CN110743200A - Super-hydrophobic and super-oleophilic three-dimensional porous material and preparation method and application thereof - Google Patents
Super-hydrophobic and super-oleophilic three-dimensional porous material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110743200A CN110743200A CN201810812815.8A CN201810812815A CN110743200A CN 110743200 A CN110743200 A CN 110743200A CN 201810812815 A CN201810812815 A CN 201810812815A CN 110743200 A CN110743200 A CN 110743200A
- Authority
- CN
- China
- Prior art keywords
- dimensional porous
- super
- porous material
- polymer material
- organic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a super-hydrophobic super-oleophylic three-dimensional porous material and a preparation method and application thereof, belonging to the technical field of oil-water separation; the super-hydrophobic and super-oleophilic three-dimensional porous material comprises a three-dimensional porous skeleton and an organic polymer material coated on the surface of the three-dimensional porous skeleton; the super-hydrophobic super-oleophilic three-dimensional porous material has a static contact angle of more than 130 degrees to water and a static contact angle of less than 5 degrees to oil in air. The surface characteristics of the hydrophobic and oleophilic organic polymer material are effectively utilized, so that the surface of the three-dimensional porous framework also has the hydrophobic and oleophilic characteristics, the planar hydrophobic and oleophilic characteristics are amplified in the three-dimensional porous material with a specific aperture range by the capillary phenomenon principle, the coated three-dimensional porous material does not damage the original structure of the three-dimensional porous framework, the original mechanical properties are maintained, the super-hydrophobic and super-oleophilic properties are achieved, and the method is widely applied to 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 technical field of oil-water separation, and further relates to a super-hydrophobic and super-oleophilic three-dimensional porous material 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 three-dimensional porous material is light and porous, has a large specific surface area, can selectively adsorb organic solvents, crude oil and the like, and has a good oil-water separation effect.
In 2004, Angewandte Chemie, stage 43, 2012 and 2012, discloses an article entitled A Super-Hydrophobic and Super-Oleophilic Coating Mesh Film for the Separation of oil and Water, in which the assumption of using Super-Hydrophobic/Super-Oleophilic materials for oil-Water Separation was first mentioned. 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%. Chinese patent with publication number CN1721030A discloses a super-hydrophobic/super-oleophilic oil-water separation net, which adopts perfluorosilane to modify an adsorption material to obtain the oil-water separation net with the film thickness of 20-50 nm. Chinese patent publication No. CN102660046A discloses a preparation method of a super-hydrophobic super-oleophylic sponge, which adopts a dip-coating process, takes a polyperfluoroalkyl siloxane-ethanol mixed solution as a modified material, modifies a polyurethane three-dimensional porous material to obtain a super-hydrophobic super-oleophylic three-dimensional porous material, and enhances the oil-water separation capability of the super-hydrophobic super-oleophylic three-dimensional porous 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 patent with publication number CN103342827A discloses a preparation method of a hydrophobic oleophilic polyurethane three-dimensional porous material, which comprises the steps of preparing expanded graphite by using flake graphite, refluxing the expanded graphite in concentrated nitric acid for 36 hours, carrying out ultrasonic treatment in a mixed solution of ammonia water and ethanol for 3 hours, and finally carrying out ultrasonic treatment on the obtained substance in an ethanol solution for 90 minutes to obtain the few-layer graphene nanosheet. The polyurethane three-dimensional porous material ultrasonically cleaned by acetone and deionized water is soaked in graphene ethanol solution, and the hydrophobic oleophylic effect of the three-dimensional porous material is measured after the coating, so that the method has a very good hydrophobic effect. Chinese patent publication No. CN103626171A discloses a method for preparing an oil-water separation material, in which a three-dimensional porous material is immersed in a graphene oxide solution, and the obtained three-dimensional porous material is taken out and centrifuged to obtain a graphene oxide-coated three-dimensional porous material; and carrying out reduction reaction on the graphene oxide coated three-dimensional porous material under the action of a reducing agent to obtain an oil-water separation material. The oil-water separation material prepared by the patent is a reduced graphene oxide coated three-dimensional porous material, the graphene layer is uniformly coated and tightly coated, the good rebound resilience and the good mechanical stability are achieved, and the reduced graphene oxide layer provides good hydrophobic property and lipophilicity and can be used for an oil-water separation technology. The use of graphene is too costly to be industrially applied.
