CN114507350A - Polyphosphazene anion exchange membrane loaded with adamantyl quaternary phosphonium cation unit and preparation method thereof - Google Patents
Polyphosphazene anion exchange membrane loaded with adamantyl quaternary phosphonium cation unit and preparation method thereof Download PDFInfo
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Abstract
A polyphosphazene anion exchange membrane loaded with adamantyl quaternary phosphonium cation units and a preparation method thereof belong to the technical field of anion exchange membranes for fuel cells. The anion exchange membrane is a polyphosphazene material containing adamantyl quaternary phosphonium cations, and the structural formula is shown as a formula (1). The anion exchange membrane is obtained by reacting adamantyl quaternary phosphonium cation with phenolic hydroxyl with polydichlorophosphazene to obtain polyphosphazene material loaded with adamantyl quaternary phosphonium cation units, and finally forming a membrane in a culture dish and performing ion exchange. The load provided by the inventionCompared with most quaternary ammonium anion exchange membranes, the adamantyl quaternary phosphonium cation polyphosphazene anion exchange membrane has stronger alkali stability and higher ionic conductivity.
Description
Technical Field
The present invention belongs to the field of anion exchange membrane fuel cell membrane technology. In particular to an anion exchange membrane containing an adamantyl quaternary phosphonium cation structure and a preparation method thereof.
Background
With the increase of population and the consumption of energy, fossil fuels on which human beings live are nearly exhausted. Fuel cells are a power generation technology that can directly convert chemical energy into electrical energy, have the characteristics of cleanliness, high efficiency and the like, and are considered to be one of the most promising energy sources. Compared with other types of fuel cells, Anion Exchange Membrane Fuel Cells (AEMFCs) have the characteristics of fast oxygen reduction kinetics and low cost, can use non-noble metals, and are widely researched by various scholars. Anion exchange membranes, which are one of the key components of alkaline fuel cells, play an important role in the transport of anions and the separation of fuels. At present, the most widely researched common main chain structures of polyphenyl ether, polybenzimidazole, polysulfone, polyketone, poly (arylene ether) and the like have the problems of difficult film formation, overlarge rigidity and the like, and the problems that more conductive cationic groups such as quaternary ammonium salt, imidazolium, guanidinium and the like are easy to degrade under high-alkaline conditions and high-temperature conditions are researched, so that the ion conductivity of an anion exchange membrane is remarkably reduced, the service life of a fuel cell is greatly shortened and the like are caused, and the practical application of the anion exchange membrane is limited.
The technique disclosed in document 1 (Hong-SaHan, Hongmei Ma, sting-Hua Yu, Hong Zhu, Zhong-Ming Wang Preparation and performance of novel tetraphenylphosphonium-functionalized polyphosphazene membranes for alkaline functional cells [ J ]. European Polymer Journal,2019,114,109-117.) shows that tetraphenyl quaternary phosphonium cationic groups are grafted to the polyphosphazene backbone via phenolic hydroxyl structures, improving the alkali resistance of the quaternary phosphonium salts due to the absence of benzyl groups therein. This study contained aromatic structures and did not contain adamantane.
The technique disclosed in chinese patent application No. 201610312219.4 shows that tetraphenyl quaternary phosphonium cationic groups are grafted to the polyphosphazene backbone via phenolic hydroxyl groups, which improves the alkali resistance of the quaternary phosphonium salts due to the absence of benzyl groups in the quaternary phosphonium salts. This study contained aromatic structures and did not contain adamantane.
These documents and patents do not deal with the studies of the adamantyl quaternary phosphonium cation polyphosphazene anion exchange membranes. The invention selects polyphosphazene high molecular polymer as basic skeleton, grafts adamantyl quaternary phosphonium cation to polyphosphazene skeleton, prepares polyphosphazene material containing adamantyl quaternary phosphonium cation structure, and finally obtains anion exchange membrane by common membrane preparation method. Compared with the conventional quaternary phosphonium cation group, the adamantyl quaternary phosphonium cation has larger steric hindrance, so that the protected quaternary phosphonium cation is not easily attacked by hydroxide ions, the alkali resistance of the anion exchange membrane is greatly improved, and the service life of the anion exchange membrane is prolonged.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyphosphazene anion-exchange membrane containing load adamantyl quaternary phosphonium cation units, so that the prepared anion-exchange membrane has higher hydroxide ion conductivity, excellent alkali resistance and better film-forming property.
