CN115010983B - 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
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- CN115010983B CN115010983B CN202210811263.5A CN202210811263A CN115010983B CN 115010983 B CN115010983 B CN 115010983B CN 202210811263 A CN202210811263 A CN 202210811263A CN 115010983 B CN115010983 B CN 115010983B
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- B01D—SEPARATION
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- C08F2/00—Processes of polymerisation
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
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- 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
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- 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
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- 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
Abstract
The invention discloses a super-hydrophobic modified flexible foam, 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 pore diameter 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 modified monomer, initiator, cross-linking agent, emulsifying agent, low surface energy modifying agent 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 marketing popularization of materials, and realizes the application of the materials in treating large-area water pollution separation oil-water mixtures.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a super-hydrophobic modified flexible foam, and a preparation method and application thereof.
Background
The oil-containing sewage generated by the oil tanker during the operation, the submarine oil extraction and the petrochemical process brings destructive disasters to the environment, for example, the oil tanker of the Front Altair number causes a great amount of crude oil leakage due to the torpedo explosion. Therefore, there is an urgent need to develop green and safe oil-water separation materials such as fibers, copper mesh, molecular sieves, sponges, woven fabrics, etc., and to find a technology for effectively separating oil-water mixtures. The three-dimensional porous flexible foam has the advantages of low cost, light weight, environment friendliness, inherent micropore structure and the like, and has wide application prospect in large-scale oily wastewater treatment. However, the inherent hydrophilicity and lipophilicity of 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 development of super-hydrophobic/super-oleophilic flexible foam sponge.
Although the design concept for modification of superhydrophobic flexible foams is elaborate, in practice, the modification process of 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 pore diameter of the three-dimensional porous flexible foam is too large, so that the oil-water emulsion cannot be effectively separated, and the large-scale industrial application is limited. Therefore, developing simple, low-cost and environmentally friendly modified flexible foams and using them widely for oil-water separation remains a challenge.
Disclosure of Invention
The invention provides a preparation method of super-hydrophobic modified flexible foam, which solves the problems in the prior art and comprises the following steps: and carrying out surface coating treatment on the flexible foam by using a hydrophobic modified concentrated emulsion, so that the concentrated emulsion is fully absorbed in the foam, then carrying out emulsion polymerization under the heating condition, forming a nano pore structure in the foam, and finally washing and drying to obtain the super-hydrophobic modified flexible foam, wherein the hydrophobic modified emulsion comprises a modified monomer, an initiator, a cross-linking agent, an emulsifying agent, a low surface energy modifying agent 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 modified monomer to the cross-linking agent is 3:2.
In order to enable the hydrophobically modified concentrated emulsion to smoothly and fully enter the foam and simultaneously react in the foam to form a porous material with a nanoscale void structure smaller than the pore size of the foam, as a preferred embodiment, the invention controls the water phase content in the process of preparing the hydrophobically modified concentrated emulsion to be between 74 and 100 percent, 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 an initiator-containing solution A, uniformly mixing a modified monomer, a cross-linking agent, an emulsifying agent and a low-surface-energy modifying agent 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.
Because the concentrated emulsion prepared by the invention is 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 for a plurality of times, and each dripping requires that oil completely covers water and then dripping is carried out next time, otherwise, the next dripping is carried out without completely covering the water, so that the stable and uniform concentrated emulsion cannot be formed.
Preferably, the hydrophobic modified concentrated emulsion is prepared by dripping the solution A into the mixed solution B from slow to fast by using a rubber head dropper while stirring.
Preferably, the stirring speed is controlled to 3500-8000 rpm.
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, azodiisobutyronitrile, dimethyl azodiisobutyrate and ammonium persulfate/sodium bisulfite composite system.
Wherein the cross-linking agent is one of divinylbenzene, glycol dimethacrylate, dipentaerythritol pentaacrylate and N, N-methylene bisacrylamide.
Wherein the emulsifier is one of Tween80, span80, hexadecyl ammonium chloride, N-dodecyl dimethylamine and sodium dodecyl sulfonate.
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 hydrophobically modified concentrated emulsion is uniformly coated on 5-50 parts by weight of the flexible foam surface.
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 filtration is carried out under reduced pressure under the condition of 0.02-0.1 MPa.
Wherein the emulsion polymerization is specifically carried out at 25-80 ℃ for 4-24h.
Wherein the drying treatment is specifically drying at 40-100deg.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 arranged on the surface of the foam after the solidification forming of the concentrated emulsion, the impurities are required to be removed by soaking with absolute ethyl alcohol after the reaction is finished, and the final product is obtained by drying the foam at the temperature of 40-100 ℃ by blowing to remove the absolute ethyl alcohol.
Preferably, after the concentrated emulsion is fully 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 better introduce the concentrated emulsion into the porous structure of the foam, when the foam coated with the concentrated emulsion is reacted after being sealed, the invention can keep all the concentrated emulsion in the foam structure as far as possible, if the concentrated emulsion is directly heated in the air for reaction, a part of 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 foam, and is commercially available, but foam products with high porosity and open cell structure are preferred for better results.
The invention further discloses the super-hydrophobic modified flexible foam prepared by the preparation method and application of the super-hydrophobic modified flexible foam 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 the super-hydrophobic modified flexible foam in oil-water emulsion separation.
The invention has the following advantages and beneficial effects:
the super-hydrophobic modified flexible foam disclosed by the invention has the advantages of simple preparation process, mild chemical reaction conditions, short required period, low cost and no pollution to the environment, accords with the concept of green environmental protection sustainable development, and is expected to realize macro preparation and marketing 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 mixed system and a micro-nano oil-water emulsion mixture in a gravity mode, and is expected to realize the application of the material in treating 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 pore diameter of the modified flexible foam is reduced from original 100-1000 micrometers to 100 nanometers-10 micrometers based on the size screening 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 super-hydrophobic modified flexible foam low magnification (b) of example 1, and a super-hydrophobic modified flexible foam high magnification (c) of example 1;
FIG. 2 shows the static contact angles of the flexible foam (a) before modification and the super-hydrophobic modified flexible foam (b) (c) of example 1;
FIG. 3 is a macro wettability test of the superhydrophobic modified flexible foam of example 1;
FIG. 4 shows the oil-water separation test of the super-hydrophobic modified flexible foam of example 1 on petroleum ether/water mixture (a) and chloroform/water mixture (b), respectively;
fig. 5 is a water-in-toluene emulsion separation test of the superhydrophobic modified flexible foam of example 1 for surfactant stabilization under gravity.
Detailed Description
The prior three-dimensional foam porous material has insufficient pore size for separating oil-water emulsion, and most of the porous material is oil-water emulsion mixture in actual conditions such as offshore crude oil leakage, factory oil leakage and the like, and the porous material cannot be practically applied if the problem of emulsion separation is not solved. Based on the advantages of low cost, light weight, environmental friendliness and the like of the three-dimensional porous commercial flexible foam, and the complex process, expensive equipment and reagents are required by 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 surfactant-stabilized oil-water emulsion type wastewater or oil-gas field produced liquid. The preparation method of the super-hydrophobic modified flexible foam provided by the invention can be carried out according to the following steps:
(1) Dispersing 1 part by weight of initiator in 100-5000 parts by weight of deionized water to obtain initiator-containing solution A;
(2) Dispersing 50 parts by weight of a modified monomer and a cross-linking agent (the ratio of the modified monomer to the cross-linking agent is 3:2), 10-30 parts by weight of an emulsifier and 5-20 parts by weight of a low surface energy modifier to prepare a mixed solution B;
(3) Dropwise adding the solution A into the mixed solution B by using a rubber head dropper from slow to fast while stirring to prepare concentrated emulsion C, so that the water phase content in the whole concentrated emulsion C is more than or equal to 74%, wherein the mechanical stirring speed is 3500-8000 rpm;
(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 penetrating the concentrated emulsion C into a porous structure of the flexible foam by adopting a decompression suction filtration mode under the condition of 0.02-0.1 MPa;
(5) Sealing the flexible foam permeated with the concentrated emulsion C, then placing the flexible foam in an environment of 25-80 ℃ for reaction for 4-24 hours, washing the product with absolute ethyl alcohol, and then drying the product by blowing air for 8-24 hours at 40-100 ℃ 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 principle: the concentrated emulsion is fully introduced into the foam structure through the modes of coating, decompression and suction filtration, emulsion polymerization is carried out under the heating condition, the foam structure after modification is the macroporous structure of the original flexible foam, the introduced small pore structure is filled with the original flexible foam, the original flexible foam is hydrophilic and oleophylic, the low surface energy is given to the material by adding the low surface energy modifying reagent, the super-hydrophobic modification of the flexible foam is realized through increasing the roughness and reducing the surface energy, and the super-hydrophobic and super-oleophylic characteristics are achieved.
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting. Wherein the flexible foam used in the examples below was purchased from Chengdu Mer's new materials technology Co., ltd, and had an apparent density of 6-12kg/m 3 The porosity was 99%.
Example 1
The super-hydrophobic modified melamine foam is prepared by the following steps:
(1) Dispersing 2 parts by weight of sodium persulfate initiator in 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) The solution A is added into the mixed solution B by using a rubber head dropper from slow to fast, and is mechanically stirred to prepare concentrated emulsion C, wherein the mechanical stirring speed is 5000 revolutions per minute;
(4) Uniformly coating 1000 parts by weight of concentrated emulsion C on the surface of 5 parts by weight of melamine flexible foam, completely penetrating the concentrated emulsion C into the porous structure of the flexible foam in a decompression suction filtration mode, sealing the coated flexible foam, placing the flexible foam in an oven at 65 ℃ for reaction for 8 hours, washing a product with absolute ethyl alcohol, and then drying the product by blowing at 50 ℃ for 12 hours to obtain the super-hydrophobic modified melamine foam.
Example 2
The super-hydrophobic modified melamine foam is prepared by the following steps:
(1) Dispersing 3 parts by weight of sodium persulfate initiator in 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-aminopropyl triethoxysilane to obtain a solution B;
(3) The solution A is added into the mixed solution B by using a rubber head dropper from slow to fast, and is mechanically stirred to prepare concentrated emulsion C, wherein the mechanical stirring speed is 3500 revolutions per minute;
(4) Uniformly coating 2000 parts by weight of concentrated emulsion C on 6 parts by weight of flexible foam surface, completely penetrating the concentrated emulsion C into the porous structure of the melamine foam by a decompression and suction filtration mode, sealing the coated melamine foam, placing the melamine foam in an oven at 60 ℃ for reaction for 6 hours, washing the product with absolute ethyl alcohol, and then drying the product by blowing at 60 ℃ for 10 hours to obtain the super-hydrophobic modified melamine foam.
Example 3
The super-hydrophobic modified polyurethane foam of the embodiment is prepared by the following steps:
(1) Dispersing 3 parts by weight of azobisisobutyronitrile initiator in 3000 parts by weight of deionized water to obtain azobisisobutyronitrile-containing solution A;
(2) Mixing 36 parts by weight of methyl methacrylate, 24 parts by weight of dipentaerythritol pentaacrylate, 25 parts by weight of emulsifier cetyl 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 by using a rubber head dropper from slow to fast, and is mechanically stirred to prepare 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 5 parts by weight of polyurethane foam surface, completely penetrating the concentrated emulsion C into the porous structure of the polyurethane foam by means of vacuum filtration, sealing the coated polyurethane foam, placing the polyurethane foam in an oven for reaction at 55 ℃ for 5 hours, washing the 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 of the embodiment is prepared by the following steps:
(1) Dispersing 3 parts by weight of dimethyl azodiisobutyrate initiator in 2500 parts by weight of deionized water to obtain a 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 vinyltriethoxysilane to obtain a solution B;
(3) The solution A is added into the mixed solution B by using a rubber head dropper from slow to fast, and is mechanically stirred to prepare concentrated emulsion C, wherein the mechanical stirring speed is 3500 revolutions per minute;
(4) Uniformly coating 3000 parts by weight of concentrated emulsion C on 7 parts by weight of polyethylene foam surface, completely penetrating the concentrated emulsion C into a porous structure of the polyethylene foam by a decompression and suction filtration mode, sealing the coated polyethylene foam, placing the sealed polyethylene foam in an oven at 50 ℃ for reaction for 6 hours, washing a product with absolute ethyl alcohol, and then drying by 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 in 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 cetyl ammonium chloride as an emulsifier and 10 parts by weight of polydimethylsiloxane to obtain a solution B;
(3) The solution A is added into the mixed solution B by using a rubber head dropper from slow to fast, and is mechanically stirred to prepare concentrated emulsion C, wherein the mechanical stirring speed is 3500 revolutions per minute;
(4) Uniformly coating 4000 parts of concentrated emulsion C on the surface of 8 parts of phenolic foam, completely penetrating the concentrated emulsion C into the porous structure of the phenolic foam in a decompression and suction filtration mode, sealing the coated phenolic foam, placing the phenolic foam in an oven for reaction at 70 ℃ for 8 hours, washing the product with absolute ethyl alcohol, and then drying the product at 70 ℃ in a blowing mode for 12 hours to obtain the super-hydrophobic modified phenolic foam.
Structure characterization and Performance test case
1. Scanning Electron Microscope (SEM)
The morphology of the original flexible foam and the modified flexible foam of the first embodiment is analyzed by adopting a JSM-7500F scanning electron microscope, the accelerating voltage is 20.0KV, surface metal spraying treatment is needed before the sample test, and the structural characterization is shown in figure 1. As can be seen from the figure, the pore diameter of the original flexible foam is tens and hundreds of micrometers, the pore diameter of the modified flexible foam in the embodiment 1 is tens and hundreds of nanometers, and the difference is about 100 times, and the invention introduces a small pore structure of the concentrated emulsion into the flexible foam without influencing the skeleton and the pore diameter of the original flexible foam before modification, so that the flexible foam has a structure with small pores in large pores after modification, and the pore diameter of the foam is further reduced as a whole, thereby being directly used for separating the emulsion.
2. Static contact Angle test (WCA)
The test uses an OCA25 tester from Dataphysics, germany to conduct a static water contact angle test on the surface of a modified foam, which is an example of an original flexible foam, and the results are shown in fig. 2.
3. Macroscopic wettability
The surface of the modified flexible foam was tested for macroscopic wettability using a small amount of deionized water from a 2.5ml syringe, the results of which are shown in figure 3.
4. Macroscopic oil-water separation test
The petroleum ether and the red oil O are dyed by using the oil-soluble pigment methyl orange, and the water is dyed by using the water-soluble pigment bromophenol blue. The oil-water separation test was performed on the light oil/water mixture and the heavy oil/water mixture using the modified flexible foam of example one, and the results are shown in fig. 4.
5. Surfactant stabilized oil-Water emulsion separation test on modified Flexible foam of example one
The specific test method comprises the following steps: (1) preparation of oil-water emulsion: surfactant-stabilized water-in-toluene emulsions were prepared. At V Water and its preparation method ：V Toluene (toluene) =1: under the condition of 99, 1g/L Span80 surfactant is added, and the mixture is stirred for 1h at 1500r/min to obtain stable water-in-toluene emulsion; (2) oil-water emulsion separation: solidifying a proper amount of the modified foam prepared in the first embodimentIs positioned at the neck of the funnel.
Under the action of gravity, the modified foam achieved surfactant-stabilized water-in-toluene emulsion separation based on hydrophobic oleophilic phase opposing intermolecular forces and size sieving effects, as shown in fig. 5 (a). The liquids before and after separation were observed using an eyepiece-free inverted fluorescence digital microscope, and many droplets were present in the milky water-in-toluene emulsion before separation as shown in fig. 5 (d), but a transparent oil phase was obtained after separation, and no droplets were observed in the filtrate after separation as shown in fig. 5 (c). Because the pore diameter of the modified foam is mostly in the nanometer level, when the oil-water emulsion is separated, the nanometer level pores are enough to realize separation through the size screening effect, and therefore, the better separation effect can be achieved without reducing the pore diameter through a compression mode
The super-hydrophobic modified flexible foam prepared in examples 2-5 was subjected to the above structural characterization and performance test, and the results were similar to those of example 1, thus demonstrating that the super-hydrophobic modified flexible foam prepared in the invention has excellent hydrophobic and oleophylic properties, and can be used for separation of oil-water mixtures.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It is also possible to make several alternatives or modifications to the described embodiments without departing from the inventive concept, which alternatives or modifications are to be considered as falling within the scope of the invention.
Claims (7)
1. The preparation method of the super-hydrophobic modified flexible foam is characterized by comprising the following steps of: the preparation method comprises the steps of carrying out surface coating treatment on flexible foam by using hydrophobic modified concentrated emulsion, fully absorbing the concentrated emulsion in the foam, carrying out emulsion polymerization under a heating condition, forming a nano pore diameter structure in the foam, and finally washing and drying to obtain 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 emulsifying agent, a low surface energy modifying agent and water;
the preparation method of the hydrophobically modified concentrated emulsion comprises the following steps: dispersing an initiator in deionized water to obtain a solution A containing the initiator, uniformly mixing a modified monomer, a cross-linking agent, an emulsifying agent and a low-surface-energy modifying agent 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;
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;
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 the hydrophobically modified concentrated emulsion on the surface of 5-50 parts by weight of the flexible foam.
2. The method for preparing the super-hydrophobic modified flexible foam according to claim 1, wherein: the hydrophobic modified concentrated emulsion comprises 40-60 parts by weight of modified monomers and cross-linking agents in total, 1-5 parts by weight of initiator, 10-30 parts by weight of emulsifier, 5-20 parts by weight of low surface energy modifier and 100-5000 parts by weight of water; the mass dosage ratio of the modified monomer to the cross-linking agent is 3:2; the water phase content of the hydrophobically modified concentrated emulsion is controlled to be not less than 74%.
3. The method for preparing the superhydrophobic modified flexible foam according to any one of claims 1-2, wherein: the initiator is one of potassium persulfate, sodium persulfate, azodiisobutyronitrile, dimethyl azodiisobutyrate and ammonium persulfate/sodium bisulfite composite system; the cross-linking agent is one of divinylbenzene, glycol dimethacrylate, dipentaerythritol pentaacrylate and N, N-methylene bisacrylamide.
4. A method of preparing a superhydrophobic modified flexible foam according to claim 3, characterized in that: the emulsifier is one of Tween80, span80, hexadecyl ammonium chloride, N-dodecyl dimethylamine and sodium dodecyl sulfonate.
5. The method for preparing the super-hydrophobic modified flexible foam according to claim 4, wherein: after the surface coating treatment, adopting a decompression suction filtration mode to fully absorb the concentrated emulsion in the foam; vacuum filtering under 0.02-0.1 MPa; emulsion polymerization is carried out in a sealed environment; emulsion polymerization is carried out specifically at 25-80 ℃ for 4-24h; the drying treatment is specifically air drying at 40-100deg.C for 8-24 hr.
6. A superhydrophobic modified flexible foam prepared by the method for preparing a superhydrophobic modified flexible foam according to any one of claims 1 to 5.
7. Use of the superhydrophobic modified flexible foam of claim 6 in oil-water separation.
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| 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 |
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| 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 |
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