CN110743201A - Super-hydrophobic and super-oleophilic porous net film and preparation method and application thereof - Google Patents
Super-hydrophobic and super-oleophilic porous net film and preparation method and application thereof Download PDFInfo
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- CN110743201A CN110743201A CN201810811614.6A CN201810811614A CN110743201A CN 110743201 A CN110743201 A CN 110743201A CN 201810811614 A CN201810811614 A CN 201810811614A CN 110743201 A CN110743201 A CN 110743201A
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- 238000002360 preparation method Methods 0.000 title abstract description 23
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- 229920000620 organic polymer Polymers 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a super-hydrophobic super-oleophylic porous net film in the field of oil-water separation materials, a preparation method and application thereof; the super-hydrophobic and super-oleophilic porous net film comprises a porous net film framework and an organic high polymer material coated on the surface of the porous net film framework; the organic polymer material is at least one of plastic and plastic modified products; the plastic is selected from thermosetting plastics and/or thermoplastic plastics; the organic polymer material accounts for 0.01-99% of the total weight of the porous net film. The super-hydrophobic and super-oleophilic porous net film has a static contact angle of more than 120 degrees to water and a static contact angle of less than 5 degrees to oil in the air. The porous net membrane has good thermal stability, excellent mechanical property and good circulation stability, is a novel and efficient oil-water separation material, and has wide application prospect in the fields of organic chemical solvent treatment, oil-containing wastewater separation, leaked crude oil recovery and the like.
Description
Technical Field
The invention relates to the field of oil-water separation materials, in particular to a super-hydrophobic and super-oleophilic porous net film and a preparation method and application thereof.
Background
The oil-water separation material is a material for realizing the processes of separation, purification, concentration and the like of organic and inorganic components of liquid by utilizing the selective separation of the material, has the advantages of high efficiency, energy conservation, environmental protection, simple separation process, cyclic utilization and the like, and is widely applied to the fields of food, medicine, environmental protection, chemical industry, metallurgy, energy, petroleum, water treatment and the like. The separation effect of the oil-water separation material depends on the properties of the material. The super-hydrophobic super-oleophylic porous net film has a good oil-water separation effect because the super-hydrophobic super-oleophylic porous net film can selectively pass through organic solvents, crude oil and the like.
An article entitled a Super-Hydrophobic and Super-Oleophilic Coating Mesh Film for the Separation of oil and Water was disclosed in 2004, Angewandte Chemie, paragraph 43, pages 2012 to 2012, the first of which mentions the concept of using Super-Hydrophobic/Super-Oleophilic materials for oil-Water Separation. The article utilizes polytetrafluoroethylene, polyvinyl acetate, polyvinyl alcohol, sodium dodecyl benzene sulfonate and other materials to prepare sol, after a copper mesh is coated, the sol is dried for 30min at 350 ℃ to obtain a super-hydrophobic/super-oleophylic material, and the super-hydrophobic/super-oleophylic material is successfully used for separating diesel oil from water, and the separation efficiency reaches 95%. The Chinese patent with the publication number of CN1721030A adopts perfluorosilane to modify an adsorption material to obtain an oil-water separation net with the film thickness of 20-50 nm. The Chinese patent with publication number CN100344341A adopts a dip-coating process, takes a polyperfluoroalkyl siloxane-ethanol mixed solution as a modified material, and modifies a fabric mesh to obtain the super-hydrophobic and super-oleophilic oil-water separation material. The raw materials of the methods reported in the two documents are all fluorine-containing materials which are harmful to the environment and human bodies, the preparation process is not green, and the cost is high.
Chinese patents CN101708384A, CN101518695A, CN105854622A, CN102764536A and CN107050928A respectively disclose an oil-water separation net membrane having super-hydrophobic and super-oleophilic functions without using fluorine-containing materials. Although the oil-water separation net film has an oil-water separation effect, the oil-water separation net film has the defects that the preparation process is complicated, chemical etching is required to be carried out on some net films, and inorganic nano-particles are required to be loaded on some net films; in addition, the preparation process of the oil-water separation mesh membrane needs to use organic solvents which are not friendly to human bodies and the environment, and is not green enough, so that how to prepare the super-hydrophobic super-oleophylic porous mesh membrane which is cheap, efficient and applicable to industry and can be further prepared into green is still a difficult problem, and the development of the material has huge application prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a super-hydrophobic and super-oleophilic porous net film. In particular to a super-hydrophobic and super-oleophylic porous net film and a preparation method and application thereof.
