CN109233274A - A kind of polybenzimidazole membrane and preparation method thereof with nano-porous structure - Google Patents
A kind of polybenzimidazole membrane and preparation method thereof with nano-porous structure Download PDFInfo
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- C08J2379/00—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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
A kind of polybenzimidazole membrane and preparation method thereof with nano-porous structure, belongs to speciality polymer function technical field of membrane；It is that filler dispersion liquid is added in polybenzimidazoles solution, is sufficiently mixed filtering after-pouring on clean glass plate, and heating removal solvent obtains polybenzimidazole membrane on a glass；Then certain time is impregnated in etching agent, is washed with boiling water and sloughs residual etching agent, and drying obtains the polybenzimidazole membrane of nano-porous structure, has high phosphate-doped horizontal and high proton conductivity, can be used for high-temperature fuel cell.The present invention is using zeolite imidazole ester skeleton ZIFs series material as pore-foaming agent, selection phosphoric acid is etching agent, nano-pore structure is formed in situ in polybenzimidazole membrane, since ZIFs material can be by adjusting the molecular structure of imidazole ligands and the type of metal ion, different crystalline sizes and pattern is obtained, prepared porous membrane pore size, hole pattern, pore-size distribution and the connectivity in hole can regulate and control.
Description
Technical field
The invention belongs to speciality polymer function technical field of membrane, and in particular to a kind of polyphenyl with nano-porous structure
And imidazoles film and preparation method thereof.
Background technique
Nano-porous polymer film has the characteristics that large specific surface area, density are small, stability is high and processability is good, has both more
The double dominant of pore membrane and polymer material, in adsorbing separation, microreactor, catalyst carrier, sensor and high-temperature fuel
Battery proton exchange membrane field has a wide range of applications.But there is pore-size distributions for the apertured polymeric film of current method preparation
The problem of wider, pore size size can not regulate and control, preparation process is cumbersome and wastage pollution environment.
Polybenzimidazoles is the heterocyclic ladder polymer in a kind of backbone repeat unit containing imidazole group, is had excellent
Stability, mechanical strength and chemical corrosion resistance.Since the imidazoles nitrogen in half trapezium structure and main chain of polybenzimidazoles is former
Son presence, belong to glassy polymers, chain rigidity is larger, decomposition temperature up to 550 DEG C, and main chain contain imidazole radicals can be simultaneously
As proton donor and proton carrier, it is widely used in high-temperature fuel cell proton exchange membrane field.Usually by polyphenyl and miaow
Azoles is grafted, is copolymerized, is blended, is crosslinked or backbone modification introduces the mode of sulfonic group or large volume side group to improve phosphate adsorption
Amount and proton conductivity, this kind of method of modifying is mostly cumbersome, and proton conductivity raising is limited, and the organic solvent used is to environment
It pollutes, is unfavorable for industrial application.
The common method for preparing apertured polymeric film at present has pore-foaming agent pore, solvent volatilization pore, Polymer-pyrolysis, embedding
Section copolymer self assembly etc..Wherein pore-foaming agent pore is due to causing extensive research interest with universality.And it generallys use
Such as repefral, diethyl phthalate, dibutyl phthalate, diphenyl phthalate, phosphoric acid
The polybenzimidazole membrane that the small organic molecules pore-foaming agent such as triphenylmethyl methacrylate frequently results in pore size in high porosity is micron dimension, hole
Gap is larger, and can not accurately regulate and control the size and distribution in hole, be easy to cause phosphoric acid fast when as phosphate-doped proton exchange membrane
Speed is lost, and declines proton conductivity.
Therefore, exploitation has that nano-pore structure, aperture is adjustable and size distribution is uniform, the simple polyphenyl of preparation method and miaow
Azoles membrane material is of great significance for high-temperature fuel cell proton exchange membrane field.
Summary of the invention
The purpose of the present invention is to provide a kind of polybenzimidazole membrane and preparation method thereof with nano-porous structure.
A kind of preparation method of polybenzimidazole membrane with nano-porous structure of the present invention, its step are as follows:
1) filler dispersion liquid is added in polybenzimidazoles solution, is sufficiently mixed filtering after-pouring in clean glass plate
On, heating removal solvent, to obtain polybenzimidazole membrane on a glass；
2) the obtained polybenzimidazole membrane of step 1) is impregnated certain time in etching agent, is then washed with boiling water de-
Remove residual etching agent, the polybenzimidazole membrane obtained by drying to nano-porous structure of the present invention.
In above-mentioned technical proposal, solvent used in step 1) filler dispersion liquid with it is molten used in polybenzimidazoles solution
Agent is identical, is n,N-dimethylacetamide (DMAc), n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N- methyl
One or more of pyrrolidones (NMP).
In above-mentioned technical proposal, filler described in step 1) is the zeolite that imidazole nitrogen atom and metal Coordinate self-assembly are formed
Imidazate framework material ZIFs series, including ZIF-N nanoparticle (N=1~100, N are integer), the filler size are to receive
Rice or micron dimension, particle diameter distribution is uniform, can regulate and control polyphenyl and miaow by controlling the size and shape of ZIFs nanoparticle
The pore size and form of azoles film, pore size are adjustable in nanometer scale to micron dimension.
It the quality of filler and polybenzimidazoles and is calculated by 100%, the quality of filler in above-mentioned technical proposal, in step 1)
Percentage composition is 1~40%, remaining is polybenzimidazoles；It can be adjusted by adjusting the usage ratio of filler and polybenzimidazoles
Control the porosity of the polybenzimidazole membrane of nano-porous structure and the connected state in hole.
In above-mentioned technical proposal, polybenzimidazoles described in step 1) include mPBI, OPBI, pPBI, phPBI,
SO3PBI、SO2PBI、F6PBI etc..They are that one kind as made of four ammonia monomers and diacid monomer polycondensation has half trapezoidal chemistry knot
The speciality polymer resin of structure, structural formula are as follows:
In above-mentioned technical proposal, ultrasound 30min in polybenzimidazoles solution described in step 1) and filler mixed process~
1h or 8000~12000 rev/min of high-speed stirred 30min~1h makes the two is evenly dispersed to be sufficiently mixed, this step is for prepared
Aperture, form and the pore-size distribution of polybenzimidazole membrane mesoporous have important influence.
In above-mentioned technical proposal, the method for the solvent of heating removal described in step 1) be dry 10 at 75~85 DEG C~
15h, dry 10~15h at 95~105 DEG C, dry 10~15h at 115~125 DEG C, finally vacuumize and do at 115~125 DEG C
Dry 10~15h.
In above-mentioned technical proposal, etching agent described in step 2) is the phosphoric acid of 70%~85% (wt), uses phosphoric acid dip
The temperature of polybenzimidazole membrane be 80 DEG C~200 DEG C, impregnate polybenzimidazole membrane time be for 24 hours more than.
It with the time of boiling water elution etching agent is 1h or more described in step 2), until by film in above-mentioned technical proposal
The ion elution that interior remaining phosphoric acid and part do not exchange is clean.
In above-mentioned technical proposal, filler is etched with phosphoric acid described in step 2) and is carved with boiling water elution residual phosphoric acid
The step of losing agent be repeated 2 times it is above, until the filler is washed off completely.
The present invention using zeolite imidazole ester skeleton ZIFs series material as pore-foaming agent, selection phosphoric acid be etching agent, polyphenyl simultaneously
Nano-pore structure is formed in situ in imidazoles film, due to ZIFs material can by adjust imidazole ligands molecular structure and metal from
The type of son, to obtain different crystalline sizes and pattern, thus prepared porous membrane pore size, hole pattern, aperture point
The connectivity in cloth and hole can regulate and control.
Due to containing imidazole group in polybenzimidazoles main chain in the present invention, contain 2 or 2 in each repetitive unit
Above lewis base property nitrogen-atoms soda acid interaction can occur with phosphoric acid molecules and adsorb a large amount of phosphoric acid molecules, make to gather
Benzimidazole film surface and internal ZIFs nanoparticle pore-foaming agent can come into full contact with phosphoric acid and crystal structure caused to destroy, from
And metal ion and small organic molecule are released, the phosphate and ion and small molecule of generation can be by a large amount of phosphoric acid molecules
It is exchanged with later period boiling water treating, therefore the etching agent that the present invention uses is phosphoric acid.In addition, being handed in high-temperature fuel cell proton
It changes in film application, used proton carrier is also mostly phosphoric acid.
Nanoporous polybenzimidazoles membrane preparation method of the invention has the advantage that (1) preparation process is simple, easily
In industrialization, organic solvent is not necessarily to during pore, the phosphoric acid etching agent of use is low in cost, it is easily recycled recycling,
Reduce disposal of pollutants；(2) zeolite imidazole ester skeleton ZIFs material is used, it can aperture to perforated membrane, hole pattern, hole connectivity
Regulated and controled, pore size can arbitrarily be adjusted as needed in nanometer to micron dimension.(3) polybenzimidazole material is a kind of advanced
Other engineering plastics, have excellent stability and mechanical strength, and decomposition temperature is up to 550 DEG C, the nano-porous structure of preparation
It can keep excellent stability.(4) contain basic group in polybenzimidazoles main chain, phosphoric acid can be adsorbed, and the present invention draws
The nano-pore structure entered provides bigger inner space again, so as to have ultrafast and superelevation phosphate adsorption speed to phosphoric acid
Rate and doped level, and aperture is adjustable as nanometer scale, phosphoric acid not easily runs off, and internal connected pore channel can store phosphoric acid point
Son improves proton conductivity, has in high-temperature fuel cell proton exchange membrane field huge to introduce more free phosphoric acid
Application potential.
Detailed description of the invention
Fig. 1, Fig. 2 are the scanning electrons that nanoporous polybenzimidazoles film amplifies 30000 times and 100000 times in embodiment 1
Microscope cross-section diagram.
Fig. 3 is porous obtained in gained mixed substrate membrane containing nano-grade molecular sieve ZIF-8/OPBI, pure OPBI film and embodiment 1 in comparative example 1
The phosphate adsorption behavior curve graph of film.
Fig. 4 is nanoporous polybenzimidazoles film (porous OPBI) and fine and close polybenzimidazole membrane (OPBI) in embodiment 1
The proton conductivity curve of different temperatures under 120 DEG C of absorption phosphoric acid for 24 hours the same terms.
As shown in figure 3, polybenzimidazoles perforated membrane is phosphate-doped at 24 hours in the phosphate adsorption behavior curve of 3 kinds of films
Level reaches 28, far more than dense film and the mixed substrate membrane containing nano-grade molecular sieve etched without peroxophosphoric acid, and adsorbs water in doping in 1 hour
It is flat just to have reached 16, show its ultrafast phosphate adsorption rate.This is attributed to the porous structure in film with bigger surface
Product enables phosphoric acid molecules to be adsorbed onto film rapidly, a large amount of free phosphoric acid can be accommodated in hole, and then improve proton conductivity.
As shown in figure 4, the proton conductivity of the resulting porous polybenzimidazole membrane of the method for the present invention under the same conditions is wanted
Much higher than the polybenzimidazole membrane of untreated densification.
Specific embodiment
Embodiment 1
1) by the ZIF-8 nanoparticle ultrasonic disperse of size about 100nm in DMAc, it is added to the DMAc solution of OPBI
In, ZIF-8 and OPBI mass ratio are 2:8, ultrasonic disperse and are vigorously stirred, and both make uniformly mixing, are filtered out with 400 mesh filter clothes
Impurity is cast on clean glass plate, 80 DEG C of dry 12h in vacuum drying oven, 100 DEG C of dry 12h, 120 DEG C of dry 12h,
It finally vacuumizes and keeps 120 DEG C of dry 12h, to obtain polybenzimidazole membrane.
2) obtained polybenzimidazole membrane is impregnated for 24 hours in (wt) phosphoric acid 85% at 120 DEG C, then washs 5h with boiling water
Slough residual etching agent, 120 DEG C of dry 12h；Above-mentioned washing, drying process are repeated twice to get the polyphenyl of nano-porous structure
And imidazoles film.
The polybenzimidazole membrane of nano-porous structure obtained in the present embodiment has been subjected to scanning electron microscope characterization,
As depicted in figs. 1 and 2, film section has porous structure and is connected pore channel, and aperture is in 800nm or so；As shown in Figure 3, Figure 4,
Proton conductivity is when 24 hours phosphate-doped horizontal 200 DEG C up to 28,24 hours doping phosphoric acid films under the conditions of 120 DEG C
150mS/cm。
In above-mentioned technical proposal, the method for the solvent of heating removal described in step 2) be dry 10~15h at 75~85 DEG C,
Dry 10~15h at 95~105 DEG C, dry 10~15h at 115~125 DEG C, finally vacuumize dry 10 at 115~125 DEG C
~15h.
Embodiment 2
1) by the ZIF-8 nanoparticle ultrasonic disperse of size about 150nm in DMAc, it is added to the DMAc solution of OPBI
In, ZIF-8 and OPBI mass ratio are 2:8, ultrasonic disperse and are vigorously stirred, and both make uniformly mixing, are filtered out with 400 mesh filter clothes
Impurity is cast on clean glass plate, 80 DEG C of dry 12h in vacuum drying oven, 100 DEG C of dry 12h, 120 DEG C of dry 12h,
It finally vacuumizes and keeps 120 DEG C of dry 12h, to obtain polybenzimidazole membrane.
2) obtained polybenzimidazole membrane is impregnated into 12h in (wt) phosphoric acid 85% at 120 DEG C, then washs 5h with boiling water
Residual etching agent is sloughed, 120 DEG C of dry 12h are to get the polybenzimidazole membrane of nano-porous structure, and aperture is in 850nm or so.
