CN107903416A - Amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure and preparation method thereof - Google Patents
Amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to ion exchange membrane technology field, discloses a kind of amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure and preparation method thereof.The amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure is dissolved in solvent after being mixed by the poly(aryl ether ketone) of naphthyridine ketone structure containing halomethyl with sulfonation poly(aryl ether ketone) containing naphthyridine ketone structure and prepares Casting solution, striking forms a film, obtain blend support membrane, it is soaked in polyamine or pyridine solution and amination treatment is carried out to halomethyl, is obtained i.e. containing sulfonic acid group and the amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure containing quaternary ammonium group or pyridine groups.Due to containing the diazanaphthalene terphenyl structure of full aromatic ring distortion non-co-planar in polymer molecular chain, there is good chemical stability in strong acid strong oxidizing solution, there is macroion selectivity and conductibility at the same time, there is extraordinary application prospect in all-vanadium flow battery field.
Description
Technical field
The invention belongs to ion exchange membrane technology field, be related specifically to the both sexes of poly(aryl ether ketone) containing naphthyridine ketone structure from
Proton exchange and its preparation method.
Background technology
Amberplex is a kind of polymeric membrane with ion-selective permeability energy, is oozed in electrodialysis, diffusion
Analysis, electrolysis, Proton Exchange Membrane Fuel Cells, flow battery, sensor and other technical fields have been widely used.With
Constantly widening for amberplex application field, it is also increasing to the demand of amberplex function diversification.Ion exchange
The function of film depends mainly on the species of fixed ion cation exchange groups on film, electrically charged electrical and its in film distribution.
Based on the difference of film function, amberplex can be divided into cation-exchange membrane, anion-exchange membrane, Bipolar Membrane, amphion
Exchange membrane etc..Since amphoteric ion exchange membrane contains cation exchange group and anion exchange groups at the same time, had concurrently sun from
The characteristics of proton exchange and anion-exchange membrane, get more and more people's extensive concerning in recent years.
Xi etc. [Journal of Materials Chemistry, 2008,18 (11), 1232-1238] uses electrolyte
Self-assembling technique is in Nafion membrane surface alternating sorbent diallyl dimethyl ammoniumchloride (PDDA) and kayexalate
(PSS) solution is prepared for Nafion- [PDDA-PSS] n multilayer amphoteric ion exchange membranes, have relatively low vanadium ion permeability, compared with
High coulombic efficiency and energy efficiency (compared with Nafion membrane)；Qiu etc. [Journal of Membrane Science,
2009,334 (1-2), 9-15, Journal of Membrane Science, 2009,342 (1-2), 215-219] using radiation
Crosslinking technology is respectively modified pvdf membrane and ETFE as grafted monomers using styrene and Dimethylaminoethyl Methacrylate
Amphoteric ion exchange membrane used for all-vanadium redox flow battery is prepared for, there is higher conductivity and relatively low vanadium ion permeability, institute's group
The coulombic efficiency and energy efficiency for filling all-vanadium flow battery are above Nafion membrane；But current amphoteric ion exchange membrane is still deposited
Preparation process it is more difficult industrialization or film stability it is not good enough the deficiencies of.
With constantly widening for amberplex application field, ion exchange membrane material is also by initial styrene-diethyl
The polymer of alkenyl benzene, expands to isoprene-styrene block copolymer, styrene-butadiene copolymer and fluorine-containing poly-
Compound, and the aromatic polymer such as polysulfones, polyether sulfone, polyphenylene oxide.But industrial circle still cannot be met to amberplex
Requirement, exploitation novel ion exchange membrane be still the hot spot studied both at home and abroad.Poly(aryl ether ketone) containing naphthyridine ketone structure is one
The new polyarylether resin of class, since the diazanaphthalene terphenyl structure of full aromatic ring distortion non-co-planar is introduced main polymer chain
In, assign new Ether Ketone Ketone not only high temperature resistant but also can dissolve, there is superior chemical stability.By containing naphthyridine ketone structure
Anion-exchange membrane of the poly(aryl ether ketone) prepared by by introducing lotus positive charged group or bear electric group, it is saturating to show preferably selection
The property crossed and chemical stability.In amberplex field by with boundless application prospect.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of amphion of poly(aryl ether ketone) containing naphthyridine ketone structure to exchange
Film and preparation method thereof, prepares high stability, macroion selectivity, low-resistance poly(aryl ether ketone) containing naphthyridine ketone structure two
Property amberplex.