One of the purposes of the invention is to provide a super-hydrophobic and super-oleophilic porous net film, which comprises a porous net film framework and an organic polymer material coated on the surface of the porous net film framework; wherein the material of the porous net membrane skeleton is selected from at least one of a metal material, a polymer material, a ceramic material and a carbon material. The super-hydrophobic and super-oleophylic porous mesh membrane raw material is cheap and easy to obtain, has good thermal stability, excellent mechanical property, high separation speed, high selectivity and good circulation stability, and is a novel and efficient oil-water separation material.
The super-hydrophobic super-oleophylic porous net film comprises, by weight, 0.01% -99%, preferably 0.05% -80%, and more preferably 0.1% -50% of an organic polymer material coated on the surface of a porous net film skeleton.
The porous net membrane skeleton is a skeleton material with a porous net membrane structure. The material of the porous net membrane framework is preferably at least one of a metal material and a polymer material, and is preferably at least one of polypropylene (polypropylene), polyacrylonitrile (acrylic), polyvinyl chloride (polyvinyl chloride), polyurethane (spandex), polyamide (nylon), polyester (terylene), cotton (natural polymer fiber), stainless steel, copper and iron; more preferably at least one of stainless steel, copper, iron, polyamide and polyester.
Wherein,
the average pore diameter of meshes of the porous net film skeleton made of the metal material, the ceramic material and the carbon material is 1-1000 micrometers, preferably 5-800 micrometers, more preferably 10-500 micrometers, and further preferably 10-300 micrometers;
the average pore diameter of the meshes of the porous mesh framework of the polymer material is 200-1500 micrometers, preferably 200-1000 micrometers, more preferably 200-800 micrometers, and further preferably 200-400 micrometers.
The organic polymer material coated on the surface of the porous mesh membrane skeleton is at least one of plastic and plastic modified products. The plastic is selected from thermosetting plastics and/or thermoplastic plastics; the organic polymer material coated on the surface of the porous mesh membrane skeleton is preferably an organic polymer material with a plane static contact angle to water of more than 90 degrees and a plane static contact angle to oil of less than 90 degrees in the air. According to the principle of capillary phenomenon, if the wall of the capillary tube is soaked in a certain liquid (the contact angle is less than 90 degrees), the liquid can be subjected to great pressure for entering the capillary tube, so that the liquid level is raised; conversely, if the wall of the capillary is not wetted with a liquid (the contact angle is greater than 90 °), the liquid will be subjected to a great pressure that prevents it from entering the capillary, and the liquid level will drop. In the system, the planar static contact angle of the organic polymer material coated on the surface of the porous net membrane skeleton to water in the air is preferably larger than 90 degrees, so that a water body can be better prevented from entering the pore channels of the porous net membrane; the plane static contact angle to oil is less than 90 degrees, so that the oil can more quickly and smoothly enter the pore canal of the porous net film.
The organic polymer material coated on the surface of the porous network membrane framework is selected from polyolefin, poly-4-methyl-1-pentene, polyamide resin (such as nylon-5, nylon-12, nylon-6/6, nylon-6/10 and nylon-11), polycarbonate resin, homopolymerized and/or copolymerized formaldehyde, linear polyester prepared by condensation polymerization of saturated dibasic acid and dihydric alcohol, aromatic ring polymer (polymer of which the molecule is only composed of aromatic rings and connecting groups, such as polyphenyl, polyphenyl ether, polyphenyl thioether, polyarylsulfone, polyarylketone, polyaryl ester and aromatic polyamide), heterocyclic polymer (polymer of which the main chain of the molecule is provided with heterocyclic rings besides aromatic rings, such as polybenzimidazole), fluorine-containing polymer, acrylic resin, urethane, methyl methacrylate, methyl, At least one of epoxy resin, phenolic resin, urea resin and melamine formaldehyde resin; wherein, at least one of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, acrylic resin, urea resin, phenolic resin and epoxy resin is preferred; more preferably at least one of acrylic resin, urea resin, phenol resin and epoxy resin; most preferred is a phenolic resin.
