CN104437145A - Method for preparing zwitterion membrane by use of alkaline anion exchange membrane solution and acid cation exchange membrane solution - Google Patents
Method for preparing zwitterion membrane by use of alkaline anion exchange membrane solution and acid cation exchange membrane solution Download PDFInfo
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Abstract
The invention relates to the technical field of membrane and discloses a method for preparing a zwitterion membrane by use of alkaline anion exchange membrane solution and acid cation exchange membrane solution. The acid cation exchange membrane solution is prepared from polyving alcohol (PVA) and polysilicon copolymer containing -COOH group or acid-type sulfonated polyphenylene oxide containing -SO3 group; the alkaline anion exchange membrane solution is prepared from PVA, alkaline ammonium polyphenylene oxide containing -N+(CH3)3OH- group and micromolecule alkoxyl silane crosslinking agent. The acid cation exchange membrane solution and the alkaline anion exchange membrane solution are blended through pre-sol-gel reaction, so that the acid group (-COOH or -SO3) can be combined with the alkaline group (-N+(CH3)3OH-) to form an ion pair, and a self-assembly structure is formed through combination of ionic bonds, therefore, the zwitterion membrane has a closely-connected ion pair structure and the stability and the separating property of the membrane can be improved.
Description
Technical field
The invention belongs to membrane preparation technology field, relate to a kind of method utilizing alkaline cavity block liquid and acid anode membrane liquid to prepare amphion film, the ionic bond effect specifically by basic group and acidic-group forms amphion film.
Background technology
Double cation cation exchange groups and anion exchange groups in amphion film, cation exchange group is generally-SO
3 -na
+with-COOH, anion exchange groups is generally-N
+r
3x
-(X represents halogen).Except-COOH group, all the other groups do not have obvious Acidity of Aikalinity.Therefore, in the amphion film of routine, between group, only there is the weak force such as hydrogen bond and electrostatic attraction, lack strong ionic bond active force, make to be difficult between ion-exchange group in film form self-assembled structures, ion-exchange group presents random distribution state to a great extent in film.
Chinese Patent Application No. 200710021240X discloses a kind of hybrid inorganic-organic amphion to the preparation method of membrane material, first carrying out aminating reaction to presoma makes it contain a kind of anion exchange groups, and then carry out sulfonation or oxidation reaction makes it contain a kind of cation exchange group, namely obtain amphion simultaneously containing anions and canons cation exchange groups to film.In film, ion-exchange group is arranged on molecular backbone or main chain both sides, the better softness of film, but owing to adopting Small molecular reaction film forming, film strength and homogeneity deficiency, in film, anions and canons cation exchange groups is not containing obvious Acidity of Aikalinity, without strong ionic bond active force between group.
Chinese Patent Application No. 2013101938772 discloses a kind of preparation method of quaternized amphion film, first utilizes dibasic monomer solution to carry out irradiation grafting to commercial membranes, introduces sulfonic acid group and quaternized ammonium groups, then film is soaked hydrochloric acid solution, generation-SO
3h and-N
+r
3cl
-group.Film preparation process steps is simple, but irradiation grafting needs specific equipment and environment, there is no strong ionic bond active force between group.
" deleterious material magazine " (Journal ofHazardousMaterials, 173,2010,438 – 444) report and utilize the Small molecular containing bisgallic acid anhydride group to carry out chemical reaction with containing the Small molecular silane of-NH-group, obtain holding concurrently containing-COOH and-N
+r
3br
-the amphion film of group.Material prepared by the method can be applicable to adsorb Pb
2+ion, but owing to adopting Small molecular to carry out chemical reaction in preparation process always, the activity of-NH-, acid anhydrides and bromoethane is low, and the extent of reaction is not high, makes product lack pliability and film forming ability, can only form the irregular material of fragility.
