CN115010983A - Super-hydrophobic modified flexible foam and preparation method and application thereof - Google Patents
Super-hydrophobic modified flexible foam and preparation method and application thereof Download PDFInfo
- Publication number
- CN115010983A CN115010983A CN202210811263.5A CN202210811263A CN115010983A CN 115010983 A CN115010983 A CN 115010983A CN 202210811263 A CN202210811263 A CN 202210811263A CN 115010983 A CN115010983 A CN 115010983A
- Authority
- CN
- China
- Prior art keywords
- foam
- flexible foam
- modified
- parts
- hydrophobic modified
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses super-hydrophobic modified flexible foam and a preparation method and application thereof, and belongs to the technical field of functional material preparation. The invention uses hydrophobic modified concentrated emulsion to carry out surface coating treatment on flexible foam, so that the concentrated emulsion is fully absorbed in the foam, then emulsion polymerization is carried out under the heating condition, a nano-aperture structure is formed in the foam, and finally super-hydrophobic modified flexible foam is obtained through washing and drying treatment, wherein the hydrophobic modified concentrated emulsion comprises a modified monomer, an initiator, a cross-linking agent, an emulsifier, a low surface energy modifier and water. The super-hydrophobic modified flexible foam prepared by the invention has excellent hydrophobic and oleophylic properties, simple process, mild reaction conditions, no toxic or harmful solvent, low cost and short period, is expected to realize macro preparation and marketization popularization of the material, and realizes application of the material in treating large-area water pollution and separating oil-water mixtures.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to super-hydrophobic modified flexible foam and a preparation method and application thereof.
Background
Oily sewage generated by oil tankers during operations, subsea oil production and petrochemical processes causes a devastating disaster to the environment, for example, the oil tanker "Front Altair" causes a large leakage of crude oil due to a torpedo explosion. Therefore, it is urgently required to develop green and safe oil-water separation materials such as fibers, copper mesh, molecular sieve, sponge, woven fabric and the like, and to find a technology for effectively separating oil-water mixture. The three-dimensional porous flexible foam has the advantages of low cost, light weight, environmental friendliness, inherent microporous structure and the like, and has wide application prospect in large-scale oily wastewater treatment. However, the inherent hydrophilicity and lipophilicity of the flexible foam can reduce the efficiency of oil-water separation, making the foam a flammable secondary pollutant. Therefore, the premise of improving the separation efficiency of the sponge oil-water mixture is to improve the selectivity of the sponge oil-water mixture, such as developing super-hydrophobic/super-oleophilic flexible foam sponge.
Although the design considerations for the modification of superhydrophobic flexible foams are elaborate, in practice, the modification process for most three-dimensional porous flexible foams is complex, and the reagents and associated equipment used are expensive. Meanwhile, the modification process is harmful to the environment, and the aperture of the three-dimensional porous flexible foam is too large, so that oil-water emulsion cannot be effectively separated, and large-scale industrial application is limited. Therefore, it remains a challenge to develop an easy, low-cost and environmentally friendly modified flexible foam and to widely use it for oil-water separation.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and firstly provides a preparation method of super-hydrophobic modified flexible foam, which comprises the following steps: the method comprises the steps of carrying out surface coating treatment on flexible foam by using hydrophobic modified concentrated emulsion to enable the concentrated emulsion to be fully absorbed in the foam, then carrying out emulsion polymerization under the heating condition to form a nano-pore structure in the foam, and finally carrying out washing and drying treatment to obtain the super-hydrophobic modified flexible foam, wherein the hydrophobic modified emulsion comprises a modified monomer, an initiator, a cross-linking agent, an emulsifier, a low-surface-energy modifier and water.
Specifically, the total weight of the modified monomer and the cross-linking agent in the hydrophobic modified concentrated emulsion is 40-60 parts, the initiator is 1-5 parts, the emulsifier is 10-30 parts, the low surface energy modifier is 5-20 parts, and the water is 100-5000 parts.
Preferably, the mass ratio of the modifying monomer to the cross-linking agent is 3: 2.