Chinese patent publication No. CN103951843A discloses a method for preparing a superhydrophobic three-dimensional porous material, which comprises modifying a melamine three-dimensional porous material with polydopamine and perfluorododecanethiol to obtain a superhydrophobic and superoleophilic melamine three-dimensional porous material, but the method involves a polymerization reaction of dopamine on the surface of the melamine three-dimensional porous material and a multi-step chemical reaction of grafting perfluorododecanethiol to polydopamine, and the process is complicated, and the cost of the used chemical modification reagent is high, so that the method is limited in practical application.
The Chinese patent with publication number CN102660046A discloses a preparation method of super-hydrophobic super-oleophylic sponge, which comprises the steps of corroding a polyurethane three-dimensional porous material with chromic acid washing liquor by means of chemical reaction, and then modifying the polyurethane three-dimensional porous material by a polyperfluoroalkyl siloxane-ethanol solution to reduce the surface energy of the polyurethane three-dimensional porous material so as to achieve the super-hydrophobic super-oleophylic function.
Meanwhile, the preparation method has no exception, needs to use organic solvents which are not friendly to human bodies and environment, and is not green enough.
Therefore, how to prepare the super-hydrophobic super-oleophylic three-dimensional porous material which is cheap, efficient and applicable to industrial application, and further has a great application prospect if the green super-hydrophobic super-oleophylic three-dimensional porous material can be prepared is still a difficult problem.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a super-hydrophobic and super-oleophilic three-dimensional porous material. In particular to a super-hydrophobic super-oleophilic three-dimensional porous material and a preparation method and application thereof.
One of the purposes of the invention is to provide a super-hydrophobic super-oleophilic three-dimensional porous material, which comprises a three-dimensional porous skeleton and an organic polymer material coated on the surface of the three-dimensional porous skeleton; wherein the material of the three-dimensional porous skeleton is at least one selected from polymer materials, metal materials, ceramic materials and carbon materials. The super-hydrophobic and super-oleophylic three-dimensional porous material has the advantages of cheap and easily available raw materials, good thermal stability, excellent mechanical property, high oil absorption rate, high oil absorption multiplying power and good circulation stability, and is a novel and efficient oil-water separation material.
The super-hydrophobic super-oleophylic three-dimensional porous material comprises, by mass, 1% -99%, preferably 10% -95%, and more preferably 20% -90% of an organic polymer material coated on the surface of a three-dimensional porous skeleton.
The three-dimensional porous framework refers to a framework material with a three-dimensional porous structure. The material of the three-dimensional porous framework can be at least one selected from a polymer material, a metal material, a ceramic material and a carbon material, and is preferably a polymer material. The metal material can be at least one of stainless steel and copper; the ceramic material can be selected from at least one of alumina ceramic and silica ceramic; the carbon material may be at least one selected from graphite and activated carbon; the polymer material can be selected from at least one of natural rubber, ethylene propylene rubber, polypropylene, polystyrene, polyether, polyester, polyvinyl alcohol, melamine formaldehyde resin and polyurethane; preferably at least one of melamine formaldehyde resin and polyurethane. More preferably, the three-dimensional porous skeleton material may be at least one selected from melamine formaldehyde resin and polyurethane, and more preferably, melamine formaldehyde resin.
The average pore diameter of the three-dimensional porous framework can be 0.1-1000 micrometers, preferably 10-500 micrometers, and more preferably 50-250 micrometers.
The porosity of the three-dimensional porous framework is generally 10-99.999%, preferably 50-99.99%, and more preferably 80-99.9%.
The aperture ratio of the three-dimensional porous skeleton is generally 50 to 99.999 percent, preferably 70 to 99.99 percent, and more preferably 90 to 99.9 percent. Wherein the open porosity is the ratio of open pores in the pores.
The organic polymer material coated on the surface of the three-dimensional porous skeleton is at least one of plastic and plastic modified products. The organic polymer material coated on the surface of the three-dimensional porous 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 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 three-dimensional porous material system, the planar static contact angle of the organic polymer material coated on the surface of the three-dimensional porous skeleton to water in the air is preferably larger than 90 degrees, so that a water body can be better prevented from entering a pore channel of the three-dimensional porous material; the plane static contact angle to oil is less than 90 degrees, so that the oil can more quickly and smoothly enter the pore channel of the three-dimensional porous material.
Wherein the plastic can be selected from thermosetting plastics and/or thermoplastic plastics in the prior art. 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.
