CN117339400B - Aquaporin hydrophilic membrane and preparation method thereof - Google Patents
Aquaporin hydrophilic membrane and preparation method thereof Download PDFInfo
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- CN117339400B CN117339400B CN202311648684.1A CN202311648684A CN117339400B CN 117339400 B CN117339400 B CN 117339400B CN 202311648684 A CN202311648684 A CN 202311648684A CN 117339400 B CN117339400 B CN 117339400B
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- 102000010637 Aquaporins Human genes 0.000 title claims abstract description 53
- 108010063290 Aquaporins Proteins 0.000 title claims abstract description 53
- 239000012528 membrane Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 12
- 239000011147 inorganic material Substances 0.000 claims abstract description 12
- 238000009998 heat setting Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000003484 crystal nucleating agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002861 polymer material Substances 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- -1 polypropylene Polymers 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 150000004703 alkoxides Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 6
- 229920005597 polymer membrane Polymers 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000012982 microporous membrane Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 108091006146 Channels Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a aquaporin hydrophilic membrane and a preparation method thereof, and belongs to the technical field of membrane separation. The preparation method of the hydrophilic film comprises the following steps: firstly, a nano-scale inorganic material and an organic material are hybridized by a sol-gel method to obtain a aquaporin body, then aquaporin and a high polymer material are mixed uniformly, a beta crystal nucleating agent is added, a mixture solution is obtained by heating, and then a diaphragm material for dispersing the aquaporin body on a high polymer film is obtained after extrusion casting, biaxial stretching and heat setting in sequence.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a aquaporin hydrophilic membrane and a preparation method thereof.
Background
The membrane separation technology has the advantages of low energy consumption, simple process, high separation efficiency, no environmental pollution and the like, is an important high-new technology for solving the problems of current energy, resources and environment, and has been applied to the fields of chemical industry, food, medicine, biochemistry, environmental protection and the like. Semi-crystalline polyolefin plastics, such as polypropylene (pp) and High Density Polyethylene (HDPE), have been used as film forming materials to prepare porous films of high porosity and find application because of their excellent properties, low cost and easy processability. However, the surface of the polyolefin has hydrophobicity, so that water is not easy to penetrate through the micropore channels of the porous membrane; meanwhile, the hydrophobic surface is easy to pollute and difficult to clean, is extremely easy to be polluted in the use process, reduces the separation capacity and improves the cost, thereby limiting the application of the polypropylene microporous membrane in the membrane separation industry, improving the hydrophilicity of the polypropylene microporous membrane, further improving the anti-pollution capacity, and having important significance in practical application.
Hydrophilic modification of polypropylene microporous membrane includes physical modification, chemical modification and physical and chemical modification, and the physical method mainly includes blending method, surface adsorption method and plasma treatment method. The current chemical method modification of the polypropylene microporous membrane mainly comprises the modification of the surface of the membrane, and the introduction of chemically bonded-NH on the surface of the polypropylene microporous membrane 2 Polar groups such as-OH and-COOH convert the surface of the film from nonpolar to polar, raise the surface energy and improve the hydrophilicity and adhesiveness. The physicochemical method is to use physical means such as plasma, gamma rays, ozone, ultraviolet light and the like to generate active centers on the surface of the polypropylene microporous membrane, and then use chemical method to graft other polymers on the surface of the membrane so as to achieve the purpose of modification. Because of the structural stability of the polypropylene material, the three modifications are not truly grafted to the polypropylene functional groups, but are only adsorbed on the surface of the membrane material, and the hydrophilicity of the membrane is attenuated along with the extension of the filtration period, so that the permanent hydrophilic modification of the membrane is not fundamentally solved.