In order to ensure that the hydrophobically modified concentrated emulsion can smoothly and fully enter the foam, and meanwhile, a porous material with a nanometer-scale void structure smaller than the pore diameter of the foam can be formed in the foam through reaction, as a preferred embodiment, the invention controls the water phase content to be between 74 and 100 percent in the process of preparing the hydrophobically modified concentrated emulsion, wherein the water phase content refers to the mass percent of water in the emulsion.
The preparation method of the hydrophobic modified concentrated emulsion comprises the steps of dispersing an initiator in deionized water to obtain a solution A containing the initiator, uniformly mixing a modified monomer, a cross-linking agent, an emulsifier and a low-surface-energy modifier to obtain a mixed solution B, and dispersing the mixed solution A in the solution B to obtain the hydrophobic modified concentrated emulsion.
Preferably, in the process of preparing the hydrophobic modified concentrated emulsion, the weight ratio of the mixed solution B to the solution A is 1-40: 35-1000.
Since the concentrated emulsion prepared by the invention is of water-in-oil type, in order to achieve a stable and uniform emulsion state, as a preferred embodiment, the solution A containing the initiator needs to be dripped into the solution B a small amount of times, and each dripping needs to be carried out after the oil completely wraps the water, otherwise, the next dripping is carried out if the water is not completely wrapped, and a stable and uniform concentrated emulsion cannot be formed.
Preferably, the solution A is dripped into the mixed solution B by using a rubber head dropper from slow to fast while stirring, so as to prepare the hydrophobic modified concentrated emulsion.
Preferably, the stirring speed is controlled at 3500-.
Wherein the modified monomer is one of phenylacetamide, styrene, acrylonitrile, methyl methacrylate, vinyl acetate and butyl acrylate.
Wherein the low surface energy modifier is one of gamma-aminopropyl triethoxysilane, polydimethylsiloxane, stearic acid, calcium stearate, dodecyl mercaptan and vinyl triethoxysilane.
Wherein the initiator is one of potassium persulfate, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate and an ammonium persulfate/sodium bisulfite composite system.
Wherein the cross-linking agent is one of divinylbenzene, ethylene glycol dimethacrylate, dipentaerythritol pentaacrylate and N, N-methylenebisacrylamide.
Wherein the emulsifier is one of Tween80, Span80, hexadecyl ammonium chloride, N-dodecyl dimethylamine and sodium dodecyl sulfate.
Wherein the flexible foam is one of polyurethane foam, phenolic foam, polyimide foam, melamine foam, polyethylene foam and rubber foam.
Preferably, 1000-4000 parts by weight of the hydrophobic modified concentrated emulsion is uniformly coated on 5-50 parts by weight of the surface of the flexible foam.
Preferably, after the surface coating treatment, the concentrated emulsion is fully absorbed in the foam by adopting a reduced pressure suction filtration mode.
Preferably, the pressure is reduced and the filtration is carried out under the condition of 0.02-0.1 MPa.
Wherein the emulsion polymerization is carried out for 4-24h at 25-80 ℃.
Wherein the drying treatment is air drying at 40-100 deg.C for 8-24 hr.
The reaction is the solidification forming of the concentrated emulsion at the temperature of 25-80 ℃, a small amount of unreacted or redundant other medicines are left on the surface of the foam after the solidification forming of the concentrated emulsion, the foam is soaked by absolute ethyl alcohol to remove impurities after the reaction is finished, and then the foam is placed at the temperature of 40-100 ℃ to be dried by air blowing to remove the absolute ethyl alcohol, so that the final product is obtained.
Preferably, after the concentrated emulsion is sufficiently absorbed in the foam, the reaction system is sealed and then placed in an oil bath, a water bath or an oven for reaction, and then taken out, washed and dried. In order to introduce the concentrated emulsion into the porous structure of the foam better, the invention can retain all the concentrated emulsion in the foam structure as far as possible when the foam coated with the concentrated emulsion is sealed and then reacts, if the reaction is directly heated in the air, a part of the concentrated emulsion can be separated from water phase in the reaction process, thereby influencing the porous structure of the product and the subsequent oil-water separation performance.