Technical scheme：
A kind of amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure, described gathers virtue containing naphthyridine ketone structure
The main knot containing phthalazone by halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure and sulfonation of ether ketone amphoteric ion exchange membrane
Structure poly(aryl ether ketone) is blended, film, inorganic salt solution immersion, amination, acidifying be made；
The skeleton symbol of halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure is as follows：
Wherein：X is Cl or Br；
R1For H, CH3Or CH2X；
Ar is
The halomethyl content of halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure is between 0.2-2.0mmol/g；
The skeleton symbol of sulfonation poly(aryl ether ketone) containing naphthyridine ketone structure is as follows：
Wherein：R2And R3Respectively H and SO3H, H andWith
Ar is
The sulfonic acid group content of sulfonation poly(aryl ether ketone) containing naphthyridine ketone structure is between 0.2-2.0mmol/g.
A kind of amphoteric ion exchange membrane preparation method of poly(aryl ether ketone) containing naphthyridine ketone structure, step are as follows：
1) by halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure and sulfonation, poly(aryl ether ketone) containing naphthyridine ketone structure is mixed
Conjunction, which is dissolved in solvent, prepares casting solution, and after filtering, deaeration, striking film forming, heating evaporation solvent, is then immersed in precipitating reagent and obtains
To blend support membrane；Wherein, halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure and sulfonation polyarylether containing naphthyridine ketone structure
The mass ratio of ketone is 1:99~99:1, the two total concentration in casting solution is 3-30wt%；
2) blend support membrane is soaked in inorganic salt solution, it is sulfonate type to make sulfonic acid Hydrogen group transformations in blend support membrane
Group；Wherein, inorganic salt solution concentration is 0.1-3.0mol/L, and when soaking time is 1-48 small, soaking temperature is 10-50 DEG C；
3) sulfonate type basement membrane is soaked in polynary amine aqueous solution or pyridine solution, makes halomethyl that aminating reaction occur；Its
In, polynary amine aqueous solution or pyridine solution concentration is 5-50wt%, and amination temperature is 5-80 DEG C, when the amination time is 1-72 small；
4) film after amination is soaked in acid solution, neutralizes unreacted polyamine or pyridine, while by sulfonate type
It is changed into sulfonic acid Hydrogen group, then is washed through deionized water, obtains the exchange of the amphion of poly(aryl ether ketone) containing naphthyridine ketone structure
Film；Acid solutions are 0.1-3.0mol/L, 10-60 DEG C of souring temperature, when acidificatoin time 1-36 is small.
The solvent of the casting solution is chloroform, dichloromethane, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, N, N- bis-
One or two or more kinds of mixed solutions in methylacetamide and n-methyl-2-pyrrolidone；The precipitating reagent is water, first
One or two or more kinds of mixed solutions in alcohol, ethanol, propyl alcohol, ether, tetrahydrofuran, acetone, ethyl acetate.
The inorganic salt solution include sodium chloride, sodium sulphate, sodium carbonate, potassium chloride, potassium sulfate, potassium carbonate, magnesium chloride,
One or both of magnesium sulfate solution mixed above, inorganic salt solution concentration are 0.5-2.5mol/L, soaking time 12-36
Hour, soaking temperature is 20-40 DEG C.
The condition of the evaporation of the solvent is：Temperature is 20-150 DEG C, when the time is 0.5-30 small.
The polyamine is ethylenediamine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, 1,1,2,2- tetramethylethylenediamines
In one or two or more kinds of mixtures, amination temperature be 10-50 DEG C, the amination time for 5-60 it is small when.
The acid solution includes one or two or more kinds of mixed aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and acid is molten
The concentration of liquid is 0.5-2.5mol/L, when acidificatoin time is 6-24 small.
The condition of the evaporation of the solvent is：Temperature is 30-90 DEG C, when the time is 0.5-12 small.
Beneficial effects of the present invention：
1) the diazanaphthalene terphenyl knot containing full aromatic ring distortion non-co-planar in polymer molecule segment used in the present invention
Structure, has good chemical stability in strong acid strong oxidizing solution,
2) amphoteric ion exchange membrane of the invention not only containing cation exchange group but also contains anion exchange groups, sun from
Sub- cation exchange groups may advantageously facilitate it is hydrionic conduction, anion exchange groups be conducive to prevent vanadium ion infiltration, make both sexes
Amberplex has macroion selectivity and high ion-conductivity, before having extraordinary application in all-vanadium flow battery field
Scape.