The plastic modified product is a modified product obtained by modifying the plastic by adopting the existing plastic modification method. The plastic modification method may include, but is not limited to, the following methods: graft modification of polar or non-polar monomers or polymers thereof; the material is modified by melt blending with inorganic or organic reinforcing materials, toughening materials, stiffening materials, heat resistance increasing materials and the like.
Most preferably, the organic polymer material coated on the surface of the porous mesh membrane skeleton is an organic polymer material which can be dissolved in a solvent which is friendly to human bodies and environment, so that the preparation process is 'green'; the total content of ethanol and/or water in the solvent friendly to human body and environment accounts for 50-100 wt% of the weight of the solvent; preferably, the human and environment friendly solvent is selected from ethanol and/or water, wherein the ethanol and water may be mixed in any ratio. Such as acrylic resin, urea resin, phenol resin, epoxy resin, etc., can be dissolved in a solvent which is friendly to human body and environment, especially phenol resin, epoxy resin, etc.
The super-hydrophobic and super-oleophilic porous net film has a static contact angle to water in air of more than 120 degrees, preferably more than 130 degrees, and more preferably more than 140 degrees; a static contact angle to oil of less than 5 °, preferably less than 4 °, more preferably less than 3 °; has good oil-water separation effect.
The invention also aims to provide a preparation method of the super-hydrophobic and super-oleophilic porous net membrane. The surface of the organic high molecular material coated porous net film framework is obtained by immersing the porous net film framework into a solution of the organic high molecular material, then heating the porous net film framework containing the solution of the organic high molecular material, and removing a solvent in the solution of the organic high molecular material to separate out or solidify the organic high molecular material on the surface of the porous net film framework. The preparation method has simple and easy process flow and is easy to realize large-scale preparation. The process of the present method is "green", more preferably if a human and environmentally friendly solvent is used.
The preparation method specifically comprises the following steps:
a. dissolving an organic high polymer material for coating the porous net film framework by using a solvent to obtain an organic high polymer material solution for coating;
b. b, immersing the porous net membrane framework into the organic polymer material solution for coating obtained in the step a, so that the meshes of the porous net membrane framework are fully filled with the organic polymer material solution for coating; wherein the dosage of the organic polymer material solution for coating is that the porous net membrane skeleton is immersed in the solution.
c. And d, taking out the porous net membrane obtained in the step b, drying to separate out or solidify the organic polymer material for coating, and coating the organic polymer material on the surface of the porous net membrane skeleton to obtain the super-hydrophobic and super-oleophylic porous net membrane.
Wherein,
in the step a, the weight concentration of the organic polymer material in the organic polymer material solution for coating (i.e. the weight of the polymer material dissolved in the solvent per mL) is 0.001 to 1g/mL, preferably 0.002 to 0.8g/mL, more preferably 0.003 to 0.5g/mL, and even more preferably 0.003 to 0.02g/mL, based on the volume of the solvent.
In the step a, a corresponding good solvent in the prior art can be selected according to different types of organic polymer materials for coating to be dissolved under a proper condition; the good solvent is preferably at least one of the following solvents: benzene, toluene, xylene (including p-xylene), trichlorobenzene, chloroform, cyclohexane, ethyl hexanoate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water, alcohols; wherein the alcohol is preferably at least one selected from propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1, 4-butanediol, isopropanol, and ethanol. The good solvent is more preferably a solvent comprising water and/or ethanol; further preferably water and/or ethanol.
Specifically, polyethylene and polypropylene can be dissolved by using a solvent such as paraxylene, trichlorobenzene and the like; the polystyrene can be dissolved by using solvents such as benzene, toluene, trichloromethane, cyclohexane, butyl acetate, carbon disulfide and the like; the polyvinyl chloride can be dissolved by tetrahydrofuran, cyclohexanone, ketone, dimethylformamide and the like; the polymethyl methacrylate can be dissolved by solvents such as trichloromethane, acetone, ethyl caproate, tetrahydrofuran, toluene and the like; the alcohol-soluble varieties of acrylic resin, urea resin, phenolic resin and epoxy resin can be well dissolved by solvents such as ethanol and/or water.
In the step b, the pores of the porous mesh membrane skeleton may be completely filled with the organic polymer material solution for coating without extrusion, or preferably, the pores are fully filled with the organic polymer material solution for coating by extrusion several times.
In the step b, the immersion time can ensure that the organic polymer material solution for coating can fully infiltrate the porous net film, and generally can be 0.5-30 min, preferably 1-10 min.
After the porous mesh membrane obtained in the step b is taken out in the step c, the excess organic polymer material solution for coating in the porous mesh membrane skeleton obtained in the step b can be removed without taking measures, and the excess organic polymer material solution for coating can also be removed by taking one or two measures including but not limited to extrusion and centrifugal operation.
The drying in the step c can adopt various drying modes in the prior art, and specifically can comprise heating drying modes in the prior art such as oven heating, infrared heating and the like, wherein the heating temperature range is 60-200 ℃, and is preferably 80-180 ℃; the microwave drying mode can be included, and the microwave drying is high in efficiency and even in heating. The power of the microwave for microwave drying is 1W-100 KW, preferably 500W-10 KW, and the action time is 2-200 min, preferably 20-200 min.
When the organic polymer material for coating in the preparation method of the invention is thermoplastic plastic, the organic polymer material for coating is precipitated after heating in the step c and is coated on the surface of the porous net film framework.
When the organic polymer material for coating in the preparation method is thermoplastic, the organic polymer material for coating can be added with additives commonly used in plastic processing processes, such as an antioxidant, an antioxidant aid, a heat stabilizer, a light stabilizer, an ozone stabilizer, a processing aid, a plasticizer, a softener, an anti-blocking agent, a foaming agent, a dye, a pigment, wax, an extender, an organic acid, a flame retardant, a coupling agent and the like. The dosage of the used auxiliary agent is conventional dosage or is adjusted according to the requirements of actual conditions.
When the organic polymer material for coating in the preparation method of the invention is thermosetting plastic, the organic polymer material for coating is cured after being heated in the step c and is coated on the surface of the porous mesh membrane skeleton.
When the organic polymer material for coating in the preparation method is thermosetting plastic, whether a curing system is required or not can be considered according to the selected thermosetting plastic in the step a; the curing is to prepare a proper curing system for a common curing formula of the selected thermosetting plastic, and to select a corresponding good solvent to dissolve the organic polymer material for coating and the curing system thereof to obtain an organic polymer material solution for coating.
When the organic polymer material for coating in the preparation method is thermosetting plastic, one or more optional additives selected from the following additives can be added in the preparation process of the organic polymer material curing system for coating: cure accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, drip retardants, antiblock agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents, and the like. The dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions.
The equipment and process conditions adopted in the preparation method are common equipment and conditions.
The invention also aims to provide application of the super-hydrophobic and super-oleophilic porous net film, in particular application in the fields of oil-water separation, organic solvent treatment, oily wastewater separation and leaked crude oil recovery.
The invention effectively utilizes the surface characteristics of the hydrophobic and oleophylic organic polymer material, so that the surface of the porous net membrane framework also has the hydrophobic and oleophylic characteristics, the planar hydrophobic and oleophylic characteristics are amplified in the porous net membrane in a specific aperture range by the capillary phenomenon principle, and the coated porous net membrane achieves super-hydrophobic and super-oleophylic properties. And the method does not damage the original structure of the porous net membrane and keeps the original mechanical property. The preparation process of the porous net membrane is green, raw materials are cheap and easy to obtain, the process flow is simple and easy to implement, large-scale preparation is easy to realize, the thermal stability is good, and the mechanical property is excellent. In a preferred technical scheme of the invention, phenolic resin is used as a high polymer material for coating, in the preparation method, the phenolic resin is dissolved by a solvent which is water and/or ethanol and is friendly to human and environment, the solvent is not required to be heated in the dissolving process, the phenolic resin used as thermosetting plastic has better mechanical property, and the phenolic resin is better and more durable in combination with a framework.