Disclosure of Invention
The invention aims to provide a aquaporin hydrophilic membrane and a preparation method thereof, and the membrane for dispersing aquaporin on a polymer membrane is prepared by mixing aquaporin and polymer particles according to a certain proportion and a membrane preparation process, so that the membrane can realize the effect of freely passing water molecules, and the hydrophilic function of the membrane is not reduced along with the passing of the water molecules, and the hydrophilic permeability and permanence of the membrane are effectively improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a aquaporin hydrophilic membrane, comprising the steps of:
s1, preparing a aquaporin: the sol-gel method is adopted to uniformly mix metal alkoxide and nanoscale lamellar inorganic materials in a ratio of 1:1.1-1.5, then chelating agent, dispersing agent and solvent are added to stir uniformly, the PH of the solution is regulated to 5-7, nano-scale inorganic-organic hybrid sol is obtained after uniform dispersion, namely the aquaporin body is prepared by taking inorganic materials as carriers, hydrophilic intermediates are coated on the outer layer of the inorganic materials, the aquaporin body is mainly prepared by the sol-gel method from the metal alkoxide and the nanoscale lamellar inorganic materials, van der Waals force between the metal alkoxide and the nanoscale lamellar inorganic materials is polymerized, the inorganic lamellar materials have the characteristics of long-term stability, long service life and the like, one main advantage of the organic polymer compared with the inorganic materials is that the organic polymer has good toughness and easy molding processing, and the organic/inorganic hybrid material realizes molecular level compounding of the organic high polymer materials and the inorganic materials, has the characteristics of the two materials, and has the advantages of excellent performance or function, thereby obtaining excellent benefits;
s2, preparing a aquaporin hydrophilic membrane: uniformly mixing the aquaporin and the high polymer material according to the mass ratio of 1:5-10, adding a beta-crystal nucleating agent, heating to 220-250 ℃ to obtain a mixture solution, and then sequentially carrying out tape casting, biaxial stretching and heat setting to obtain the aquaporin hydrophilic film.
Further, the metal alkoxide is one of sodium ethoxide, potassium ethoxide, magnesium ethoxide and potassium tert-butoxide; the nanoscale layered inorganic material is one of silicate clay, phosphate, graphite and transition metal oxide.
Further, the dispersing agent is sodium dodecyl benzene sulfonate, the addition amount is 3-8 per mill of metal alkoxide, the chelating agent is phosphate, the addition amount is 1-3 per mill of metal alkoxide, the solvent is one of nitromethane and methylene dichloride, and the addition amount is 400-500% of metal alkoxide.
Further, the polymer material is polypropylene, the beta-crystal nucleating agent is norbornene dodecamic acid zinc salt, and the addition amount of the beta-crystal nucleating agent is 1% -5% of that of the polypropylene.
A hydrophilic aquaporin membrane prepared by the method for preparing the hydrophilic aquaporin membrane comprises aquaporin bodies and a polymer membrane, wherein the aquaporin bodies are dispersed and penetrated in the polymer membrane.
The invention has the advantages that:
1. the aquaporin hydrophilic membrane consists of aquaporin bodies and a polymer membrane, wherein the aquaporin bodies are dispersed on the polymer membrane; the water channel protein body on the polymer film is formed by hybridization of a nano-scale inorganic material and metal alkoxide, the inorganic nano-scale material has the characteristics of stable performance, long service life and the like, the ultraviolet spectrum is narrower, the metal alkoxide has a three-dimensional layered structure, the metal alkoxide has good toughness and is easy to process and form, the metal alkoxide has hydrophilic and lipophilic groups, the metal alkoxide and the hydrophilic and lipophilic groups are well compatible through a sol-gel method, nano-scale inorganic organic crystals are prepared, the nano-scale inorganic crystals are well fused into a whole through Van der Waals force, the nano-scale inorganic crystals play a supporting role, organisms play a role in conveying water, and the water channel protein body plays a role in conveying water in a diaphragm gap;
2. the hydrophilic membrane material with the water channel protein body has the advantages of good water permeability, high wettability, strong tearing resistance, high water permeability, high performance and permanence;
3. the preparation method provided by the invention is environment-friendly, pollution-free and low in process cost.
Drawings
Fig. 1 is a contact angle test picture of the product prepared in example 1.
Fig. 2 is a contact angle test picture of the product prepared in comparative example 1.
Detailed Description
The water flux and transparency of the hydrophilic film of the present invention were tested as follows: the water flux is measured according to the method in GB/T34242-2017, the test solution is 2000ppm magnesium sulfate solution, and the test pressure is 0.08MPa MP; the air permeability was measured according to the method in GB/T458-2008. Contact Angle according to GB/T30047-2013
The specific water flux test method is as follows: placing a Buchner funnel with the diameter of 150mm on a conical flask, cutting a hydrophilic modified polypropylene non-woven fabric diaphragm into a circular sheet with the diameter of 150mm, placing the cut circular sheet into the Buchner funnel, pouring tap water into the Buchner funnel with a filter membrane placed therein, enabling the highest liquid level to be not more than 10mm away from the upper edge of the Buchner funnel, sealing the upper end of the Buchner funnel tightly, vacuumizing by a vacuum pump, and enabling the tap water to enter the conical flask through the hydrophilic modified membrane under internal pressure.
Example 1
A preparation method of a aquaporin hydrophilic membrane comprises the following steps:
(1) Preparation of aquaporin bodies: weighing 10g of sodium ethoxide and 15g of magnesium-rich aluminosilicate clay nano particles, adding 0.05g of sodium dodecyl benzene sulfonate, 50mL of nitromethane and 0.02g of sodium phosphate, uniformly mixing, stirring and dispersing uniformly, adding a proper amount of acetic acid to adjust the pH value of the solution to be=5.5, and drying for 1h through a vacuum drying oven to prepare the nano-scale inorganic organic hybrid aquaporin body.
(2) Preparation of hydrophilic separator: weighing 5g of aquaporin and 50g of polypropylene, adding 3g of norbornene dodecamic acid zinc salt, and heating to 225 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare a hydrophilic film, wherein the water flux of the hydrophilic film is tested to be 121.6L m -2 ·h -1 The air permeability was 564.3. 564.3S/100 ml.
Comparative example 1:
(1) Preparation of aquaporin bodies: 15g of magnesium-rich aluminosilicate clay nano particles are weighed, 0.05g of sodium dodecyl benzene sulfonate, 50mL of nitromethane and 0.02g of sodium phosphate salt are added to be uniformly mixed, the mixture is stirred and uniformly dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be=5.5, and the solution is dried for 1h through a vacuum drying oven to prepare the water channel protein body.
(2) Preparation of hydrophilic separator: weighing 5g of aquaporin and 50g of polypropylene, adding 3g of norbornene dodecamic acid zinc salt, and heating to 225 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare a hydrophilic film, wherein the water flux of the hydrophilic film is 385.6 L.m -2 ·h -1 The air permeability was 0S/100ml.
Example 2:
(1) Preparation of aquaporin bodies: weighing 10g of magnesium ethoxide and 15g of aluminum hydroxide particles, adding 0.05g of sodium dodecyl benzene sulfonate, 50mL of nitromethane and 0.02g of sodium phosphate, uniformly mixing, stirring and dispersing uniformly, adding a proper amount of acetic acid to adjust the pH value of the solution to be less than or equal to 5.5, and drying for 1h by a vacuum drying oven to prepare the nano-scale inorganic organic hybrid aquaporin body.
(2) Preparation of hydrophilic separator: weighing 5g of aquaporin and 50g of polypropylene, adding 3g of norbornene dodecamic acid zinc salt, and heating to 220 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare a hydrophilic film, wherein the water flux of the hydrophilic film is 652.9L m -2 ·h -1 The air permeability was 101.3S/100ml.
Comparative example 2
(1) Preparation of aquaporin bodies: 10g of sodium ethoxide is weighed, 0.05g of sodium dodecyl benzene sulfonate, 50mL of nitromethane and 0.02g of sodium phosphate salt are added, uniformly mixed, stirred and dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be less than 5.5, and the solution is dried for 1h by a vacuum drying oven to prepare the water channel protein body.
(2) Preparation of hydrophilic separator: weighing 5g of aquaporin and 50g of polypropylene, adding 3g of norbornene dodecamic acid zinc salt, and heating to 225 ℃ to obtain a melt; extruding and casting the melt from a die head, and cooling on a cooling rollCooling the cast sheet, taking the cooled cast sheet, biaxially stretching at 135 ℃, and finally performing heat setting at 80 ℃ to prepare a hydrophilic film, wherein the water flux of the hydrophilic film is measured to be 562.8L.m -2 · h -1 The air permeability was 97.6S/100ml.
Example 3
(1) Preparation of aquaporin bodies: 10g of potassium tert-butoxide and 11g of copper sulfate are weighed, 0.04g of sodium dodecyl benzene sulfonate, 50mL of dichloromethane and 0.02g of sodium phosphate are added to be uniformly mixed, the mixture is stirred and uniformly dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be less than 5.5, and the solution is dried for 1h through a vacuum drying oven, so that the nano-scale inorganic organic hybrid aquaporin body is prepared.
(2) Preparation of hydrophilic separator: weighing 5g of aquaporin and 50g of polypropylene, adding 3g of norbornene dodecamic acid zinc salt, and heating to 225 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare a hydrophilic film, wherein the water flux of the hydrophilic film is tested to be 98.4 L.m -2 ·h -1 The air permeability was 635.7S/100ml.
Comparative example 3
And directly preparing the polypropylene film without adding aquaporin. Test hydrophilic film having a water flux of 381.6 L.m -2 ·h -1 The air permeability was 0S/100ml.
Specifically, the test data for examples 1-3 and comparative examples 1-3 are shown in Table 1 below:
the contact angle test results are shown in table 2:
。
Claims (2)
1. a method for preparing a aquaporin hydrophilic membrane, comprising the steps of:
s1, preparing a aquaporin: uniformly mixing metal alkoxide and a nanoscale lamellar inorganic material according to a ratio of 1:1.1-1.5 by adopting a sol-gel method, adding a chelating agent, a dispersing agent and a solvent, uniformly stirring, regulating the PH of the solution to be 5-7, and uniformly dispersing to obtain nanoscale inorganic-organic hybrid sol, namely a aquaporin body, wherein the metal alkoxide is one of sodium ethoxide, potassium ethoxide, magnesium ethoxide and potassium tert-butoxide; the nanoscale lamellar inorganic material is one of silicate clay, phosphate, graphite and transition metal oxide; the dispersing agent is sodium dodecyl benzene sulfonate, the addition amount of the dispersing agent is 3-8 per mill of metal alkoxide, the chelating agent is phosphate, the addition amount of the chelating agent is 1-3 per mill of metal alkoxide, the solvent is one of nitromethane and methylene dichloride, and the addition amount of the solvent is 400-500% of metal alkoxide;
s2, preparing a aquaporin hydrophilic membrane: uniformly mixing the aquaporin and a high polymer material according to the mass ratio of 1:5-10, adding a beta-crystal nucleating agent, heating to 220-250 ℃ to obtain a mixture solution, and then sequentially carrying out tape casting, biaxial stretching and heat setting to obtain the aquaporin hydrophilic film, wherein the high polymer material is polypropylene, the beta-crystal nucleating agent is norbornene dodecamic acid zinc salt, and the addition amount of the beta-crystal nucleating agent is 1-5% of that of polypropylene.
2. The aquaporin hydrophilic membrane prepared by the method of preparing an aquaporin hydrophilic membrane of claim 1, wherein: aquaporins are dispersed throughout the polymer membrane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63221804A (en) * | 1987-03-11 | 1988-09-14 | Ngk Insulators Ltd | Porous diaphragm and its manufacture |
| RU95109670A (en) * | 1995-06-08 | 1997-06-20 | В.В. Назаров | Ceramic ultra- and nanofiltration membrane with selective layer based on transition metal oxides and method of manufacturing thereof |
| CN101959798A (en) * | 2008-02-25 | 2011-01-26 | 中央硝子株式会社 | Organosol containing magnesium fluoride hydroxide, and manufacturing method therefor |
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