3) modification poly(aryl ether ketone) containing the naphthyridine ketone structure membrane material that the present invention uses, backbone structure is close, compatibility
It is good；Solution blended process film at the same time, preparation process is easy, is easy to carry out industrialized production.
Embodiment
Below by instantiation, technical scheme is further illustrated.Embodiment lists part
The preparation process and performance of amphoteric ion exchange membrane, these examples do not limit this hair just to which the present invention will be described
Bright protection domain.
Embodiment 1
To contain bromomethyl Phthalazinone poly(aryl ether ketone) (BPPEK-80, bromomethyl content 1.76mmol/g) and the miscellaneous naphthalene of sulfonation
Amphoteric ion exchange membrane is made in biphenyl poly(aryl ether ketone) (SPPEK, sulfonic group content 1.37mmol/g) blending：BPPEK-80 and
SPPEK (IEC=1.37mmol/g) is mixed using mass ratio as 9/1,7/3 and 5/5, is dissolved in 1-methyl-2-pyrrolidinone and is matched somebody with somebody
(NMP) casting solution of 13wt.% is made.Then filter, deaeration, striking forms a film on a glass at 60 DEG C, is immersed in the water after 4h
Obtain blend support membrane BPPEK-80/SPPEK.Blend support membrane is soaked in the NaCl solution (25 DEG C) of 1mol/L, 24 it is small when after
Take out in the trimethylamine solution for immersing 33%, aminating reaction 48h at 40 DEG C.Film is put into 0.5mol/L hydrochloric acid after reaction
Unnecessary trimethylamine is removed, is sulfonic acid Hydrogen group by sulfonic acid sodium form group transformations, it is remaining then to clean removing with deionized water
Hydrochloric acid, amphoteric ion exchange membrane will be obtained.Name respectively and be by BPPEK-80/SPPEK (IEC=1.37mmol/g) mass ratio
9/1st, 7/3 and 5/5 made amphoteric ion exchange membrane is QB80/S137-10, QB80/S137-30 and QB80/S137-50.Pass through
Acid base titration method test blend film each component ion exchange capacity, obtain QB80/S137 films quaternary ammonium group component and
Sulfonic acid group component IEC is approached with its theoretical value.The water suction of QB80/S137-10, QB80/S137-30 and QB80/S137-50 film
Rate is respectively 32.0%, 27.2% and 22.4%.QB80/S137-10, QB80/S137-30 and QB80/S137-50 membrane surface resistance
Respectively 0.89 Ω cm2、0.90Ωcm2With 1.33 Ω cm2；Vanadium infiltration coefficient is respectively 4.31 × 10-5cm/min、1.75×10-5Cm/min and 0.25 × 10-5cm/min.Current density 40mA/cm2Lower test QB80/S137 amphoteric ion exchange membranes assemble vanadium
Cell single cells performance, coulombic efficiency (CE), voltage efficiency (VE) and the energy efficiency (EE) of vanadium cell are as shown in table 1.
1 QB80/S137 film vanadium cell performances (40mA/cm of table2)
IECa-M、IECa-TThe respectively ion exchange capacity test value and theoretical value of quaternary ammonium group；IECc-M、IECc-TRespectively
For the ion exchange capacity test value and theoretical value of sulfonic acid group.
Embodiment 2
Bromomethyl Phthalazinone poly(aryl ether ketone) (BPPEK-90, bromomethyl content 1.80mmol/g) and IEC=will be contained
Amphoteric ion exchange membrane is made in the sulfonated polymer SPPEK blendings of 0.7mmol/g：BPPEK-90 and SPPEK (IEC=
0.7mmol/g) mixed by 9/1 and 7/3 of mass ratio, be dissolved in the casting film that 1-methyl-2-pyrrolidinone is configured to 13wt.%
Liquid.Then filter, deaeration, striking forms a film on a glass at 90 DEG C, and blend support membrane BPPEK-90/SPPEK is obtained after 4h.Will be altogether
Mixed radix film is immersed in the NaCl solution (25 DEG C) of 1mol/L, 24 it is small when after take out immerse 33% trimethylamine solution in, 40 DEG C
Lower aminating reaction 48h.Film is put into 0.5mol/L hydrochloric acid after reaction and removes unnecessary trimethylamine, and by sulfonic acid sodium form base
Group is changed into sulfonic acid Hydrogen group, is then cleaned with deionized water and removes remaining hydrochloric acid, will obtain amphoteric ion exchange membrane.Point
It is that 9/1 and 7/3 made amphoteric ion exchange membrane is not name by BPPEK-90/SPPEK (IEC=0.7mmol/g) mass ratio
QB90/S07-10 and QB90/S07-30.The quaternary ammonium group component and sulfonic acid group component IEC of QB90/S07 films and its theoretical value
It is close.The water absorption rate of QB90/S07-10 and QB90/S07-30 films is respectively 30.9% and 23.0%, and surface resistance is respectively 0.78
Ωcm2With 1.38 Ω cm2, vanadium infiltration coefficient is respectively 1.70 × 10-5Cm/min and 0.85 × 10-5cm/min。
2 QB90/S07 film vanadium cell performances (40mA/cm of table2)
IECa-M、IECa-TThe respectively ion exchange capacity test value and theoretical value of quaternary ammonium group；IECc-M、IECc-TRespectively
For the ion exchange capacity test value and theoretical value of sulfonic acid group.
