CN106633136B - 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation and application - Google Patents
1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of, and the 1- methylimidazole based on polyether-ether-ketone/TMPD cooperates with amination film, it is using polyether-ether-ketone as membrane matrix, using the N for having hydrophobic benzene ring structure, N, N ', N '-tetramethyl-para-phenylene diamine (TMPD) and 1- methylimidazole are as collaboration amination reagent, and TMPD is due to double combination site, be introduced into film be conducive to form partial cross-linking structure, while not expendable film ion exchange capacity and ionic conductivity can effectively reinforced film mechanical performance and dimensional stability.The presence of 1- methylimidazole then guarantees that the active group on polymer segment reacts completely and avoids excessively being crosslinked.Two kinds of aminating agent synergistic effects enable the comprehensive performance of film to significantly improve, and water absorption rate is 22.65~38.94wt.%, and mechanical strength is 24.81~44.18MPa, and ion exchange capacity is 2.279~2.564mmol.g‑1, hydroxide ion conductivity is 0.015~0.028S cm at room temperature‑1。
Description
Technical field
The present invention relates to a kind of the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation and application, belong to
Homogeneous-phase anion exchange film technical field.
Background technique
Anion-exchange membrane has ion-selective permeability and ion transport special due to being rich in cationic reactive groups in film
Property, it is the critical material of separation and purification, electrochemical assembly.Wherein, homogeneous-phase anion exchange film intermediate ion cation exchange groups and poly-
Owner's chain is closed by chemistry key connection, there are the advantages such as structure is uniform, surface resistance is small and performance is stablized, be widely used in electrodialysis
With the fields such as fuel cell.
The preparation of conventional homogeneous anion-exchange membrane mostly uses the mode of basilar memebrane impregnated monomer, thermal polymerization of pressurizeing to form a film,
Functionalization is carried out to film by impregnating again, preparation process is cumbersome.Basement membrane material used itself cannot by chloromethylation, because
And there are still a large amount of " blank areas " in the anion-exchange membrane of preparation, this region cannot transmit ion, and film resistance is big.And season
Ammonium process is in such a way that basement membrane impregnates trimethylamine solution, and trimethylamine solution dosage is big, difficult recycling, cause wastage of material, at
This raising, meanwhile, trimethylamine volatility is big and has fish raw meat stench, has to the eye of human body, nose, throat and respiratory tract strong
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 processing after casting film, drawbacks described above can be overcome, self-cradling type anion-exchange membrane is prepared.
Publication date is 2012.10.17, and a kind of homogeneous yin is disclosed in the Chinese patent of Patent No. 201210205298.0
The preparation method of amberplex, the film are grafted after carrying out chloromethylation modification using aromatic high polymer as film material of main part
Benzimidazole function small molecule, is prepared self-cradling type anion-exchange membrane.The preparation process of the film is easy, but due to not
With cross-linked structure, increase mechanical strength and dimensional stability that the ion exchange capacity in film will weaken film, film comprehensive performance
It is difficult to effectively be promoted.
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
In the process in addition to trimethylamine is added, while introducing rudimentary secondary amine (such as diethylamine, di-n-propylamine, dibutyl amine) and being used as quaternary ammoniated examination
Agent prepares cross-linking type homogeneous-phase anion exchange film to obtain partial cross-linking structure.The stability and satisfactory mechanical property of the film,
But using rudimentary secondary amine as crosslinking agent, as the degree of cross linking increases, the ion exchange capacity in film is significantly reduced.
Summary of the invention
For the above-mentioned prior art, the present invention provides a kind of 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination
Film preparation and application prepare cross-linking type homogeneous-phase anion exchange film, simultaneously to overcome the defect of conventional anion exchange film preparation
The ion transport characteristic and mechanical performance of reinforced film.
In order to solve the above-mentioned technical problem, a kind of 1- methylimidazole based on polyether-ether-ketone proposed by the present invention/TMPD association
It is N, N, N using polyether-ether-ketone as membrane matrix with amination film ', N '-tetramethyl-para-phenylene diamine and 1- methylimidazole are 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 are 2.279~2.564mmol.g-1, at room temperature hydroxide ion conductivity be 0.015~
0.028S cm-1.The film is applied to fuel cell or electrodialysis plant.
