrogen, halogen or alkyl of C1-C10;
m is an integer of 0 to 3;
r is an integer of 0 to 10;
Figure BDA0002929608370000082
in the preparation process, in the step A), firstly, the aryl compound shown as the formula (III) or the aryl compound shown as the formula (IV) and the ketone compound shown as the formula (V) are subjected to Friedel-crafts reaction in a catalyst and a solvent to obtain an initial polymer; the nucleophilic addition condensation reaction occurs in the above process, the obtained solution is precipitated in potassium carbonate solution, and the initial polymer is obtained after repeated washing by deionized water and drying. The molar ratio of the aryl compound to the ketone compound is 1: 1-1: 1.2, the catalyst is selected from trifluoromethanesulfonic acid and trifluoroacetic acid, the volume ratio of the catalyst to the trifluoroacetic acid is 10: 1-20: 1, and the solvent is selected from one or more of dichloromethane, trichloromethane and 1, 2-dichloroethane; the volume ratio of the solvent to the catalyst is (0-1): 1. the reaction temperature is-0-30 ℃, and the reaction time is 0.5-24 h. The aryl compound is specifically selected from the group consisting of biphenyl, p-terphenyl, m-terphenyl, 2-methylbiphenyl and 2,2' -dimethylbiphenyl; the ketone monomer is one selected from hexafluoroacetone, 1,1, 1-trifluoroacetone, 4- (trifluoroacetyl) toluene and 2,2, 2-trifluoroacetophenone.
Step B) is first a halomethylation of the initial polymer, said halomethylation comprising bromomethylation or chloromethylation, said halogenating agent being N-bromosuccinimide or chloro (methoxy) methane; in the halomethylation process, the solvent is selected from any one of tetrachloroethylene, chlorobenzene and carbon tetrachloride; the concentration of the initial polymer and the second solvent is 2-5% w/v; the halogenation degree can be controlled by changing the feeding ratio of the halogenating agent and the initial polymer, and the adjustable range of the halogenation degree is 0-200%. After the halogenated polymer is obtained, it is subjected to a side chain anionic graft substitution reaction: carrying out substitution reaction on a halogenated polymer, micromolecules with ionized groups and an acid-binding agent in a solvent to obtain a polyelectrolyte material; in this process, the solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone; the concentration of the brominated polymer is 10-20 mg/mL; the regulation and control of the ion exchange capacity of the cation exchange polymer can be realized by changing the reaction time and the reaction temperature, and the longer the reaction time is, the higher the reaction temperature is, and the larger the ion exchange capacity of the cation exchange polymer is. The sulfonation reagent is any one of concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, sulfamic acid and sulfite.
The application also provides an acidic polyelectrolyte membrane, which is obtained by ion exchange of the polyelectrolyte material in an acidic solution; specifically, the polyelectrolyte material is dissolved in a solvent, is cast on a base material, is evaporated at 25-80 ℃ to form a membrane, and the obtained cation exchange membrane is soaked in 1mol/L HCl or H2SO4Changing the acid solution once per hour for 12-36 hours in the solution, and then washing with deionized water for 12-36 hours to obtain the cation H+The acidic polyelectrolyte membrane of (1); in the above process, the solvent is selected from one or more of dichloromethane, chloroform, chlorobenzene, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the concentration of the cation exchange polymer and the solvent is 2-10% w/v. The thickness of the cation exchange membrane is 4-400 mu m.
The invention discloses a polyelectrolyte material with high chemical stability, a preparation method thereof and an acidic polyelectrolyte membrane, which specifically comprise the following contents: a homopolymer or copolymer main chain is prepared by adopting a superacid catalysis Friedel-Crafts polymerization method, and a plurality of side chains with different structures can be grafted after the polymer main chain is subjected to halomethylation, so that the side chain ionization type cation exchange membrane is finally obtained. The prepared cation exchange membrane has excellent mechanical strength, swelling resistance, ionic conductivity and chemical stability. The membrane can be used for electrochemical application in various acidic environments such as proton exchange membrane fuel cells, electrodialysis, divalent ion separation, water electrolysis and the like.