Embodiment 3
Bromomethyl Phthalazinone poly(aryl ether ketone) (BPPEK-70, bromomethyl content 1.45mmol/g) and IEC=will be contained
Amphoteric ion exchange membrane is made in the sulfonated polymer SPPEK blendings of 0.7mmol/g：BPPEK-70 and SPPEK (IEC=
0.7mmol/g) mixed using mass ratio as 9/1,7/3 and 5/5, be dissolved in 1-methyl-2-pyrrolidinone and be configured to 13wt.%'s
Casting solution.Then filter, deaeration, striking forms a film on a glass at 70 DEG C, and blend support membrane BPPEK-70/SPPEK is obtained after 4h.
Blend support membrane is immersed in the NaCl solution (25 DEG C) of 1mol/L 24 it is small when after take out in the trimethylamine solution for immersing 33%, 40
DEG C amination 48h.Film is put into 0.5mol/L hydrochloric acid after reaction and removes unnecessary trimethylamine, is then cleaned with deionized water
Remaining hydrochloric acid is removed, obtains QBPPEK-70/SPPEK (IEC=0.7mmol/g) amphoteric ion exchange membrane.Name respectively by
BPPEK-70/SPPEK (IEC=0.7mmol/g) mass ratio is that 9/1 and 7/3 amphoteric ion exchange membrane prepared is QB70/S07-
10 and QB70/S07-30.The quaternary ammonium group component and sulfonic acid group component IEC of QB70/S07 films are approached with its theoretical value.QB70/
The water absorption rate of S07-10 and QB70/S07-30 films is respectively 20.8% and 16.9%, and membrane surface resistance is respectively 1.00 Ω cm2And
2.30Ωcm2, vanadium infiltration coefficient is respectively 0.85 × 10-5Cm/min and 0.17 × 10-5cm/min.Current density 40mA/cm2Under
The monocell performance of QB70/S07 amphoteric ion exchange membranes assembling vanadium cell is tested, the battery efficiency of vanadium cell is as shown in table 3.
3 QB70/S07 film vanadium cell performances (40mA/cm of table2)
IECa-M、IECa-TThe respectively ion exchange capacity test value and theoretical value of quaternary ammonium group；IECc-M、IECc-TRespectively
For the ion exchange capacity test value and theoretical value of sulfonic acid group.
Embodiment 4
By DCM=1.0mmol/g Phthalazinones containing chloromethyl poly(aryl ether ketone) (CMPPEK) and the sulphur of IEC=1.37mmol/g
Amphoteric ion exchange membrane is made in fluidized polymer SPPEK blendings：CMPPEK and SPPEK (IEC=1.37mmol/g) using mass ratio as
9/1st, 5/5 and 1/9 mixed, be dissolved in the casting solution that 13wt.% is made with (NMP) for 1-methyl-2-pyrrolidinone.Then filter,
Deaeration, striking forms a film on a glass at 70 DEG C, and blend support membrane CMPPEK/SPPEK is obtained after 4h.Blend support membrane is immersed in
In the NaCl solution (25 DEG C) of 1mol/L 24 it is small when after take out immerse 33% trimethylamine solution in, 40 DEG C of amination 48h.Reaction knot
Film is put into 0.5mol/L hydrochloric acid after beam and removes unnecessary trimethylamine, is then cleaned with deionized water and removes remaining hydrochloric acid,
It will obtain QAPPEK/SPPEK (IEC=1.37mmol/g) film.Name respectively by CMPPEK/SPPEK (IEC=1.37mmol/g)
Mass ratio is that the made amberplex in 9/1,7/3 and 5/5 is QA/S137-10, QA/S137-50 and QA/S137-90.QA/
The water absorption rate of S137-10, QA/S137-50 and QA/S137-90 film is respectively 26.9%, 26.0% and 27.7%.QA/S137-
10th, QA/S137-50 and QA/S137-90 membrane surface resistances are respectively 3.89 Ω cm2、2.50Ωcm2With 1.79 Ω cm2.Current density
40mA/cm2The monocell of lower test QAPPEK/SPPEK (IEC=1.37mmol/g) amphoteric ion exchange membrane assembling vanadium cell
Can, the battery efficiency of vanadium cell is as shown in table 4.