The present invention is based on the 1- of polyether-ether-ketone methylimidazole/TMPD collaboration amination film preparation methods, comprising the following steps:
Obtain homogeneous phase solution Step 1: polyether-ether-ketone is dissolved in the concentrated sulfuric acid, gained homogeneous phase solution mass fraction be 1~
The volume mass ratio of 10wt.%, the addition chloromethyl Octyl Ether into the homogeneous phase solution, chloromethyl Octyl Ether and polyether-ether-ketone is 15
~20mL/g, reacts 20~60min under the conditions of -10 DEG C, and chloromethylation polyether-ether-ketone is precipitated in water, filters and wash into
Property, 40 DEG C of vacuum drying 48h, for use；
Quality is configured to Step 2: the chloromethylation polyether-ether-ketone that step 1 obtains is dissolved in N,N-dimethylformamide
Volumetric concentration is the polymer solution of 0.05~0.2mg/L, and 1- methylimidazole, 1- methylimidazole are added into the polymer solution
Volume mass with chloromethylation polyether-ether-ketone adds N, N, N after stirring 3h at room temperature than 0.0875~0.1125mL/g ',
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；1- methylimidazole is finally added into solution again, again
The 1- methylimidazole of addition and the volume mass ratio of chloromethylation polyether-ether-ketone are 0.25mL/g, obtain casting solution after stirring 3h；
Step 3: dry 10~12h, rises at 60 DEG C by being cast on a glass after casting solution deaeration that step 2 obtains
Temperature carries out 6~12h of annealing to 80~100 DEG C, gained membrane material be immersed in 48h in 1M NaOH solution carry out adequately from
Son displacement, then cleaned repeatedly with deionized water to neutrality, the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration is obtained after dry
Amination film.
The chloromethylation degree for the chloromethylation polyether-ether-ketone that the step of preparation method of the present invention one is prepared is 0.66
~0.93, by controlling reaction time controllable chloromethylation degree.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is based on the 1- of polyether-ether-ketone methylimidazole/TMPD to cooperate with amination film, using polyether-ether-ketone as membrane matrix, N,
N, N ', N '-tetramethyl-para-phenylene diamine (TMPD) and 1- methylimidazole are as collaboration amination reagent.TMPD is due to binode coincidence
Point is introduced into and is conducive to form partial cross-linking structure in film, can have while not expendable film ion exchange capacity and ionic conductivity
Imitate the mechanical performance and dimensional stability of reinforced film.The presence of 1- methylimidazole then guarantees that the active group on polymer segment is complete
Full response and avoid excessively being crosslinked.Two kinds of aminating agent synergistic effects enable the comprehensive performance of film to significantly improve.
Detailed description of the invention
Fig. 1 is chloromethylation polyether-ether-ketone made from the differential responses time of the present invention1H NMR spectra；
Fig. 2 is the figure of film section part SEM made from comparative example；
Fig. 3 is the figure of film section part SEM made from the embodiment of the present invention 1；
Fig. 4 is the figure of film section part SEM made from the embodiment of the present invention 2；
Fig. 5 is the figure of film section part SEM made from the embodiment of the present invention 3；
Fig. 6 is the figure of film section part SEM made from the embodiment of the present invention 4；
Fig. 7 is the figure of film section part SEM made from the embodiment of the present invention 5.
Specific embodiment
The present invention is based on the 1- of polyether-ether-ketone methylimidazole/TMPD collaboration amination film be using polyether-ether-ketone as membrane matrix,
N, N, N ', N '-tetramethyl-para-phenylene diamine and 1- methylimidazole are as collaboration amination reagent；The average thickness of film is about 70 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 at room temperature-1.The film can be applied to fuel cell
Or electrodialysis plant.
Technical solution of the present invention is described in further detail in the following with reference to the drawings and specific embodiments, it is described specific
Embodiment is only explained the present invention, is not intended to limit the invention.
The preparation of the pure imidazoles salt form polyether-ether-ketone (ImPEEK) of comparative example 1
It prepares chloromethylation polyether-ether-ketone (CMPEEK): at -10 DEG C, 4g polyether-ether-ketone being taken to be dissolved in the 240mL concentrated sulfuric acid, machine
Tool stirring 4h makes it completely dissolved, addition 80mL chloromethyl Octyl Ether, and solution is poured into a large amount of deionizations after 20~60min of stirring
In water, macromolecule product chloromethylation polyether-ether-ketone is precipitated.Products obtained therefrom is filtered out, is washed repeatedly using ethyl alcohol and deionized water,
Impurity and extremely neutrality are removed, 48h is dried in vacuo under the conditions of 40 DEG C, obtains CMPEEK, the chloromethyl for the CMPEEK being prepared
Change degree is 0.66~0.93, can be regulated and controled by the reaction time.Fig. 1 show CMPEEK made from the differential responses time
's1H NMR spectra.The chloromethylation degree of CMPEEK can be calculated by formula (1):
Wherein, A (Hd) and A (Hc) it is respectively HdAnd HcPeak area.CMPEEK-X (the reaction time X obtained by map
=20,40,60min) chloromethylation degree is respectively 0.66,078,093.Chloromethylation degree is higher, the dissolubility of CMPEEK
Better, the swellbility after film forming increases, the dissolubility and the swellbility after film forming for comprehensively considering CMPEEK-X, final choice
CMPEEK-40 is as CMPEEK used in this research.
CMPEEK made from 0.4g above-mentioned steps one is taken to be dissolved in 6mL DMF, stirring 3h to polymer is completely dissolved, then plus
Enter 0.5mL 1- methylimidazole, stirs and solution-cast is heated into 12h on glass plate, being placed in 60 DEG C of baking ovens after 3h, then heat up
To 80 DEG C of processing 12h.After cooling, it descends obtained film from removing on glass plate and is immersed in 48h in 1MNaOH solution to carry out
Sufficient ion exchange, then film is cleaned repeatedly with deionized water, until washing lotion pH value display neutrality, film is placed in baking oven and is done
It is dry, pure ImPEEK film is obtained, what is be film-made is average about 70 μm thick, and Fig. 2 shows the section part SEM of the pure ImPEEK film
Figure.
Embodiment 1: the preparation of the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film, steps are as follows:
Step 1: CMPEEK preparation method is the same as comparative example 1.
Step 2: 0.4g CMPEEK is taken to be dissolved in 3mL n,N-Dimethylformamide, 0.05mL 1- methylimidazole is added
To avoid gel-forming, 0.01g N, N, N are added after stirring 3h at room temperature ', N '-tetramethyl-para-phenylene diamine (TMPD), high speed
It is in uniform bluish violet that 1h, which is stirred, to solution, adds 0.1mL 1- methylimidazole, into solution finally to ensure the chloromethane in solution
Base sufficiently reacts, and obtains casting solution after stirring 3h.
Step 3: gained casting solution is cast on a glass, be placed in 60 DEG C of baking ovens dry 12h, then be warming up to 80 DEG C into
Row annealing 12h.After cooling, it descends obtained film from removing on glass plate and is immersed in 48h in 1M NaOH solution to carry out
Sufficient ion exchange, then film is cleaned repeatedly with deionized water, until washing lotion pH value display neutrality, film is placed in 60 DEG C of baking ovens
It is dry, the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film is obtained, ImPEEK/TMPD-2.5 is denoted as, wherein
TMPD is 2.5% to the mass fraction of CMPEEK, and what is be film-made is average about 70 μm thick, and Fig. 3 shows film made from embodiment 1
Section part SEM figure.
Embodiment 2: the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation
Preparation process is similar to Example 1, and the TMPD being only added in step 2 casting solution process for preparation is changed by 0.01g
For 0.02g, remaining condition is constant, and ImPEEK/TMPD-5.0 is finally prepared, wherein mass fraction of the TMPD to CMPEEK
It is 5.0%, what is be film-made is average about 70 μm thick, and Fig. 4 shows the section part SEM figure of film made from embodiment 2.
Embodiment 3: the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation
Preparation process is similar to Example 1, and the TMPD being only added in step 2 casting solution process for preparation is changed by 0.01g
For 0.03g, remaining condition is constant, and ImPEEK/TMPD-7.5 is finally prepared, wherein mass fraction of the TMPD to CMPEEK
It is 7.5%, what is be film-made is average about 70 μm thick, and Fig. 5 shows the section part SEM figure of film made from embodiment 3.
Embodiment 4: the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation
Preparation process is similar to Example 1, be only added in step 2 casting solution process for preparation the TMPD of addition by
0.01g is changed to 0.04g, remaining condition is constant, ImPEEK/TMPD-10.0 is finally prepared, wherein TMPD is to CMPEEK's
Mass fraction is 10.0%, and what is be film-made is average about 70 μm thick, and Fig. 6 shows the section part SEM of film made from embodiment 4
Figure.
Embodiment 5: the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation
Preparation process is similar to Example 1, and the TMPD being only added in step 2 casting solution process for preparation is changed by 0.01g
For 0.06g, remaining condition is constant, and ImPEEK/TMPD-15.0 is finally prepared, wherein mass fraction of the TMPD to CMPEEK
It is 15.0%, what is be film-made is average about 70 μm thick, and Fig. 7 shows the section part SEM figure of film made from embodiment 5.