" deleterious material magazine " (Journal ofHazardous Materials, 261,2013,114 – 122) report and utilize two kinds of film liquid, containing-SO in a kind of film liquid
3na group, containing N in a kind of film liquid
+r
3cl
-group, two kinds of blended rear formation composite membranes of film liquid.Two kinds of groups are random distribution to a great extent in film, be difficult to form ion pair form, be difficult to form self-assembled structures between group
Summary of the invention
The object of the present invention is to provide a kind of method utilizing alkaline cavity block liquid and acid anode membrane liquid to prepare amphion film, it is characterized in that, comprise the following steps:
Step one, prepare alkaline cavity block liquid: select bromine type ammonium polyphenylene oxide to heat 2 – 8h 60 – 110 DEG C, be soaked in 1 – 6h in 0.5 – 2mol/LNaOH solution again, be immersed in after taking-up in water, and water is changed 3-8 time in 2 – 6h, dry 1 – 6 days in sealed environment, being dissolved in volume ratio is N, dinethylformamide: form the alkaline ammonium polyphenylene oxide solution that mass concentration is 0.08 – 0.20g/mL in the mixed solvent of ethanol=1:0.2-0.6, be alkaline ammonium polyphenylene oxide in mass ratio: crosslinking agent=1:0.12 – 0.47 adds crosslinking agent in alkaline ammonium polyphenylene oxide solution, at 25 –, 50 DEG C of stirring reaction 1 – 6h, obtain hydridization alkalescence ammonium polyphenylene oxide solution, be hydridization alkalescence ammonium polyphenylene oxide in mass ratio: it is 25 – 65 DEG C that hydridization alkalescence ammonium polyphenylene oxide solution is added dropwise to temperature by polyvinyl alcohol=1:0.3-0.8 in 0.5 – 1.5h, mass concentration is in the polyvinyl alcohol water solution of 3% – 5%, dropwise rear continuation at 25 –, 65 DEG C of stirring reaction 12-36h.
Step 2, prepare acid anode membrane liquid: be acid macromolecule in mass ratio: acid macromolecule is added dropwise in 0.5-1.5h that temperature is 25 – 65 DEG C, mass concentration is in the poly-vinyl alcohol solution of 3% – 5% by polyvinyl alcohol=0.3-0.8:1, dropwises rear continuation at 25 –, 65 DEG C of stirring reaction 12-36h.
Step 3, prepare amphion film: by Solute mass than being alkaline cavity block liquid: alkaline cavity block liquid is added dropwise in the acid anode membrane liquid of 25 – 65 DEG C by acid anode membrane liquid=0.4 – 2.5 in 0.2 – 1h, dropwise rear continuation and stir 12 – 36h 25 – 65 DEG C, film is on matrix, be dried in room temperature ventilated environment and form uniform and stable gel layer and diaphragm, diaphragm is taken off from matrix, diaphragm is placed in the environment of 60-80 DEG C, with the ramp of 5-15 DEG C/h to 120-140 DEG C, and at 120-140 DEG C of insulation 2-8h, obtained of the present invention have amphion film.
Described crosslinking agent is selected from two kinds of silane in the tetramethoxy-silicane of equimolar amounts, tetraethoxysilane, phenyl triethoxysilane and phenyltrimethoxysila,e.
Described acid macromolecule comprises Hydrogen sulfonated poly (phenylene oxide) or the many siliceous copolymers containing-COOH group.
Described matrix comprises glass plate, polyfluortetraethylene plate, aluminium sheet or polyvinyl chloride panel.
The present invention first prepares a kind of containing-N
+(CH
3)
3oH
-the alkaline cavity block liquid of group ,-N
+(CH
3)
3oH
-group can dissociate has alkaline OH
-counter ion; Preparation is a kind of containing-SO again
3the acid anode membrane liquid of H or-COOH group ,-SO
3h and-COOH group can dissociate acid H
+counter ion.When blended alkaline cavity block liquid and acid anode membrane liquid, OH
-and H
+can be there is neutralization reaction and generate water in counter ion, impel between two kinds of groups and form ionic bond, produces ion pair form and self-assembled structures, i.e.-N
+(CH
3)
3sO
3 -or-N
+(CH
3)
3cOO
-structure.This ion pair form will produce cooperative effect to effects of ion absorption, ion transport, improve stability and the separating power of film.