The porous net film is a novel and efficient oil-water separation material, and has wide application prospects in the fields of oil-water separation, organic chemical solvent treatment, oil-containing wastewater separation, leaked crude oil recovery and the like.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
Example 1
(1) Weighing 5g of liquid phenolic resin (2152, a chemical industry of Jiningbai, the planar static contact angle of the phenolic resin to water in the air is 95 degrees, and the planar static contact angle to oil is 50 degrees) in a beaker, pouring 500mL of ethanol, and stirring for 1 hour by using a magnetic rotor until the ethanol is dissolved;
(2) soaking a 10 × 10cm (3g) porous net membrane skeleton (Baidun wire gauze Co., Ltd., stainless steel net, mesh average pore diameter 250 micrometers) made of stainless steel into the prepared solution for 5min, so that the solution fully enters the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, supporting the porous net membrane by using a frame, putting the porous net membrane into a stainless steel tray, and heating the porous net membrane in an oven at the temperature of 180 ℃ for 2 hours to obtain the super-hydrophobic super-oleophylic porous net membrane. Wherein the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 1 wt% of the super-hydrophobic super-oleophylic porous net membrane product.
Example 2
(1) Weighing 3g of powdered phenolic resin (2123, bermaja Sakura industries, Ltd. in New rural areas, the planar static contact angle of the phenolic resin to water in air is 95 degrees, the planar static contact angle to oil is 50 degrees) and 0.36g of hexamethylenetetramine curing agent in a beaker, pouring 500mL of ethanol, and stirring with a magnetic rotor for 1 hour until dissolving;
(2) soaking a 10 × 10cm (3g) porous net membrane skeleton (Baidun wire mesh, Inc., copper mesh, mesh average pore diameter 150 μm) made of copper into the prepared solution for 5min to make the solution fully enter the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, supporting the porous net membrane by using a frame, putting the porous net membrane into a stainless steel tray, and heating the porous net membrane in an oven at the temperature of 180 ℃ for 2 hours to obtain the super-hydrophobic super-oleophylic porous net membrane. Wherein the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 0.7 wt% of the super-hydrophobic super-oleophylic porous net membrane product.
Example 3
(1) Weighing 4g of liquid phenolic resin (2152, cheynin-bai chemical), pouring 300mL of ethanol into a beaker, stirring with a magnetic rotor for 1 hour until the ethanol is dissolved, and slowly adding 200mL of deionized water;
(2) soaking a 10 × 10cm (0.4g) porous net membrane skeleton (Shanghai Sieve mesh manufacturing Co., Ltd., nylon net, mesh average pore diameter 200 μm) made of nylon in the prepared solution for 8min to make the solution fully enter the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, erecting the porous net membrane by using a frame, placing the porous net membrane into a tray, and placing the tray in a household microwave oven for microwave treatment at 700w for 1 hour to obtain the super-hydrophobic super-oleophylic porous net membrane. Wherein the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 30 wt% of the super-hydrophobic super-oleophylic porous net membrane product.
Example 4
(1) Weighing 3g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, pouring 300mL of ethanol, stirring with a magnetic rotor for 1 hour until the ethanol is dissolved, and slowly adding 200mL of deionized water;
(2) soaking a 10 × 10cm (3g) porous net membrane skeleton (Baidun wire gauze Co., Ltd., stainless steel net, with a mesh average pore size of 75 microns) made of stainless steel into the prepared solution for 3min, so that the solution fully enters the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, supporting the porous net membrane by using a frame, putting the porous net membrane into a stainless steel tray, and heating the porous net membrane in an oven at the temperature of 140 ℃ for 3 hours to obtain the super-hydrophobic super-oleophylic porous net membrane. The organic polymer material coated on the surface of the porous mesh membrane skeleton accounts for 0.8 wt% of the super-hydrophobic super-oleophylic porous mesh membrane product.
Example 5
(1) Weighing 2g of liquid phenolic resin (2152, cheynin-bai chemical), pouring 400mL of ethanol into a beaker, stirring for 1 hour by using a magnetic rotor until the ethanol is dissolved, and slowly adding 100mL of deionized water;
(2) soaking a 10 × 10cm (3g) porous net membrane skeleton (Baidun wire gauze Co., Ltd., stainless steel net, mesh average pore diameter 38 micrometers) made of stainless steel into the prepared solution for 3min, so that the solution fully enters the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, supporting the porous net membrane by using a frame, putting the porous net membrane into a stainless steel tray, and heating the porous net membrane in an oven at 160 ℃ for 3 hours to obtain the super-hydrophobic super-oleophylic porous net membrane. Wherein the organic polymer material coated on the surface of the porous mesh membrane skeleton accounts for 0.9 wt% of the super-hydrophobic super-oleophylic porous mesh membrane product.
Example 6
(1) Weighing 3g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, pouring 500mL of ethanol, and stirring with a magnetic rotor for 1 hour until the solution is dissolved;
(2) soaking 10 × 10cm (0.4g) porous net membrane skeleton (Shanghai Sieve silk net manufacturing Co., Ltd., Dacron net, average mesh diameter 250 μm) made of Dacron into the prepared solution for 5min to make the solution fully enter into pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net film, supporting the porous net film by using a frame, putting the porous net film into a tray, and placing the tray in a household microwave oven for microwave treatment at 700w for half an hour to obtain the super-hydrophobic super-oleophylic porous net film. Wherein the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 25 wt% of the super-hydrophobic super-oleophylic porous net membrane product.
Example 7
(1) Weighing 3g of epoxy resin (E-51, tomb petrochemical), 1g of low molecular weight polyamide 650 (Yichungxingwang chemical Co., Ltd.) and 0.36g of hexamethylenetetramine curing agent in a beaker, pouring 500mL of ethanol, and stirring with a magnetic rotor for 1 hour until the epoxy resin, the polyamide and the hexamethylenetetramine curing agent are dissolved; (the mixture obtained by curing the same epoxy resin and polyamide in the same proportion under the same curing system and curing conditions has a plane static contact angle of 93 degrees to water and a plane static contact angle of 55 degrees to oil) in air
(2) Soaking a 10 × 10cm (3g) porous net membrane skeleton (Baidun wire gauze Co., Ltd., wire gauze, mesh average pore diameter 150 μm) made of iron into the prepared solution for 5min to make the solution fully enter the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, supporting the porous net membrane by using a frame, putting the porous net membrane into a stainless steel tray, and heating the porous net membrane in an oven at 160 ℃ for 3 hours to obtain the super-hydrophobic super-oleophylic porous net membrane. Wherein the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 1 wt% of the super-hydrophobic super-oleophylic porous net membrane product.
Example 8
(1) Weighing 2g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, pouring 300mL of ethanol, stirring with a magnetic rotor for 1 hour until the ethanol is dissolved, and slowly adding 200mL of deionized water;
(2) soaking a 10 × 10cm (0.4g) 80-mesh porous net membrane skeleton (Nanzuo textile manufacturing Co., Ltd., cotton gauze net, mesh average pore diameter 300 μm) into the prepared solution for 2min to make the solution fully enter the pore channels of the porous net membrane skeleton;
(3) and taking out the soaked porous net membrane, supporting the porous net membrane by using a frame, putting the porous net membrane into a stainless steel tray, and heating the porous net membrane in an oven at the temperature of 140 ℃ for 3 hours to obtain the super-hydrophobic super-oleophylic porous net membrane. Wherein the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 50 wt% of the super-hydrophobic super-oleophylic porous net membrane product.