Proton conductivity is when 24 hours phosphate-doped horizontal 200 DEG C up to 25,24 hours doping phosphoric acid films under the conditions of 120 DEG C
115mS/cm。
Embodiment 3
1) by the ZIF-8 nanoparticle ultrasonic disperse of size about 200nm in DMAc, it is added to the DMAc solution of OPBI
In, ZIF-8 and OPBI mass ratio are 1:9, ultrasonic disperse and are vigorously stirred, both make uniformly mixing, filters out impurity with filter cloth,
It casts on clean glass plate, 80 DEG C of dry 12h in vacuum drying oven, 100 DEG C of dry 12h, 120 DEG C of dry 12h finally take out
Vacuum keeps 120 DEG C of dry 12h, to obtain polybenzimidazole membrane.
2) obtained polybenzimidazole membrane is impregnated for 24 hours in (wt) phosphoric acid 85% at 120 DEG C, then washs 5h with boiling water
Residual etching agent is sloughed, 120 DEG C of dry 12h are to get the polybenzimidazole membrane of nano-porous structure, and aperture is in 750nm or so.
Under the conditions of 120 DEG C 24 hours it is phosphate-doped it is horizontal up to 23,24 hours 200 DEG C of doping phosphoric acid film when proton conductivity be
100mS/cm。
Embodiment 4
1) by the ZIF-8 nanoparticle ultrasonic disperse of size about 150nm in DMAc, it is added to the DMAc solution of OPBI
In, ZIF-8 and OPBI mass ratio are 3:7, ultrasonic disperse and are vigorously stirred, both make uniformly mixing, filters out impurity with filter cloth,
It casts on clean glass plate, 80 DEG C of dry 12h in vacuum drying oven, 100 DEG C of dry 12h, 120 DEG C of dry 12h finally take out
Vacuum keeps 120 DEG C of dry 12h, to obtain polybenzimidazole membrane.
2) obtained polybenzimidazole membrane is impregnated for 24 hours in (wt) phosphoric acid 85% at 120 DEG C, then washs 5h with boiling water
Slough residual etching agent, 120 DEG C of dry 12h to get nano-porous structure polybenzimidazole membrane, aperture in 900nm or so,
Under the conditions of 120 DEG C 24 hours it is phosphate-doped it is horizontal up to 25,24 hours 200 DEG C of doping phosphoric acid film when proton conductivity be
110mS/cm。
Embodiment 5
1) by the ZIF-8 nanoparticle ultrasonic disperse of size about 200nm in DMAc, it is added to the DMAc solution of OPBI
In, ZIF-8 and OPBI mass ratio are 3:7, ultrasonic disperse and are vigorously stirred, both make uniformly mixing, filters out impurity with filter cloth,
It casts on clean glass plate, 80 DEG C of dry 12h in vacuum drying oven, 100 DEG C of dry 12h, 120 DEG C of dry 12h finally take out
Vacuum keeps 120 DEG C of dry 12h, to obtain polybenzimidazole membrane.
2) obtained polybenzimidazole membrane is impregnated into 12h in (wt) phosphoric acid 85% at 120 DEG C, then washs 5h with boiling water
Residual etching agent is sloughed, 120 DEG C of dry 12h are to get the polybenzimidazole membrane of nano-porous structure, and aperture is at 1 μm or so.120
Under the conditions of DEG C 24 hours it is phosphate-doped it is horizontal up to 28,24 hours 200 DEG C of doping phosphoric acid film when proton conductivity be
150mS/cm。
Comparative example 1
By the ZIF-8 nanoparticle ultrasonic disperse of size about 100nm in DMAc, it is added in the DMAc solution of OPBI,
ZIF-8 and OPBI mass ratio are 2:8, ultrasonic disperse and are vigorously stirred, and both make uniformly mixing, filter out impurity with filter cloth, pour
Casting is on clean glass plate, 80 DEG C of dry 12h in vacuum drying oven, 100 DEG C of dry 12h, 120 DEG C of dry 12h, finally takes out true
Sky keeps 120 DEG C of dry 12h, obtains mixed substrate membrane containing nano-grade molecular sieve.24 hours phosphate-doped levels are 18,24 hours under the conditions of 120 DEG C
Proton conductivity at 200 DEG C of doping phosphoric acid film is 80mS/cm.