The invention has no special requirements for the selection of flexible foams, and is commercially available, but in order to obtain better results, foam products with high porosity and open-cell structure are preferably selected.
The invention further discloses the super-hydrophobic modified flexible foam prepared by the preparation method and application in oil-water separation.
The invention relates to an application of super-hydrophobic modified flexible foam in oil-water separation, in particular to an application of super-hydrophobic modified flexible foam in oil-water separation.
The invention has the following advantages and beneficial effects:
the super-hydrophobic modified flexible foam disclosed by the invention is simple in preparation process, mild in chemical reaction condition, short in required period, low in cost, free of pollution to the environment, and capable of meeting the concept of green, environment-friendly and sustainable development, and is expected to realize macro preparation and marketization popularization of materials;
the super-hydrophobic modified flexible foam prepared by the invention has excellent hydrophobic and oleophylic properties, can continuously and efficiently separate an incompatible oil-water mixing system and a micro-nano-grade oil-water emulsion mixture in a gravity mode, and is expected to realize the application of the material in the treatment of large-area water pollution;
according to the invention, the micro-porous structure of the concentrated emulsion is introduced into the flexible foam through emulsion polymerization, and the aperture of the modified flexible foam is reduced from the original 100-1000 microns to 100-10 microns based on the size sieving effect, so that the water-in-oil emulsion separation with stable surfactant is realized.
Drawings
FIG. 1 is a scanning electron microscope image of a flexible foam (a) before modification, a low magnification (b) of a superhydrophobic-modified flexible foam of example 1, and a high magnification (c) of a superhydrophobic-modified flexible foam of example 1;
FIG. 2 is the static contact angle of the flexible foam before modification (a), the superhydrophobic-modified flexible foam of example 1 (b) (c);
FIG. 3 is a macro wetting performance test of the superhydrophobic-modified flexible foam of example 1;
FIG. 4 shows the oil-water separation test of the superhydrophobic-modified flexible foam of example 1 on a petroleum ether/water mixture (a) and a chloroform/water mixture (b), respectively;
FIG. 5 is a water-in-toluene emulsion separation test for surfactant stabilization of superhydrophobic-modified flexible foams of example 1 under the force of gravity.
Detailed Description
The pore size of the existing three-dimensional foam porous material is not enough to separate oil-water emulsion, but most of the three-dimensional foam porous material is oil-water emulsion mixture in the practical situations of offshore crude oil leakage, factory oil leakage and the like, and the three-dimensional foam porous material can not be practically applied without solving the problem of separating the emulsion. Based on the advantages of low cost, light weight, environmental friendliness and the like of the three-dimensional porous commercial flexible foam, and the requirement of complex process, expensive equipment and reagents in the existing foam surface modification technology, the invention designs a simple, green, efficient and low-cost preparation method of the super-hydrophobic modified flexible foam, which is expected to be used for treating large-scale oily wastewater, in particular to oil-water emulsion type wastewater or oil-gas field produced liquid with stable surfactant. The invention provides a preparation method of super-hydrophobic modified flexible foam, which comprises the following steps:
(1) dispersing 1 weight part of initiator in 100-5000 weight parts of deionized water to obtain a solution A containing the initiator;
(2) dispersing 50 parts by weight of modified monomer and crosslinking agent (the ratio of the modified monomer to the crosslinking agent is 3: 2), 10-30 parts by weight of emulsifier and 5-20 parts by weight of low surface energy modifier to prepare a mixed solution B;
(3) dripping the solution A into the mixed solution B from slow to fast by using a rubber head dropper while stirring to prepare a concentrated emulsion C, wherein the water phase content in the whole concentrated emulsion C is more than or equal to 74 percent, and the mechanical stirring speed is 3500-;
(4) uniformly coating 1000-4000 parts by weight of concentrated emulsion C on the surface of 5-50 parts by weight of flexible foam, and completely permeating the concentrated emulsion C into the porous structure of the flexible foam by adopting a reduced pressure suction filtration mode under the condition of 0.02-0.1 MPa;
(5) sealing the flexible foam permeated with the concentrated emulsion C, placing the flexible foam in an environment with the temperature of 25-80 ℃ for reacting for 4-24h, cleaning the product with absolute ethyl alcohol, and then performing forced air drying at the temperature of 40-100 ℃ for 8-24h to obtain the super-hydrophobic modified flexible foam.