Specifically, the organic polymer material is preferably selected from polyolefin, poly-4-methyl-1-pentene, polyamide resin (such as nylon-5, nylon-12, nylon-6/6, nylon-6/10, nylon-11), polycarbonate resin, linear polyester obtained by condensation polymerization of homo-and/or co-polyformaldehyde, saturated dibasic acid and dihydric alcohol, aromatic ring polymer (polymer whose molecule is composed of aromatic ring and connecting group only, such as polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulfone, polyaryl ketone, polyaryl ester, and aromatic polyamide), heterocyclic polymer (polymer whose molecule main chain contains heterocyclic rings in addition to aromatic ring, such as polybenzimidazole), fluorine-containing polymer, acrylic resin, urethane, epoxy resin, and aromatic hydrocarbon, At least one of phenol resin, urea resin, melamine formaldehyde resin, and the like. At least one of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, acrylic resin, urea resin, phenol resin, and epoxy resin may be further preferred. More preferably at least one of acrylic resin, urea resin, phenol resin and epoxy resin. Most preferred is a phenolic resin.
Most preferably, the organic polymer material coated on the surface of the three-dimensional porous 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 more 'green'. The total content of ethanol and/or water in the solvent which is friendly to human bodies and environment accounts for 50-100 wt% of the mass 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 static contact angle of the super-hydrophobic and super-oleophilic three-dimensional porous material to water in the air is larger than 130 degrees, preferably larger than 140 degrees, and more preferably larger than 150 degrees; a static contact angle to oil of less than 5 °, preferably less than 4 °, more preferably less than 3 °; has good oil absorption effect.
The invention also aims to provide a preparation method of the super-hydrophobic and super-oleophilic three-dimensional porous material. The organic polymer material is coated on the surface of the three-dimensional porous skeleton, and the coating is achieved by immersing the three-dimensional porous skeleton into a solution of the organic polymer material, then heating the three-dimensional porous skeleton containing the solution of the organic polymer material, and removing a solvent in the solution of the organic polymer material to separate out or solidify the organic polymer material on the surface of the three-dimensional porous skeleton. 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 the organic high polymer material for coating the three-dimensional porous framework by using a solvent to obtain an organic high polymer material solution for coating;
b. b, immersing the three-dimensional porous framework into the organic polymer material solution for coating obtained in the step a, so that the pores of the three-dimensional porous framework are fully filled with the organic polymer material solution for coating; the dosage of the organic polymer material solution for coating can be that the framework material is immersed in the solution.
c. And c, taking out the three-dimensional porous material treated 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 three-dimensional porous skeleton to obtain the super-hydrophobic and super-oleophylic three-dimensional porous material.
Wherein the content of the first and second substances,
in the step a, the mass concentration of the organic polymer material in the organic polymer material solution for coating (i.e. the mass of the polymer material dissolved in each milliliter of solvent) is 0.001-1 g/mL, preferably 0.002-0.8 g/mL, and more preferably 0.003-0.5 g/mL.
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 organic polymer material solution for coating may be completely filled in the pores of the three-dimensional porous skeleton without extrusion, or preferably, the organic polymer material solution for coating may be fully filled in the pores of the three-dimensional porous skeleton 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 three-dimensional porous framework material, and generally can be 0.1-100 min, preferably 1-20 min.
After the three-dimensional porous material obtained in the step b is taken out in the step c, the redundant organic polymer material solution for coating in the three-dimensional porous framework obtained in the step b can be removed without taking measures, and the redundant organic polymer material solution for coating can also be removed by taking one or two measures including but not limited to extrusion, centrifugal operation and the like.
The drying in step c can adopt various drying modes in the prior art. The method can comprise the heating and drying modes in the prior art such as oven heating, infrared heating and the like, wherein the heating temperature range is 60-200 ℃, and 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 can be 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 is thermoplastic plastic, the organic polymer material for coating is separated out and coated on the surface of the three-dimensional porous skeleton after heating in the step c.
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 three-dimensional porous framework.
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 three-dimensional porous material in the fields of oil-water separation, organic solvent treatment, oil-containing wastewater separation and leaked crude oil recovery.
The preparation method effectively utilizes the surface characteristics of the hydrophobic and oleophylic organic polymer material, so that the surface of the three-dimensional porous skeleton has the hydrophobic and oleophylic characteristics, the planar hydrophobic and oleophylic characteristics are amplified in the three-dimensional porous material with a specific aperture range by the capillary phenomenon principle, and the coated three-dimensional porous material achieves super-hydrophobic and super-oleophylic properties. In addition, the method does not need heating, does not damage the original structure of the three-dimensional porous framework, and keeps the original mechanical property. The preparation process of the three-dimensional porous material 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, the mechanical property is excellent, the oil absorption rate is high, the oil absorption multiplying power is high, and the circulation stability is good. 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 three-dimensional porous material is a novel and efficient oil-water separation material, and has wide application prospects in the fields of organic chemical solvent treatment, separation of oily wastewater, recovery of leaked crude oil and the like.