Detailed description of the invention
Set forth the present invention further below in conjunction with specific embodiment, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1: utilize many siliceous copolymers to prepare acid anode membrane liquid and amphion film
(1) raw material prepares:
1) preparation of bromine type ammonium polyphenylene oxide (QPPO-Br): preparation method is with reference to the report of " membrane science magazine " (Journalof Membrane Science, 347,2010,240-249).Getting the Benzylphosphonium Bromide degree that 6g Shandong Tian Weimo company produces is the brominated polyphenylether of 53.1%, is dissolved in chlorobenzene and forms the solution that concentration is 0.25g/mL, then add DMF (DMF) and form the dilution that concentration is 0.10g/mL; In dilution, drip trimethylamine/ethanolic solution that 16mL concentration is 0.2g/mL, stir simultaneously, time for adding is 0.5h.After dropwising, be warming up to 55 DEG C of stirring reaction 18h, on a glass, under ventilation room temperature environment, drying 1 day, takes off in solution coating.
2) dissolving of polyvinyl alcohol (PVA): PVA is from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group, the degree of polymerization is 1750 ± 50, get 42.4g PVA solid, to be soaked in 760mL water one day, under agitation, with the ramp of 8 DEG C/h to 102 DEG C, at 102 DEG C of insulations, 2.5 hours (h), obtain the solution of homogeneous transparent, for subsequent use after being cooled to room temperature, the mass concentration of solution is 5%.Separately get 480mL solution add 160mL water dilution stir, obtain the solution that mass concentration is 3.75%.
3) preparation of many siliceous copolymers, raw materials and method bibliography report (J.W.Hao, M.Gong, Y.H.Wu, C.M.Wu, J.Y.Luo, T.W.Xu, Alkali recovery using PVA/SiO
2cationexchange membranes with different – COOH contents, Journal ofHazardous Materials, 244-245,2013,348-356).Under waterproof condition, mixing 18.3g acrylic acid (AA, 0.255mol), 10.7mL methacrylic acid trimethoxy silicon propyl ester (KH-570,0.045mol), 0.786g azodiisobutyronitrile, 360mL toluene and 120mL DMF, 70 DEG C of stirring reaction 24h, remove solvent toluene by rotary evaporation, obtain the many siliceous copolymers containing-COOH group that mass concentration is 0.17g/mL.
(2) preparation of alkaline cavity block liquid: QPPO-Br is at 60 DEG C of heating 5h, get 35g and be soaked in 4h in 0.5mol/LNaOH solution, distilled water immersion 4h is used after taking out, water is changed 6 times between soak period, put into the desiccator 3 days with drier, be dissolved in 100mL DMF and 40mL ethanol again, obtain the QPPO-OH solution that mass concentration is 0.14g/mL, 4.46mL tetraethoxysilane (0.02mol) and 4.83mL phenyl triethoxysilane (0.02mol) is added in solution, at 50 DEG C of stirring reaction 1h, obtain QPPO-OH/SiO
2solution (32.7g), solution is instilled in 1h temperature is 50 DEG C, volume is 640mL, mass concentration is (24g) in the PVA solution of 3.75%, keep in dropping process stirring, after dropwising, continue at 50 DEG C of stirring reaction 24h, recording solution concentration is 0.062g/mL.
(3) preparation of acid anode membrane liquid: 73.5mL many siliceous copolymers solution (12.5g) is added dropwise in 0.5h temperature is 65 DEG C, volume is 360mL, mass concentration is in the PVA solution of 5%, keep in dropping process stirring, after dropwising, continue at 65 DEG C of stirring reaction 24h, the concentration recording solution is 0.065g/mL.
(4) preparation of amphion film: 161.3mL alkalescence cavity block liquid (10g) is added dropwise in 1h acid anode membrane liquid (10g) of 50 DEG C of 153.8mL, keep in dropping process stirring, after dropwising, continue at 50 DEG C of stirring reaction 24h, film on a glass, volatilize 2 days under room temperature ventilated environment, form uniform and stable gel layer and diaphragm, diaphragm is taken off from glass plate, heat up from 60 DEG C in an oven, heating rate is 10 DEG C/h, until 130 DEG C and 130 DEG C insulation 4h, obtain amphion film.
(5) obtained above-mentioned amphion film is tested as follows:
1) film outward appearance: transparency and the homogeneity of being observed film by digital photograph, measure the average thickness of film by slide measure.