The invention provides a polyphosphazene polymer containing an adamantyl quaternary phosphonium cation structure, which is characterized in that P-Cl of a polyphosphazene main chain is OR1And adamantyl quaternary phosphonium cation structures, having the structure shown in (1):
wherein, R is1Is C1～C18An aliphatic group of (a); the R is2Is adamantane or C1～C18R3 is adamantane or C1-C18 fatty group.
N is the polymerization degree of polyphosphazene, and the values of x and n are as follows: 2n > x ≧ 0, 2n > y > 0, and x + y ═ 2 n. Preferably, y/2n is 15% to 55%.
The preparation method of the polyphosphazene anion exchange membrane with the adamantyl quaternary phosphonium cation structure comprises the following steps:
(1) dissolving adamantyl quaternary phosphonium cation with the structure shown in the formula (2) in an anhydrous tetrahydrofuran solution, adding 1.2eq of metal sodium, and reacting at normal temperature to obtain adamantyl quaternary phosphonium cation sodium salt;
(2) adding the adamantyl quaternary phosphonium cation sodium salt into a THF solution of polydichlorophosphazene for reaction;
(3) c is to be1～C18Fatty alcohol R of1OH and 1.2eq of metallic sodium or NaH to TReacting in HF at normal temperature to obtain a THF solution of fatty alcohol sodium salt;
(4) adding the THF solution of the fatty alcohol sodium salt obtained in the step (3) into the solution obtained in the step (2) according to the dosage relation of each group in the polymer, continuing to react, cooling, removing the solvent in the reaction solution to obtain a viscous substance, and washing with deionized water to obtain an elastomer polymer;
and (4) further preparing the corresponding membrane material by using the elastomer polymer obtained in the step (4), and performing hydroxide ion exchange to obtain the required alkali-resistant anion-exchange membrane.
According to the invention, the adamantyl quaternary phosphonium cation has larger steric hindrance, so that the protected quaternary phosphonium cation is not easily attacked by hydroxide ions, the alkali resistance of an anion exchange membrane is greatly improved, the prepared membrane is soaked in an alkaline solution for a long time, the conductivity and the ion exchange capacity of the membrane cannot be reduced quickly, and the service life of the membrane is prolonged.
Drawings
FIG. 1 shows a hydrogen spectrum and a phosphorus spectrum of an adamantyl quaternary phosphonium cation.
FIG. 2 is an infrared test chart of adamantyl quaternary phosphonium cations and polymers
FIG. 3 shows adamantyl quaternary phosphonium anion exchange membranes OH of examples 1-4 with different grafting ratios-Graph of the change in ion conductivity with temperature.
FIG. 4 is an alkali resistance test chart; example 4A graph showing the change of conductivity and ion exchange capacity of a membrane at 80 ℃ with soaking time after an adamantyl quaternary phosphonium anion exchange membrane having a grafting ratio of 45% is treated with a 2mol/L KOH solution and then the residual alkali solution on the surface of the membrane is washed away.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
0.21g of an adamantyl quaternary phosphonium cation structure (R) represented by the formula (2)2Is adamantane, R3N-butane) in anhydrous tetrahydrofuranAdding 1.2eq of metal sodium into the solution, and stirring at normal temperature for reaction for 24 hours to obtain adamantyl quaternary phosphonium cation sodium salt; adding the adamantyl quaternary phosphonium cation into a THF solution containing 0.3g of polydichlorophosphazene, and reacting for 48h at 60 ℃;
adding 1.25g of n-amyl alcohol and 1.2eq of alkali metal sodium into an anhydrous tetrahydrofuran solution, reacting at normal temperature for 6 hours, and taking out unreacted sodium blocks to obtain a tetrahydrofuran solution of the n-amyl alcohol sodium;
adding the obtained n-amyl alcohol sodium tetrahydrofuran solution into the solution, continuously reacting for 24 hours, cooling to room temperature, removing a large amount of solvent, and washing residual viscous liquid with a large amount of deionized water to obtain a light yellow elastomer;
dissolving the elastomer in 5ml of tetrahydrofuran, and removing the solvent in a culture dish to form a membrane;
after the solvent is removed, deionized water is added into a culture dish to strip the alkaline membrane, the culture dish is soaked in 2M/L KOH solution for 48 hours for ion exchange, after the ion exchange is finished, the surface of the membrane is washed by the deionized water to obtain an alkaline anion composite membrane PDCP-HDABPB-15% with the proportion of grafted adamantyl quaternary phosphonium cations of 15%, then the ion exchange capacity is determined by an inverse titration method, and the conductivity is determined by an alternating current impedance method.
Example 2
0.35g of an adamantyl quaternary phosphonium cation structure (R) represented by the formula (2)2Is adamantane, R3N-butane) is dissolved in anhydrous tetrahydrofuran solution, 1.2eq of metal sodium is added, and the mixture is stirred and reacts for 24 hours at normal temperature to obtain adamantyl quaternary phosphonium cation sodium salt; adding the adamantyl quaternary phosphonium cation into a THF solution containing 0.3g of polydichlorophosphazene, and reacting for 48h at 60 ℃;
adding 1.25g of n-amyl alcohol and 1.2eq of alkali metal sodium into an anhydrous tetrahydrofuran solution, reacting at normal temperature for 6 hours, and taking out unreacted sodium blocks to obtain a tetrahydrofuran solution of the n-amyl alcohol sodium;
adding the obtained n-amyl alcohol sodium tetrahydrofuran solution into the solution, continuously reacting for 24 hours, cooling to room temperature, removing a large amount of solvent, and washing residual viscous liquid with a large amount of deionized water to obtain a light yellow elastomer;
dissolving the elastomer in 5ml of tetrahydrofuran, and removing the solvent in a culture dish to form a membrane;
after the solvent is cleaned, deionized water is added into a culture dish to strip the alkaline membrane, the culture dish is soaked in 2M/L KOH solution for 48 hours for ion exchange, after the ion exchange is finished, the surface of the membrane is washed by the deionized water to obtain an alkaline anion composite membrane PDCP-HDABPB-25% with the proportion of grafted adamantyl quaternary phosphonium cations of 25%, then the ion exchange capacity is determined by using a back titration method, and the conductivity is determined by using an alternating current impedance method.
Example 3
0.49g of an adamantyl quaternary phosphonium cation structure (R) represented by the formula (2)2Is adamantane, R3N-butane) is dissolved in anhydrous tetrahydrofuran solution, 1.2eq of metal sodium is added, and the mixture is stirred and reacts for 24 hours at normal temperature to obtain adamantyl quaternary phosphonium cation sodium salt; adding the adamantyl quaternary phosphonium cation into a THF solution containing 0.3g of polydichlorophosphazene, and reacting for 48h at 60 ℃;
adding 1.25g of n-amyl alcohol and 1.2eq of alkali metal sodium into an anhydrous tetrahydrofuran solution, reacting at normal temperature for 6 hours, and taking out unreacted sodium blocks to obtain a tetrahydrofuran solution of the n-amyl alcohol sodium;
adding the obtained n-amyl alcohol sodium tetrahydrofuran solution into the solution, continuously reacting for 24 hours, cooling to room temperature, removing a large amount of solvent, and washing residual viscous liquid with a large amount of deionized water to obtain a light yellow elastomer;
dissolving the elastomer in 5ml of tetrahydrofuran, and removing the solvent in a culture dish to form a membrane;
after the solvent is removed, deionized water is added into a culture dish to strip the alkaline membrane, the culture dish is soaked in 2M/L KOH solution for 48 hours for ion exchange, after the ion exchange is finished, the surface of the membrane is washed by the deionized water to obtain an alkaline anion composite membrane PDCP-HDABPB-35% with the proportion of grafted adamantyl quaternary phosphonium cations of 35%, then the ion exchange capacity is determined by an inverse titration method, and the conductivity is determined by an alternating current impedance method.
Example 4
0.63g of an adamantyl quaternary phosphonium cation structure (R) represented by the formula (2)2Is adamantane, R3N-butane) in anhydrous tetrahydrofuranAdding 1.2eq of metal sodium into the solution, and stirring and reacting at normal temperature for 24 hours to obtain adamantyl quaternary phosphonium cation sodium salt; adding the adamantyl quaternary phosphonium cation into a THF solution containing 0.3g of polydichlorophosphazene, and reacting for 48h at 60 ℃;
adding 1.25g of n-amyl alcohol and 1.2eq of alkali metal sodium into an anhydrous tetrahydrofuran solution, reacting at normal temperature for 6 hours, and taking out unreacted sodium blocks to obtain a tetrahydrofuran solution of the n-amyl alcohol sodium;
adding the obtained n-amyl alcohol sodium tetrahydrofuran solution into the solution, continuously reacting for 24 hours, cooling to room temperature, removing a large amount of solvent, and washing residual viscous liquid with a large amount of deionized water to obtain a light yellow elastomer;
dissolving the elastomer in 5ml of tetrahydrofuran, and removing the solvent in a culture dish to form a membrane;
after the solvent is cleaned, deionized water is added into a culture dish to strip the alkaline membrane, the culture dish is soaked in 2M/L KOH solution for 48 hours for ion exchange, after the ion exchange is finished, the surface of the membrane is washed by the deionized water to obtain an alkaline anion composite membrane PDCP-HDABPB-45% with the proportion of grafted adamantyl quaternary phosphonium cations of 45%, then the ion exchange capacity is determined by an inverse titration method, and the conductivity is determined by an alternating current impedance method.
Claims (6)
1. A polyphosphazene polymer comprising an adamantyl quaternary phosphonium cation structure wherein the polyphosphazene backbone is bound by the adamantyl quaternary phosphonium cation structure and OR1A structural graft having the structure of formula (1):
wherein R1 is a fatty group of C1-C18; r2 is adamantane or a fatty group of C1-C18; r3 is adamantane or fatty group of C1-C18.
2. A polyphosphazene polymer comprising an adamantyl quaternary phosphonium cation structure according to claim 1 wherein n is the degree of polyphosphazene polymerization, and x and n have the values: 2n > x ≧ 0, 2n > y > 0, and x + y ═ 2 n. Preferably, y/2n is 15% to 45%.
3. A method of preparing a polyphosphazene anion exchange membrane comprising an adamantyl quaternary phosphonium cation structure according to claim 1 comprising the steps of:
(1) dissolving adamantyl quaternary phosphonium cation with the structure shown in the formula (2) in an anhydrous tetrahydrofuran solution, adding 1.2eq of metal sodium, and reacting at normal temperature to obtain adamantyl quaternary phosphonium cation sodium salt;
(2) adding the adamantyl quaternary phosphonium cation sodium salt into a THF solution of polydichlorophosphazene for reaction;
(3) mixing C1-C18 fatty alcohol R1Adding OH and 1.2eq of metal sodium or NaH into THF, and reacting at normal temperature to obtain a THF solution of fatty alcohol sodium salt;
(4) adding the THF solution of the fatty alcohol sodium salt obtained in the step (3) into the solution obtained in the step (2) according to the dosage relation of each group in the polymer, continuing to react, cooling, removing the solvent in the reaction solution to obtain a viscous substance, and washing with deionized water to obtain an elastomer polymer;
(5) further preparing corresponding membrane materials by using the elastomer polymer obtained in the step (4), and performing hydroxide ion exchange to obtain the required alkali-resistant anion exchange membrane;
4. the method of claim 3, wherein the ratio of x to y is adjusted by adjusting the amount of the C1-C18 fatty alcohol and the amount of the adamantyl quaternary phosphonium cation of the structure of formula (2).
5. A polyphosphazene anion exchange membrane comprising the adamantyl quaternary phosphonium cation structure of claim 1.
6. Use of a polyphosphazene anion exchange membrane comprising an adamantyl quaternary phosphonium cation structure according to claim 1 in a fuel cell.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024043246A1 (en) * | 2022-08-22 | 2024-02-29 | 三井化学株式会社 | Anion exchange-type polymer electrolyte membrane, water electrolysis device, carbon dioxide electrolysis device, fuel cell, and production method for anion exchange-type polymer electrolyte membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024043246A1 (en) * | 2022-08-22 | 2024-02-29 | 三井化学株式会社 | Anion exchange-type polymer electrolyte membrane, water electrolysis device, carbon dioxide electrolysis device, fuel cell, and production method for anion exchange-type polymer electrolyte membrane |
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