CN106633136A - Preparation method and application of 1-methylimidazole/TMPD (Tetramethyl-para-Phenylene Diamine) collaborative amination membrane based on polyether-ether-ketone - Google Patents
Preparation method and application of 1-methylimidazole/TMPD (Tetramethyl-para-Phenylene Diamine) collaborative amination membrane based on polyether-ether-ketone Download PDFInfo
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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 1-methylimidazole/TMPD (Tetramethyl-para-Phenylene Diamine) collaborative amination membrane based on polyether-ether-ketone and is prepared by taking the polyether-ether-ketone as a membrane matrix and adopting N,N,N',N'-TMPD with a hydrophobic benzene ring structure and 1-methylimidazole as collaborative amination agents; the TMPD has double bonding sites, and is introduced into the membrane to favorably form a local crosslinking structure; mechanical properties and dimensional stability of the membrane can be effectively intensified while the membrane ion exchange capacity and the ionic conductivity are not sacrificed. Due to the existence of the 1-methylimidazole, active groups on a polymer chain segment are enabled to completely react and excessive crosslinking is avoided. By using the synergism of the two amination agents, the overall properties of the membrane are remarkably improved; the water absorption rate of the membrane is 22.65 to 38.94 weight percent, the mechanical strength is 24.81 to 44.18MPa, the ion exchange capacity is 2.279 to 2.564mmol.g<-1>, and the conductivity of hydroxide ions at room temperature is 0.015 to 0.028Scm<-1>.
Description
Technical field
The present invention relates to a kind of 1- methylimidazoles/TMPD collaboration amination film preparations and application based on polyether-ether-ketone, belongs to
Homogeneous-phase anion exchange film technical field.
Background technology
Anion-exchange membrane is special with ion-selective permeability and ion transport due to being rich in cationic reactive groups in film
Property, it is the critical material of Separation & Purification, electrochemical assembly.Wherein, homogeneous-phase anion exchange film intermediate ion cation exchange groups with it is poly-
Compound main chain is bonded by chemistry, with even structure, surface resistance be little and the advantage such as stable performance, is widely used in electrodialysis
With the field such as fuel cell.
More than the preparation of conventional homogeneous anion-exchange membrane using basilar memebrane impregnated monomer, pressurization thermal polymerization by the way of film forming,
Again functionalization is carried out to film by immersion, preparation process is loaded down with trivial details.Basement membrane material used itself can not by chloromethylation, because
And a large amount of " clear areas " is yet suffered from the anion-exchange membrane for preparing, this region can not transmit ion, and film resistance is big.And season
Ammonium process by the way of basement membrane immersion trimethylamine solution, trimethylamine solution consumption is big, it is difficult reclaim, cause wastage of material, into
This raising, meanwhile, greatly and with fish raw meat stench, the eye, nose, throat and respiratory tract to human body has strong to trimethylamine volatility
Stimulation.Disadvantage mentioned above limits the application of this series anion-exchange membrane.
Using the excellent polymer of mechanical performance as film material of main part, polymer is changed in homogeneous phase solution system
Property process after casting film, drawbacks described above can be overcome, prepare self-cradling type anion-exchange membrane.
Publication date is 2012.10.17, and a kind of homogeneous the moon is disclosed in the Chinese patent of Patent No. 201210205298.0
The preparation method of amberplex, the film carries out being grafted after chloromethylation modification using aromatic high polymer as film material of main part
Benzimidazole function small molecule, prepares self-cradling type anion-exchange membrane.The preparation process of the film is easy, but due to not
With cross-linked structure, increasing the ion exchange capacity in film will weaken the mechanical strength and dimensional stability of film, film combination property
It is difficult to effectively be lifted.
Publication date is 2010.10.20, and a kind of self-crosslinking is disclosed in the Chinese patent of Patent No. 201010174360.5
The preparation method of polymer anion-exchange membrane, it is similar with the preparation method of above-mentioned homogeneous-phase anion exchange film, but quaternized
During except add trimethylamine in addition to, while introducing rudimentary secondary amine (such as diethylamine, di-n-propylamine, dibutyl amine) as quaternary ammoniated examination
Agent, to obtain partial cross-linking structure, prepares cross-linking type homogeneous-phase anion exchange film.The stability and satisfactory mechanical property of the film,
But by the use of rudimentary secondary amine as crosslinking agent, as the degree of cross linking increases, the ion exchange capacity in film is significantly reduced.