The invention introduces the micro-porous structure of the concentrated emulsion into the flexible foam through emulsion polymerization reaction, and relates to the following principles: the method comprises the following steps of fully feeding concentrated emulsion into a foam structure through modes of coating, pressure reduction, suction filtration and the like, carrying out emulsion polymerization under a heating condition, wherein the modified foam structure is a small hole structure which is fully filled in a large hole structure of original flexible foam, the original flexible foam is hydrophilic and oleophilic, a low surface energy modification reagent is added to endow the material with low surface energy, and the super-hydrophobic modification of the flexible foam is realized by increasing roughness and reducing surface energy, so that the super-hydrophobic and super-oleophilic characteristics are realized.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention. Wherein the flexible foam used in the examples described below was purchased from Chengdu beautiful and navy new materials science and technology Limited and has an apparent density of 6-12kg/m 3 The porosity was 99%.
Example 1
The super-hydrophobic modified melamine foam of the embodiment is prepared by the following steps:
(1) dispersing 2 parts by weight of sodium persulfate initiator into 1500 parts by weight of deionized water to obtain a solution A containing sodium persulfate;
(2) mixing 30 parts by weight of styrene, 20 parts by weight of divinylbenzene, 15 parts by weight of emulsifier Span80 and 5 parts by weight of polydimethylsiloxane to obtain a solution B;
(3) using a rubber head dropper to stir the solution A into the mixed solution B from slow to fast while dripping to prepare a concentrated emulsion C, wherein the mechanical stirring speed is 5000 r/min;
(4) uniformly coating 1000 parts by weight of concentrated emulsion C on the surface of 5 parts by weight of melamine flexible foam, then completely permeating the concentrated emulsion C into a porous structure of the flexible foam in a decompression suction filtration mode, sealing the coated flexible foam, placing the sealed flexible foam in an oven for reacting for 8 hours at 65 ℃, cleaning a product with absolute ethyl alcohol, and then drying by air blowing at 50 ℃ for 12 hours to obtain the super-hydrophobic modified melamine foam.
Example 2
The super-hydrophobic modified melamine foam of the embodiment is prepared by the following steps:
(1) dispersing 3 parts by weight of sodium persulfate initiator into 3000 parts by weight of deionized water to obtain a solution A containing sodium persulfate;
(2) mixing 30 parts by weight of phenylacetamide, 20 parts by weight of ethylene glycol dimethacrylate, 20 parts by weight of emulsifier Tween80 and 10 parts by weight of gamma-aminopropyltriethoxysilane to obtain a solution B;
(3) using a rubber head dropper to stir the solution A into the mixed solution B from slow to fast while dripping to prepare a concentrated emulsion C, wherein the mechanical stirring speed is 3500 rpm;
(4) uniformly coating 2000 parts by weight of concentrated emulsion C on the surface of 6 parts by weight of flexible foam, then completely permeating the concentrated emulsion C into a porous structure of melamine foam in a decompression suction filtration mode, sealing the coated melamine foam, placing the sealed melamine foam in an oven for reaction at 60 ℃ for 6 hours, cleaning a product with absolute ethyl alcohol, and then drying the product by air blowing at 60 ℃ for 10 hours to obtain the super-hydrophobic modified melamine foam.