It is as follows to the characterization method and condition of film obtained by the present invention:
(1) the hydroxide ion conductivity test of film
Using electrochemical workstation (Compactstat, IVIUM Tech.) using two electrode AC impedance method test films
Ionic conductivity (horizontal direction) is first impregnated for 24 hours with 1M sodium hydroxide solution before film test, then cleans film table repeatedly with deionized water
Face remains lye.Film should be cut into 1 × 2.5cm when test2Rectangle, be placed between two platinum filaments, carried out under the conditions of 25 DEG C
Test.Examples 1 to 5 and comparative example 1 are film-made at 25 DEG C, and hydroxide ion conductivity is as shown in table 1 under the conditions of saturated humidity:
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 instrument company, model WDW-2) test.
When preparing sample.Film is cut into 1 × 3cm2Strip, both 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.Examples 1 to 5 and comparison at room temperature
The ultimate tensile strength that example 1 is film-made is as shown in table 2:
Table 2
TMPD is introduced it can be seen from Tables 1 and 2 can effectively improve ion transport characteristic in film, while enhance film machinery
Performance.When the additional amount of TMPD reaches 10.0wt.%, (ionic conductivity is the hydroxide ion conductivity highest of film at room temperature
0.02697S cm-1), while there is good ultimate tensile strength (mechanical strength 30.54MPa).The water absorption rate of room temperature lower film
For 35.1wt.%, there is preferable dimensional stability；Further use back titration method measure the ion exchange capacity of the film for
2.3mmol.g-1, observing film section structure by scanning electron microscope (SEM), (Fig. 3 to Fig. 7), shown film section structure are uniform
Zero defect is expected to be applied to ion-exchange membrane fuel cell field.
Although above in conjunction with figure, invention has been described, and the invention is not limited to above-mentioned specific embodiment parties
Formula, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are in this hair
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to guarantor of the invention
Within shield.
Claims (3)
1. a kind of 1- methylimidazole based on polyether-ether-ketone/TMPD cooperates with amination film, which is characterized in that using polyether-ether-ketone as film
Matrix, N, N, N ', N '-tetramethyl-para-phenylene diamine and 1- methylimidazole are 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 at room temperature-1；Specific step is as follows:
Obtain homogeneous phase solution Step 1: polyether-ether-ketone is dissolved in the concentrated sulfuric acid, gained homogeneous phase solution mass fraction be 1~
The volume mass ratio of 10wt.%, the addition chloromethyl Octyl Ether into the homogeneous phase solution, chloromethyl Octyl Ether and polyether-ether-ketone is 15
~20mL/g, reacts 20~60min under the conditions of -10 DEG C, and chloromethylation polyether-ether-ketone is precipitated in water, filters and wash into
Property, 40 DEG C of vacuum drying 48h, for use；
Quality volume is configured to Step 2: the chloromethylation polyether-ether-ketone that step 1 obtains is dissolved in N,N-dimethylformamide
Concentration is the polymer solution of 0.05~0.2mg/L, and 1- methylimidazole, 1- methylimidazole and chlorine are added into the polymer solution
The volume mass of methylation polyether-ether-ketone adds N, N, N after stirring 3h at room temperature than 0.0875~0.1125mL/g ', 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 are in uniform bluish violet；1- methylimidazole is finally added into solution again, is added again
The volume mass ratio of 1- methylimidazole and chloromethylation polyether-ether-ketone is 0.25mL/g, obtains casting solution after stirring 3h；
Step 3: dry 10~12h, is warming up at 60 DEG C by being cast on a glass after casting solution deaeration that step 2 obtains
80~100 DEG C carry out 6~12h of annealing, and gained membrane material is immersed in the sufficient ion of 48h progress in 1M NaOH solution and sets
It changes, then is cleaned repeatedly with deionized water to neutrality, the 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination is obtained after dry
Film.
2. the 1- methylimidazole based on polyether-ether-ketone/TMPD cooperates with amination film according to claim 1, which is characterized in that step
The chloromethylation degree of the rapid one chloromethylation polyether-ether-ketone being prepared is 0.66~0.93.
3. a kind of 1- methylimidazole based on polyether-ether-ketone as described in claim 1/TMPD collaboration amination film is used for fuel cell
Or the purposes of electrodialysis plant.
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| CN101862608A (en) * | 2010-05-11 | 2010-10-20 | 武汉大学 | Method for preparing self-crosslinking polymer anion exchange membrane |
| CN102731811A (en) * | 2012-06-20 | 2012-10-17 | 中国科学技术大学 | Homogeneous anion exchange membrane and preparation method thereof |
| KR20160063715A (en) * | 2014-11-27 | 2016-06-07 | 연세대학교 원주산학협력단 | Preparation method for polyimide blend from water soluble polyamic acid |
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