CN113842794A - A membrane of equalling pores for water treatment - Google Patents
A membrane of equalling pores for water treatment Download PDFInfo
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- CN113842794A CN113842794A CN202111111181.1A CN202111111181A CN113842794A CN 113842794 A CN113842794 A CN 113842794A CN 202111111181 A CN202111111181 A CN 202111111181A CN 113842794 A CN113842794 A CN 113842794A
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- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 239000011148 porous material Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 13
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000000741 silica gel Substances 0.000 claims abstract description 11
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000004945 silicone rubber Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000007731 hot pressing Methods 0.000 claims description 12
- -1 polydimethylsiloxane Polymers 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001728 nano-filtration Methods 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920005597 polymer membrane Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a uniform pore membrane for water treatment, and relates to the field of high polymer materials. The homogeneous pore membrane for water treatment comprises the following raw materials in parts by weight: 30-70 parts of ethylene vinyl alcohol copolymer, 20-60 parts of hydrophilic organic nano material, 10-20 parts of sodium hydroxide aqueous solution, 10-20 parts of silica gel elastic condensate, 14-25 parts of silicone rubber, 5-10 parts of diluent, 2-5 parts of additive, 10-20 parts of phenol, 20-30 parts of formaldehyde solution, 1-14 parts of cross-linking agent, 2-10 parts of catalyst, 20-30 parts of dimethylformamide and 10-18 parts of ethanol. The polymer membrane of the nano material is prepared from the hydrophilic organic nano material, the ethylene vinyl alcohol copolymer, the elastic cured silica gel, the silicone rubber and the organic solvent, so that the membrane with a uniform pore size structure can be obtained, the pore shape and the pore diameter of the membrane can be adjusted, and the membrane has the characteristics of high strength, uniform pore size distribution, high porosity and the like, and solves the problems that the existing nanofiltration membrane is easy to adsorb pollution and the membrane pores are not uniform.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a uniform pore membrane for water treatment.
Background
In recent years, the membrane separation technology has been rapidly developed in the field of substance separation and purification by virtue of the advantages of energy conservation, high efficiency and environmental protection, wherein nanofiltration is taken as a novel pressure-driven membrane separation process and becomes a hotspot of the research of the membrane separation technology, the aperture and the molecular weight cut-off of a nanofiltration membrane are positioned between a reverse osmosis membrane and an ultrafiltration membrane, the separation of substances is mainly realized by the aperture sieving action and the electrostatic repulsion action, the common nanofiltration membrane has higher cut-off rate on multivalent salt ions and organic substances with molecular weight more than 200, and the cut-off rate on monovalent salt ions and organic substances with low molecular weight is very low, so that the selective separation of substances can be realized, and the nanofiltration membrane has the unique separation effect and is widely used for the separation and purification of substances in the fields of water softening, wastewater treatment, biopharmaceutical, petroleum and the like, and in order to further improve the precision of the membrane separation process, the selectivity and the permeability are synchronously improved, the pore diameter homogenization of the separation membrane is an inevitable way, the homogeneous pore membrane is produced at the same time, and the homogeneous pore membrane has uniform pore diameter and uniform pore canal shape and vertically penetrates through the whole separation layer.
However, the materials selected by the existing thermally induced phase separation method are mainly polyvinylidene fluoride, polypropylene, polyethylene and other hydrophobic materials, and the prepared membrane is easy to cause adsorption pollution in use, and the aperture of the formed membrane is not uniform and is not convenient for size adjustment.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a uniform-pore membrane for water treatment, which solves the problems that the existing nanofiltration membrane is easy to adsorb pollution and membrane pores are not uniform.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a homogeneous pore membrane for water treatment comprises the following raw materials in parts by weight: 30 parts of ethylene vinyl alcohol copolymer, 20 parts of hydrophilic organic nano material, 10 parts of sodium hydroxide aqueous solution, 10 parts of silica gel elastic condensate, 14 parts of silicon rubber, 5 parts of diluent, 2 parts of additive, 10 parts of phenol, 20 parts of formaldehyde solution, 1 part of cross-linking agent, 2 parts of catalyst, 20 parts of dimethylformamide and 10 parts of ethanol.
Preferably, the preparation method of the homogeneous pore membrane for water treatment comprises the following steps:
s1, preparation of prepolymer:
(1) weighing raw materials according to the weight parts, adding a sodium hydroxide aqueous solution into molten phenol, uniformly stirring, adding a formaldehyde solution, reacting the solution at 60-90 ℃ for 0.5-2 h, and adjusting the solution to be neutral by using a hydrochloric acid solution to obtain a phenolic resin prepolymer;
(2) mixing ethylene vinyl alcohol copolymer, hydrophilic organic nano material, silica gel elastic condensate, silicon rubber, diluent and additive, and ultrasonically dispersing, wherein the power of ultrasonic dispersion is 50 w-1000 w, the time of ultrasonic dispersion is 0.1 h-10 h, the temperature is 150-210 ℃, and then the temperature is reduced to 90-120 ℃ to obtain a mixed prepolymer;
s2 composite process
Mixing and stirring the mixed prepolymer and the phenolic resin prepolymer for 2-5 h, standing and defoaming for 2-4 h, transferring to a culture dish, heating and curing for 1-4h after a solvent is completely volatilized to obtain a compound membrane, placing the compound membrane in dimethylformamide containing a cross-linking agent with a certain concentration and a corresponding catalyst, heating and treating for 1-8h at the temperature of 70-100 ℃, soaking in ethanol for 1-3 h, taking out, and placing on a polydimethylsiloxane layer to obtain an imprinting membrane layer;
s3 pore-forming process
And carrying out hot pressing on the imprinting film layer and the microneedle template at the melting temperature, obtaining a porous film with uniform pore size after the hot pressing is carried out for 20min, cooling the porous film to room temperature, and carrying out hot pressing treatment at the melting temperature for different times to obtain the porous film with the uniform adjustable pore size structure.
Preferably, the crosslinking agent is one of 1, 4-dichlorobenzyl, 1, 4-dibromobutane and 1, 4-terephthaloyl chloride.
Preferably, the catalyst is one of anhydrous ferric trichloride, anhydrous aluminum trichloride and anhydrous stannic chloride.
Preferably, the ratio of phenol: sodium hydroxide: the molar ratio of formaldehyde is 10:1: 20.
(III) advantageous effects
The invention provides a homogeneous pore membrane for water treatment. The method has the following beneficial effects:
the invention prepares the polymer film of the nano material by the hydrophilic organic nano material, the ethylene vinyl alcohol copolymer, the elastic cured silicone rubber, the silicone rubber and the organic solvent, because the hydrophilic organic nano material has the functions of a pore-forming agent and a hydrophilic modifier and has the characteristic of self-dispersibility, the prepared nano-filtration membrane has the unique advantages of high flux and low pollution, and is beneficial to reducing the pollution of protein, carbohydrate, natural organic matters and polysaccharide organic matters in water bodies to the surface of the composite membrane, can obtain a membrane with a structure with uniform pore size, the pore shape and the pore diameter of the membrane can be adjusted, and the membrane has the characteristics of high strength, uniform pore size distribution, high porosity and the like, can be used for separating divalent ions and monovalent ions in aqueous solution, can be separated by water chemical engineering and the like, and solves the problems that the existing nanofiltration membrane is easy to adsorb pollution and membrane pores are not uniform.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the embodiment of the invention provides a uniform pore membrane for water treatment, which comprises the following raw materials in parts by weight: 30-70 parts of ethylene vinyl alcohol copolymer, 20-60 parts of hydrophilic organic nano material, 10-20 parts of sodium hydroxide aqueous solution, 10-20 parts of silica gel elastic condensate, 14-25 parts of silicone rubber, 5-10 parts of diluent, 2-5 parts of additive, 10-20 parts of phenol, 20-30 parts of formaldehyde solution, 1-14 parts of cross-linking agent, 2-10 parts of catalyst, 20-30 parts of dimethylformamide and 10-18 parts of ethanol.
The hydrophilic organic nano material has the functions of pore-forming agent and hydrophilic modifier and has the characteristic of self-dispersibility, so that the polymer composite membrane has the unique advantages of high flux and low pollution, the prepared nanofiltration membrane is favorable for reducing the pollution of protein, carbohydrate, natural organic matters and polysaccharide organic matters in water body to the surface of the composite membrane, can be used for separating divalent ions and monovalent ions in aqueous solution, can be separated by using water chemical industry and the like, and is used for the fields of water treatment, chemical industry separation and the like.
A preparation method of a homogeneous pore membrane for water treatment comprises the following steps:
s1, preparation of prepolymer:
(1) weighing raw materials according to the weight parts, adding a sodium hydroxide aqueous solution into molten phenol, uniformly stirring, adding a formaldehyde solution, reacting the solution at 60-90 ℃ for 0.5-2 h, and adjusting the solution to be neutral by using a hydrochloric acid solution to obtain a phenolic resin prepolymer;
(2) mixing ethylene vinyl alcohol copolymer, hydrophilic organic nano material, silica gel elastic condensate, silicon rubber, diluent and additive, and ultrasonically dispersing, wherein the power of ultrasonic dispersion is 50 w-1000 w, the time of ultrasonic dispersion is 0.1 h-10 h, the temperature is 150-210 ℃, and then the temperature is reduced to 90-120 ℃ to obtain a mixed prepolymer;
s2 composite process
Mixing the mixed prepolymer and the phenolic resin prepolymer, stirring for 2-5 h, standing for defoaming for 2-4 h, transferring to a culture dish, heating and curing for 1-4h after the solvent is completely volatilized to obtain a compound membrane, placing the compound membrane in dimethylformamide containing a cross-linking agent with a certain concentration and a corresponding catalyst, heating at 70-100 ℃ for 1-8h, immersing in ethanol for 1-3 h, taking out, and placing on a polydimethylsiloxane layer to obtain an imprinting membrane layer;
s3 pore-forming process
And carrying out hot pressing on the imprinting film layer and the microneedle template at the melting temperature, obtaining a porous film with uniform pore size after the hot pressing is carried out for 20min, cooling the porous film to room temperature, and carrying out hot pressing treatment at the melting temperature for different times to obtain the porous film with the uniform adjustable pore size structure.
Wherein the cross-linking agent is one of 1, 4-p-dichlorobenzyl, 1, 4-dibromobutane and 1, 4-terephthaloyl chloride, the catalyst is one of anhydrous ferric trichloride, anhydrous aluminum trichloride and anhydrous stannic chloride, and the phenol: sodium hydroxide: the molar ratio of formaldehyde is 10:1: 20.
The charge property and the hydrophilicity and the hydrophobicity of the material can be easily realized by adjusting the composition and the proportion of the copolymer monomer, the membrane with a structure with uniform pore size can be obtained by the microneedle template, the pore shape and the pore diameter of the membrane can be adjusted, and the membrane has the characteristics of high strength, uniform pore size distribution, high porosity and the like.
Example two:
the embodiment of the invention provides a uniform pore membrane for water treatment, which comprises the following raw materials in parts by weight: 70 parts of ethylene vinyl alcohol copolymer, 60 parts of hydrophilic organic nano material, 20 parts of sodium hydroxide aqueous solution, 20 parts of silica gel elastic condensate, 25 parts of silicon rubber, 10 parts of diluent, 5 parts of additive, 20 parts of phenol, 30 parts of formaldehyde solution, 14 parts of cross-linking agent, 10 parts of catalyst, 30 parts of dimethylformamide and 18 parts of ethanol.
The polymer membrane of the nano material is prepared from the hydrophilic organic nano material, the ethylene vinyl alcohol copolymer, the elastic cured silica gel, the silicone rubber and the organic solvent, and the hydrophilic organic nano material has the functions of a pore-forming agent and a hydrophilic modifier and has the characteristic of self-dispersibility, so that the polymer composite membrane has the unique advantages of high flux and low pollution, and the prepared nanofiltration membrane is beneficial to reducing the pollution of protein, carbohydrate, natural organic matters and polysaccharide organic matters in water bodies to the surface of the composite membrane and is used in the fields of water treatment and chemical separation.
A preparation method of a homogeneous pore membrane for water treatment comprises the following steps:
s1, preparation of prepolymer:
(1) weighing raw materials according to the weight parts, adding a sodium hydroxide aqueous solution into molten phenol, uniformly stirring, adding a formaldehyde solution, reacting the solution at 60-90 ℃ for 0.5-2 h, and adjusting the solution to be neutral by using a hydrochloric acid solution to obtain a phenolic resin prepolymer;
(2) mixing ethylene vinyl alcohol copolymer, hydrophilic organic nano material, silica gel elastic condensate, silicon rubber, diluent and additive, and ultrasonically dispersing, wherein the power of ultrasonic dispersion is 50 w-1000 w, the time of ultrasonic dispersion is 0.1 h-10 h, the temperature is 150-210 ℃, and then the temperature is reduced to 90-120 ℃ to obtain a mixed prepolymer;
s2 composite process
Mixing the mixed prepolymer and the phenolic resin prepolymer, stirring for 2-5 h, standing for defoaming for 2-4 h, transferring to a culture dish, heating and curing for 1-4h after the solvent is completely volatilized to obtain a compound membrane, placing the compound membrane in dimethylformamide containing a cross-linking agent with a certain concentration and a corresponding catalyst, heating at 70-100 ℃ for 1-8h, immersing in ethanol for 1-3 h, taking out, and placing on a polydimethylsiloxane layer to obtain an imprinting membrane layer;
s3 pore-forming process
And carrying out hot pressing on the imprinting film layer and the microneedle template at the melting temperature, obtaining a porous film with uniform pore size after the hot pressing is carried out for 20min, cooling the porous film to room temperature, and carrying out hot pressing treatment at the melting temperature for different times to obtain the porous film with the uniform adjustable pore size structure.
Wherein the cross-linking agent is one of 1, 4-p-dichlorobenzyl, 1, 4-dibromobutane and 1, 4-terephthaloyl chloride, the catalyst is one of anhydrous ferric trichloride, anhydrous aluminum trichloride and anhydrous stannic chloride, and the phenol: sodium hydroxide: the molar ratio of formaldehyde is 10:1: 20.
The charge property and the hydrophilicity and the hydrophobicity of the material can be easily realized by adjusting the composition and the proportion of the copolymer monomer, the membrane with a structure with uniform pore size can be obtained by the microneedle template, the pore shape and the pore diameter of the membrane can be adjusted, and the membrane has the characteristics of high strength, uniform pore size distribution, high porosity and the like.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A homogeneous pore membrane for water treatment, comprising: the feed comprises the following raw materials in parts by weight: 30-70 parts of ethylene vinyl alcohol copolymer, 20-60 parts of hydrophilic organic nano material, 10-20 parts of sodium hydroxide aqueous solution, 10-20 parts of silica gel elastic condensate, 14-25 parts of silicone rubber, 5-10 parts of diluent, 2-5 parts of additive, 10-20 parts of phenol, 20-30 parts of formaldehyde solution, 1-14 parts of cross-linking agent, 2-10 parts of catalyst, 20-30 parts of dimethylformamide and 10-18 parts of ethanol.
2. The method for preparing a homogeneous pore membrane for water treatment according to claim 1, wherein: the method comprises the following steps:
s1, preparation of prepolymer:
(1) weighing raw materials according to the weight parts, adding a sodium hydroxide aqueous solution into molten phenol, uniformly stirring, adding a formaldehyde solution, reacting the solution at 60-90 ℃ for 0.5-2 h, and adjusting the solution to be neutral by using a hydrochloric acid solution to obtain a phenolic resin prepolymer;
(2) mixing ethylene vinyl alcohol copolymer, hydrophilic organic nano material, silica gel elastic condensate, silicon rubber, diluent and additive, and ultrasonically dispersing, wherein the power of ultrasonic dispersion is 50 w-1000 w, the time of ultrasonic dispersion is 0.1 h-10 h, the temperature is 150-210 ℃, and then the temperature is reduced to 90-120 ℃ to obtain a mixed prepolymer;
s2 composite process
Mixing and stirring the mixed prepolymer and the phenolic resin prepolymer for 2-5 h, standing and defoaming for 2-4 h, transferring to a culture dish, heating and curing for 1-4h after a solvent is completely volatilized to obtain a compound membrane, placing the compound membrane in dimethylformamide containing a cross-linking agent with a certain concentration and a corresponding catalyst, heating and treating for 1-8h at the temperature of 70-100 ℃, soaking in ethanol for 1-3 h, taking out, and placing on a polydimethylsiloxane layer to obtain an imprinting membrane layer;
s3 pore-forming process
And carrying out hot pressing on the imprinting film layer and the microneedle template at the melting temperature, obtaining a porous film with uniform pore size after the hot pressing is carried out for 20min, cooling the porous film to room temperature, and carrying out hot pressing treatment at the melting temperature for different times to obtain the porous film with the uniform adjustable pore size structure.
3. The method for preparing a homogeneous pore membrane for water treatment according to claim 2, wherein: the cross-linking agent is one of 1, 4-dichlorobenzyl, 1, 4-dibromobutane and 1, 4-terephthaloyl chloride.
4. The method for preparing a homogeneous pore membrane for water treatment according to claim 2, wherein: the catalyst is one of anhydrous ferric trichloride, anhydrous aluminum trichloride and anhydrous stannic chloride.
5. The method for preparing a homogeneous pore membrane for water treatment according to claim 2, wherein: the phenol: sodium hydroxide: the molar ratio of formaldehyde is 10:1: 20.
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| CN101862607A (en) * | 2010-06-04 | 2010-10-20 | 北京伟思德克科技有限责任公司 | Ethylene-vinyl alcohol copolymer hollow fiber microporous film and preparation method thereof |
| CN102580560A (en) * | 2012-02-24 | 2012-07-18 | 哈尔滨工业大学 | Method for preparing nano-material-doped polymer film |
| CN103212313A (en) * | 2013-04-24 | 2013-07-24 | 清华大学 | TS-1 type molecular sieve filled silicone rubber ethanol-permselective composite membrane and preparation method of TS-1 type molecular sieve filled silicone rubber ethanol-permselective composite membrane |
| CN104107644A (en) * | 2014-08-12 | 2014-10-22 | 娄尤来 | Preparation method of silicone rubber composite film capable of permeating alcohol |
| CN105536580A (en) * | 2016-03-14 | 2016-05-04 | 南京工业大学 | Preparation method of homopore membrane |
| CN105666902A (en) * | 2016-01-14 | 2016-06-15 | 南京大学 | Preparation method for porous membrane with adjustable and uniform pore size |
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2021
- 2021-09-23 CN CN202111111181.1A patent/CN113842794A/en active Pending
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