Example 3
The super-hydrophobic modified polyurethane foam is prepared by the following steps:
(1) dispersing 3 parts by weight of azobisisobutyronitrile initiator into 3000 parts by weight of deionized water to obtain a solution A containing azobisisobutyronitrile;
(2) mixing 36 parts by weight of methyl methacrylate, 24 parts by weight of dipentaerythritol pentaacrylate, 25 parts by weight of emulsifier hexadecyl ammonium chloride and 12 parts by weight of stearic acid to obtain a solution B;
(3) the solution A is added into the mixed solution B from slow to fast by using a rubber head dropper while being added dropwise and mechanically stirred to prepare a concentrated emulsion C, wherein the mechanical stirring speed is 8000 revolutions per minute;
(4) uniformly coating 1500 parts by weight of concentrated emulsion C on the surface of 5 parts by weight of polyurethane foam, then completely permeating the concentrated emulsion C into a porous structure of the polyurethane foam in a decompression suction filtration mode, sealing the coated polyurethane foam, placing the sealed polyurethane foam in an oven at 55 ℃ for reaction for 5 hours, cleaning a product with absolute ethyl alcohol, and then drying the product by blowing at 70 ℃ for 8 hours to obtain the super-hydrophobic modified polyurethane foam.
Example 4
The super-hydrophobic modified polyethylene foam is prepared by the following steps:
(1) dispersing 3 parts by weight of dimethyl azodiisobutyrate initiator into 2500 parts by weight of deionized water to obtain solution A containing dimethyl azodiisobutyrate;
(2) mixing 40 parts by weight of butyl acrylate, 20 parts by weight of N, N-methylene bisacrylamide, 15 parts by weight of emulsifier sodium dodecyl sulfate and 8 parts by weight of vinyl triethoxysilane to obtain a solution B;
(3) mechanically stirring the solution A into the mixed solution B from slow to fast by using a rubber head dropper, and dropwise adding at the same time to prepare a concentrated emulsion C, wherein the mechanical stirring speed is 3500 rpm;
(4) uniformly coating 3000 parts by weight of concentrated emulsion C on the surface of 7 parts by weight of polyethylene foam, then completely permeating the concentrated emulsion C into a porous structure of the polyethylene foam in a decompression suction filtration mode, sealing the coated polyethylene foam, placing the sealed polyethylene foam in an oven for reaction at 50 ℃ for 6 hours, cleaning a product with absolute ethyl alcohol, and then drying the product by air blowing at 80 ℃ for 8 hours to obtain the super-hydrophobic modified polyethylene foam.
Example 5
The super-hydrophobic modified phenolic foam of the embodiment is prepared by the following steps:
(1) dispersing 5 parts by weight of potassium persulfate initiator into 2000 parts by weight of deionized water to obtain a solution A containing potassium persulfate;
(2) mixing 30 parts by weight of acrylonitrile, 20 parts by weight of divinylbenzene, 25 parts by weight of emulsifier hexadecyl ammonium chloride and 10 parts by weight of polydimethylsiloxane to obtain a solution B;
(3) using a rubber head dropper to stir the solution A into the mixed solution B from slow to fast while dripping to prepare a concentrated emulsion C, wherein the mechanical stirring speed is 3500 rpm;
(4) uniformly coating 4000 parts of concentrated emulsion C on the surface of 8 parts of phenolic foam by weight, then completely permeating the concentrated emulsion C into a porous structure of the phenolic foam in a reduced pressure suction filtration mode, sealing the coated phenolic foam, placing the sealed phenolic foam in an oven at 70 ℃ for reacting for 8h, cleaning a product with absolute ethyl alcohol, and then drying by air blowing at 70 ℃ for 12h to obtain the super-hydrophobic modified phenolic foam.
Structural characterization and Performance test example
1. Scanning Electron microscope Picture (SEM)
JSM-7500F scanning electron microscope is adopted to analyze the morphology of original flexible foam and embodiment modified flexible foam, the accelerating voltage is 20.0KV, surface metal spraying treatment is needed before sample test, and the structural characterization is shown in figure 1. As can be seen from the figure, the aperture of the original flexible foam is dozens of microns and hundreds of microns, the aperture of the modified flexible foam in example 1 is dozens of nanometers and hundreds of nanometers, and the difference is about 100 times.
2. Static contact Angle test (WCA)
The static water contact angle of the surface of the modified foam of the original flexible foam example was measured using a model OCA25 tester from Dataphysics, germany, and the results are shown in fig. 2.
3. Macroscopic wetting Properties
A small amount of deionized water was taken through a 2.5ml syringe and the surface of the modified flexible foam was subjected to macroscopic wetting performance testing, the results of which are shown in fig. 3.
4. Macroscopic oil-water separation test
Petroleum ether and red oil O are dyed with oil soluble pigment methyl orange, and water is dyed with water soluble pigment bromophenol blue. The results of the oil-water separation test using the modified flexible foam of example on the light oil/water mixture and the heavy oil/water mixture are shown in fig. 4.
5. Surfactant-stabilized oil-water emulsion separation test on modified Flexible foam of example
The specific test method comprises the following steps: (1) preparing an oil-water emulsion: surfactant stabilized water-in-toluene emulsions were prepared. At V Water (W) ：V Toluene 1: under the condition of 99, adding 1g/L of Span80 surfactant, and stirring for 1h at 1500r/min to obtain stable water-in-toluene emulsion; (2) oil-water emulsion separation: the appropriate amount of modified foam prepared in example one was secured to the neck of the funnel.
Under the action of gravity, the modified foam realizes the separation of the surfactant-stabilized water-in-toluene emulsion based on the hydrophobic-lipophilic opposite intermolecular force and the size sieving effect, as shown in fig. 5 (a). The liquid before and after separation was observed by an eyepiece-free inverted fluorescence digital microscope, and there were many droplets in the milky water-in-toluene emulsion before separation as shown in fig. 5(d), but a clear oil phase was obtained after separation and no droplets were observed in the filtrate after separation as shown in fig. 5 (c). The pore diameter of the modified foam is mostly in the nanometer level, so that when the oil-water emulsion is separated, the nanometer level pores are enough to realize separation through size screening, and a better separation effect can be achieved without reducing the pore diameter in a compression mode
The above structural characterization and performance test results of the super-hydrophobic modified flexible foams prepared in examples 2-5 are similar to those of example 1, so that the super-hydrophobic modified flexible foams prepared in the invention have excellent hydrophobic and oleophilic properties and can be used for separating oil-water mixtures.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. Several alternatives or modifications to these described embodiments may be made without departing from the inventive concept and should be considered as falling within the scope of the invention.
Claims (10)
1. A preparation method of super-hydrophobic modified flexible foam is characterized by comprising the following steps: the method comprises the steps of carrying out surface coating treatment on flexible foam by using hydrophobic modified concentrated emulsion to enable the concentrated emulsion to be fully absorbed in the foam, then carrying out emulsion polymerization under the heating condition to form a nano-pore structure in the foam, and finally carrying out washing and drying treatment to obtain the super-hydrophobic modified flexible foam, thereby obtaining the super-hydrophobic modified flexible foam, wherein the hydrophobic modified concentrated emulsion comprises a modified monomer, an initiator, a cross-linking agent, an emulsifier, a low-surface-energy modifier and water.
2. The method for preparing the superhydrophobic-modified flexible foam of claim 1, wherein the method comprises the following steps: the hydrophobic modified concentrated emulsion comprises, by weight, 40-60 parts of modified monomer and crosslinking agent, 1-5 parts of initiator, 10-30 parts of emulsifier, 5-20 parts of low surface energy modifier and 100 parts of water and 5000 parts of cross-linking agent; the mass ratio of the modified monomer to the cross-linking agent is 3: 2; the water phase content of the hydrophobic modified concentrated emulsion is controlled to be not less than 74%.
3. The method for preparing the superhydrophobic-modified flexible foam of claim 1 or 2, characterized in that the method for preparing the hydrophobically-modified concentrated emulsion comprises the steps of: dispersing an initiator in deionized water to obtain a solution A containing the initiator, uniformly mixing a modified monomer, a cross-linking agent, an emulsifier and a low-surface-energy modifier to obtain a mixed solution B, and dispersing the mixed solution A in the solution B to obtain a hydrophobic modified concentrated emulsion; the weight ratio of the mixed solution B to the solution A is 1-40: 35-1000.