For further understanding of the present invention, the polyelectrolyte material provided by the present invention will be described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
This example provides an acidic polyelectrolyte membrane prepared by the following route:
Figure BDA0002929608370000101
the preparation method is as follows:
(1) synthesis of polymer backbone: weighing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone into a 100mL round-bottom flask, adding 20mL of dichloromethane, adding 20mL of trifluoromethanesulfonic acid at 0 ℃, and reacting for 1.5 hours; precipitating the product in a potassium carbonate solution, fully washing the product by using deionized water, filtering the product to obtain a white solid, and drying the white solid in an oven at the temperature of between 60 and 80 ℃ for 24 hours to obtain an initial polymer; FIG. 1 is a nuclear magnetic hydrogen spectrum of a starting polymer, as shown in FIG. 1;
(2) brominated polymer: dissolving 5.0g of the initial polymer in 150mL of chlorobenzene, adding N-bromosuccinimide and azobisisobutyronitrile at 130 ℃, and reacting for 4 hours; pouring the reaction product into 1000mL of ethanol for precipitation to obtain a white precipitate, washing the white precipitate with ethanol for multiple times, and performing suction filtration and drying to obtain a brominated polymer; FIG. 2 is a nuclear magnetic hydrogen spectrum of a brominated polymer;
(3) preparing a cation exchange membrane: the above brominated polymer 1.70g (5mmol), 1.0778g (5.5mmol) of sodium 4-hydroxybenzenesulfonate and 2.2803g (16.5mmol) of potassium carbonate were weighed into 120mL of N-methylpyrrolidone, reacted at 100 ℃ for 3 days, the reaction product was poured into ether to precipitate to obtain yellow precipitate, which was washed several times with ether, washed with water and dried to obtain a cation exchange polymer. FIG. 3 is a nuclear magnetic hydrogen spectrum of an acidic polyelectrolyte material.
(4) Film formation and ion exchange: weighing 1g of the cationic polymer, adding 20mL of N, N-dimethylformamide, fully dissolving into a uniform and transparent solution, coating the solution on a glass plate, drying at 50 ℃ to form a film, and stripping the film from the glass plate; soaking the cation exchange polymer membrane in 1M H2SO4Ion exchange is carried out in the solution for 24 hours at 30 ℃ to obtain a cation H+The acidic polyelectrolyte membrane of (1).
In this example, 4- (trifluoroacetyl) toluene, 2,2, 2-trifluoroacetophenone and hexafluoroacetone were used instead of 1,1, 1-trifluoroacetone to obtain an acidic polyelectrolyte membrane of similar properties.
In this example, an acid polyelectrolyte membrane having similar properties can be obtained by using sodium m-hydroxybenzenesulfonate, sodium 1-naphthol-3-sulfonate, sodium 1-naphthol-3, 6-disulfonate, sodium 4-hydroxybutane-1-sulfonate, or the like, instead of sodium 4-hydroxybenzenesulfonate.
Chemical stability test by soaking cation exchange membranes in Fenton's reagent (3% H) at 80 deg.C2O2，2ppm FeSO4) The membranes were tested for mass retention after washing with deionized water to remove excess fenton reagent and drying in a 60 ℃ oven for 24 hours, with the results shown in table 1:
TABLE 1 data table of the performance of cation exchange membranes prepared in this example
Figure BDA0002929608370000111
Example 2
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out by replacing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2 '-dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 with 5.1817g (22.5mmol) of p-terphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone, and the remaining preparation methods were the same as in example 1.
Example 3
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out by replacing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2 '-dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 with 5.1817g (22.5mmol) of m-terphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone, and the remaining preparation methods were the same as in example 1.
Example 4
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out in the same manner as in example 1 except that 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2 '-dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 were changed to 5.4681g (30mmol) of 2,2' -dimethylbiphenyl and 4.0338g (36mmol) of 1,1, 1-trifluoroacetone.
Example 5
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out by replacing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 with 4.101g (22.5mmol) of biphenyl, 3.7854g (22.5mmol) of 2-methylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone, and the rest of the preparation was the same as in example 1.
Example 6
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out by replacing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 with 5.0472g (30mmol) of 2-methylbiphenyl and 4.0338g (36mmol) of 1,1, 1-trifluoroacetone, and the rest of the preparation was the same as in example 1.
Example 7
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out by replacing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 with 5.1817g (22.5mmol) of p-terphenyl, 3.7854g (22.5mmol) of 2-methylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone, and the rest of the preparation process was the same as in example 1.
Example 8
The only difference from example 1 is: the preparation of an acid polyelectrolyte membrane was carried out by replacing 4.101g (22.5mmol) of biphenyl, 3.469g (22.5mmol) of 2,2' -dimethylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone used in step (1) of example 1 with 5.1817g (22.5mmol) of m-terphenyl, 3.7854g (22.5mmol) of 2-methylbiphenyl and 8.0676g (54mmol) of 1,1, 1-trifluoroacetone, and the rest of the preparation was the same as in example 1.
Example 9
This example provides an acidic polyelectrolyte membrane prepared by the following route:
Figure BDA0002929608370000131
(1) synthesis of polymer backbone: 3.0842g (20mmol) of biphenyl and 4.5156g (24mmol) of 4- (trifluoroacetyl) toluene were weighed into a 50mL round bottom flask, and 7mL of dichloromethane was added to dissolve the reaction monomers; 2.5mL of trifluoroacetic acid and 25mL of trifluoromethanesulfonic acid were added at 0 ℃ and reacted for 12 hours. Precipitating the product in a potassium carbonate solution, fully washing the product by using deionized water, filtering the product to obtain a white solid, and drying the white solid in an oven at the temperature of between 60 and 80 ℃ for 24 hours to obtain a polymer;
(2) brominated polymer: brominated polymer starting material was synthesized according to the procedure of example 1;
(3) preparing a cation exchange membrane: weighing 2.0101g (5mmol) of the brominated polymer, 1.0788g (4.4mmol) of sodium 4-hydroxybenzenesulfonate and 2.2168g (13.2mmol) of potassium carbonate in 200mL of N-methylpyrrolidone, reacting for 3 days at 100 ℃, pouring the reaction product into diethyl ether for precipitation to obtain yellow precipitate, washing with diethyl ether for a plurality of times, washing with water and drying to obtain a cation exchange polymer;
(4) film formation and ion exchange: weighing 1g of the cationic polymer, adding 20mL of N, N-dimethylformamide, fully dissolving into a uniform and transparent solution, coating the solution on a glass plate, drying at 50 ℃ to form a film, and stripping the film from the glass plate; soaking the cation exchange polymer membrane in 1M H2SO4Ion exchange is carried out in the solution for 24 hours at 30 ℃ to obtain a cation H+The acidic polyelectrolyte membrane of (1).
Example 10
The only difference from example 8 is: 3.0842g (20mmol) of biphenyl and 4.5156g (24mmol) of 4- (trifluoroacetyl) toluene used in step (1) of example 8 were replaced by 4.0606g (20mmol) of p-terphenyl and 4.5156g (24mmol) of 4- (trifluoroacetyl) toluene, and the remaining preparation method was the same as in example 9.
Example 11
The only difference from example 8 is: 3.0842g (20mmol) of biphenyl and 4.5156g (24mmol) of 4- (trifluoroacetyl) toluene used in step (1) of example 8 were replaced by 4.0606g (20mmol) of m-terphenyl and 4.5156g (24mmol) of 4- (trifluoroacetyl) toluene, and the remaining preparation method was the same as in example 9.
Example 12
This example provides an acidic polyelectrolyte membrane prepared by the following route:
Figure BDA0002929608370000141
(1) synthesis of polymer backbone: weighing 3.0842g (20mmol) of biphenyl, 4.1788g (24mmol) of 2,2, 2-trifluoro acetophenone, adding 6mL of dichloromethane to dissolve a reaction monomer, adding 2.1mL of trifluoroacetic acid and 21mL of trifluoromethanesulfonic acid at 0 ℃ and reacting for 10 hours; precipitating the product in a potassium carbonate solution, fully washing the product by using deionized water, filtering the product to obtain a white solid, and drying the white solid in an oven at the temperature of between 60 and 80 ℃ for 24 hours to obtain a polymer;
(2) sulfonated polymer: weighing 3.101g (10mmol) of the polymer in a 100mL round-bottom flask, slowly dropwise adding 45mL of concentrated sulfuric acid at 30 ℃, reacting for 4 hours at 90 ℃, pouring the reaction solution into ice water after the reaction is finished, precipitating the polymer in the form of white fibers, washing for a plurality of times in a sodium bicarbonate solution and deionized water, and drying to obtain a sulfonated polymer;
(3) film formation and ion exchange: weighing 1g of the cationic polymer, adding 20mL of N, N-dimethylformamide, fully dissolving into a uniform and transparent solution, coating the solution on a glass plate, drying at 50 ℃ to form a film, and stripping the film from the glass plate; soaking the cation exchange polymer membrane in 1M H2SO4Ion exchange is carried out in the solution for 24 hours at 30 ℃ to obtain a cation H+The acidic polyelectrolyte membrane of (1).
Example 13
The only difference from example 12 is: the acid polyelectrolyte membrane was prepared by replacing 3.0842g (20mmol) of biphenyl and 4.1788g (24mmol) of 2,2, 2-trifluoroacetophenone used in step (1) of example 12 with 4.606g (20mmol) of p-terphenyl and 4.1788g (24mmol) of 2,2, 2-trifluoroacetophenone, and the rest of the preparation was the same as in example 12.
Example 14
The only difference from example 12 is: the acid polyelectrolyte membrane was prepared by replacing 3.0842g (20mmol) of biphenyl and 4.1788g (24mmol) of 2,2, 2-trifluoroacetophenone used in step (1) of example 12 with 4.606g (20mmol) of m-terphenyl and 4.1788g (24mmol) of 2,2, 2-trifluoroacetophenone, and the rest of the preparation was the same as in example 12.
Figure BDA0002929608370000151
Example 15
The only differences from examples 12, 13 and 14 are: during the preparation of the acid polyelectrolyte membranes, the sulfonation sites of step (2) in examples 12, 13 and 14 were changed from 2,2, 2-trifluoroacetophenone to Ar, and the remaining preparation methods were the same as those in examples 12, 13 and 14, respectively.
Example 16
And (3) testing tensile strength:
the tensile strength of the cation exchange membrane at room temperature was measured using a dynamic mechanical analyzer (model: Q800, manufacturer: TAInstrunebts). Fig. 4 is a graph showing tensile strength of the acid polymer electrolyte membrane prepared in example 1.
And (3) testing chemical stability:
soaking cation exchange membrane in Fenton's reagent (3% H) at 80 deg.C2O2，2ppm FeSO4) Then, the membrane was tested for mass remaining rate after washing with deionized water to remove excess fenton reagent and drying in an oven at 60 ℃ for 24 hours. As shown in fig. 5, fig. 5 is a graph illustrating the chemical stability of the acidic polyelectrolyte membrane prepared in example 1. And (3) ion conductivity test:
the ionic conductivity of the membrane in a full-wet state was measured on the acidic polyelectrolyte membrane obtained in example 1 by a four-electrode AC impedance method, and the specific test requirements and parameters were as follows: a membrane material with the length of 4cm, the width of 1cm and the thickness of 40um is taken and soaked in 1mol/L sulfuric acid solution for 24 hours, then deionized water is used for repeatedly washing for 24 hours, an Autolab PGSTAT 30 electrochemical test system is used for carrying out alternating current impedance test within the frequency of 100Hz-1MHz, and the hydrogen ion conductance of the membrane in pure water is recorded. As shown in fig. 6, fig. 6 is a graph of temperature-rising conductivity of the acidic polyelectrolyte membrane prepared in example 1.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A polyelectrolyte material comprising a group of formula (I) or a group of formula (II),
Figure FDA0002929608360000011
wherein Ar is independently selected from formula (a) or formula (b);
R1and R2Independently selected from formula (c), formula (d), formula (e), formula (f) or formula (g);
d is an ionizing group;
Figure FDA0002929608360000012
wherein R is3～R10Independently selected from hydrogen, halogen or alkyl of C1-C10;
m is an integer of 0 to 3;
r is an integer of 0 to 10;
n represents the degree of polymerization.
2. The polyelectrolyte material according to claim 1, wherein D is a small molecule containing sulfonic acid groups represented by formula (h);
Figure FDA0002929608360000021
wherein R' is selected from formula (h1), formula (h2) or formula (h 3);
Figure FDA0002929608360000022
n is an integer of 1 to 10.
3. The polyelectrolyte material according to claim 1 or 2, wherein D is sodium 4-hydroxybenzenesulfonate, sodium 1-naphthol-3-sulfonate, sodium 1-naphthol-3, 6-disulfonate or 4-hydroxybutane-1-sulfonic acid.
4. A method for preparing a polyelectrolyte material according to claim 1, comprising the steps of:
A) carrying out Friedel-crafts reaction on an aryl compound shown as a formula (III) or an aryl compound shown as a formula (IV) and a ketone compound shown as a formula (V) in a catalyst and a solvent to obtain an initial polymer;
B) carrying out halogenation reaction on the initial polymer, a solvent and a halogen methylation reagent to obtain a halogenated polymer;
carrying out substitution reaction on a halogenated polymer, micromolecules with ionized groups and an acid-binding agent in a solvent to obtain a polyelectrolyte material;
or B') carrying out sulfonation reaction on the initial polymer and a sulfonation reagent to obtain a polyelectrolyte material;
Figure FDA0002929608360000031
wherein R is1And R2Independently selected from formula (c), formula (d), formula (e), formula (f) or formula (g);
R3～R10independently selected from hydrogen, halogen or alkyl of C1-C10;
m is an integer of 0 to 3;
r is an integer of 0 to 10;
Figure FDA0002929608360000032
5. the method according to claim 4, wherein in step A), the solvent is one or more selected from the group consisting of dichloromethane, chloroform and 1, 2-dichloroethane; the catalyst is selected from one or two of trifluoroacetic acid and trifluoromethanesulfonic acid; the reaction temperature is-0-30 ℃; the reaction time is 0.5-24 h.
6. The method according to claim 4, wherein in the step of obtaining the halogenated polymer in step B), the solvent is selected from one or more of tetrachloroethylene, chlorobenzene and carbon tetrachloride; the concentration of the initial polymer and solvent is 2-5% w/v; the halomethylation reagent is N-bromosuccinimide and chloro (methoxy) methane; the temperature of the halogenation reaction is 70-140 ℃; the halogenation reaction time is 3-6 h.
7. The preparation method according to claim 4, wherein in the step of obtaining the polyelectrolyte material in step B), the small molecule with an ionizing group is selected from one or more of sodium 4-hydroxybenzenesulfonate, sodium 1-naphthol-3-sulfonate, sodium 1-naphthol-3, 6-disulfonate and 4-hydroxybutane-1-sulfonic acid; the acid-binding agent is selected from one or more of anhydrous potassium carbonate, triethylamine, pyridine and diisopropylethylamine; the solvent is selected from one or more of N, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the molar ratio of the halogenated polymer to the small molecule with the ionized group is (0.8-1): 1; the mole ratio of the acid-binding agent to the small molecules with the ionized groups is (1-4): 1; the reaction temperature is 80-120 ℃; the reaction time is 1-3 days.
8. The method according to claim 4, wherein in step B'), the sulfonating agent is selected from one of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, sulfamic acid and sulfite.
9. An acidic polyelectrolyte membrane obtained by ion-exchanging the polyelectrolyte material according to any one of claims 1 to 3 or the polyelectrolyte material prepared by the preparation method according to any one of claims 4 to 8 in an acidic solution.
10. The acidic polyelectrolyte membrane according to claim 9, wherein the acidic solution is hydrochloric acid or sulfuric acid; the concentration of the acidic solution is 1-3 mol/L; the exchange time is 12-24 h.
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