Example 9
The porous mesh membranes prepared in examples 1 to 8 and uncoated blanks were subjected to a contact angle test of water and oil at room temperature (the contact angle measuring instrument used was DSA 20E)
GmbH, germany), 5 points were measured per sample and finally averaged as shown in table 1. Wherein the blank sample is specifically blank sample 1: stainless steel porous mesh skeleton (baidun wire gauze ltd, stainless steel mesh, mesh average pore size 38 μm), blank 2: uncoated porous mesh membrane skeleton made of copper (baidun wire gauze, cu mesh, mesh average pore size 150 μm), blank 3: porous mesh membrane skeleton (shanghai screen mesh manufacturing ltd., nylon mesh, mesh average pore diameter 200 μm), blank 4: the material is porous net membrane skeleton of dacron (shanghai sieve silk net manufacturing limited company, dacron net, the average aperture of mesh is 250 microns), blank sample 5: porous mesh membrane skeleton (Baidun wire gauze Co., Ltd., wire gauze, mesh average pore diameter 150 μm) made of iron, blank sample 6: the material was an 80 mesh porous mesh membrane skeleton of cotton (Daiday, Nanzuo textile manufacturing Co., Ltd., cotton gauze, mesh average pore size 300 μm).
TABLE 1
| Examples | Contact angle to water | Contact angle to oil |
| 1 | 138.3° | 0 |
| 2 | 135.8° | 0 |
| 3 | 136.4° | 0 |
| 4 | 143.9° | 0 |
| 5 | 144.2° | 0 |
| 6 | 132.5° | 0 |
| 7 | 127.4° | 0 |
| 8 | 140.9° | 0 |
| Blank sample 1 | 0 | 0 |
| Blank sample 2 | 0 | 0 |
| Blank 3 | 0 | 0 |
| Blank sample 4 | 0 | 0 |
| Blank sample 5 | 0 | 0 |
| Blank sample 6 | 0 | 0 |
As can be seen from the data in table 1, the porous mesh film of the present example achieved superhydrophobic, superoleophilic properties, improving the oleophilic but also hydrophilic properties of the uncoated framework material; the porous net membranes obtained after being coated by the method have super-hydrophobic and super-oleophilic characteristics, can be used as efficient oil-water separation materials, and are widely applied to the fields of organic chemical solvent treatment, oil-containing wastewater separation, leaked crude oil recovery and the like.
Claims (15)
1. A super-hydrophobic super-oleophylic porous net film is characterized by comprising a porous net film framework and an organic high polymer material coated on the surface of the porous net film framework; wherein the material of the porous mesh membrane skeleton is selected from at least one of a metal material, a polymer material, a ceramic material and a carbon material, and the organic polymer material coated on the surface of the porous mesh membrane skeleton is at least one of plastic and a plastic modified product; the plastic is selected from thermosetting plastics and/or thermoplastic plastics;
wherein, the organic polymer material coated on the surface of the porous net membrane skeleton accounts for 0.01-99 percent of the total weight of the super-hydrophobic and super-oleophilic porous net membrane, preferably 0.05-80 percent, and more preferably 0.1-50 percent.
2. The superhydrophobic, superoleophilic porous mesh membrane of claim 1, wherein: the material of the porous net membrane framework is selected from at least one of metal materials and polymer materials, preferably at least one of polypropylene, polyacrylonitrile, polyvinyl chloride, polyurethane, polyamide, polyester, cotton, stainless steel, copper and iron; more preferably at least one of stainless steel, copper, iron, polyamide and polyester.
3. The superhydrophobic, superoleophilic porous mesh membrane of claim 1, wherein: the average pore diameter of meshes of the porous net film framework of the metal material, the ceramic material and the carbon material is 1-1000 micrometers, preferably 5-800 micrometers, and more preferably 10-500 micrometers;
the average pore diameter of the meshes of the porous mesh framework of the polymer material is 200-1500 micrometers, preferably 200-1000 micrometers, and more preferably 200-800 micrometers.
4. The superhydrophobic, superoleophilic porous mesh membrane of claim 1, wherein:
the organic polymer material coated on the surface of the porous net membrane framework is selected from at least one of polyolefin, poly-4-methyl-1-pentene, polyamide resin, polycarbonate resin, linear polyester prepared by homopolymerization and/or copolymerization of formaldehyde, saturated dibasic acid and dihydric alcohol through condensation polymerization, aromatic ring polymer, heterocyclic polymer, fluorine-containing polymer, acrylic resin, urethane, epoxy resin, phenolic resin, urea resin and melamine formaldehyde resin; wherein, at least one of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, acrylic resin, urea resin, phenolic resin and epoxy resin is preferred; more preferably at least one of acrylic resin, urea resin, phenol resin and epoxy resin; most preferred is a phenolic resin.
5. The superhydrophobic, superoleophilic porous mesh membrane of claim 4, wherein:
the organic polymer material coated on the surface of the porous mesh membrane skeleton has a plane static contact angle to water of more than 90 degrees and a plane static contact angle to oil of less than 90 degrees in air.
6. The superhydrophobic, superoleophilic porous mesh membrane of claim 4, wherein:
the polyamide resin is selected from at least one of nylon-5, nylon-12, nylon-6/6, nylon-6/10 and nylon-11;
the aromatic ring polymer is at least one selected from polyphenyl, polyphenyl ether, polyphenylene sulfide, polyarylsulfone, polyarone, polyaryl ester and aromatic polyamide.
7. The superhydrophobic, superoleophilic porous mesh membrane of claim 1, wherein:
the organic polymer material coated on the surface of the porous mesh membrane skeleton is an organic polymer material which can be dissolved in a solvent which is friendly to human bodies and environment.
8. The superhydrophobic, superoleophilic porous web of claim 7, wherein:
the total content of ethanol and/or water in the solvent friendly to human body and environment accounts for 50-100 wt% of the weight of the solvent; the human body and environment friendly solvent is preferably ethanol and/or water.
9. The superhydrophobic, superoleophilic porous web according to any one of claims 1-8, wherein:
the super-hydrophobic super-oleophilic porous net film has a static contact angle to water in air of more than 120 degrees, preferably more than 130 degrees, and more preferably more than 140 degrees; the static contact angle to oil is less than 5 °, preferably less than 4 °, more preferably less than 3 °.
10. The method for preparing a superhydrophobic and superoleophilic porous mesh membrane according to any one of claims 1 to 9, comprising the steps of:
a. dissolving the organic polymer material for coating the porous net film by using a solvent to obtain an organic polymer material solution for coating;
b. b, immersing the porous net membrane framework into the organic polymer material solution for coating obtained in the step a, so that the meshes of the porous net membrane framework are fully filled with the organic polymer material solution for coating;
c. and c, taking out the porous net membrane obtained after the treatment in the step b, drying the porous net membrane to separate out or solidify the organic polymer material for coating, and coating the organic polymer material on the surface of the porous net membrane skeleton to obtain the super-hydrophobic and super-oleophylic porous net membrane.
11. The method of preparing a superhydrophobic, superoleophilic porous web according to claim 10, wherein:
in the step a, the weight concentration of the organic polymer material in the organic polymer material solution for coating is 0.001-1 g/mL, preferably 0.002-0.8 g/mL, and more preferably 0.003-0.5 g/mL, in terms of the volume of the solvent.
12. The method of preparing a superhydrophobic, superoleophilic porous web according to claim 10, wherein:
the solvent in the step a is selected from good solvents for dissolving the coating polymer material, and preferably at least one of the following solvents: benzene, toluene, xylene, trichlorobenzene, trichloromethane, cyclohexane, ethyl hexanoate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water and alcohols; the alcohol solvent is preferably at least one selected from ethanol, propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1, 4-butanediol and isopropanol; the good solvent preferably comprises water and/or ethanol.
13. The method of preparing a superhydrophobic, superoleophilic porous web according to claim 10, wherein:
in the step c, the drying is heating drying or microwave drying; the heating temperature range of the heating and drying is 60-200 ℃, and preferably 80-180 ℃; the power of the microwave for microwave drying is 1W-100 KW, preferably 500W-10 KW, and the action time is 2-200 min, preferably 20-200 min.
14. The method of preparing a superhydrophobic, superoleophilic porous web according to claim 10, wherein:
in the step b, the immersion time is 0.5-30 min, preferably 1-10 min.
15. The use of the superhydrophobic, superoleophilic porous mesh membrane according to any one of claims 1-9 in the fields of oil-water separation, organic solvent treatment, separation of oily wastewater, and recovery of leaked crude oil.
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