4. A method of preparing a superhydrophobic-modified flexible foam according to any one of claims 1-3, wherein: the modified monomer is one of phenylacetamide, styrene, acrylonitrile, methyl methacrylate, vinyl acetate and butyl acrylate; the low surface energy modifier is one of gamma-aminopropyl triethoxysilane, polydimethylsiloxane, stearic acid, calcium stearate, dodecyl mercaptan and vinyl triethoxysilane.
5. The method of preparing superhydrophobic-modified flexible foam according to any one of claims 1-4, wherein: the initiator is one of potassium persulfate, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate and an ammonium persulfate/sodium bisulfite composite system; the cross-linking agent is one of divinylbenzene, ethylene glycol dimethacrylate, dipentaerythritol pentaacrylate and N, N-methylenebisacrylamide.
6. The method of preparing superhydrophobic-modified flexible foam according to any one of claims 1-5, wherein: the emulsifier is one of Tween80, Span80, hexadecyl ammonium chloride, N-dodecyl dimethylamine and sodium dodecyl sulfate.
7. The method of preparing a superhydrophobic-modified flexible foam according to any one of claims 1-6, wherein: the flexible foam is one of polyurethane foam, phenolic foam, polyimide foam, melamine foam, polyethylene foam and rubber foam; and uniformly coating 1000-4000 parts by weight of hydrophobic modified concentrated emulsion on the surface of 5-50 parts by weight of flexible foam.
8. The method of preparing a superhydrophobic-modified flexible foam according to any one of claims 1-7, wherein: after the surface coating treatment, a reduced pressure suction filtration mode is adopted to ensure that the concentrated emulsion is fully absorbed in the foam; vacuum filtering under 0.02-0.1 MPa; the emulsion polymerization is carried out in a sealed environment; emulsion polymerization is carried out for 4-24h at 25-80 ℃; the drying treatment is specifically air drying at 40-100 deg.C for 8-24 h.
9. The super-hydrophobic modified flexible foam prepared by the preparation method of any one of claims 1 to 8.
10. Use of the superhydrophobic-modified flexible foam of claim 9 in oil-water separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210811263.5A CN115010983B (en) | 2022-07-11 | 2022-07-11 | Super-hydrophobic modified flexible foam and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210811263.5A CN115010983B (en) | 2022-07-11 | 2022-07-11 | Super-hydrophobic modified flexible foam and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115010983A true CN115010983A (en) | 2022-09-06 |
| CN115010983B CN115010983B (en) | 2023-08-11 |
Family
ID=83082220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210811263.5A Active CN115010983B (en) | 2022-07-11 | 2022-07-11 | Super-hydrophobic modified flexible foam and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115010983B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116014453A (en) * | 2022-10-27 | 2023-04-25 | 电子科技大学 | Super-hydrophobic terahertz wave absorber based on MXene and cage-shaped structure three-dimensional foam |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030011092A1 (en) * | 2001-06-13 | 2003-01-16 | 3M Innovative Properties Company | Uncrosslinked foams made from emulsions |
| US6573305B1 (en) * | 1999-09-17 | 2003-06-03 | 3M Innovative Properties Company | Foams made by photopolymerization of emulsions |
| US6750261B1 (en) * | 2003-04-08 | 2004-06-15 | 3M Innovative Properties Company | High internal phase emulsion foams containing polyelectrolytes |
| CN105777998A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院化学研究所 | Cone-shaped Janus particle, preparation method and application thereof |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN113788977A (en) * | 2021-09-07 | 2021-12-14 | 浙江理工大学 | Preparation method of flexible pore material |
| CN114369278A (en) * | 2022-01-24 | 2022-04-19 | 西南石油大学 | Method for preparing super-hydrophobic porous material based on double-emulsion template |
-
2022
- 2022-07-11 CN CN202210811263.5A patent/CN115010983B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6573305B1 (en) * | 1999-09-17 | 2003-06-03 | 3M Innovative Properties Company | Foams made by photopolymerization of emulsions |
| US20030011092A1 (en) * | 2001-06-13 | 2003-01-16 | 3M Innovative Properties Company | Uncrosslinked foams made from emulsions |