2) water content: operation is all at room temperature carried out, and clip one piece of weight is m
1diaphragm, m
1scope at 0.10-0.30 gram, be immersed in water after 2 days, take out diaphragm, dry the water of membrane surface with filter paper, the gravimetric value obtained after weighing is designated as m
2.Water content=(the m of diaphragm
2-m
1) × 100%/m
1.
3) anion-exchange capacity (IEC-is cloudy): operation is all at room temperature carried out, and clip one piece of weight is m
1diaphragm, m
1scope at 0.15-0.25g, be immersed in 80mL 1mol/L NaCl solution after 2 days, take out diaphragm, between soak period, change water 4 times with distilled water immersion 24h, be finally soaked in 80mL 0.5mol/LNa
2sO
4in solution 2 days; With the K of 0.05g/mL
2crO
4for indicator, use 0.1mol/LAgNO
3to the Na soaking membrane sample
2sO
4solution carries out titration, until the color from yellow of solution becomes field gray, and the AgNO that record consumes
3volume V.IEC-the moon=(0.1 × V)/m
1, unit mmol/g.
4) cation exchange capacity (IEC-sun): operation is all at room temperature carried out, and clip one piece of weight is m
1diaphragm, m
1scope at 0.15-0.40g, be soak after 2 days in the HCl of 1mol/L in concentration, take out diaphragm, in soak period, water is changed 4 times with distilled water immersion one day, diaphragm being immersed in 80mL concentration is in the NaOH solution of 0.04mol/L two days again, with phenolphthalein indicator, be that the HCl of 0.04mol/L carries out back titration to the NaOH solution after immersion by concentration.IEC-sun=the molal quantity of the HCl of 0.04mol/L (concentration to be the molal quantity-concentration of the KOH of 0.04mol/L be)/m
1.
5) the swelling test of water resistant: clip one piece of weight range, at the diaphragm of 0.15-0.30g, is immersed in 192h in the water of 65 DEG C, dry the water on surface, weighing weight in wet base is m
1.Dried to constant weight at 85 DEG C by wet sample, again weighing dry weight is m
2.The swellbility of calculation sample is (m
1– m
2) × 100%/m
2.
6) alkali resistance test, weighs the diaphragm of one piece of weight range at 0.15-0.30g, is immersed in 60h in 65 DEG C of 2mol/LNaOH, then washes 4 times in 12h, dries the moisture of membrane surface, weigh and be designated as m with filter paper
1, the sample that will wet is dried to constant weight at 85 DEG C, and note weight is designated as m
2.The swellbility of calculation sample is (m
1– m
2) × 100%/m
2.
7) diffusion dialysis: be separated HCl/FeCl by diffusion dialysis
2the method that the test employing of solution is consistent with Chinese patent CN201210206572.6, by diffusion dialysis NaOH separating/NaAlO
2the method that test adopts and " membrane science magazine " (Journal of Membrane Science, 469,2014,436 – 446) are consistent of solution, measures dialysis coefficent and the separation factor of film.
Test result shows: the amphion film yellow homogeneous prepared by the present embodiment, thickness 135 μm, and water content is 59.0%; IEC-the moon is 1.61mmol/g, IEC-sun is 2.42mmol/g, illustrates in film and holds concurrently containing anion exchange groups and cation exchange group, have amphion film feature.
The swellbility of film in 65 DEG C of water after 192h is 122.8%; The swellbility of film in 65 DEG C of 2mol/L NaOH after 60h is 154.4%.Therefore, the amphion film prepared by the present embodiment has good swelling resistance.
Film is separated HCl/FeCl by diffusion dialysis
2result show, during room temperature, the dialysis coefficent of HCl is 0.0283m/h, and separation factor is 13.6.Relative to business cavity block DF-120 (0.009m/h, 18.5), film has slightly low separation factor and the dialysis coefficent of Geng Gao.Film is by diffusion dialysis NaOH separating/NaAlO
2result show, during room temperature, NaOH dialysis coefficent is 0.0083m/h, and separation factor is 20.6, is better than the separating resulting (0.0029m/h, 8.2) of business anode membrane SPPO.
Comprehensive above test result, known the present embodiment obtains the amphion film had good stability, and can be separated acid solution can be separated alkaline solution again by diffusion dialysis, reaches the object reclaiming acid or alkali.
Embodiment 2: low consumption crosslinking agent and alkaline cavity block liquid prepare amphion film
(1) raw material prepares: the preparation of QPPO-Br and many siliceous copolymers and the dissolving of PVA are with embodiment 1.Separately get 300mL mass concentration be 5% PVA solution add 200mL water dilution stir, obtain the solution that mass concentration is 3%.
(2) preparation of alkaline cavity block liquid: QPPO-Br is at 90 DEG C of heating 8h, get 35g and be soaked in 1h in 2mol/LNaOH solution, distilled water immersion 2h is used after taking out, water is changed 8 times between soak period, put into the desiccator that vacuumizes with drier, room temperature 1 day, be dissolved in 80mL DMF and 16mL ethanol again, obtain the QPPO-OH solution that mass concentration is 0.20g/mL, 1.49mL tetramethoxy-silicane (0.01mol) and 1.87mL phenyltrimethoxysila,e (0.01mol) is added in solution, at 25 DEG C of stirring reaction 6h, obtain QPPO-OH/SiO
2solution (30.8g), solution is instilled in 0.5h temperature is 65 DEG C, volume is 492mL, mass concentration is (24.6g) in the PVA solution of 5%, keep in dropping process stirring, after dropwising, continue at 65 DEG C of stirring reaction 12h, recording solution concentration is 0.086g/mL.
(3) preparation of acid anode membrane liquid: 73.5mL many siliceous copolymers solution (12.5g) is added dropwise in 1.5h temperature is 25 DEG C, volume is 520.8mL, mass concentration is in the PVA solution of 3%, keep in dropping process stirring, after dropwising, continue at 25 DEG C of stirring reaction 36h, the concentration recording solution is 0.048g/mL.
(4) preparation of amphion film: 46.5mL alkalescence cavity block liquid (4g) is added dropwise in 0.2h acid anode membrane liquid (10g) of 25 DEG C of 209mL, keep in dropping process stirring, after dropwising, continue at 25 DEG C of stirring reaction 36h, film is on aluminium sheet, volatilize 3 days under room temperature ventilated environment, form uniform and stable gel layer and diaphragm, diaphragm is taken off from aluminium sheet, heat up from 80 DEG C in an oven, heating rate is 5 DEG C/h, until 120 DEG C and 120 DEG C insulation 8h, obtain amphion film.
(5) test shows, the amphion film yellow homogeneous prepared by the present embodiment, thickness 90 μm, and water content is 71.3%; IEC-the moon is 0.62mmol/g, IEC-sun is 2.91mmol/g.The swellbility of film in 65 DEG C of water after 192h is 154.9%; The swellbility of film in 65 DEG C of 2mol/LNaOH after 60h is 181.6%.
Film is separated HCl/FeCl by diffusion dialysis
2result show, during room temperature, the dialysis coefficent of HCl is 0.0195m/h, and separation factor is 22.7.Film is by diffusion dialysis NaOH separating/NaAlO
2result show, during room temperature, NaOH dialysis coefficent is 0.0110m/h, and separation factor is 18.4.
Compare visible by above test result with embodiment 1, because the present embodiment reduces the consumption of dosage of crosslinking agent and alkaline cavity block liquid, film swellbility in water is increased, and the dialysis coefficent of separating acid reduces, and the dialysis coefficent being separated alkali increases; And separation factor is contrary with dialysis coefficent variation tendency.
Embodiment 3: utilize acid type sulfonated poly (phenylene oxide) (SPPO-H) to prepare acid anode membrane liquid and amphion film
(1) preparation of raw material
1) preparation of QPPO-Br is with embodiment 1; The dissolving similar embodiment 1 of PVA, is just soaked in 960mL water by 42.4g PVA, after heating stirring and dissolving, obtains the solution that mass concentration is 4%.
2) preparation of SPPO-H solution, by 20g Chinese herbal medicine shape sodium form sulfonated poly (phenylene oxide) (SPPO-Na, Shandong Tianwei Membrane Technology Co., Ltd. produces) to be immersed in 500mL 1mol/L HCl 2 days, period changes HCl once, the remaining HCl of 6 removings is washed again in 2 days, putting after taking-up ventilates on a glass dries 3 days, is dissolved in DMF and forms the SPPO-H solution that mass concentration is 0.20g/mL.
(2) preparation of alkaline cavity block liquid: QPPO-Br is at 110 DEG C of heating 2h, get 35g and be soaked in 6h in 1mol/LNaOH solution, distilled water immersion 6h is used after taking out, water is changed 3 times between soak period, put into room temperature desiccator 6 days, be dissolved in 185mL DMF and 111mL ethanol again, obtain the QPPO-OH solution that mass concentration is 0.08g/mL, 6.69mL tetraethoxysilane (0.03mol) and 7.24mL phenyl triethoxysilane (0.03mol) is added in solution, at 40 DEG C of stirring reaction 3h, obtain QPPO-OH/SiO
2solution (34.6g), solution is instilled in 1.5h temperature is 25 DEG C, volume is 260mL, mass concentration is (10.4g) in the PVA solution of 4%, keep in dropping process stirring, after dropwising, continue at 25 DEG C of stirring reaction 36h, recording solution concentration is 0.075g/mL.
(3) preparation of acid anode membrane liquid: get 30mL SPPO-H solution and be added dropwise in PVA (20g) solution that temperature is 60 DEG C, mass concentration is 4%, volume is 500mL in 0.6h, stir in dropping process simultaneously, dropwise rear continuation and stir 12h at 60 DEG C, the density measuring solution is 0.050g/mL.
(4) preparation of amphion film: get 133mL alkalescence cavity block liquid (10g), be added dropwise in 65 DEG C of acid anode membrane liquid of 80mL (4g) in 0.5h, keep stirring in dropping process, after dropwising, continue at 65 DEG C of stirring reaction 12h, film is on polyvinyl chloride panel, volatilize 2 days under room temperature ventilated environment, form uniform and stable gel layer and diaphragm, take diaphragm off from polyvinyl chloride panel, heat up from 70 DEG C in an oven, heating rate is 10 DEG C/h, until 130 DEG C and 130 DEG C insulation 5h, obtain amphion film.
Test result shows: the film thickness prepared by the present embodiment is 95 μm, and water content is 78.4%; IEC-sun is 0.87mmol/g, IEC-the moon is 1.78mmol/g, illustrates that film has amphion film feature.The swellbility of film in 65 DEG C of 2mol/L NaOH solution after 60h is 252.0%.
Diffusion dialysis is separated HCl/FeCl
2test shows, during room temperature, the sour dialysis coefficent of film is 0.0162m/h, and separation factor is 37.6.Diffusion dialysis NaOH separating/NaAlO
2test shows, during room temperature, the alkali dialysis coefficent of film is for being 0.0071m/h, and separation factor is 16.2.
Embodiment 4: high-temperature heat treatment prepares amphion film
(1) preparation of raw material: the preparation of QPPO-Br and SPPO-H solution is with embodiment 1; The dissolving similar embodiment 1 of PVA, is just soaked in 647mL water by 21.2g PVA, after heating stirring and dissolving, obtains the solution that mass concentration is 3%.
(2) preparation of alkaline cavity block liquid: QPPO-Br is at 100 DEG C of heating 5h, get 35g and be soaked in 4h in 1mol/LNaOH solution, distilled water immersion 3h is used after taking out, water is changed 4 times between soak period, put into room temperature in vacuo case 3 days, be dissolved in 120mL DMF and 60mL ethanol again, obtain the QPPO-OH solution that mass concentration is 0.12g/mL, 2.98mL tetramethoxy-silicane (0.02mol) and 3.74mL phenyltrimethoxysila,e (0.02mol) is added in solution, at 30 DEG C of stirring reaction 4h, obtain QPPO-OH/SiO
2solution (32.2g), solution is instilled in 1h temperature is 40 DEG C, volume is 644mL, mass concentration is (19.3g) in the PVA solution of 3%, keep in dropping process stirring, after dropwising, continue at 40 DEG C of stirring reaction 18h, the mass concentration recording solution is 0.059g/mL.
(3) preparation of acid anode membrane liquid: get 45mL SPPO-H (9g) solution and be added dropwise in PVA (18g) solution that temperature is 40 DEG C, mass concentration is 3%, volume is 600mL in 1h, stir in dropping process simultaneously, dropwise rear continuation and stir 18h at 40 DEG C, the density measuring solution is 0.043g/mL.
(4) preparation of amphion film: get 254mL alkalescence cavity block liquid (15g), be added dropwise in 40 DEG C of acid anode membrane liquid of 233mL (10g) in 1h, keep stirring in dropping process, after dropwising, continue at 40 DEG C of stirring reaction 18h, film is on polyfluortetraethylene plate, volatilize 3 days under room temperature ventilated environment, form uniform and stable gel layer and diaphragm, take diaphragm off from polyfluortetraethylene plate, heat up from 60 DEG C in an oven, heating rate is 15 DEG C/h, until 140 DEG C and 140 DEG C insulation 2h, obtain amphion film.
Test result shows: the film thickness prepared by the present embodiment is 85 μm, and water content is 54.2%; IEC-sun is 1.32mmol/g, IEC-the moon is 1.36mmol/g.The swellbility of film in 65 DEG C of water after 192h is 178.0%.The swellbility of film in 65 DEG C of 2mol/L NaOH solution after 60h is 185.6%.Diffusion dialysis is separated HCl/FeCl
2test shows, during room temperature, the sour dialysis coefficent of film is 0.0144m/h, and separation factor is 40.5.Diffusion dialysis NaOH separating/NaAlO
2test shows, during room temperature, the alkali dialysis coefficent of film is for being 0.0067m/h, and separation factor is 22.7.
Comprehensive above test result, after the heat treatment temperature (140 DEG C) of known raising film, swellbility and the dialysis coefficent of film all decline, but separation factor rises.
Claims (4)
1. utilize alkaline cavity block liquid and acid anode membrane liquid to prepare a method for amphion film, it is characterized in that: comprise the following steps:
Step one, prepare alkaline cavity block liquid: select bromine type ammonium polyphenylene oxide to heat 2 – 8h 60 – 110 DEG C, be soaked in 1 – 6h in 0.5 – 2mol/LNaOH solution again, be immersed in after taking-up in water, and water is changed 3-8 time in 2 – 6h, dry 1 – 6 days in sealed environment, being dissolved in volume ratio is N, dinethylformamide: form the alkaline ammonium polyphenylene oxide solution that mass concentration is 0.08 – 0.20g/mL in the mixed solvent of ethanol=1:0.2-0.6, be alkaline ammonium polyphenylene oxide in mass ratio: crosslinking agent=1:0.12 – 0.47 adds crosslinking agent in alkaline ammonium polyphenylene oxide solution, at 25 –, 50 DEG C of stirring reaction 1 – 6h, obtain hydridization alkalescence ammonium polyphenylene oxide solution, be hydridization alkalescence ammonium polyphenylene oxide in mass ratio: it is 25 – 65 DEG C that hydridization alkalescence ammonium polyphenylene oxide solution is added dropwise to temperature by polyvinyl alcohol=1:0.3-0.8 in 0.5 – 1.5h, mass concentration is in the polyvinyl alcohol water solution of 3% – 5%, dropwise rear continuation at 25 –, 65 DEG C of stirring reaction 12-36h.
Step 2, prepare acid anode membrane liquid: be acid macromolecule in mass ratio: acid macromolecule is added dropwise in 0.5-1.5h that temperature is 25 – 65 DEG C, mass concentration is in the poly-vinyl alcohol solution of 3% – 5% by polyvinyl alcohol=0.3-0.8:1, dropwises rear continuation at 25 –, 65 DEG C of stirring reaction 12-36h.
Step 3, prepare amphion film: by Solute mass than being alkaline cavity block liquid: alkaline cavity block liquid is added dropwise in the acid anode membrane liquid of 25 – 65 DEG C by acid anode membrane liquid=0.4 – 2.5 in 0.2 – 1h, dropwise rear continuation and stir 12 – 36h 25 – 65 DEG C, film is on matrix, be dried in room temperature ventilated environment and form uniform and stable gel layer and diaphragm, diaphragm is taken off from matrix, diaphragm is placed in the environment of 60-80 DEG C, with the ramp of 5-15 DEG C/h to 120-140 DEG C, and at 120-140 DEG C of insulation 2-8h, obtained of the present invention have amphion film.
2. a kind of method utilizing alkaline cavity block liquid and acid anode membrane liquid to prepare amphion film as claimed in claim 1, it is characterized in that, described crosslinking agent is selected from two kinds of silane in the tetramethoxy-silicane of equimolar amounts, tetraethoxysilane, phenyl triethoxysilane and phenyltrimethoxysila,e.
3. a kind of method utilizing alkaline cavity block liquid and acid anode membrane liquid to prepare amphion film as claimed in claim 2, is characterized in that, described acid macromolecule comprises Hydrogen sulfonated poly (phenylene oxide) or the many siliceous copolymers containing-COOH group.
4. a kind of method utilizing alkaline cavity block liquid and acid anode membrane liquid to prepare amphion film as claimed in claim 3, it is characterized in that, described matrix comprises glass plate, polyfluortetraethylene plate, aluminium sheet or polyvinyl chloride panel.
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| CN201410634673.2A CN104437145B (en) | 2014-11-12 | 2014-11-12 | A method of amphoteric ion film is prepared using alkaline cavity block liquid and acid anode membrane liquid |
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| CN106040013A (en) * | 2016-06-24 | 2016-10-26 | 盐城师范学院 | Bipolar membrane and preparation method thereof |
| CN106139926A (en) * | 2016-07-13 | 2016-11-23 | 合肥工业大学 | Polyelectrolyte composite membrane, its preparation method and the method for diffusion dialysis desalination |
| CN106334588A (en) * | 2016-10-27 | 2017-01-18 | 刘昊天 | Ionic membrane |
| CN106519272A (en) * | 2016-10-27 | 2017-03-22 | 刘昊天 | Preparation method of ionic membrane |
| CN106519273A (en) * | 2016-10-27 | 2017-03-22 | 刘昊天 | Anionic membrane |
| CN114364450A (en) * | 2019-09-13 | 2022-04-15 | 东洋纺株式会社 | Composite film and method for producing composite film |
| CN115926425A (en) * | 2022-12-14 | 2023-04-07 | 武汉轻工大学 | Cross-linked anion exchange membrane and preparation method thereof |
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| US7119126B2 (en) * | 1999-02-26 | 2006-10-10 | Evionyx, Inc. | Polymer matrix material |
| CN101138707A (en) * | 2007-08-02 | 2008-03-12 | 中国科学技术大学 | Double pole film with hyperbranched polymericcompound as the intermediate boundary layer and method of preparing the same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040013A (en) * | 2016-06-24 | 2016-10-26 | 盐城师范学院 | Bipolar membrane and preparation method thereof |
| CN106139926A (en) * | 2016-07-13 | 2016-11-23 | 合肥工业大学 | Polyelectrolyte composite membrane, its preparation method and the method for diffusion dialysis desalination |
| CN106139926B (en) * | 2016-07-13 | 2019-03-22 | 合肥工业大学 | The method of polyelectrolyte composite membrane, preparation method and diffusion dialysis desalination |
| CN106334588A (en) * | 2016-10-27 | 2017-01-18 | 刘昊天 | Ionic membrane |
| CN106519272A (en) * | 2016-10-27 | 2017-03-22 | 刘昊天 | Preparation method of ionic membrane |
| CN106519273A (en) * | 2016-10-27 | 2017-03-22 | 刘昊天 | Anionic membrane |
| CN114364450A (en) * | 2019-09-13 | 2022-04-15 | 东洋纺株式会社 | Composite film and method for producing composite film |
| CN114364450B (en) * | 2019-09-13 | 2023-12-22 | 东洋纺株式会社 | Composite film and method for producing composite film |
| CN115926425A (en) * | 2022-12-14 | 2023-04-07 | 武汉轻工大学 | Cross-linked anion exchange membrane and preparation method thereof |
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