By embodiment 1 obtains the polybenzimidazole membrane of nano-porous structure and comparative example 1 obtains mixed substrate membrane containing nano-grade molecular sieve 120
Phosphoric acid is adsorbed at DEG C, and the variable quantity of phosphoric acid is adsorbed in record 24 hours, obtains Fig. 3 phosphate adsorption behavior curve graph.
From Fig. 3 phosphate adsorption behavior curve can be seen that the resulting perforated membrane of embodiment 1 due to nano aperture, therefore table
The phosphate-doped level for revealing ultrafast phosphate adsorption rate and superelevation can reach ADL (phosphate-doped level) in 1h
For 16 high phosphoric acid adsorbance, and when for 24 hours ADL up to 28.And ZIF-8/OPBI mixed substrate membrane containing nano-grade molecular sieve obtained in comparative example 1
It is less desirable to the absorption behavior of phosphoric acid.
Therefore, the polybenzimidazole membrane of this nano-porous structure has wide in high-temperature fuel cell proton exchange membrane field
Application prospect.
Claims (9)
1. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure, its step are as follows:
1) filler dispersion liquid is added in polybenzimidazoles solution, is sufficiently mixed filtering after-pouring on clean glass plate, adds
Heat abstraction solvent, obtains polybenzimidazole membrane on a glass；Filler is that imidazole nitrogen atom and metal Coordinate self-assembly are formed
One of zeolitic imidazolate framework material ZIFs series ZIF-N nanoparticle, N=1~100, N are integer；Polybenzimidazoles
For mPBI, OPBI, pPBI, phPBI, SO3PBI、SO2PBI or F6PBI；
2) the obtained polybenzimidazole membrane of step 1) is impregnated certain time in etching agent, then washed with boiling water slough it is residual
Stay etching agent, the polybenzimidazole membrane obtained by drying to nano-porous structure；
3) the high temperature proton that the porous polybenzimidazole membrane prepared by can be used for the high proton conductivity of high phosphate-doped level is handed over
Change film.
2. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: solvent used in filler dispersion liquid is identical as solvent used in polybenzimidazoles solution in step 1), is N, N- diformazan
One or more of yl acetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone.
3. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: it the quality of filler and polybenzimidazoles and is calculated by 100% in step 1), the mass percentage of filler is 1~40%,
Remaining is polybenzimidazoles.
4. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: 30min~1h or 8000~12000 rev/min of ultrasound in polybenzimidazoles solution described in step 1) and filler mixed process
Stirring 30min~1h makes the two is evenly dispersed to be sufficiently mixed.
5. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: step 1) method of heating removal solvent be at 75~85 DEG C dry 10~15h, dry 10 at 95~105 DEG C~
15h, dry 10~15h at 115~125 DEG C finally vacuumize dry 10~15h at 115~125 DEG C.
6. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: etching agent described in step 2) is the phosphoric acid of 70%~85% (wt), and the temperature with phosphoric acid dip polybenzimidazole membrane is
80 DEG C~200 DEG C, impregnate polybenzimidazole membrane time be for 24 hours more than.
7. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: described in step 2) with boiling water elution etching agent time be 1h or more, until by phosphoric acid remaining in film and part not
The ion elution exchanged is clean.
8. a kind of preparation method of the polybenzimidazole membrane with nano-porous structure as described in claim 1, feature exist
In: described in step 2) by filler with phosphoric acid etch and with boiling water elute residual phosphoric acid etching agent the step of be repeated 2 times with
On, until the filler is washed off completely.
9. a kind of polybenzimidazole membrane with nano-porous structure, it is characterised in that: be by claim 1~8 any one
The method is prepared.
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| CN110812687A (en) * | 2019-11-18 | 2020-02-21 | 山东君合春医药科技有限公司 | Preparation method of porous polymer microneedle |
| CN113036174A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof |
| CN113036174B (en) * | 2019-12-09 | 2022-05-31 | 中国科学院大连化学物理研究所 | Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof |
| CN112259771A (en) * | 2020-09-16 | 2021-01-22 | 深圳大学 | Proton exchange membrane with wide operating temperature, and preparation method and application thereof |
| CN112259771B (en) * | 2020-09-16 | 2022-02-18 | 深圳大学 | Proton exchange membrane with wide operating temperature, and preparation method and application thereof |
| CN114614060A (en) * | 2022-03-08 | 2022-06-10 | 东北师范大学 | Proton exchange membrane, preparation method and application thereof, and fuel cell comprising proton exchange membrane |
| CN114614060B (en) * | 2022-03-08 | 2023-03-28 | 东北师范大学 | Proton exchange membrane, preparation method and application thereof, and fuel cell comprising proton exchange membrane |
| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
| CN117276611B (en) * | 2023-11-22 | 2024-02-23 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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