Drawings
FIG. 1-a, FIG. 1-b, FIG. 1-c, and FIG. 1-d are Scanning Electron Microscope (SEM) characterization results of the three-dimensional porous skeleton before and after being coated with the organic polymer material in example 1;
specifically, the method comprises the following steps: FIG. 1-a is a Scanning Electron Microscope (SEM) representation (magnification: 100 times) of the three-dimensional porous skeleton before being coated with the organic polymer material in example 1; FIG. 1 b is a Scanning Electron Microscope (SEM) representation (magnification: 10 ten thousand times) of the three-dimensional porous skeleton before being coated with the organic polymer material in example 1; FIG. 1-c is a Scanning Electron Microscope (SEM) representation (magnification: 100 times) of the three-dimensional porous skeleton coated with the organic polymer material in example 1; FIG. 1 d is a Scanning Electron Microscope (SEM) representation of the three-dimensional porous skeleton coated with an organic polymer material in example 1 (magnification: 10 ten thousand);
FIG. 2 is a result of an experiment in which a sample was placed in a water body before and after a three-dimensional porous skeleton was coated with an organic polymer material in example 1; the three-dimensional porous skeleton sample before coating is immersed in the beaker, and the three-dimensional porous skeleton after coating by the organic polymer material is floated on the water surface;
FIG. 3 shows the experimental results of the forced immersion of the three-dimensional porous skeleton obtained in example 1 in a water body after the skeleton is coated with an organic polymer material;
FIGS. 4-a, 4-b, 4-c, and 4-d show the results of the contact angle tests for water and oil at 0s, 0.5s, 1.0s, and 1.5s, respectively, after the three-dimensional porous skeleton obtained in example 1 was coated with the organic polymer material. Wherein the label 1 is a water droplet and the label 2 is an oil droplet.
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 3g 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) a material weighing 0.06g and having a thickness of 3 × 2 × 1cm was used as a three-dimensional porous skeleton of melamine formaldehyde resin (basf,
the average pore diameter is 100 microns, the porosity is 99.5 percent, and the opening rate is 99.9 percent) is soaked in the prepared solution for 5min, and the solution is extruded for a plurality of times during the soaking period, so that the solution fully enters the pore channel of the three-dimensional porous framework;
(3) and taking out the soaked three-dimensional porous material, putting the three-dimensional porous material into a stainless steel tray, and putting the stainless steel tray into an oven for heating for 2 hours at 180 ℃ to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. The organic polymer material coated on the surface of the three-dimensional porous framework accounts for 60 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
FIGS. 1-a, 1-b, 1-c, and 1-d are Scanning Electron Microscope (SEM) characterization results of the three-dimensional porous skeleton of example 1 before and after being coated with the organic polymer material, and comparison shows that the three-dimensional porous structure before and after coating is a cross-linked mesh structure, wherein the pore size of the macropores ranges from 40 to 400 μm. The fiber surface of the sample is smooth and flat before coating, and after coating, the three-dimensional porous structure of the three-dimensional porous framework is not damaged, the framework has the surface characteristic of a high polymer material used for coating, and meanwhile, the wrinkles are increased, and the roughness is improved.
Fig. 2 shows the experimental results of placing the three-dimensional porous skeleton sample and the sample coated with the organic polymer material in the water body in example 1: the three-dimensional porous framework which is sunk into the water bottom in the beaker before being coated is a three-dimensional porous framework which is floated on the water surface and coated by the organic polymer material. The contrast shows that the three-dimensional porous framework can sink to the water bottom, and the three-dimensional porous framework material coated by the organic polymer material, namely the three-dimensional porous material can float on the water surface.
Fig. 3 is an experimental result of forcedly immersing the three-dimensional porous framework obtained in example 1 into a water body after being coated with an organic polymer material, and a silvery and shiny air film appears on the surface immersed in the water body, which proves that the three-dimensional porous framework can effectively prevent the water body from entering the porous material after being coated with the organic polymer material.
Fig. 4-a, 4-b, 4-c, and 4-d are the results of the contact angle experiments on water and oil at 0s, 0.5s, 1.0s, and 1.5s after the three-dimensional porous skeleton obtained in example 1 is coated with the organic polymer material, respectively, and it is shown by comparison that the contact angle on water is as high as 158.2 ° after the three-dimensional porous skeleton is coated with the organic polymer material, and the contact angle on oil is 0, which is super-oleophilic.