The content of the invention
For above-mentioned prior art, the present invention provides a kind of 1- methylimidazoles/TMPD collaboration aminations based on polyether-ether-ketone
Film preparation and application, to overcome conventional anion to exchange the defect of film preparation, prepare cross-linking type homogeneous-phase anion exchange film, while
The ion transport characteristic of reinforced film and mechanical performance.
In order to solve above-mentioned technical problem, a kind of 1- methylimidazoles/TMPD associations based on polyether-ether-ketone proposed by the present invention
It is using polyether-ether-ketone as membrane matrix, N, N, N with amination film ', N '-tetramethyl-para-phenylene diamine and 1- methylimidazoles are used as collaboration
Amination reagent;Film thickness be 60~80 μm, water absorption rate be 22.65~38.94wt.%, mechanical strength be 24.81~
44.18MPa, ion exchange capacity is 2.279~2.564mmol.g-1, under room temperature hydroxide ion conductivity be 0.015~
0.028S cm-1.The film is applied into fuel cell or electrodialysis plant.
1- methylimidazole/TMPD of the present invention based on polyether-ether-ketone cooperates with the preparation method of amination film, comprises the following steps:
Step one, polyether-ether-ketone is dissolved in the concentrated sulfuric acid obtaining homogeneous phase solution, gained homogeneous phase solution mass fraction is 1~
10wt.%, chloromethyl Octyl Ether is added in the homogeneous phase solution, and chloromethyl Octyl Ether is 15 with the volume mass ratio of polyether-ether-ketone
~20mL/g, reacts 20~60min under the conditions of -10 DEG C, and chloromethylation polyether-ether-ketone separates out in water, filters and wash into
Property, 40 DEG C of vacuum drying 48h are stand-by;
Step 2, the chloromethylation polyether-ether-ketone for obtaining step one are dissolved in N,N-dimethylformamide and are configured to quality
Volumetric concentration is the polymer solution of 0.05~0.2mg/L, and 1- methylimidazoles, 1- methylimidazoles are added in the polymer solution
With the volume mass of chloromethylation polyether-ether-ketone than 0.0875~0.1125mL/g, stir under room temperature after 3h and add N, N, N ',
N '-tetramethyl-para-phenylene diamine solution, wherein, N, N, N ', N '-tetramethyl-para-phenylene diamine quality is chloromethylation polyether-ether-ketone quality
2.5~15.0%, high-speed stirred 1h to solution be in uniform bluish violet;It is last to add 1- methylimidazoles in solution again, again
The 1- methylimidazoles of addition are 0.25mL/g with the volume mass ratio of chloromethylation polyether-ether-ketone, and after stirring 3h casting solution is obtained;
It is cast on a glass after step 3, the casting solution deaeration for obtaining step 2,10~12h is dried at 60 DEG C, rises
Temperature to 80~100 DEG C carry out 6~12h of annealing, gained membrane material be immersed in 48h in 1M NaOH solutions carry out sufficiently from
Son is replaced, then deionized water is cleaned to neutrality repeatedly, and the 1- methylimidazoles/TMPD collaborations based on polyether-ether-ketone are obtained after being dried
Amination film.
The chloromethylation degree of the chloromethylation polyether-ether-ketone that the step of preparation method of the present invention one prepares is 0.66
~0.93, by controlling reaction time controllable chloromethylation degree.
Compared with prior art, the invention has the beneficial effects as follows:
1- methylimidazole/TMPD collaboration amination film of the present invention based on polyether-ether-ketone, using polyether-ether-ketone as membrane matrix, N,
N, N ', N '-tetramethyl-para-phenylene diamine (TMPD) and 1- methylimidazoles are used as collaboration amination reagent.TMPD is due to double combination position
Point, is introduced into film beneficial to partial cross-linking structure is formed, and can have while not expendable film ion exchange capacity and ionic conductance
The mechanical performance and dimensional stability of effect reinforced film.The presence of 1- methylimidazoles then ensures that the active group on polymer segment is complete
Full response and avoid excessively crosslinking.Two kinds of aminating agent synergies enable the combination property of film to significantly improve.
Description of the drawings
Fig. 1 is chloromethylation polyether-ether-ketone obtained in the differential responses time of the present invention1H NMR spectras;
Fig. 2 is film section local SEM figures obtained in comparative example;
Fig. 3 is film section local SEM figures obtained in the embodiment of the present invention 1;
Fig. 4 is film section local SEM figures obtained in the embodiment of the present invention 2;
Fig. 5 is film section local SEM figures obtained in the embodiment of the present invention 3;
Fig. 6 is film section local SEM figures obtained in the embodiment of the present invention 4;
Fig. 7 is film section local SEM figures obtained in the embodiment of the present invention 5.
Specific embodiment
1- methylimidazole/TMPD collaboration amination film of the present invention based on polyether-ether-ketone be using polyether-ether-ketone as membrane matrix,
N, N, N ', N '-tetramethyl-para-phenylene diamine and 1- methylimidazoles are used as collaboration amination reagent;The average thickness of film is about 70 μm, inhales
Water rate be 22.65~38.94wt.%, mechanical strength be 24.81~44.18MPa, ion exchange capacity be 2.279~
2.564mmol.g-1, hydroxide ion conductivity is 0.015~0.028S cm under room temperature-1.The film can be applicable to fuel cell
Or electrodialysis plant.
Below in conjunction with the accompanying drawings technical solution of the present invention is described in further detail with specific embodiment, described is concrete
Embodiment is only explained to the present invention, not to limit the present invention.
The preparation of the pure imidazoles salt form polyether-ether-ketone (ImPEEK) of comparative example 1
Prepare chloromethylation polyether-ether-ketone (CMPEEK):At -10 DEG C, take 4g polyether-ether-ketones and be dissolved in the 240mL concentrated sulfuric acids, machine
Tool stirring 4h is completely dissolved it, adds 80mL chloromethyl Octyl Ethers, and solution is poured into a large amount of deionizations after 20~60min of stirring
In water, macromolecule product chloromethylation polyether-ether-ketone is separated out.Products obtained therefrom is leached, using ethanol and deionized water cyclic washing,
Go the removal of impurity and to neutral, under the conditions of 40 DEG C 48h is vacuum dried, obtain CMPEEK, the chloromethyl of the CMPEEK for preparing
Change degree is 0.66~0.93, can be regulated and controled by the reaction time.Fig. 1 show CMPEEK obtained in the differential responses time
's1H NMR spectras.The chloromethylation degree of CMPEEK can be calculated by formula (1):
Wherein, A (Hd) and A (Hc) it is respectively HdAnd HcPeak area.(reaction time is X to the CMPEEK-X obtained by collection of illustrative plates
=20,40,60min) chloromethylation degree is respectively 0.66,078,093.Chloromethylation degree is higher, the dissolubility of CMPEEK
Better, after film forming swellbility increase, considers the swellbility after the dissolubility and film forming of CMPEEK-X, final choice
CMPEEK-40 is used as this research institute CMPEEK.
CMPEEK obtained in taking 0.4g above-mentioned steps one is dissolved in 6mL DMF, and stirring 3h is completely dissolved to polymer, then adds
Enter 0.5mL 1- methylimidazoles, after stirring 3h solution-cast is placed in 60 DEG C of baking ovens and heats 12h on glass plate, then heat up
To 80 DEG C of process 12h.After cooling, lower obtained film is peeled off from glass plate and 48h in 1MNaOH solution is immersed in is carried out
Sufficiently ion exchange, then deionized water cleans film repeatedly, until washing lotion pH value shows neutral, film is placed in baking oven and is done
It is dry, pure ImPEEK films are obtained, the average thick of institute's masking is about 70 μm, and Fig. 2 shows the section local SEM of the pure ImPEEK films
Figure.
Embodiment 1:1- methylimidazoles based on polyether-ether-ketone/TMPD cooperates with the preparation of amination film, and step is as follows:
Step one, CMPEEK preparation methods are with comparative example 1.
Step 2, take 0.4g CMPEEK and be dissolved in 3mL DMFs, add 0.05mL 1- methylimidazoles
To avoid gel-forming, stir under room temperature after 3h and add 0.01g N, N, N ', N '-tetramethyl-para-phenylene diamine (TMPD), at a high speed
Stirring 1h to solution be in uniform bluish violet, 0.1mL 1- methylimidazoles are added in most backward solution, to guarantee solution in chloromethane
Base fully reacts, and after stirring 3h casting solution is obtained.
Step 3, gained casting solution are cast on a glass, are placed in 60 DEG C of baking ovens and are dried 12h, then be warming up to 80 DEG C
Row annealing 12h.After cooling, lower obtained film is peeled off from glass plate and 48h in 1M NaOH solutions is immersed in is carried out
Sufficiently ion exchange, then deionized water cleans film repeatedly, until washing lotion pH value shows neutral, film is placed in 60 DEG C of baking ovens
It is dried, obtains the 1- methylimidazoles/TMPD collaboration amination films based on polyether-ether-ketone, is designated as ImPEEK/TMPD-2.5, wherein,
TMPD is 2.5% to the mass fraction of CMPEEK, and the average thick of institute's masking is about 70 μm, and Fig. 3 shows film obtained in embodiment 1
Section local SEM figure.
Embodiment 2:1- methylimidazoles based on polyether-ether-ketone/TMPD cooperates with the preparation of amination film
Preparation process is similar to Example 1, and the TMPD for simply adding in step 2 casting solution process for preparation is changed by 0.01g
For 0.02g, remaining condition is constant, finally prepares ImPEEK/TMPD-5.0, wherein, mass fractions of the TMPD to CMPEEK
For 5.0%, institute's masking it is average thick about 70 μm, Fig. 4 shows the section local SEM figures of film obtained in embodiment 2.
Embodiment 3:1- methylimidazoles based on polyether-ether-ketone/TMPD cooperates with the preparation of amination film
Preparation process is similar to Example 1, and the TMPD for simply adding in step 2 casting solution process for preparation is changed by 0.01g
For 0.03g, remaining condition is constant, finally prepares ImPEEK/TMPD-7.5, wherein, mass fractions of the TMPD to CMPEEK
For 7.5%, institute's masking it is average thick about 70 μm, Fig. 5 shows the section local SEM figures of film obtained in embodiment 3.
Embodiment 4:1- methylimidazoles based on polyether-ether-ketone/TMPD cooperates with the preparation of amination film
Preparation process is similar to Example 1, simply in step 2 casting solution process for preparation addition TMPD by
0.01g is changed to 0.04g, and remaining condition is constant, finally prepares ImPEEK/TMPD-10.0, wherein, TMPD is to CMPEEK's
Mass fraction is 10.0%, and the average thick of institute's masking is about 70 μm, and Fig. 6 shows the section local SEM of film obtained in embodiment 4
Figure.
Embodiment 5:1- methylimidazoles based on polyether-ether-ketone/TMPD cooperates with the preparation of amination film
Preparation process is similar to Example 1, and the TMPD for simply adding in step 2 casting solution process for preparation is changed by 0.01g
For 0.06g, remaining condition is constant, finally prepares ImPEEK/TMPD-15.0, wherein, mass fractions of the TMPD to CMPEEK
For 15.0%, institute's masking it is average thick about 70 μm, Fig. 7 shows the section local SEM figures of film obtained in embodiment 5.
It is as follows to the characterization method and condition of present invention gained film:
(1) the hydroxide ion conductivity test of film
Using electrochemical workstation (Compactstat, IVIUM Tech.) using two electrode AC impedance method test films
Ionic conductance (level to), first with 1M sodium hydroxide solutions immersion 24h, then deionized water film table is cleaned before film test repeatedly
Face remains alkali lye.Film should be cut into 1 × 2.5cm during test2Rectangle, be placed between two platinum filaments, carry out under the conditions of 25 DEG C
Test., at 25 DEG C, hydroxide ion conductivity is as shown in table 1 under the conditions of saturated humidity for 1 masking of embodiment 1~5 and comparative example:
Table 1
(2) the ultimate tensile strength test of film
The ultimate tensile strength of film is obtained by electronic tensilometer (Yangzhou Zhong Ke measuring instruments company, model WDW-2) test.
When preparing sample.Film is cut into 1 × 3cm2Strip, two ends are fixed on the stretching accessory of tester, with 10mm min-1's
Rate tensile, records load-deformation curve, obtains the ultimate tensile strength of film.Embodiment 1~5 and contrast at ambient temperature
The ultimate tensile strength of 1 masking of example is as shown in table 2:
Table 2
By Tables 1 and 2 as can be seen that introducing TMPD can effectively improve ion transport characteristic in film, while strengthening film machinery
Performance.When the addition of TMPD reaches 10.0wt.%, (ionic conductance is the hydroxide ion conductivity highest of film under room temperature
0.02697S cm-1), while with good ultimate tensile strength (mechanical strength is 30.54MPa).The water absorption rate of room temperature lower film
For 35.1wt.%, with preferable dimensional stability;Further adopt back titration method to measure the ion exchange capacity of the film for
2.3mmol.g-1, film section structure (Fig. 3 to Fig. 7) is observed by SEM (SEM), shown film section structure is homogeneous
Zero defect, is expected to be applied to ion-exchange membrane fuel cell field.
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned specific embodiment is only schematic, rather than restricted, and one of ordinary skill in the art is at this
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the guarantor of the present invention
Within shield.
Claims (4)
1. a kind of 1- methylimidazoles/TMPD based on polyether-ether-ketone cooperates with amination film, it is characterised in that using polyether-ether-ketone as film
Matrix, N, N, N ', N '-tetramethyl-para-phenylene diamine and 1- methylimidazoles are used as collaboration amination reagent;Film thickness is 60~80 μm, is inhaled
Water rate be 22.65~38.94wt.%, mechanical strength be 24.81~44.18MPa, ion exchange capacity be 2.279~
2.564mmol.g-1, hydroxide ion conductivity is 0.015~0.028S cm under room temperature-1。
2. 1- methylimidazoles according to claim 1 based on polyether-ether-ketone/TMPD cooperates with the preparation method of amination film, and it is special
Levy and be, comprise the following steps:
Step one, polyether-ether-ketone is dissolved in the concentrated sulfuric acid obtaining homogeneous phase solution, gained homogeneous phase solution mass fraction is 1~
10wt.%, chloromethyl Octyl Ether is added in the homogeneous phase solution, and chloromethyl Octyl Ether is 15 with the volume mass ratio of polyether-ether-ketone
~20mL/g, reacts 20~60min under the conditions of -10 DEG C, and chloromethylation polyether-ether-ketone separates out in water, filters and wash into
Property, 40 DEG C of vacuum drying 48h are stand-by;
Step 2, the chloromethylation polyether-ether-ketone for obtaining step one are dissolved in N,N-dimethylformamide and are configured to quality volume
Concentration is the polymer solution of 0.05~0.2mg/L, and 1- methylimidazoles, 1- methylimidazoles and chlorine are added in the polymer solution
Methylate polyether-ether-ketone volume mass than 0.0875~0.1125mL/g, under room temperature stir 3h after add N, N, N ', N '-four
Dimethyl-p-phenylenediamine solution, wherein, N, N, N ', N '-tetramethyl-para-phenylene diamine quality is the 2.5 of chloromethylation polyether-ether-ketone quality
~15.0%, high-speed stirred 1h to solution is in uniform bluish violet;It is last to add 1- methylimidazoles in solution again, add again
1- methylimidazoles are 0.25mL/g with the volume mass ratio of chloromethylation polyether-ether-ketone, and after stirring 3h casting solution is obtained;
It is cast on a glass after step 3, the casting solution deaeration for obtaining step 2,10~12h is dried at 60 DEG C, is warming up to
80~100 DEG C carry out 6~12h of annealing, and gained membrane material is immersed in 48h in 1M NaOH solutions to carry out sufficient ion and put
Change, then deionized water is cleaned to neutrality repeatedly, and the 1- methylimidazoles/TMPD collaboration aminations based on polyether-ether-ketone are obtained after being dried
Film.
3. 1- methylimidazoles according to claim 2 based on polyether-ether-ketone/TMPD cooperates with the preparation method of amination film, and it is special
Levy and be, the chloromethylation degree of the chloromethylation polyether-ether-ketone that step one is prepared is 0.66~0.93.
4. a kind of 1- methylimidazoles/TMPD collaboration amination films as claimed in claim 1 based on polyether-ether-ketone are applied to fuel electricity
Pond or electrodialysis plant.
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