Table 4 QAPPEK/SPPEK (IEC=1.37mmol/g) film vanadium cell performance (40mA/cm2)
IECa-M、IECa-TThe respectively ion exchange capacity test value and theoretical value of quaternary ammonium group；IECc-M、IECc-TRespectively
For the ion exchange capacity test value and theoretical value of sulfonic acid group.
Embodiment 5
With IEC it is respectively 1.37mmol/ by DCM=1.0mmol/g Phthalazinones containing chloromethyl poly(aryl ether ketone) (CMPPEK)
G, the SPPEK of 1.70mmol/g and 1.90mmol/g is mixed with mass ratio 5/5, is dissolved in 1-methyl-2-pyrrolidinone and is matched somebody with somebody
(NMP) casting solution of 13wt.% is made.Then filter, deaeration, striking forms a film on a glass at 70 DEG C, is blended after 4h
Basement membrane CMPPEK/SPPEK.Blend support membrane is immersed in the NaCl solution (25 DEG C) of 1mol/L 24 it is small when after take out and immerse 33%
Trimethylamine solution in, 40 DEG C of amination 48h.Film is put into 0.5mol/L HCl after reaction and removes unnecessary trimethylamine,
Cleaned with deionized water and remove remaining hydrochloric acid, obtain amphoteric ion exchange membrane.Respectively name IEC for 1.37mmol/g,
Amphoteric ion exchange membrane QAPPEK/SPPEK films made of the SPPEK of 1.70mmol/g and 1.90mmol/g for QA/S137-50,
QA/S170-50 and QA/S190-50.The water absorption rate of QA/S137-50, QA/S170-50 and QA/S190-50 film is respectively
26.0%th, 30.1 and 33.1%, membrane surface resistance is respectively 3.89 Ω cm2、1.96Ωcm2With 1.81 Ω cm2.Current density 40mA/
cm2The monocell performance of lower test QAPPEK/SPPEK amphoteric ion exchange membranes assembling vanadium cell, coulombic efficiency, the electricity of vanadium cell
Press efficiency and energy efficiency as shown in table 5.
5 QAPPEK/SPPEK film vanadium cell performances (40mA/cm of table2)
IECa-M、IECa-TThe respectively ion exchange capacity test value and theoretical value of quaternary ammonium group；IECc-M、IECc-TRespectively
For the ion exchange capacity test value and theoretical value of sulfonic acid group.
Under the conditions of same test, using the vanadium cell of the amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure assembling
Coulombic efficiency is all higher than the value (95.7%) of Nafion117 films；Number of the energy efficiency near or above the Nafion117 with the conditions of
It is worth (85.7%), illustrates that the amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure has preferable application in terms of vanadium cell
Prospect.
Claims (10)
1. a kind of amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure, it is characterised in that described contains benzodiazine
Ketone structure poly(aryl ether ketone) amphoteric ion exchange membrane mainly contains two by halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure and sulfonation
Azepine naphthalenone structure poly(aryl ether ketone) is blended, film, inorganic salt solution immersion, amination, acidifying be made；
The skeleton symbol of halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure is as follows：
Wherein：X is Cl or Br；
R1For H, CH3Or CH2X；
Ar is
The halomethyl content of halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure is between 0.2-2.0mmol/g；
The skeleton symbol of sulfonation poly(aryl ether ketone) containing naphthyridine ketone structure is as follows：
Wherein：R2And R3Respectively H and SO3H, H and
Ar is
The sulfonic acid group content of sulfonation poly(aryl ether ketone) containing naphthyridine ketone structure is between 0.2-2.0mmol/g.
2. a kind of amphoteric ion exchange membrane preparation method of poly(aryl ether ketone) containing naphthyridine ketone structure, it is characterised in that step is as follows：
1) by halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure and sulfonation, the mixing of poly(aryl ether ketone) containing naphthyridine ketone structure is molten
Solution prepares casting solution in solvent, and after filtering, deaeration, striking film forming, heating evaporation solvent, is then immersed in precipitating reagent and is total to
Mixed radix film；Wherein, halomethylation poly(aryl ether ketone) containing naphthyridine ketone structure and sulfonation poly(aryl ether ketone) containing naphthyridine ketone structure
Mass ratio is 1:99~99:1, the two total concentration in casting solution is 3-30wt%；
2) blend support membrane is soaked in inorganic salt solution, it is sulfonate type base to make sulfonic acid Hydrogen group transformations in blend support membrane
Group；Wherein, inorganic salt solution concentration is 0.1-3.0mol/L, and when soaking time is 1-48 small, soaking temperature is 10-50 DEG C；
3) sulfonate type basement membrane is soaked in polynary amine aqueous solution or pyridine solution, makes halomethyl that aminating reaction occur；Wherein, it is more
First amine aqueous solution or pyridine solution concentration is 5-50wt%, and amination temperature is 5-80 DEG C, when the amination time is 1-72 small；
4) film after amination is soaked in acid solution, neutralizes unreacted polyamine or pyridine, while sulfonate type is changed
For sulfonic acid Hydrogen group, then wash through deionized water, obtain the amphoteric ion exchange membrane of poly(aryl ether ketone) containing naphthyridine ketone structure；Acid
Solution concentration is 0.1-3.0mol/L, 10-60 DEG C of souring temperature, when acidificatoin time 1-36 is small.
3. preparation method according to claim 2, it is characterised in that the solvent of the casting solution is chloroform, dichloromethane, two
One kind in methyl sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and n-methyl-2-pyrrolidone or two kinds with
On mixed solution；The precipitating reagent is water, in methanol, ethanol, propyl alcohol, ether, tetrahydrofuran, acetone, ethyl acetate
One or two or more kinds of mixed solutions.
4. according to the preparation method of Claims 2 or 3, it is characterised in that the inorganic salt solution includes sodium chloride, sulfuric acid
One or both of sodium, sodium carbonate, potassium chloride, potassium sulfate, potassium carbonate, magnesium chloride, magnesium sulfate solution mixed above, inorganic salts
Solution concentration is 0.5-2.5mol/L, and when soaking time is 12-36 small, soaking temperature is 20-40 DEG C.
5. preparation method according to claim 4, it is characterised in that the condition of the evaporation of the solvent is：Temperature is 20-150
DEG C, when the time is 0.5-30 small.
6. according to the preparation method of claim 2,3 or 5, it is characterised in that the polyamine is ethylenediamine, trimethylamine, three
Ethamine, tripropyl amine (TPA), tri-n-butylamine, 1, one or two or more kinds of mixtures in 1,2,2- tetramethylethylenediamine, amination temperature are
10-50 DEG C, when the amination time is 5-60 small.
7. preparation method according to claim 6, it is characterised in that the acid solution includes hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid
One or two or more kinds of mixed aqueous solutions, the concentration of acid solution is 0.5-2.5mol/L, acidificatoin time for 6-24 it is small when.
8. according to the preparation method of claim 2,3,5 or 7, it is characterised in that the condition of the evaporation of the solvent is：Temperature is
30-90 DEG C, when the time is 0.5-12 small.
9. preparation method according to claim 4, it is characterised in that the condition of the evaporation of the solvent is：Temperature is 30-90
DEG C, when the time is 0.5-12 small.
10. preparation method according to claim 6, it is characterised in that the condition of the evaporation of the solvent is：Temperature is 30-90
DEG C, when the time is 0.5-12 small.
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| CN109876678A (en) * | 2019-04-02 | 2019-06-14 | 浙江迪萧环保科技有限公司 | A kind of bipolar membrane and preparation method |
| CN111499916A (en) * | 2020-05-12 | 2020-08-07 | 福建师范大学 | Preparation method of monolithic polyaryletherketone bipolar membrane with phthalocyanine group-containing side group |
| CN111499916B (en) * | 2020-05-12 | 2022-05-06 | 福建师范大学 | Preparation method of monolithic polyaryletherketone bipolar membrane with phthalocyanine group-containing side group |
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