| US6750261B1 (en) * | 2003-04-08 | 2004-06-15 | 3M Innovative Properties Company | High internal phase emulsion foams containing polyelectrolytes |
| CN105777998A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院化学研究所 | Cone-shaped Janus particle, preparation method and application thereof |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN113788977A (en) * | 2021-09-07 | 2021-12-14 | 浙江理工大学 | Preparation method of flexible pore material |
| CN114369278A (en) * | 2022-01-24 | 2022-04-19 | 西南石油大学 | Method for preparing super-hydrophobic porous material based on double-emulsion template |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116014453A (en) * | 2022-10-27 | 2023-04-25 | 电子科技大学 | Super-hydrophobic terahertz wave absorber based on MXene and cage-shaped structure three-dimensional foam |
| CN116014453B (en) * | 2022-10-27 | 2023-08-15 | 电子科技大学 | Super-hydrophobic terahertz wave absorber based on MXene and cage-shaped structure three-dimensional foam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115010983B (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Robust superhydrophobic attapulgite coated polyurethane sponge for efficient immiscible oil/water mixture and emulsion separation | |
| Zhou et al. | One-pot synthesis of robust superhydrophobic, functionalized graphene/polyurethane sponge for effective continuous oil–water separation | |
| CN106807338B (en) | A kind of preparation method of the modified graphene enhancing polyurethane sponge for water-oil separating | |
| CN103893999B (en) | A kind of super oil-water separation mesh film that is hydrophilic and super oleophobic under water and preparation method thereof | |
| Hu et al. | Designing high-caliber nonwoven filter mats for coalescence filtration of oil/water emulsions | |
| Liu et al. | Surface modification of porous substrates for oil/water separation using crosslinkable polybenzoxazine as an agent | |
| Xue et al. | Hierarchical superhydrophobic polydimethylsiloxane/copper terephthalate/polyurethane sponge for highly efficient oil/water separation | |
| Zhao et al. | Poly (dimethylsiloxane)/graphene oxide composite sponge: a robust and reusable adsorbent for efficient oil/water separation | |
| Jiang et al. | Coaxial electrospun nanofibrous aerogels for effective removal of oils and separation of water-in-oil emulsions | |
| CN115010983A (en) | Super-hydrophobic modified flexible foam and preparation method and application thereof | |
| CN104826363A (en) | Super-hydrophobic super-lipophilic emulsion separating mesh membrane, and production method and application thereof | |
| Chen et al. | Incorporation of UiO-66-NH2 into modified PAN nanofibers to enhance adsorption capacity and selectivity for oil removal | |
| Jiang et al. | Fabrication of superhydrophobic cotton fabrics using crosslinking polymerization method | |
| Meng et al. | Preparation and modification of cellulose sponge and application of oil/water separation | |
| CN106283851A (en) | A kind of graphene oxide modification oil-water separation filter paper and preparation method thereof | |
| Zhiheng et al. | A bio-inspired green method to fabricate pH-responsive sponge with switchable surface wettability for multitasking and effective oil-water separation | |
| CN114369191B (en) | Preparation method of super-hydrophobic polystyrene porous material | |
| Chen et al. | Functionalization of biodegradable PLA nonwoven fabrics as super-wetting membranes for simultaneous efficient dye and oil/water separation | |
| CN110280048B (en) | Underwater super-oleophobic and oil-super-hydrophobic material for oil-water emulsion separation and solvent-free preparation method thereof | |
| Huang et al. | Superhydrophobic and magnetic PS/Fe 3 O 4 sponge for remote oil removal under magnetic driven, continuous oil collection, and oil/water emulsion separation | |
| Chen et al. | Surface glycopolymer-modified functional macroporous polyHIPE obtained by ATRP for the removal of boron in water | |
| Guo et al. | Preparation of polymer-based foam for efficient oil–water separation based on surface engineering | |
| Zhang et al. | Polyester fabrics coated with cupric hydroxide and cellulose for the treatment of kitchen oily wastewater | |
| CN104707582A (en) | Super-hydrophobic porous Fe3O4/PS nano composite material and preparation method thereof | |
| CN106925238B (en) | A kind of sponge support type organic solvent absorbent 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |