CN112898539A - Long-side-chain polyaromatic hydrocarbon isatin alkaline membrane for fuel cell and preparation method thereof - Google Patents
Long-side-chain polyaromatic hydrocarbon isatin alkaline membrane for fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a long side chain type polyaromatic hydrocarbon isatin alkaline membrane for a fuel cell and a preparation method thereof, belonging to the technical field of fuel cells; carrying out polymerization reaction on an isatin monomer substituted by bromoalkyl and a biphenyl monomer to obtain a polymer main chain, taking a quaternary ammonium group as a cationic functional group, and finally carrying out tape casting to form a film; the side chain length of such a basic membrane can be controlled by substituting isatin with different side chains. The main chain does not contain ether bond, and the structure of the long-time side chain enables the cationic group to be far away from the main chain, so that the membrane has strong alkali resistance. The structure of the hydrophobic long side chain can construct a micro-phase separation structure in the membrane to form a high-efficiency ion transmission channel, so that the membrane has high ion conductivity. Meanwhile, the alkaline membrane has excellent mechanical properties and wide application prospect.
Description
Technical Field
The invention relates to an alkaline membrane and a preparation method thereof, in particular to a long-side chain type polyaromatic hydrocarbon isatin alkaline membrane for a fuel cell and a preparation method thereof, belonging to the technical field of preparation of the alkaline membrane for the fuel cell.
Technical Field
In recent years, alkaline membrane fuel cells (AAEMFCs) have received increasing attention because they can use non-noble metal catalysts in alkaline environments and possess faster redox reaction kinetics at the cathode, providing a possible approach to the realization of inexpensive low-platinum or platinum-free fuel cell technologies, in anticipation of being able to replace high-cost Proton Exchange Membrane Fuel Cells (PEMFCs).
The core component of the anion exchange membrane fuel cell is an Anion Exchange Membrane (AEM), also called an alkaline membrane, which mainly functions to conduct hydroxide ions and isolate anode and cathode fuels, and therefore, the preparation of a high-performance alkaline membrane becomes a major challenge in developing the fuel cell, however, the existing alkaline membrane has the problems of: (1) the ionic conductivity is low; (2) poor alkali resistance; (3) the mechanical properties are poor.
In the conventional polymer main chain, due to the existence of electron-withdrawing groups such as sulfone group or ether bond, the main chain is easily attacked by hydroxide ions under an alkaline condition, so that the main chain of the membrane is degraded, and the performance of the alkaline membrane is reduced.
In recent years, scientists have prepared polybiphenylpiperidines basic membranes with strong alkali resistance, however, the cationic groups of the polybiphenylpiperidines basic membranes are still directly attached to the polymer backbone, limiting their alkali resistance and ionic conductivity.
Therefore, the development of an alkaline membrane which is easy to prepare, has high ionic conductivity, strong alkali resistance and dimensional stability and a preparation method thereof has very important practical significance for the application of an alkaline membrane fuel cell.
Disclosure of Invention
One of the objects of the present invention is to provide a long side chain type polyaromatic hydrocarbon isatin alkali membrane for fuel cells, which has the characteristics of high ionic conductivity, strong alkali resistance and mechanical stability.
The above object of the present invention is achieved by the following technical solutions:
a long side chain type polyaromatic hydrocarbon isatin alkaline membrane for a fuel cell is prepared from a long side chain type polyaromatic hydrocarbon isatin polymer, wherein the structural formula of the main chain of the long side chain type polyaromatic hydrocarbon isatin is as follows, wherein n is 2-8;
Preferably, the main chain is obtained by condensation reaction of an isatin monomer containing alkyl bromide substitution and a biphenyl monomer.
Preferably, the structural general formula of the alkyl bromide substituted isatin monomer is shown as follows, wherein n is 2-8.
Preferably, the biphenyl monomer is biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl.
Preferably, the monomer containing the tertiary amine group is trimethylamine, N-methylpyrrolidine or N-methylpiperidine.
The invention also aims to provide a preparation method of the long-side-chain polyaromatic hydrocarbon isatin alkaline membrane, wherein the polymer main chain is prepared by condensation reaction of an isatin monomer containing alkyl bromide substitution and a biphenyl monomer, and nucleophilic substitution reaction is carried out on the isatin monomer and a monomer containing a tertiary amine group to obtain the long-side-chain polyaromatic hydrocarbon isatin alkaline membrane.
The above object of the present invention is achieved by the following technical solutions:
the preparation method of the long side chain type polyaromatic hydrocarbon isatin alkaline membrane for the fuel cell comprises the following steps:
(1) dissolving a 2, 3-diketone indoline (isatin) monomer in a solvent, adding sodium hydride and dibromoalkane, stirring for 20 minutes at 0 ℃, heating and stirring for reaction, adding deionized water after the reaction is finished to quench the reaction, adding an organic solvent to extract a product, separating an organic layer, drying, carrying out rotary evaporation on the organic layer to obtain a crude product, and finally purifying by column chromatography to obtain a bromoalkyl isatin product;
(2) dissolving bromoalkyl isatin and biphenyl monomers obtained in the step (1) in dichloromethane, adding trifluoroacetic acid and trifluoromethanesulfonic acid in an ice bath, stirring for reaction, and after the reaction is finished, separating out a product in methanol and washing the product with deionized water to obtain a polyaromatic hydrocarbon isatin polymer;
(3) stirring and reacting the polyaromatic hydrocarbon isatin polymer obtained in the step (2) and a monomer containing a tertiary amine group in a solution, after the reaction is finished, precipitating and washing the polyaromatic hydrocarbon isatin polymer in deionized water, and filtering to obtain the quaternized polyaromatic hydrocarbon isatin polyelectrolyte;
(4) and (3) dissolving the quaternized polyaromatic hydrocarbon isatin polyelectrolyte prepared in the step (3) in dimethyl sulfoxide, carrying out tape casting on the solution to form a film, and soaking the film in a sodium hydroxide solution after drying to form the film, thereby obtaining the hydroxide radical type alkaline film.
Preferably, in the step (1), the molar ratio (mass ratio) of the isatin to the dibromoalkane is 1:1 to 1: 1.2.
Preferably, in step (1), the molar ratio of isatin to sodium hydride is from 1:1 to 1: 1.5.
Preferably, in the step (1), the number of carbon atoms of the dibromoalkane is 2 to 8.
Preferably, in the step (1), the reaction temperature of the heating reaction is 60 ℃ and the reaction time is 4 hours.
Preferably, in the step (1), the solvent used in the column chromatography purification is a mixed solvent of n-hexane and ethyl acetate, wherein the ratio of n-hexane: ethyl acetate 10:3-10: 4.
Preferably, in the step (2), the reaction temperature is room temperature and the reaction time is 3 to 5 hours.
Preferably, in the step (2), the biphenyl monomer is biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl.
Preferably, in the step (2), the molar ratio of the biphenyl monomer to the bromoalkylisatin is 1:1-1: 1.2.
Preferably, in the step (2), the molar ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to the biphenyl monomers is 8:8:1-10:10: 1.
Preferably, the monomer containing a tertiary amine group in step (3) is N-methylpiperidine, N-methyl or trimethylamine.
Preferably, the molar ratio of the polyaromatic isatin polymer to the tertiary amine group-containing monomer in step (3) is from 1:1 to 1: 1.2.
Preferably, the reaction temperature in step (3) is 25 to 80 ℃ and the reaction time is 12 to 48 hours.
Has the advantages that:
the long-side chain type polyaromatic hydrocarbon isatin alkaline membrane for the fuel cell can control the performances of the synthesized alkaline membrane, such as ion exchange capacity, water absorption, mechanical strength and the like, by using different types of biphenyl monomers; the polymer synthesized by the method has no unstable ether bond in the main chain, has the characteristic of strong alkali resistance, and has high efficiency and simple synthesis method. The long side chain of the invention enables the cation functional group to be far away from the main chain of the polymer, further improves the alkali resistance of the membrane, prolongs the service life of the membrane, and simultaneously, the existence of the hydrophobic long alkyl side chain can promote the construction of a micro phase separation structure in the membrane, form a high-speed ion transmission channel in the membrane and greatly improve the ion conductivity of the membrane.
The invention is further illustrated by the following figures and specific examples, which are not meant to limit the scope of the invention.
Drawings
FIG. 1 is a schematic of the synthesis of quaternized poly-p-terphenyl-bromohexyl isatin of example 1 of the present invention.
FIG. 2 is a nuclear magnetic map of bromohexylisatin of example 1 of the present invention.
FIG. 3 is a nuclear magnetic diagram of a poly-p-terphenyl-bromohexylisatin backbone of example 1 of the present invention.
FIG. 4 is a nuclear magnetic diagram of quaternized poly-p-terphenyl-bromohexyl isatin according to example 1 of the present invention.
FIG. 5 is a nuclear magnetic map of quaternized polybiphenyl-bromohexyl isatin of example 2 of the present invention.
FIG. 6 is a nuclear magnetic diagram of quaternized poly-p-terphenyl-bromopropylisatin according to example 3 of the present invention.
FIG. 7 is a graph of conductivity versus temperature for a quaternized poly-p-terphenyl-bromohexylisatin basic film of example 1 of the present invention.
Detailed Description
Unless otherwise stated, the raw materials in the examples of the present invention are conventional raw materials available on the market, the equipment used is equipment commonly used in the art, and the reaction conditions are normal conditions; the identification of the product is identified by conventional methods.
Example 1: synthesis of poly-p-terphenyl-bromohexyl isatin alkaline membrane
(1) Synthesis of 1- (6-bromohexyl) -indoline-2, 3-dione
Dissolving 5g of isatin in 200mL of N, N-Dimethylformamide (DMF), adding the solution to 0 ℃ of 100mL of DMF suspension containing 1.23g NaH, stirring for 20 minutes, adding 5.5mL of 1, 6-dibromohexane, heating the reaction mixture at 60 ℃ for 4 hours, after completion of the reaction, adding 50mL of deionized water to quench the reaction, extracting the mixture three times with ethyl acetate, drying the organic layer with anhydrous sodium sulfate for 8 hours, and after rotary evaporation of the organic solvent, obtaining a brownish red product by using N-hexane: further purifying the product by column chromatography with ethyl acetate (10: 3), and rotary evaporating the organic solution to obtain the product 1- (6-bromohexyl) -indoline-2, 3-dione (bromohexyl isatin);
(2) synthesis of poly-p-terphenyl-bromohexyl isatin backbone
Dissolving 2g of p-terphenyl and 3.1g of 1- (6-bromohexyl) -indoline-2, 3-diketone (bromohexyl isatin) prepared in the step (1) in 10mL of dichloromethane, adding 6.46mL of trifluoroacetic acid and 7.69mL of trifluoromethanesulfonic acid in an ice bath, stirring and reacting for 4 hours at room temperature, pouring the obtained thick dark green solution into methanol after the reaction is finished to obtain a white fibrous product, filtering the product, washing the product with deionized water for three to five times until the product is neutral to obtain poly-terphenyl-bromohexyl isatin polyelectrolyte, and drying for later use;
(3) preparation of quaternized poly-p-terphenyl-bromohexyl isatin
Soaking 2g of the quaternized poly-terphenyl-bromohexyl isatin prepared in the step (2) in 30 wt% of trimethylamine aqueous solution at room temperature for 48 hours, and then washing with deionized water for three to five times to obtain quaternized poly-terphenyl-bromohexyl isatin;
(4) preparation of poly-p-terphenyl-bromohexyl isatin alkaline membrane
Dissolving 2g of the quaternized poly-p-terphenyl-bromohexyl isatin prepared in the step (3) in 20mL of dimethyl sulfoxide to obtain a uniform polymer solution, uniformly coating the solution on a flat glass plate, drying at 70 ℃ for 12 hours, removing the membrane from the glass plate, soaking in 1mol/L sodium hydroxide solution for 24 hours, washing the membrane with deionized water, and removing redundant sodium hydroxide to obtain the hydroxide radical poly-p-terphenyl-bromohexyl isatin alkaline membrane.
FIG. 1 is a schematic diagram showing the synthesis of quaternized poly-p-terphenyl-bromohexyl isatin of example 1 of the present invention; as shown in fig. 2, is a nuclear magnetic diagram of bromohexylisatin of example 1 of the present invention; as shown in fig. 3, is a nuclear magnetic diagram of a poly-p-terphenyl-bromohexyl isatin backbone of example 1 of the present invention; FIG. 4 is a nuclear magnetic diagram of quaternized poly-p-terphenyl-bromohexyl isatin according to example 1 of the present invention.
Characterizing the prepared product by a nuclear magnetic resonance spectrometer, wherein the resonance frequency is 400MHz, testing the conductivity of the prepared hydroxyl poly-p-terphenyl-bromohexyl isatin alkaline membrane by a conventional electrochemical workstation by using an alternating current impedance method, and the scanning frequency range is 10-105Hz, an ion conductivity-temperature change diagram is obtained, and tests show that the ion exchange capacity of the hydroxyl type poly-p-terphenyl-bromohexyl isatin alkaline membrane prepared in the embodiment 1 is 1.85mmol/g, the conductivity at 80 ℃ can reach 112.1mS/cm, and the requirement of the fuel cell on the conductivity of the alkaline anion exchange membrane can be met.
Example 2: preparation of polybiphenyl-bromohexyl isatin alkaline membrane
(1) Synthesis of 1- (6-bromohexyl) -indoline-2, 3-dione
The same as in example 1.
(2) Synthesis of polybiphenyl-bromohexyl isatin main chain
Dissolving 2g of biphenyl and 3.48g of 1- (6-bromohexyl) -indoline-2, 3-dione (bromohexyl isatin) prepared in the step (1) in 10mL of dichloromethane, adding 9.6mL of trifluoroacetic acid and 11.5mL of trifluoromethanesulfonic acid in an ice bath, stirring and reacting for 4 hours at room temperature, obtaining a viscous dark green solution after the reaction is finished, pouring the viscous dark green solution into methanol to obtain a white fibrous product, filtering the product, washing the product with deionized water for three to five times until the product is neutral to obtain a polybiphenyl-bromohexyl isatin polyelectrolyte, and drying for later use;
(3) synthesis of quaternized polybiphenyl-bromohexyl isatin
Soaking 2g of the quaternized polybiphenyl-bromohexyl isatin prepared in the step (2) in 30 wt% trimethylamine aqueous solution at room temperature for 48 hours, and then washing with deionized water for three to five times to obtain quaternized polybiphenyl-bromohexyl isatin;
(4) preparation of polybiphenyl-bromohexyl isatin alkaline membrane
Dissolving 2g of the quaternized polybiphenyl-bromohexyl isatin prepared in the step (3) in 20mL of dimethyl sulfoxide to obtain a uniform polymer solution, uniformly coating the solution on a flat glass plate, drying at 70 ℃ for 12 hours, removing the membrane from the glass plate, soaking in 1mol/L sodium hydroxide solution for 24 hours, washing the membrane with deionized water, and removing redundant sodium hydroxide to obtain the hydroxyl polybiphenyl-bromohexyl isatin alkaline membrane.
FIG. 5 shows the nuclear magnetic diagram of quaternized polybiphenyl-bromohexyl isatin of example 2 of the present invention.
The polybiphenyl-bromohexylisatin basic membrane prepared in this example had an ion exchange capacity of 2.20mmol/g and a conductivity of 105.2mS/cm at 80 ℃ as measured in the same manner as in example 1.
Example 3: synthesis of poly-p-terphenyl-bromopropylisatin alkaline membrane
(1) Synthesis of 1- (3-bromopropyl) -indoline-2, 3-dione
Dissolving 5g of isatin in 200mL of N, N-Dimethylformamide (DMF), adding the solution to 0 ℃ of 100mL of DMF suspension containing 1.23g nah, stirring for 20 minutes, adding 3.47mL of 1, 3-dibromopropane, stirring the mixture at 60 ℃ for 4 hours, after the reaction is completed, adding 50mL of deionized water to quench the reaction, after the mixture is extracted three times with ethyl acetate, drying the organic layer with anhydrous sodium sulfate for 8 hours, and rotary-evaporating off the organic solvent to obtain a brownish red product by using N-hexane: the product was further purified by column chromatography on ethyl acetate (10: 3) and the organic solution was rotary evaporated to give 1- (3-bromopropyl) -indoline-2, 3-dione (bromopropylisatin);
(2) synthesis of poly-p-terphenyl-bromopropylisatin
Weighing 2g of p-terphenyl and 2.33g of 1- (3-bromopropyl) -indoline-2, 3-dione (bromopropylisatin) prepared in the step (1) and dissolving in 10mL of dichloromethane, adding 6.46mL of trifluoroacetic acid and 7.69mL of trifluoromethanesulfonic acid in an ice bath, stirring for 5 hours at room temperature, after the reaction is finished, pouring the obtained thick dark green solution into methanol, precipitating to obtain a white fibrous product, filtering, washing three to five times with deionized water until the solution is neutral to obtain poly-terphenyl-bromopropylisatin polyelectrolyte, and drying for later use;
(3) synthesis of quaternized poly (p-terphenyl) -bromopropylisatin
Soaking 2g of poly-p-terphenyl-bromopropylisatin prepared in the step (2) in 30 wt% of trimethylamine aqueous solution for reaction for 48 hours, and then washing three to five times with deionized water to obtain quaternized poly-p-terphenyl-bromopropylisatin;
(4) preparation of poly-p-terphenyl-bromopropyl isatin alkaline membrane
Dissolving 2g of the quaternized poly-p-terphenyl-bromopropylisatin prepared in the step (3) in 20mL of dimethyl sulfoxide to obtain a uniform polymer solution, uniformly coating the solution on a flat glass plate, drying at 70 ℃ for 12 hours, removing the membrane from the glass plate, soaking in 1mol/L sodium hydroxide solution for 24 hours, washing the membrane with deionized water, and removing redundant sodium hydroxide to obtain the hydroxide radical poly-p-terphenyl-bromopropylisatin alkaline membrane.
FIG. 6 shows the nuclear magnetic diagram of quaternized poly-p-terphenyl-bromopropylisatin according to example 3 of the present invention.
The hydroxide-type poly (p-terphenyl-bromopropylisatin) basic membrane prepared in this example had an ion exchange capacity of 2.05mmol/g and a conductivity of 98.5mS/cm at 80 ℃ as measured in the same manner as in example 1.
The method comprises the steps of carrying out polymerization reaction on an isatin monomer substituted by bromoalkyl and a biphenyl monomer to obtain a polymer main chain, taking a quaternary ammonium group as a cationic functional group, and finally carrying out tape casting to obtain a film; the side chain length of such a basic membrane can be controlled by substituting isatin with different side chains. The main chain does not contain ether bond, and the structure of the long-time side chain enables the cationic group to be far away from the main chain, so that the membrane has strong alkali resistance. The structure of the hydrophobic long side chain can construct a micro-phase separation structure in the membrane to form a high-efficiency ion transmission channel, so that the membrane has high ion conductivity. Meanwhile, the alkaline membrane has excellent mechanical properties and wide application prospect.
Claims (10)
1. A long side chain type polyaromatic hydrocarbon isatin alkaline membrane for a fuel cell, characterized in that: the structural formula of the main chain of the long side chain type polyaromatic hydrocarbon isatin is as follows, wherein n is 2-8;
2. The long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 1, characterized in that: the main chain is obtained by carrying out condensation reaction on an isatin monomer containing alkyl bromide substitution and a biphenyl monomer.
3. The long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 2, characterized in that: the structural general formula of the isatin monomer containing alkyl bromide substitution is shown as follows, wherein n is 2-8.
4. The long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 2, characterized in that: the biphenyl monomer is biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl.
5. The long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 1, characterized in that: the monomer containing the tertiary amine group is trimethylamine, N-methylpyrrolidine or N-methylpiperidine.
6. A method for producing a long side chain polyaromatic hydrocarbon isatin alkaline membrane for a fuel cell according to any one of claims 1 to 5, comprising the steps of:
(1) dissolving a 2, 3-diketone indoline monomer in a solvent in a reaction device, adding sodium hydride and dibromoalkane, stirring for 20 minutes at 0 ℃, heating and stirring for reaction, adding deionized water after the reaction is finished to quench the reaction, adding an organic solvent to extract a product, separating an organic layer, drying, carrying out rotary evaporation on the organic layer to obtain a crude product, and finally purifying by column chromatography to obtain a bromoalkyl isatin product;
(2) dissolving bromoalkyl isatin and biphenyl monomers obtained in the step (1) in dichloromethane, adding trifluoroacetic acid and trifluoromethanesulfonic acid in an ice bath, stirring for reaction, and after the reaction is finished, separating out a product in methanol and washing the product with deionized water to obtain a polyaromatic hydrocarbon isatin polymer;
(3) stirring and reacting the polyaromatic hydrocarbon isatin polymer obtained in the step (2) and a monomer containing a tertiary amine group in a solution, after the reaction is finished, precipitating and washing the polyaromatic hydrocarbon isatin polymer in deionized water, and filtering to obtain the quaternized polyaromatic hydrocarbon isatin polyelectrolyte;
(4) and (3) dissolving the quaternized polyaromatic hydrocarbon isatin polyelectrolyte prepared in the step (3) in dimethyl sulfoxide, carrying out tape casting on the solution to form a film, and soaking the film in a sodium hydroxide solution after drying to form the film, thereby obtaining the hydroxide radical type alkaline film.
7. The method for producing a long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 6, wherein: in the step (1), the molar ratio of isatin to dibromoalkane is 1:1-1:1.2, the molar ratio of isatin to sodium hydride is 1:1-1:1.5, the number of carbon atoms of dibromoalkane is 2-8, the reaction temperature of heating reaction is 60 ℃, the reaction time is 4 hours, the solvent used in column chromatography purification is a mixed solvent of n-hexane and ethyl acetate, and the weight ratio of n-hexane: ethyl acetate 10:3-10: 4.
8. The method for producing a long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 7, characterized in that: in the step (2), the reaction temperature is room temperature, the reaction time is 3-5 hours, the biphenyl monomer is biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl, the molar ratio of the biphenyl monomer to the bromoalkyl isatin is 1:1-1:1.2, and the molar ratio of trifluoroacetic acid, trifluoromethanesulfonic acid and the biphenyl monomer is 8:8:1-10:10: 1.
9. The method for producing a long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 8, wherein: the monomer containing tertiary amine group in the step (3) is N-methylpiperidine, N-methylpyrrolidine or trimethylamine.
10. The method for producing a long-side-chain polyaromatic hydrocarbon isatin-based membrane for a fuel cell according to claim 9, characterized in that: the molar ratio of the polyaromatic hydrocarbon isatin polymer to the monomer containing the tertiary amine group in the step (3) is 1:1-1:1.2, the reaction temperature is 25-80 ℃, and the reaction time is 12-48 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113871671A (en) * | 2021-09-24 | 2021-12-31 | 长春工业大学 | Preparation method of multi-cation cross-linked anion exchange membrane |
| CN114395112A (en) * | 2022-01-12 | 2022-04-26 | 北京化工大学 | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof |
| CN114524912A (en) * | 2022-03-15 | 2022-05-24 | 北京化工大学 | Side-chain piperidine cation grafted polybiphenyl alkaline membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987773A (en) * | 2018-07-16 | 2018-12-11 | 大连理工大学 | A kind of trimethylamine functional poly (hetero) aryl indole anion-exchange membrane and preparation method thereof |
| CN109119662A (en) * | 2018-07-16 | 2019-01-01 | 大连理工大学 | Poly- (hetero) aryl indole anion-exchange membrane of a kind of double pectinations of long-chain branch and preparation method thereof |
| CN109880138A (en) * | 2019-03-01 | 2019-06-14 | 大连理工大学 | A kind of poly- isatin aromatic hydrocarbons and its anion-exchange membrane, preparation method and application of high-performance belt length side chain ammonium salt |
| CN110862516A (en) * | 2019-12-02 | 2020-03-06 | 大连理工大学 | Cardo structure-containing isatin aromatic hydrocarbon copolymer, and preparation method and application thereof |
-
2020
- 2020-09-22 CN CN202011004143.1A patent/CN112898539A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987773A (en) * | 2018-07-16 | 2018-12-11 | 大连理工大学 | A kind of trimethylamine functional poly (hetero) aryl indole anion-exchange membrane and preparation method thereof |
| CN109119662A (en) * | 2018-07-16 | 2019-01-01 | 大连理工大学 | Poly- (hetero) aryl indole anion-exchange membrane of a kind of double pectinations of long-chain branch and preparation method thereof |
| CN109880138A (en) * | 2019-03-01 | 2019-06-14 | 大连理工大学 | A kind of poly- isatin aromatic hydrocarbons and its anion-exchange membrane, preparation method and application of high-performance belt length side chain ammonium salt |
| CN110862516A (en) * | 2019-12-02 | 2020-03-06 | 大连理工大学 | Cardo structure-containing isatin aromatic hydrocarbon copolymer, and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113871671A (en) * | 2021-09-24 | 2021-12-31 | 长春工业大学 | Preparation method of multi-cation cross-linked anion exchange membrane |
| CN114395112A (en) * | 2022-01-12 | 2022-04-26 | 北京化工大学 | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof |
| CN114395112B (en) * | 2022-01-12 | 2023-01-24 | 北京化工大学 | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof |
| CN114524912A (en) * | 2022-03-15 | 2022-05-24 | 北京化工大学 | Side-chain piperidine cation grafted polybiphenyl alkaline membrane and preparation method thereof |
| CN114524912B (en) * | 2022-03-15 | 2023-10-27 | 北京化工大学 | Side chain piperidine cation grafted poly biphenyl alkaline membrane and preparation method thereof |
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