CN106147197B - A kind of fuel cell more conduction site polyphenyl ether anion-exchange membranes and preparation method thereof - Google Patents
A kind of fuel cell more conduction site polyphenyl ether anion-exchange membranes and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of fuel cell more conduction site polyphenyl ether anion-exchange membranes and preparation method thereof, belong to fuel cell material technical field, the anion-exchange membrane is made of the poly ion liquid therein with structural formula I that is doped in of the quaternized polyphenylene oxide anion-exchange membrane of the N-methyl imidazoles with following constitutional repeating unit II of 99 weight % and 1 weight %：Wherein n is the integer not less than 1, and the carbon atom number of straight chained alkyl is 5 12；Wherein x is the integer not less than 0；Y is the integer not less than 0, and is 0 when x, y difference.The method simple process and low cost of the present invention.Prepared more conduction site polyphenyl ether anion-exchange membranes have many advantages, such as that high proton conductivity and thermal stability are good, and application prospect is extensive, is applicable in especially suitable for anion-exchange membrane fuel cells.
Description
Technical field
The present invention relates to a kind of fuel cell more conduction site polyphenyl ether anion-exchange membranes and preparation method thereof, belong to
In fuel cell material technical field, particularly anion exchange technical field of membrane.
Background technology
Fuel cell is a kind of efficient, clean energy conversion apparatus.In recent years, polymer-membrane fuel battery has obtained extensively
General application, the polymer film as critical material play the role of the performance of fuel cell and service life conclusive.Its
In be typically the most E.I.Du Pont Company Nafion membrane, with excellent conductivity, high mechanical properties and chemical stability,
It is the object that researcher uses for reference.However the polymer-membrane fuel battery using proton exchange membrane as electrolyte there are it is a series of not
Foot：(1) it under acid condition, needs to rely on the noble metals such as platinum, gold as catalyst, increases the cost of fuel cell；(2) it is acid
Under the conditions of, the easy CO poisonings of catalyst seriously reduce fuel battery performance；(3) fuel is identical with proton conduction orientation, be easy to cause
Electric pole short circuit.
In order to overcome disadvantage mentioned above, anion-exchange membrane is considered as the alternative material of proton exchange membrane.Anion exchange
Under alkaline condition, the stability of catalyst is high for film, thus can by the use of non-noble metallic materials such as iron, cobalt, nickel as catalyst, and
And the reduction kinetics of oxygen of the catalyst under alkaline condition is better than acid condition.But the limitation due to anion-exchange membrane in itself
Property, to reach commercial level, also need to improve the ionic conductivity, alkaline stability and mechanical performance of anion-exchange membrane energetically.
The study found that the conductivity of anion-exchange membrane can be effectively improved by increasing conduction site.Increase conduction site
Method has following two：A kind of method is by being graft-polymerized, and the ionic group containing multiple conduction sites is grafted to polymerization
On object skeleton；Another method is will to conduct the ionic liquid of hydroxide ion to be directly doped in polymer.Wherein
Two kinds of methods are more simple direct.
Polyphenylene oxide (PPO) is the high-strength engineering plastic developed by General Corporation, has prominent electrical insulating property and water-fast
Property, it is higher heat resistance, simple in structure, conducive to branch or Doped ions liquid is qualitatively and quantitatively studied to anion exchange film property
The influence of energy.
The research object of ionic liquid is independent conductive group mostly at this stage, and there are three for three imidazoles benzene of a unit
A conductive group, theoretically three imidazoles benzene of individual unit is with regard to that can increase substantially ionic conductivity.In addition, three imidazoles benzene also are able to
Higher stability is kept under alkaline condition.
It therefore, will be in the anion-exchange membrane of the ionic liquid of three imidazoles benzene incorporation polyphenylene oxide, it will be able to improve anion
The ionic conductivity and stability of exchange membrane.
Invention content
An object of the present invention is to provide a kind of more conduction site polyphenyl ether anion-exchange membranes of dye cell, makes
It is with high ion conductivity and higher stability.
The above-mentioned purpose of the present invention reaches by the following technical programs：
A kind of more conduction site polyphenyl ether anion-exchange membranes of fuel cell, it is characterised in that：The anion is handed over
Film is changed by the quaternized polyphenylene oxide anion exchange of the N-methyl imidazoles with following constitutional repeating unit II of 98-99 weight %
The poly ion liquid therein with structural formula I that is doped in of film and 1-2 weight % form：
Wherein n is the integer not less than 1, and the carbon atom number of straight chained alkyl is 5-12；
Wherein x is the integer not less than 0；Y is the integer not less than 0, and is 0 when x, y difference.
Preferably, in the structural unit II, x:Y=7:3.
Preferably, the structural formula I is poly- 1,3,5- tri- (3- amyl -1- imidazoles), poly- 1,3,5- tri- (3- octyl group -1- miaows
Azoles) or poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquid.
It is a further object to provide the preparation methods of above-mentioned more conduction site polyphenyl ether anion-exchange membranes.
The above-mentioned purpose of the present invention reaches by the following technical programs：
A kind of fuel cell preparation method of more conduction site polyphenyl ether anion-exchange membranes, includes the following steps：
(1) synthesis of polyphenylene oxide (PPO) N-methyl imidazole skeleton
Polyphenylene oxide is added in reaction unit, 40-60 DEG C is heated under nitrogen atmosphere, after polyphenylene oxide is completely dissolved,
Benzoyl peroxide (PPO) and N- bromo-succinimides (NBS) are added in, temperature is raised to 70-90 DEG C, after reacting 3-5 hours,
Room temperature is reduced the temperature to, reactant solution is rotated at 40-80 DEG C to color and becomes brown color, is then precipitated in methyl alcohol,
Faint yellow solid is obtained, faint yellow solid is dissolved with dichloromethane, rotates, precipitate, repeats this operation, is obtained pure faint yellow
Bromide PPO (BPPO), drying, be dissolved in DMF solution, until completely dissolved, add in N- methylimidazoles, reaction, by bromo
Site is completely quaternized, obtains the quaternized polyphenylene oxide of N-methyl imidazoles；
(2) preparation of poly- three imidazoles benzene ionic liquid
The preparation of (I) 1,3,5- tri- (1- imidazoles) benzene：
By 1,3,5- tribromo-benzene, imidazoles, potassium carbonate and copper sulphate are added in container, are passed through nitrogen, temperature is raised to 170-
It 190 DEG C, reacts 8-16 hours, product temperatur is down to room temperature later, is washed with deionized, and upper strata solid is collected in filtering, will be thick
Product is extracted with dichloromethane, and after collected organic layer, rotary evaporation obtains 1,3,5- tri- (1- imidazoles) benzene；
The preparation of (II) poly- three imidazoles benzene ionic liquid：
1,3,5- tri- (1- imidazoles) benzene is dissolved in 80-120 DEG C in n,N-Dimethylformamide (DMF) solution, adds in halogen
It for alkane, reacts 6-18 hours, obtains yellow solid, filtering, which is placed in baking oven, dries, and obtains poly- three imidazoles benzene ionic liquid；
(3) conduct the preparation of site polyphenyl ether anion-exchange membrane more
In the step of weighing step 2 products therefrom, adding in equivalent (1) products therefrom, ultrasound 0.5 hour and to stir 0.5 small
When, final product is poured into ultra-flat surface ware, 60 DEG C of drying in baking oven is placed in, obtains pale yellow transparent film, then soak film
It steeps in 1mol/L NaOH solutions two days, obtains final anion-exchange membrane.
Preferably, repetitive operation described in the step (1) is 3 times.
Preferably, halogenated alkane described in the step (2) is dibromo pentane, two bromooctanes or dibromo-dodecane.
Preferably, poly- three imidazoles benzene ionic liquid described in the step (2) is poly- 1,3,5- tri- (3- amyl -1- miaows
Azoles), poly- 1,3,5- tri- (3- octyl group -1- imidazoles) or poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquid.
Preferably, the amount of step (1) products therefrom described in the step (3) reduces half.
The present invention has apparent advantage compared with prior art：
1st, the preparation process of film is simple.Poly ion liquid is directly doped to polyphenylene oxide (PPO) anion-exchange membrane skeleton
In, simplify the synthesis step of film.
2nd, the ionic conductivity of film is high.The present invention introduces ternary poly ion liquid, each other than the conductivity of film itself
Unit can conduct three hydroxide ions, greatly strengthen the ionic conductivity of film.
3rd, the good stability of the dimension of film.Pure polyphenylene oxide (PPO) skeleton anion exchange film water absorbs and expansion rate is excessively high, easily
Fragmentation during the test.And after adding in ternary poly ion liquid, caudacoria is completed in test can also keep relative fullness.
Below by the drawings and specific embodiments, the present invention is described in detail.It should be understood that the reality
It applies example and only relates to the preferred embodiments of the invention, do not departing from the spirit and scope of the present invention, various composition and contain
The changes and improvements of amount are all possible.
Description of the drawings
The nuclear magnetic resoance spectrum of 1,3,5- tri- (1- imidazoles) benzene that Fig. 1 is synthesized for the present invention, H2Correspond to benzene ring hydrogen, H1、
H3、H4Three hydrogen on imidazole ring are corresponded to respectively.
Fig. 2 is that the nuclear-magnetism of poly- 1,3,5- tri- (3- pentyl -1- imidazoles) benzene ionic liquid (PTPIB) that the present invention synthesizes is total to
It shakes spectrum, wherein H1For benzene ring hydrogen, H2、H3、H4Three hydrogen respectively on imidazole ring, H5、H6It is respectively and nitrogen on imidazole ring
Hydrogen on two connected carbon, H7For hydrogen other on dodecyl chain.
Fig. 3 is that the nuclear-magnetism of poly- 1,3,5- tri- (3- octyl -1- imidazoles) benzene ionic liquid (PTOIB) that the present invention synthesizes is total to
It shakes spectrum, wherein H1For benzene ring hydrogen, H2、H3、H4Three hydrogen respectively on imidazole ring, H5、H6It is respectively and nitrogen on imidazole ring
Hydrogen on two connected carbon, H7For hydrogen other on dodecyl chain.
Fig. 4 is the nuclear-magnetism of poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquid (PTDIB) that the present invention synthesizes
Figure, wherein H1For benzene ring hydrogen, H2、H3、H4Three hydrogen respectively on imidazole ring, H5、H6It is respectively and nitrogen phase on imidazole ring
Hydrogen on two carbon even, H7For hydrogen other on dodecyl chain.
Fig. 5 is the polyphenylene oxide N-methyl imidazole anion exchange membrane that the present invention synthesizes：The quaternized polyphenyl of N-methyl imidazoles
The nuclear magnetic resoance spectrum of ether, wherein H1For the hydrogen on the methyl that connects on phenyl ring, H2For the hydrogen on the methyl that connects on quaternary ammonium salt, H3For benzene
The hydrogen of the methylene connected on ring, H4, H5For benzene ring hydrogen.
The ionic conductivity that Fig. 6 is the polyphenylene oxide N-methyl imidazole anion exchange membrane 1-4 that the present invention synthesizes becomes with temperature
The relational graph of change.
Specific embodiment
Comparative examples 1
1st, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton：
The commercially available polyphenylene oxide of 0.3g is added in the 100mL three-necked flasks equipped with blender, condenser pipe and gas-guide tube, nitrogen
Under atmosphere, 50 DEG C are heated to, after polyphenylene oxide is completely dissolved, adds in the commercially available benzoyl peroxides of 4.64g (PPO) and 0.232g cities
N- bromo-succinimides (NBS) are sold, oil bath pot temperature is raised to 80 DEG C, after reacting 4 hours, reduce the temperature to room temperature, it will be anti-
Object solution is answered to go in revolving bottle, at 60 DEG C, revolving becomes brown color to solution colour, then precipitates, obtains light in methyl alcohol
Faint yellow solid with commercially available dichloromethane is dissolved, rotated, precipitated by yellow solid, repeats this operation 3 times, is obtained pure yellowish
The 0.25g BPPO dried are dissolved in the commercially available DMF solutions of 15mL by the bromide PPO (BPPO) of color, in an oven 60 DEG C of drying,
Until completely dissolved, the commercially available N- methylimidazoles of 207 μ L are added in, are reacted 12 hours, bromo site is completely quaternized, obtain n-formyl sarcolysine
The quaternized polyphenylene oxide of base imidazoles.
As shown in figure 5, the nuclear magnetic resoance spectrum for polyphenylene oxide trimethylamine film, wherein, H1For the hydrogen on the methyl that connects on phenyl ring,
H2For the hydrogen on the methyl that connects on quaternary ammonium salt, H3Hydrogen for the methylene connected on phenyl ring, H4, H5For benzene ring hydrogen.
2nd, the preparation of polyphenyl ether anion-exchange membrane：
Step 1 products therefrom is poured into ultra-flat surface ware, 60 DEG C of drying in baking oven is placed in, obtains pale yellow transparent film,
Then film is soaked in 1mol/L NaOH solutions two days, obtains final fuel cell polyphenyl ether anion-exchange membrane
1, the thickness of film is measured with micrometer caliper.Polyphenyl ether anion-exchange membrane is comparative sample, does not add in poly ion liquid.
Embodiment 1
1st, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton：
The commercially available polyphenylene oxide of 0.3g is added in the 100mL three-necked flasks equipped with blender, condenser pipe and gas-guide tube, nitrogen
Under atmosphere, 50 DEG C are heated to, after polyphenylene oxide is completely dissolved, adds in the commercially available benzoyl peroxides of 4.64g (PPO) and 0.232g cities
N- bromo-succinimides (NBS) are sold, oil bath pot temperature is raised to 80 DEG C, after reacting 4 hours, reduce the temperature to room temperature, it will be anti-
Object solution is answered to go in revolving bottle, at 60 DEG C, revolving becomes brown color to solution colour, then precipitates, obtains light in methyl alcohol
Faint yellow solid with commercially available dichloromethane is dissolved, rotated, precipitated by yellow solid, repeats this operation 3 times, is obtained pure yellowish
The 0.25g BPPO dried are dissolved in the commercially available DMF solutions of 15mL by the bromide PPO (BPPO) of color, in an oven 60 DEG C of drying,
Until completely dissolved, the commercially available N- methylimidazoles of 207 μ L are added in, are reacted 12 hours, bromo site is completely quaternized, obtain n-formyl sarcolysine
The quaternized polyphenylene oxide of base imidazoles, nuclear magnetic resoance spectrum are as shown in Figure 5.
2nd, the preparation of poly- 1,3,5- tri- (3- amyl -1- imidazoles) benzene ionic liquid (PTPIB)：
(1), the preparation of 1,3,5- tri- (1- imidazoles) benzene：
By 2.52g commercially available 1,3,5- tribromo-benzenes, 5.44g commercial imidazoles, the commercially available potassium carbonate of 4.42g, 0.05g commercial sulfuric acid copper
It is added in 100mL there-necked flasks, is passed through nitrogen, temperature is raised to 180 DEG C, is reacted 12 hours, then product temperatur is down to room temperature,
It is washed five times, filtered with 30mL deionized waters, collect upper strata solid, the crude product commercially available dichloromethane of 30mL is extracted 5 times, is received
Rotary evaporation obtains 1,3,5- tri- (1- imidazoles) benzene after collection organic layer.
As shown in Figure 1, the nuclear magnetic resoance spectrum for 1,3,5- tri- (1- imidazoles) benzene, wherein, H1Correspond to benzene ring hydrogen, H2、
H3、H4Three hydrogen on imidazole ring are corresponded to respectively.
(2), the preparation of poly- 1,3,5- tri- (3- amyl -1- imidazoles) benzene ionic liquid (PTPIB)：
0.15g commercially available 1,3,5- tri- (1- imidazoles) benzene is dissolved in the commercially available N,N-dimethylformamides of 15mL (DMF) in 100 DEG C
In solution, the commercially available dibromo pentanes of 0.375g are added in, are reacted 12 hours, obtain yellow solid, filtering, which is placed in 60 DEG C of baking ovens, dries
It is dry, obtain poly- 1,3,5- tri- (3- pentyl -1- imidazoles) benzene ionic liquids (PTPIB).
As shown in Fig. 2, the nuclear magnetic resoance spectrum for poly- 1,3,5- tri- (3- pentyl -1- imidazoles) benzene ionic liquids (PTPIB),
Wherein, H1For benzene ring hydrogen, H2、H3、H4Three hydrogen respectively on imidazole ring, H5、H6It is to be connected with nitrogen on imidazole ring respectively
Two carbon on hydrogen, H7For hydrogen other on dodecyl chain.
3rd, the mostly preparation of conduction site polyphenyl ether anion-exchange membrane：
Step 2 products therefrom 0.003g is weighed, is added in step 1 products therefrom of equivalent, ultrasound 0.5 hour and stirs
0.5 hour, final product is poured into ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then will
Film is soaked in 1mol/L NaOH solutions two days, is obtained final fuel cell and is handed over more conduction site polyphenyl ether anion
Film 2 is changed, the thickness of film is measured with micrometer caliper.
Embodiment 2
1st, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton：
The commercially available polyphenylene oxide of 0.3g is added in the 100mL three-necked flasks equipped with blender, condenser pipe and gas-guide tube, nitrogen
Under atmosphere, 50 DEG C are heated to, after polyphenylene oxide is completely dissolved, adds in the commercially available benzoyl peroxides of 4.64g (PPO) and 0.232g cities
Sell N- bromo-succinimides (NBS), by oil bath pot temperature be raised to 80 DEG C reaction 4 hours after, reduce the temperature to room temperature, will react
Object solution is gone in revolving bottle, and 60 DEG C of revolvings become brown color to solution, then precipitate in methyl alcohol, obtain faint yellow solid,
Faint yellow solid is dissolved with commercially available dichloromethane, rotate, is precipitated, this operation 3 times is repeated, obtains pure flaxen bromo and gather
The 0.25g BPPO dried are dissolved in the commercially available DMF solutions of 15mL, wait to be completely dissolved by phenylate (BPPO), in an oven 60 DEG C of drying
Afterwards, the commercially available N- methylimidazoles of 207 μ L are added in, are reacted 12 hours, bromo site is completely quaternized, obtain N-methyl imidazoles quaternary ammonium
The polyphenylene oxide of change；
2nd, the preparation of poly- 1,3,5- tri- (3- octyl group -1- imidazoles) benzene ionic liquid (PTOIB)：
(1), the preparation of 1,3,5- tri- (1- imidazoles) benzene：
By 2.52g commercially available 1,3,5- tribromo-benzenes, 5.44g commercial imidazoles, the commercially available potassium carbonate of 4.42g, 0.05g commercial sulfuric acid copper
It is added in 100mL there-necked flasks, is passed through nitrogen, temperature is raised to 180 DEG C, is reacted 12 hours, then product temperatur is down to room temperature,
It is washed five times, filtered with 30mL deionized waters, collect upper strata solid, the crude product commercially available dichloromethane of 30mL is extracted 5 times, is received
Rotary evaporation obtains 1,3,5- tri- (1- imidazoles) benzene after collection organic layer.
(2), the preparation of poly- 1,3,5- tri- (3- octyl group -1- imidazoles) benzene ionic liquid (PTOIB)：
0.15g commercially available 1,3,5- tri- (1- imidazoles) benzene is dissolved in the commercially available N,N-dimethylformamides of 15mL (DMF) in 100 DEG C
In solution, commercially available two bromooctanes of 0.443g are added in, are reacted 12 hours, obtain yellow solid, filtering, which is placed in 60 DEG C of baking ovens, dries
It is dry, obtain poly- 1,3,5- tri- (3- octyl group -1- imidazoles) benzene ionic liquids (PTOIB).
As shown in figure 3, poly- 1,3,5- tri- (3- octyl -1- imidazoles) benzene ionic liquids (PTOIB) synthesized for the present invention
Nuclear magnetic resoance spectrum, wherein H1For benzene ring hydrogen, H2、H3、H4Three hydrogen respectively on imidazole ring, H5、H6It is and miaow respectively
The hydrogen on two carbon that nitrogen is connected on azoles ring, H7For hydrogen other on dodecyl chain.
3rd, the mostly preparation of conduction site polyphenyl ether anion-exchange membrane：
Step 2 products therefrom 0.0038g is weighed, is added in step 1 products therefrom of equivalent, ultrasound 0.5 hour and stirs
0.5 hour, final product is poured into ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then will
Film is soaked in 1mol/L NaOH solutions two days, is obtained final fuel cell and is handed over more conduction site polyphenyl ether anion
Film 3 is changed, the thickness of film is measured with micrometer caliper.
Embodiment 3
1st, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton：
The commercially available polyphenylene oxide of 0.3g is added in the 100mL three-necked flasks equipped with blender, condenser pipe and gas-guide tube, nitrogen
Under atmosphere, 50 DEG C are heated to, after polyphenylene oxide is completely dissolved, adds in the commercially available benzoyl peroxides of 4.64g (PPO) and 0.232g cities
Sell N- bromo-succinimides (NBS), by oil bath pot temperature be raised to 80 DEG C reaction 4 hours after, reduce the temperature to room temperature, will react
Object solution is gone in revolving bottle, then 60 DEG C of revolvings to solution precipitate in brown color, obtain faint yellow solid, use in methyl alcohol
Faint yellow solid is dissolved, rotated, precipitated by commercially available dichloromethane, is repeated this operation 3 times, is obtained pure flaxen bromo polyphenyl
The 0.25g BPPO dried are dissolved in the commercially available DMF solutions of 15mL, wait to be completely dissolved by ether (BPPO), in an oven 60 DEG C of drying
Afterwards, the commercially available N- methylimidazoles of 207 μ L are added in, are reacted 12 hours, bromo site is completely quaternized, obtain N-methyl imidazoles quaternary ammonium
The polyphenylene oxide of change；
2nd, the preparation of poly- 1,3,5- tri- (3- octyl group -1- imidazoles) benzene ionic liquid (PTOIB)：
(1), the preparation of 1,3,5- tri- (1- imidazoles) benzene：
By 2.52g commercially available 1,3,5- tribromo-benzenes, 5.44g commercial imidazoles, the commercially available potassium carbonate of 4.42g, 0.05g commercial sulfuric acid copper
It is added in 100mL there-necked flasks, is passed through nitrogen, temperature is raised to 180 DEG C, is reacted 12 hours, then product temperatur is down to room temperature,
It is washed five times, filtered with 30mL deionized waters, collect upper strata solid, the crude product commercially available dichloromethane of 30mL is extracted 5 times, is received
Rotary evaporation obtains final product after collection organic layer.
(2), the preparation of poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquid (PTDIB)：
0.15g commercially available 1,3,5- tri- (1- imidazoles) benzene is dissolved in the commercially available N,N-dimethylformamides of 15mL (DMF) in 100 DEG C
In solution, the commercially available dibromo-dodecanes of 0.535g are added in, are reacted 12 hours, obtain yellow solid, filtering is placed in 60 DEG C of baking ovens
Drying, obtains poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquids (PTDIB).
As shown in figure 4, poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquids synthesized for the present invention
(PTDIB) nuclear-magnetism figure, wherein H1For benzene ring hydrogen, H2、H3、H4Three hydrogen respectively on imidazole ring, H5、H6Be respectively with
The hydrogen on two carbon that nitrogen is connected on imidazole ring, H7For hydrogen other on dodecyl chain.
3rd, the mostly preparation of conduction site polyphenyl ether anion-exchange membrane：
Step 2 products therefrom 0.0049g is weighed, is added in step 1 products therefrom of equivalent, ultrasound 0.5 hour and stirs
0.5 hour, final product is poured into ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then will
Film is soaked in 1mol/L NaOH solutions two days, is obtained final fuel cell and is handed over more conduction site polyphenyl ether anion
Film 4 is changed, the thickness of film is measured with micrometer caliper.
The amount of step 1 products therefrom is added in the step 3 can reduce half.
The present invention carries out poly ion liquid doping treatment using the tape casting to film, obtain more conduction site polyphenyl ether the moon from
Proton exchange, preparation process is simple, at low cost.Prepared more conduction site polyphenyl ether anion-exchange membranes have high-quality
The advantages that sub- conductivity and good thermal stability, uniformly (120~150 μm), ionic liquid doping is 1% to thickness, application prospect
Extensively, it is applicable in especially suitable for anion-exchange membrane fuel cells.
Performance test：
With electrochemistry AC impedence method, under saturation water environment, DEG C test comparative examples 1 and embodiment from 30 DEG C to 80
The ionic conductivity of more conduction site polyphenyl ether anion-exchange membrane 1-4 of fuel cell obtained by 1-3, result such as Fig. 6 institutes
Show.
As shown in fig. 6, conduct site polyphenyl ether anion-exchange membrane 1-4 with for the fuel cell that the present invention synthesizes more
(the polyphenylene oxide N-methyl imidazole anion exchange membrane and be separately added into poly- 1,3,5- tri- (3- pentyls -1- that i.e. the present invention synthesizes
Imidazoles) benzene ionic liquid (PTPIB), poly- 1,3,5- tri- (3- octyl -1- imidazoles) benzene ionic liquid (PTOIB), poly- 1,3,5-
Three (3- dodecyl -1- imidazoles) benzene ionic liquids (PTDIB) anion-exchange membrane afterwards) ionic conductivity and temperature change
Relational graph.
The embodiment of the present invention is explained in detail above, all embodiments are under based on the technical solution of the present invention
Implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to it is above-mentioned
Embodiment.
Claims (9)
1. a kind of more conduction site polyphenyl ether anion-exchange membranes of fuel cell, it is characterised in that：The anion exchange
Film is by the quaternized polyphenylene oxide anion-exchange membrane of the N-methyl imidazoles with following constitutional repeating unit II of 98-99 weight %
It is formed with the poly ion liquid therein with structural formula I that is doped in of 1-2 weight %：
Wherein n is the integer not less than 1, and the carbon atom number of straight chained alkyl is 5-12；
Wherein x is the integer not less than 0；Y is the integer not less than 0, and is 0 when x, y difference.
2. the more conduction site polyphenyl ether anion-exchange membranes of fuel cell according to claim 1, it is characterised in that：
In the constitutional repeating unit II, x:Y=7:3.
3. the more conduction site polyphenyl ether anion-exchange membranes of fuel cell according to claim 2, it is characterised in that：
The structural formula I is poly- 1,3,5- tri- (3- amyl -1- imidazoles) benzene, poly- 1,3,5- tri- (3- octyl group -1- imidazoles) benzene or poly- 1,3,
5- tri- (3- dodecyl -1- imidazoles) benzene.
4. a kind of fuel cell preparation method of more conduction site polyphenyl ether anion-exchange membranes, includes the following steps：
(1) synthesis of polyphenylene oxide N-methyl imidazole skeleton
Polyphenylene oxide is added in reaction unit, 40-60 DEG C is heated under nitrogen atmosphere, after polyphenylene oxide is completely dissolved, is added in
Temperature is raised to 70-90 DEG C, after reacting 3-5 hours, reduces the temperature to room by benzoyl peroxide and N- bromo-succinimides
Reactant solution is rotated at 40-80 DEG C to solution colour and becomes brown color, then precipitated in methyl alcohol, obtained yellowish by temperature
Faint yellow solid with dichloromethane is dissolved, rotates, precipitates by color solid, is repeated this operation, is obtained pure flaxen bromo and gather
Phenylate, drying, is dissolved in DMF solution, until completely dissolved, adds in N- methylimidazoles, reaction, by the complete quaternary ammonium in bromo site
Change, obtain the quaternized polyphenylene oxide of N-methyl imidazoles；
(2) preparation of poly- three imidazoles benzene ionic liquid
The preparation of (I) 1,3,5- tri- (1- imidazoles) benzene：
By 1,3,5- tribromo-benzene, imidazoles, potassium carbonate and copper sulphate are added in container, are passed through nitrogen, temperature is raised to 170-190
DEG C, it reacts 8-16 hours, product temperatur is down to room temperature later, is washed with deionized, and filtering is collected upper strata solid, will slightly be produced
Object is extracted with dichloromethane, and after collected organic layer, rotary evaporation obtains 1,3,5- tri- (1- imidazoles) benzene；
The preparation of (II) poly- three imidazoles benzene ionic liquid：
1,3,5- tri- (1- imidazoles) benzene is dissolved in 80-120 DEG C in n,N-Dimethylformamide solution, adds in halogenated alkane, instead
It answers 6-18 hours, obtains yellow solid, filtering, which is placed in baking oven, dries, and obtains poly- three imidazoles benzene ionic liquid；
(3) conduct the preparation of site polyphenyl ether anion-exchange membrane more
In the step of weighing step (2) products therefrom, adding in equivalent (1) products therefrom, ultrasonic agitation is poured into final product super
It in flat surface ware, is placed in baking oven and dries, obtain pale yellow transparent film, then film is soaked in NaOH solution, obtain final
Anion-exchange membrane.
5. the fuel cell according to claim 4 preparation method of more conduction site polyphenyl ether anion-exchange membranes,
It is characterized in that：The time being stirred by ultrasonic described in the step (3) is 0.5 hour, and the drying temperature is 60 DEG C, described
A concentration of 1mol/L of NaOH solution, the soaking time are two days.
6. the fuel cell according to claim 4 preparation method of more conduction site polyphenyl ether anion-exchange membranes,
It is characterized in that：Repetitive operation described in the step (1) is 3 times.
7. the fuel cell according to claim 4 preparation method of more conduction site polyphenyl ether anion-exchange membranes,
It is characterized in that：Halogenated alkane dibromo pentane, two bromooctanes or dibromo-dodecane described in the step (2).
8. the fuel cell according to claim 4 preparation method of more conduction site polyphenyl ether anion-exchange membranes,
It is characterized in that：Poly- three imidazoles benzene ionic liquid described in the step (2) for poly- 1,3,5- tri- (3- amyl -1- imidazoles) benzene,
Poly- (3- octyl group -1- imidazoles) benzene of 1,3,5- tri- or poly- 1,3,5- tri- (3- dodecyl -1- imidazoles) benzene ionic liquid.
9. the fuel cell according to claim 4 preparation method of more conduction site polyphenyl ether anion-exchange membranes,
It is characterized in that：The addition of step (1) products therefrom described in the step (3) reduces half.
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| CN107221691B (en) * | 2017-05-26 | 2020-04-14 | 厦门大学 | Preparation method of graphene oxide/imidazole polyphenylene oxide composite anion exchange membrane |
| CN107452975A (en) * | 2017-07-25 | 2017-12-08 | 北京化工大学 | A kind of alkaline membrane of the compound substance of liquid titanium containing dissociated ion and preparation method thereof |
| CN108520971B (en) * | 2018-05-12 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Amination modified perfluorinated sulfonic acid resin ion exchange membrane and preparation method and application thereof |
| CN110330515B (en) * | 2019-07-31 | 2021-06-25 | 商丘师范学院 | Nitrogen-oxygen mixed ligand zinc complex and preparation method thereof |
| CN110330516B (en) * | 2019-07-31 | 2021-06-25 | 商丘师范学院 | Ternary imidazole ligand zinc complex and preparation method thereof |
| CN110283333B (en) * | 2019-07-31 | 2021-06-25 | 商丘师范学院 | Three-dimensional layered column structure dual-ligand zinc complex and preparation method thereof |
| CN112574448A (en) * | 2020-12-30 | 2021-03-30 | 长春工业大学 | Preparation method of side chain type polyphenyl ether anion exchange membrane containing double conduction sites for fuel cell |
| CN113981451A (en) * | 2021-08-13 | 2022-01-28 | 北京市古代建筑研究所 | Pre-filming corrosion inhibitor for iron cultural relics, and pre-filming and evaluation method thereof |
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