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) a material weighing 0.06g and having a thickness of 3 × 2 × 1cm was used as a three-dimensional porous skeleton of melamine formaldehyde resin (basf,
the average pore diameter is 100 microns, the porosity is 99.5 percent, and the opening rate is 99.9 percent) is soaked in the prepared solution for 5min, and the solution is extruded for a plurality of times to fully enter the pore channel of the three-dimensional porous framework;
(3) and taking out the soaked three-dimensional porous material, putting the three-dimensional porous material into a stainless steel tray, and putting the stainless steel tray into an oven for heating for 2 hours at 180 ℃ to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. Wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 60 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
Example 3
(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) a material weighing 0.06g and having a thickness of 3 × 2 × 1cm was used as a three-dimensional porous skeleton of melamine formaldehyde resin (basf,
the average pore diameter is 100 microns, the porosity is 99.5 percent, and the opening rate is 99.9 percent) is soaked in the prepared solution for 10min, so that the solution fully enters the pore channel of the three-dimensional porous framework;
(3) and taking out the soaked three-dimensional porous material, placing the three-dimensional porous material in a tray, and placing the tray in a household microwave oven for microwave treatment at the power of 700w for 1 hour to obtain the super-hydrophobic super-oleophylic three-dimensional porous material, wherein the organic polymer material coated on the surface of the three-dimensional porous framework accounts for 60 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
Example 4
(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) a material weighing 0.06g and having a thickness of 3 × 2 × 1cm was used as a three-dimensional porous skeleton of melamine formaldehyde resin (basf,
the average pore diameter is 100 microns, the porosity is 99.5 percent, and the opening rate is 99.9 percent) is soaked in the prepared solution for 5min, so that the solution fully enters the pore channel of the three-dimensional porous framework;
(3) and taking out the soaked three-dimensional porous material, placing the three-dimensional porous material in a tray, and placing the three-dimensional porous material in a household microwave oven for microwave treatment at the power of 700w for 1 hour to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. Wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 40 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
Example 5
(1) Weighing 1g 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) a material weighing 0.06g and having a thickness of 3 × 2 × 1cm was used as a three-dimensional porous skeleton of melamine formaldehyde resin (basf,
the average pore diameter is 100 microns, the porosity is 99.5 percent, and the opening rate is 99.9 percent) is soaked in the prepared solution for 3min, so that the solution fully enters the pore channel of the three-dimensional porous framework;
(3) and taking out the soaked three-dimensional porous material, placing the three-dimensional porous material in a tray, and placing the three-dimensional porous material in a household microwave oven for microwave treatment at the power of 700w for 1 hour to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. Wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 20 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
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 a three-dimensional porous skeleton (polyurethane sponge, mean pore diameter 150 micrometers, porosity 99%, opening rate 99%) which is 0.09g and is made of polyurethane and is 3 multiplied by 2 multiplied by 1cm in weight into the prepared solution for 8min, and extruding for several times to ensure that the solution fully enters the pore channel of the three-dimensional porous skeleton;
(3) and taking out the soaked three-dimensional porous material, putting the three-dimensional porous material into a stainless steel tray, and heating the three-dimensional porous material in an oven at 150 ℃ for 3 hours to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. Wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 50 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
Example 7
(1) Weighing 3g of epoxy resin (E-51, ba ling petrochemical) and 1g of low molecular weight polyamide 650 (Yichun xingda chemical company, Inc.) 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 and the polyamide are dissolved (the mixture obtained by curing the epoxy resin and the polyamide in the same ratio under the same curing system and curing condition has a plane static contact angle of 93 degrees to water and a plane static contact angle of 55 degrees to oil in the air);
(2) soaking a three-dimensional porous skeleton (polyurethane sponge, mean pore diameter 150 micrometers, porosity 99%, opening rate 99%) which is 0.09g and is made of polyurethane and is 3 multiplied by 2 multiplied by 1cm in weight into the prepared solution for 5min, and extruding for several times to ensure that the solution fully enters the pore channel of the three-dimensional porous skeleton;
(3) and taking out the soaked three-dimensional porous material, putting the three-dimensional porous material into a stainless steel tray, and putting the stainless steel tray into a 160 ℃ oven to heat for 3 hours to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. Wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 50 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
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 three-dimensional porous skeleton (polyurethane sponge, mean pore diameter 150 micrometers, porosity 99%, opening rate 99%) which is 0.09g and is made of polyurethane and is 3 multiplied by 2 multiplied by 1cm in weight into the prepared solution for 5min, and extruding for several times to ensure that the solution fully enters the pore channel of the three-dimensional porous skeleton;
(3) and taking out the soaked three-dimensional porous material, placing the three-dimensional porous material in a tray, placing the three-dimensional porous material in the tray, and placing the three-dimensional porous material in a household microwave oven for microwave treatment at the power of 700w for 1 hour to obtain the super-hydrophobic super-oleophylic three-dimensional porous material. Wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 30 wt% of the super-hydrophobic super-oleophylic three-dimensional porous material product.
The sample obtained was tested in the same manner as the sample of example 1, and its structure and hydrophobic-lipophilic characteristics were similar to those of the sample obtained in example 1.
Example 9
The three-dimensional porous materials prepared in examples 1 to 8, the uncoated three-dimensional porous skeleton of melamine formaldehyde resin (blank 1), and the uncoated three-dimensional porous skeleton of polyurethane (blank 2) 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, the results are shown in table 1:
TABLE 1
| Examples | Contact angle to water | Contact angle to |
| 1 | 158.2° | 0 |
| 2 | 155.6° | 0 |
| 3 | 154.7° | 0 |
| 4 | 153.2° | 0 |
| 5 | 152.0° | 0 |
| 6 | 152.3° | 0 |
| 7 | 150.7° | 0 |
| 8 | 151.9° | 0 |
| |
0 | 0 |
| |
0 | 0 |
As can be seen from the data in table 1, the three-dimensional porous material of the embodiment of the present invention realizes super-hydrophobic and super-oleophilic properties, and improves oleophilic but also hydrophilic properties of the uncoated framework material; the three-dimensional porous material obtained after coating by the method has super-hydrophobic and super-oleophilic characteristics, high oil absorption rate and high oil absorption multiplying power, can be used as an efficient oil-water separation material, and is widely applied to the fields of organic chemical solvent treatment, separation of oily wastewater, recovery of leaked crude oil and the like.
Claims (17)
1. A super-hydrophobic super-oleophilic three-dimensional porous material is characterized by comprising a three-dimensional porous skeleton and an organic polymer material coated on the surface of the three-dimensional porous skeleton; wherein the material of the three-dimensional porous skeleton is at least one selected from a polymer material, a metal material, a ceramic material and a carbon material; the organic polymer material coated on the surface of the three-dimensional porous skeleton is at least one of plastic and plastic modified products; the plastic is selected from thermosetting plastics and/or thermoplastic plastics;
wherein the organic polymer material coated on the surface of the three-dimensional porous skeleton accounts for 1-99%, preferably 10-95%, and more preferably 20-90% of the total mass of the super-hydrophobic and super-oleophilic three-dimensional porous material.
2. The superhydrophobic, superoleophilic three-dimensional porous material of claim 1, characterized in that: the polymer material of the three-dimensional porous framework is selected from at least one of natural rubber, ethylene propylene rubber, polypropylene, polystyrene, polyether, polyester, polyvinyl alcohol, melamine formaldehyde resin and polyurethane; preferably at least one of melamine formaldehyde resin and polyurethane.
3. The superhydrophobic, superoleophilic three-dimensional porous material of claim 1, characterized in that: the average pore diameter of the three-dimensional porous skeleton is 0.1-1000 micrometers, preferably 10-500 micrometers, and more preferably 50-250 micrometers.
4. The superhydrophobic, superoleophilic three-dimensional porous material of claim 1, characterized in that: the porosity of the three-dimensional porous skeleton is 10-99.999%, preferably 50-99.99%, and more preferably 80-99.9%.
5. The superhydrophobic, superoleophilic three-dimensional porous material of claim 1, characterized in that: the aperture ratio of the three-dimensional porous skeleton is 50-99.999%, preferably 70-99.99%, and more preferably 90-99.9%.
6. The superhydrophobic, superoleophilic three-dimensional porous material of claim 1, characterized in that:
the organic polymer material coated on the surface of the three-dimensional porous 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; among them, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylic resin, polymethyl methacrylate, urea resin, phenol resin, and epoxy resin are preferable; more preferably acrylic resin, urea resin, phenol resin, epoxy resin; most preferred is a phenolic resin.
7. The superhydrophobic, superoleophilic three-dimensional porous material of claim 6, characterized in that:
the organic polymer material coated on the surface of the three-dimensional porous 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.
8. The superhydrophobic, superoleophilic three-dimensional porous material of claim 6, characterized in that:
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.
9. The superhydrophobic, superoleophilic three-dimensional porous material of claim 1, characterized in that:
the organic polymer material coated on the surface of the three-dimensional porous skeleton is an organic polymer material which can be dissolved in a solvent which is friendly to human bodies and environment.
10. The superhydrophobic, superoleophilic three-dimensional porous material of claim 9, characterized in that:
the total content of ethanol and/or water in the solvent which is friendly to human bodies and environment accounts for 50-100 wt% of the mass of the solvent; the human body and environment friendly solvent is preferably ethanol and/or water.
11. The superhydrophobic, superoleophilic three-dimensional porous material according to any one of claims 1-10, characterized in that:
the static contact angle of the super-hydrophobic and super-oleophilic three-dimensional porous material to water in the air is larger than 130 degrees, preferably larger than 140 degrees, and more preferably larger than 150 degrees; the static contact angle to oil is less than 5 °, preferably less than 4 °, more preferably less than 3 °.
12. The method for preparing the superhydrophobic and superoleophilic three-dimensional porous material according to any one of claims 1 to 11, characterized by comprising the steps of:
a. dissolving the organic high polymer material for coating the three-dimensional porous framework by using a solvent to obtain an organic high polymer material solution for coating;
b. b, immersing the three-dimensional porous skeleton into the organic polymer material solution for coating obtained in the step a, so that the pores of the three-dimensional porous skeleton are fully filled with the organic polymer material solution for coating;
c. and c, taking out the three-dimensional porous material treated 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 three-dimensional porous skeleton to obtain the super-hydrophobic and super-oleophylic three-dimensional porous material.
13. The method for preparing the superhydrophobic and superoleophilic three-dimensional porous material according to claim 12, wherein the method comprises the following steps:
in the step a, the mass 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.
14. The method for preparing the superhydrophobic and superoleophilic three-dimensional porous material according to claim 12, wherein the method comprises the following steps:
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 (including p-xylene), trichlorobenzene, chloroform, cyclohexane, ethyl hexanoate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water, 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.
15. The method for preparing the superhydrophobic and superoleophilic three-dimensional porous material according to claim 12, wherein the method comprises the following steps:
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.
16. The method for preparing the superhydrophobic and superoleophilic three-dimensional porous material according to claim 12, wherein the method comprises the following steps:
in the step b, the immersion time is 0.1-100 min, preferably 1-20 min.
17. The use of the superhydrophobic, superoleophilic three-dimensional porous material according to any one of claims 1-11 in the fields of oil-water separation, organic solvent treatment, separation of oily wastewater, and recovery of leaked crude oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810812815.8A CN110743200A (en) | 2018-07-23 | 2018-07-23 | Super-hydrophobic and super-oleophilic three-dimensional porous material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810812815.8A CN110743200A (en) | 2018-07-23 | 2018-07-23 | Super-hydrophobic and super-oleophilic three-dimensional porous material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110743200A true CN110743200A (en) | 2020-02-04 |
Family
ID=69274928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810812815.8A Pending CN110743200A (en) | 2018-07-23 | 2018-07-23 | Super-hydrophobic and super-oleophilic three-dimensional porous material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110743200A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686478A (en) * | 2020-06-30 | 2020-09-22 | 成都大学 | Carbon foam membrane material for oil-water emulsion separation, preparation method and application |
| CN114106408A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Hydrophobic modifier composition, hydrophobic sponge material, preparation method and application thereof |
| CN115181340A (en) * | 2022-06-20 | 2022-10-14 | 中北大学 | Electromagnetic shielding natural rubber for effectively constructing three-dimensional conductive network structure and preparation thereof |
| CN115286894A (en) * | 2021-12-01 | 2022-11-04 | 温州医科大学 | Wear-resistant epoxy resin block-shaped super-hydrophobic material with photo-thermal effect |
| CN115849833A (en) * | 2022-12-30 | 2023-03-28 | 陕西汇丰高性能粉体材料有限公司 | Impervious concrete and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
| CN102794113A (en) * | 2012-08-24 | 2012-11-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super hydrophobic-supper lipophilic polymer porous film, preparation method and application thereof |
| CN103160177A (en) * | 2013-03-13 | 2013-06-19 | 上海大学 | Acrylic resin coating material with superhydrophobicity and preparation method thereof |
| CN105461849A (en) * | 2015-12-28 | 2016-04-06 | 重庆市环境科学研究院 | Preparation method of hydrophobic oleophilic resin and application of hydrophobic oleophilic resin in oil-water separation material |
| CN106310718A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院宁波材料技术与工程研究所 | Superhydrophobic-superolephilic porous material as well as preparation method and application thereof |
-
2018
- 2018-07-23 CN CN201810812815.8A patent/CN110743200A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
| CN102794113A (en) * | 2012-08-24 | 2012-11-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super hydrophobic-supper lipophilic polymer porous film, preparation method and application thereof |
| CN103160177A (en) * | 2013-03-13 | 2013-06-19 | 上海大学 | Acrylic resin coating material with superhydrophobicity and preparation method thereof |
| CN106310718A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院宁波材料技术与工程研究所 | Superhydrophobic-superolephilic porous material as well as preparation method and application thereof |
| CN105461849A (en) * | 2015-12-28 | 2016-04-06 | 重庆市环境科学研究院 | Preparation method of hydrophobic oleophilic resin and application of hydrophobic oleophilic resin in oil-water separation material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686478A (en) * | 2020-06-30 | 2020-09-22 | 成都大学 | Carbon foam membrane material for oil-water emulsion separation, preparation method and application |
| CN111686478B (en) * | 2020-06-30 | 2022-05-24 | 成都大学 | Carbon foam membrane material for oil-water emulsion separation, preparation method and application |
| CN114106408A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Hydrophobic modifier composition, hydrophobic sponge material, preparation method and application thereof |
| CN115286894A (en) * | 2021-12-01 | 2022-11-04 | 温州医科大学 | Wear-resistant epoxy resin block-shaped super-hydrophobic material with photo-thermal effect |
| CN115286894B (en) * | 2021-12-01 | 2023-07-18 | 温州医科大学 | Epoxy resin block-shaped super-hydrophobic material with photo-thermal effect and abrasion resistance |
| CN115181340A (en) * | 2022-06-20 | 2022-10-14 | 中北大学 | Electromagnetic shielding natural rubber for effectively constructing three-dimensional conductive network structure and preparation thereof |
| CN115181340B (en) * | 2022-06-20 | 2023-08-01 | 中北大学 | Electromagnetic shielding natural rubber for effectively constructing three-dimensional conductive network structure and preparation thereof |
| CN115849833A (en) * | 2022-12-30 | 2023-03-28 | 陕西汇丰高性能粉体材料有限公司 | Impervious concrete and preparation method thereof |
| CN115849833B (en) * | 2022-12-30 | 2023-12-08 | 陕西汇丰高性能粉体材料有限公司 | Impervious concrete and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110743200A (en) | Super-hydrophobic and super-oleophilic three-dimensional porous material and preparation method and application thereof | |
| Mi et al. | Highly durable superhydrophobic polymer foams fabricated by extrusion and supercritical CO2 foaming for selective oil absorption | |
| Deng et al. | Recent development of super-wettable materials and their applications in oil-water separation | |
| Udayakumar et al. | Foamed materials for oil-water separation | |
| CN110872741B (en) | Composite nanofiber membrane simultaneously used for emulsion separation and dye adsorption and preparation method thereof | |
| CN110743201A (en) | Super-hydrophobic and super-oleophilic porous net film and preparation method and application thereof | |
| US9724669B2 (en) | Modified hydrophobic sponges | |
| JP2016515933A (en) | Method for producing oil-absorbing hollow fiber porous membrane | |
| Dai et al. | Conversion of skin collagen fibrous material waste to an oil sorbent with pH-responsive switchable wettability for high-efficiency separation of oil/water emulsions | |
| Tang et al. | Three-dimensional adsorbent with pH induced superhydrophobic and superhydrophilic transformation for oil recycle and adsorbent regeneration | |
| CN107020071B (en) | Super-hydrophobic compound carbon aerogels oil absorption material of one kind and preparation method thereof | |
| Wang et al. | Superhydrophobic polycarbonate blend monolith with micro/nano porous structure for selective oil/water separation | |
| CN110616502B (en) | ZnO/polypyrrole modified polyacrylonitrile nanofiber membrane and preparation method thereof | |
| CN109536006B (en) | Preparation method of polysulfone superhydrophobic surface | |
| CN104368247A (en) | Hydrophilic-underwater oleophobic polymer porous membrane, preparation method and applications thereof | |
| CN111841514B (en) | High-performance underwater super-oleophobic recycled foam and preparation method thereof | |
| US9931611B2 (en) | Modified hydrophobic sponges | |
| Li et al. | Surface synthesis of a polyethylene glutaraldehyde coating for improving the oil removal from wastewater of microfiltration carbon membranes | |
| CN111892741B (en) | Hydrophobic modifier, hydrophobic modified sponge, and preparation method and application thereof | |
| Jiao et al. | Synthesis of aminopyridine-containing conjugated microporous polymers with excellent superhydrophobicity for oil/water separation | |
| CN110747643A (en) | Waterproof and breathable fabric and preparation method and application thereof | |
| CN112047427B (en) | Oil-water separation membrane with ion responsiveness, and preparation method and application thereof | |
| CN106823853A (en) | A kind of selfreparing PP membrane for water treatment and preparation method thereof | |
| Ma et al. | Hydrophobic carbon dots modified porous thermoplastic polyurethane for effective and durable oil/water separation | |
| CN114316348B (en) | Long carbon chain polyamide porous membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |