CN110656499B - Preparation method and application of double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material - Google Patents
Preparation method and application of double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention relates to a preparation method and application of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material, wherein the preparation method comprises the following steps: attaching a hydrophilic-oleophobic modified solution to the outer surface of the substrate, wherein the hydrophilic-oleophobic modified solution comprises a hydrophilic monomer, a fluoroalkyl monomer, a cross-linking agent, a photoinitiator and an organic solvent, and then forming a hydrophilic-oleophobic layer on the outer surface of the substrate after polymerization and cross-linking are carried out under the irradiation of ultraviolet light; attaching a hydrophobic-oleophobic modified solution to one side surface of the treated base material, wherein the hydrophobic-oleophobic modified solution comprises a fluoroalkyl monomer, a cross-linking agent, a photoinitiator and an organic solvent, and then forming a hydrophobic-oleophobic oil layer on one side of the base material after polymerization and cross-linking are carried out under ultraviolet irradiation. The material can be used for unidirectional moisture-conducting or moisture-absorbing quick-drying fabrics, oil-water separation, unidirectional transportation of water or aqueous solution in microfluid and the like.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a preparation method and application of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material.
Background
The Janus film refers to a film material with completely opposite performances on two sides of the film, and the concept of the asymmetric Janus film in a broad sense refers to a film material with different performances on two sides of the film, wherein the film material comprises a chemically active performance, a wetting performance, a conductive performance and the like. The Janus film with different wettability on two sides can realize directional transportation of specific liquid, and can be applied to the fields of seawater desalination, separation of oil-water mixed liquids of different types, emulsion preparation, microfluid, moisture absorption and sweat releasing intelligent textiles and the like.
At present, the realization of Janus fabric is mainly realized by a method of single-side surface modification of the fabric. Methods for surface modification include photografting, deposition, surface coating, plasma treatment, and the like.
Wang et al prepared a novel bifunctional Janus cotton fabric for separating oil-water emulsion by using a photografting method, and obtained super-hydrophobic/super-hydrophilic cotton fabric (Angewandte Chemie International Edition,2016,55(4):1291-1294.) by respectively modifying super-hydrophobic Polydimethylsiloxane (PDMS) and super-hydrophilic dimethylaminoethyl methacrylate (PDMAEMA) on both sides of the cotton fabric.
Tian et al selectively hydrophobicize one side of a hydrophilic cotton fabric using steam diffusion technology, the hydrophobicizing agent used being Perfluorooctyltrichlorosilane (POTS), the resulting Janus fabric having the ability to transport water directionally, water being transported only from the hydrophobic side to the hydrophilic side where the cotton fabric is modified, but not in reverse (Advanced Functional Materials,2014,24(38): 6023-6028.).
The Chinese invention patent with the application number of 201811581266.4 discloses a preparation method of a single-sided super-hydrophobic and single-sided super-hydrophilic Janus type fabric. According to the invention, by using a plasma method, firstly, a fabric with a single-side protection is subjected to plasma glow discharge treatment under the condition of constant oxygen pressure, after oxygen is closed, plasma glow discharge treatment is carried out again under the conditions that a grafting monomer is octamethylcyclotetrasiloxane and the steam pressure is constant, so that the single-side super-hydrophobic single-side super-hydrophilic Janus type fabric is obtained.
CN201810076295.9 discloses a preparation method of super-wetting Janus paper or paper-based super-wetting patterns, and the preparation method is characterized in that the Janus paper with one surface having super-hydrophobicity and the other surface maintaining super-hydrophilicity is obtained by ink-jet printing of hydrophobic sol solution on the paper. However, the method is complicated in steps and long in time, and the prepared Janus paper is not oleophobic.
CN201810985944.7 discloses a preparation method of a Janus forward osmosis membrane, which is composed of a first surface of a super-hydrophilic polymer microporous membrane, a polymer membrane matrix intermediate layer and a second surface far away from the first surface and coated with a super-hydrophobic inorganic nanoparticle coating, wherein the first surface of the super-hydrophilic polymer microporous membrane has a water drop immersion time of less than 2 seconds, and the water drop contact angle of the second surface coated with the super-hydrophobic inorganic nanoparticle coating is more than 150 degrees.
From the above, the currently disclosed superhydrophobic-superhydrophilic Janus fabric or membrane material does not have double-sided oleophobicity, can only realize the directional transportation of water in air, and no report related to the Janus fabric or membrane material with the directional transportation performance of water in oil exists. The material has application prospect in the fields of oil-water separation and unidirectional transportation of water or aqueous solution in microfluid.
Disclosure of Invention
The Janus material not only has the performance of quickly and efficiently directionally transporting water in the air, but also has the characteristic of double-sided oleophobic property, and can also realize the directional transportation of water under oil.
The first purpose of the invention is to provide a preparation method of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material, which comprises the following steps:
(1) attaching a hydrophilic-oleophobic modified solution to the outer surface of the substrate, wherein the hydrophilic-oleophobic modified solution comprises a hydrophilic monomer, a fluoroalkyl monomer, a cross-linking agent, a photoinitiator and an organic solvent, then polymerizing and cross-linking under the irradiation of ultraviolet light, and forming a hydrophilic-oleophobic layer on the outer surface of the substrate after the reaction is completed; the mass ratio of the hydrophilic monomer to the fluoroalkyl monomer is 10:1-1: 10;
(2) and (2) attaching a hydrophobic-oleophobic modified solution to the surface of one side of the base material treated in the step (1), wherein the hydrophobic-oleophobic modified solution comprises a fluoroalkyl monomer, a cross-linking agent, a photoinitiator, micro-nano particles and an organic solvent, then polymerizing and cross-linking under ultraviolet irradiation, and after complete reaction, forming a hydrophobic-oleophobic layer on the surface of one side of a hydrophilic-oleophobic layer to obtain the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material.
In the invention, the term "superhydrophobic" in the "double-sided oleophobic superhydrophobic-superhydrophilic Janus type material" means that the contact angle of the material to water is more than 150 degrees, and the term "superhydrophilic" means that the contact angle of the material to water is less than 10 degrees.
Further, in the step (1), the hydrophilic monomer is any one or more of acrylic acid, methacrylic acid, acrylamide and methacrylamide.
Further, in steps (1) and (2), the fluoroalkyl monomers are independently selected from compounds of the following general structural formula:
wherein R is hydrogen or methyl, m is an integer of 1 to 5, and n is an integer of 3 to 9. Preferred are fluoroalkyl monomers wherein m is 2 and n is 5 or 7. Fluoroalkyl monomers are oleophobic monomers that impart oleophobicity to fabrics.
Further, in the steps (1) and (2), the crosslinking agent is independently selected from any one or more of polyethylene glycol diacrylate, N-carboxyethyl acrylamide, 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate and POSS acrylate, and the POSS acrylate is preferred.
Further, in the steps (1) and (2), the photoinitiator is independently selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethylbenzoyl diphenylphosphine, a, -dimethylbenzyl ketal, benzophenone, 1-hydroxycyclohexyl benzophenone and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and preferably 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Further, in the step (2), the attaching method is a spray method. In the step (2), the loading amount of the hydrophobic-oleophobic coating on the surface of the substrate is 0.5-20mg/m2. "loading" refers to the quality of the hydrophobic and oleophobic coating formed by the sprayed hydrophobic and oleophobic solution after illumination.
Further, in the step (1), the substrate is soaked in the hydrophilic-oleophobic modification solution for 1-10 min.
Further, in the step (1), the mass ratio of the hydrophilic monomer to the crosslinking agent is 5:1 to 100: 1.
Further, in the step (1), the photoinitiator accounts for 0.5 to 10 wt% of the total mass of the hydrophilic-oleophobic modification solution (excluding the organic solvent). In step (2), the photoinitiator accounts for 0.5-10 wt% of the total mass of the hydrophilic-oleophobic modification solution (excluding the organic solvent).
Further, in the step (1), the base material is not affected by the material, and a woven fabric or a knitted fabric is generally used. Preferably, the fabric is polyester fabric, cotton fabric or blended fabric.
Further, in the step (2), the molar ratio of the fluoroalkyl monomer to the crosslinking agent is 5:1 to 300: 1.
Further, in the step (2), the micro-nano particles are silicon dioxide (SiO)2) Modified SiO2Aluminum oxide (Al)2O3) Zinc oxide (ZnO), ferroferric oxide (Fe)3O4) Any one or more of micro-nano particles. The particle size of the micro-nano particles is preferably 100-500 nm. The preferable micro-nano particles are hydrophobic modified SiO2Micro-nano particles, more preferably SiO modified by fluorosilane group2The particle size of the micro-nano particles is preferably 100-500 nm. Fluorosilyl-modified SiO2Micro-nano particles and methods for their preparation reference the methods in "Zhou, H., et al., Robust, Self-lubricating superior Fabrics Prepared by Two-Step Coating of Fluoro-contacting Polymer, Fluoro alkyl Silane, and Modified silicon nanoparticles advanced Functional Materials,2013.23(13): p.1664-1670". The micro-nano particles provide roughness for the surface of the base material, and the hydrophobic and oleophobic performance of the spraying side is improved.
Further, in the step (2), the micro-nano particles account for 1% -20% of the total mass of the fluoroalkyl monomer and the cross-linking agent.
Further, in the steps (1) and (2), the organic solvent is acetone, ethanol, tetrahydrofuran, N-dimethylformamide, toluene, or the like.
Further, in the steps (1) and (2), the irradiation intensity of ultraviolet irradiation is 20-120mW/cm2。
Further, in the step (1), the ultraviolet illumination time is 10-120 min; in the step (2), the ultraviolet illumination time is 5-60 min.
Further, the preparation method of the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material specifically comprises the following steps:
step 1: adding a photoinitiator into a mixed solution of a hydrophilic monomer, a cross-linking agent and a fluoroalkyl monomer, stirring for 5-10min at room temperature, mixing the solution with acetone serving as a solvent according to a volume ratio of 10:1-10:1, and stirring for 10min at 25 ℃ to obtain a hydrophilic-oleophobic modified solution;
step 2: soaking the substrate in the hydrophilic-oleophobic modified solution for 1-10min, removing the redundant solution, and irradiating for 10-120min under UV light irradiation to obtain the substrate with the hydrophilic-oleophobic layer;
and step 3: adding a photoinitiator into a mixed solution of a cross-linking agent and a fluoroalkyl monomer, stirring for 5-10min at room temperature, mixing the solution with acetone serving as a solvent in a volume ratio of 10:1-10:1, and stirring for 10min at 25 ℃ to obtain a hydrophobic-oleophobic modified solution;
and 4, step 4: and (3) fixing the substrate treated in the step (2), exposing one side surface of the substrate in the air, placing the substrate at a position of 5-30cm of a spray gun, spraying a hydrophobic-oleophobic modified solution on the surface of the substrate, and irradiating one side, which is sprayed with the hydrophobic-oleophobic modified solution, for 5-60min under the irradiation of UV light to obtain the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus material.
The invention also provides a preparation method of the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus material, which comprises the following steps of preparing a hydrophilic-oleophobic layer, modifying the hydrophilic-oleophobic layer on the outer surface of the substrate, and modifying the hydrophobic-oleophobic layer on one side surface of the hydrophilic-oleophobic layer, which is far away from the substrate.
The invention also claims the application of the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material as a directional transportation material for water in air and/or oil.
The Janus type material disclosed by the invention not only has the performance of quickly and efficiently carrying water in an oriented manner in the air, but also has the characteristic of double-sided oleophobic property, and can realize the oriented carrying of water under oil.
Furthermore, the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus material is used for preparing a one-way moisture-conducting material, a moisture-absorbing quick-drying fabric, a water vapor collecting material, an oil-water separating material and a medical material, and can also be used in the field of microfluid, for example, as a one-way water conveying material or a one-way water conveying material in microfluid. The two surfaces of the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material have super-oleophobic performance, and simultaneously, due to the super-hydrophobic/super-aqueous performance of the surfaces on the two sides, the material has the directional transportation capacity of air and oil and water.
By the scheme, the invention at least has the following advantages:
(1) compared with the traditional super-hydrophobic-super-hydrophilic Janus material, the material disclosed by the invention not only has the performance of quickly and efficiently carrying water directionally, but also has the characteristic of double-sided oleophobic property. Can realize the directional transportation of water in the air and under oil, and has wide application prospect in the fields of microfluid, anti-oil stain type moisture absorption and sweat releasing fabric and the like.
(2) The double-sided oleophobic super-hydrophobic-super-hydrophilic material prepared by the invention can realize directional transportation to extremely small water drops (5uL), the transmembrane time of water can be as short as 2s, and the directional conduction of water can be quickly realized.
(3) In the invention, the hydrophilic monomers and the fluoroalkyl monomers in the hydrophilic-hydrophobic oil layer and the fluoroalkyl monomers in the hydrophobic-hydrophobic oil layer are combined by covalent bonds, and meanwhile, a cross-linking agent is introduced to form a net-shaped cross-linking structure on the surface of the substrate, so that the functional layer on the surface of the substrate has high firmness and excellent washing resistance.
(4) The preparation method is simple, short in operation flow and wide in applicability.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic cross-sectional structure of a superhydrophobic-superhydrophilic Janus-type material of the present invention;
FIG. 2 is a result of a topography test performed on each of two side surfaces of the Janus fabric in example 2 using a cold field scanning electron microscope;
FIG. 3 shows the results of a camera test on the water transport behavior on both sides of the Janus fabric in example 2;
FIG. 4 shows the results of the hexadecane contact angle test performed on each side surface of the Janus fabric of example 2 using a contact angle meter;
fig. 5 illustrates the results of the test of the water transport behavior in hexadecane on both sides of the Janus fabric in example 2.
Description of reference numerals:
1-a substrate; 2-hydrophilic-hydrophobic layer; 3-hydrophobic-oleophobic layer.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples of the invention, hydrophobic SiO2SiO modified by fluorosilane group2The particle size of the micro-nano particles is 100-500 nm. Fluorosilyl-modified SiO2Micro-nano particles and methods for their preparation reference the methods in "Zhou, H., et al., Robust, Self-lubricating superior Fabrics Prepared by Two-Step Coating of Fluoro-contacting Polymer, Fluoro alkyl Silane, and Modified silicon nanoparticles advanced Functional Materials,2013.23(13): p.1664-1670".
Example 1
A double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type fabric is shown in figure 1 and comprises a substrate 1, wherein the surface of the substrate 1 is coated with a hydrophilic-oleophobic layer 2, and a hydrophobic-oleophobic layer 3 is sprayed on the surface of one side of the hydrophilic-oleophobic layer 2. Wherein the substrate 1 is a polyester fabric.
The preparation method of the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type fabric comprises the following specific steps:
(1) adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into a mixed solution of hydrophilic monomers methacrylic acid, POSS acrylate and perfluorohexyl ethyl acrylate, wherein the mass ratio of the methacrylic acid to the POSS acrylate is 50:1, and the mass ratio of the methacrylic acid to the perfluorohexyl ethyl acrylate is 5:2, and stirring at 25 ℃ for 10min to obtain a modified monomer solution. And (2) mixing the solution with acetone serving as a solvent in a volume ratio of 3:1, and stirring at 25 ℃ for 10min to obtain a hydrophilic-oleophobic modified solution, wherein the photoinitiator accounts for 3 wt% of the total mass of the modified monomer solution.
(2) Soaking 5cm × 5cm polyester fabric in hydrophilic-oleophobic modified solution for 1-10min, removing excessive solution, and irradiating in UV photocuring instrument with irradiation intensity of 50mW/cm for 30min2And obtaining the hydrophilic-oleophobic polyester fabric.
(3) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into perfluorohexyl ethyl acrylate, POSS acrylate and hydrophobic SiO2Obtaining a modified monomer solution in the mixed solution, wherein the mass ratio of the perfluorohexyl ethyl acrylate to the POSS acrylate is 150:1, and hydrophobic SiO is2The mass of the perfluorohexyl ethyl acrylate is 3 percent of the total mass of the POSS acrylate. And mixing acetone serving as a solvent with the solution in a volume ratio of 2:1, and stirring at 25 ℃ for 10min to obtain a hydrophobic-oleophobic modified solution, wherein the 2-hydroxy-2-methyl-1-phenyl-1-acetone accounts for 3 wt% of the total mass of the modified monomer solution.
(4) Fixing the hydrophilic-oleophobic polyester fabric obtained in the step 2 on a paperboard, placing the paperboard at a position 15cm away from a spray gun, spraying a hydrophobic-oleophobic modified solution, placing the spraying side in a UV (ultraviolet) photocuring instrument, and irradiating for 30min at an irradiation intensity of 50mW/cm2The sprayed side hydrophobic-oil-repellent layer is 2mg/m after illumination2。
And (3) carrying out a contact angle test on the polyester fabric treated in the step (4) to obtain the following results: water drops can be transported only from one side of the hydrophobic-oleophobic layer to one side of the hydrophilic-oleophobic layer and cannot be transported from one side of the hydrophilic-oleophobic layer to one side of the hydrophobic-oleophobic layer, and the time for the water drops to reach one side of the hydrophilic-oleophobic layer through one side of the hydrophobic-oleophobic layer of the fabric is 0.05 +/-0.03 s. The contact angles of hexadecane on one side of the fabric hydrophilic-oleophobic layer and one side of the fabric hydrophobic-oleophobic layer are 145.4 +/-4.9 degrees and 150.4 +/-7.1 degrees respectively. In hexadecane, water droplets can only be transported from the hydrophobic-oleophobic layer side to the hydrophilic-oleophobic layer side, but not from the hydrophilic-oleophobic layer side to the hydrophobic-oleophobic layer side.
Example 2
A preparation method of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type fabric comprises the following specific steps:
(1) adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into a mixed solution of hydrophilic monomers methacrylic acid, POSS acrylate and perfluorohexyl ethyl acrylate, wherein the mass ratio of the methacrylic acid to the POSS acrylate is 50:1, and the mass ratio of the methacrylic acid to the perfluorohexyl ethyl acrylate is 5:2, and stirring at 25 ℃ for 10min to obtain a modified monomer solution. And (2) mixing the solution with acetone serving as a solvent in a volume ratio of 3:1, and stirring at 25 ℃ for 10min to obtain a hydrophilic-oleophobic modified solution, wherein the photoinitiator accounts for 3 wt% of the total mass of the modified monomer solution.
(2) Soaking 5cm × 5cm polyester fabric in hydrophilic-oleophobic modified solution for 1-10min, removing excessive solution, and irradiating in UV photocuring instrument with irradiation intensity of 50mW/cm for 30min2And obtaining the hydrophilic-oleophobic polyester fabric.
(3) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into perfluorohexyl ethyl acrylate, POSS acrylate and hydrophobic SiO2Obtaining a modified monomer solution in the mixed solution, wherein the mass ratio of the perfluorohexyl ethyl acrylate to the POSS acrylate is 150:1, and hydrophobic SiO is2The mass of the perfluorohexyl ethyl acrylate is 3 percent of the total mass of the POSS acrylate. And mixing acetone serving as a solvent with the solution in a volume ratio of 2:1, and stirring at 25 ℃ for 10min to obtain a hydrophobic-oleophobic modified solution, wherein the 2-hydroxy-2-methyl-1-phenyl-1-acetone accounts for 3 wt% of the total mass of the modified monomer solution.
(4) Fixing the hydrophilic-oleophobic polyester fabric obtained in the step 2 on a paperboard, placing the paperboard at a position 15cm away from a spray gun, spraying a hydrophobic-oleophobic modified solution, placing the spraying side in a UV (ultraviolet) photocuring instrument, and irradiating for 30min at an irradiation intensity of 50mW/cm2The sprayed side hydrophobic-oil-repellent layer is 5mg/m after illumination2。
And 2a and b are SEM test results of the surface of the hydrophilic-oleophobic layer and the surface of the hydrophobic-oleophobic layer of the fabric obtained in the step (4), respectively, and the results show that the surface of the hydrophilic-oleophobic layer has obvious coating, the coating is smooth, and the surface of the hydrophobic-oleophobic layer has coating with a large amount of silica particles.
And (3) performing a water contact angle test on the polyester fabric treated in the step (4), as shown in fig. 3, wherein fig. 3a1-a6 shows the test result of the transportation behavior of water drops on one side surface of the hydrophobic-oleophobic layer of the fabric, and fig. 3b1-b6 shows the test result of the transportation behavior of water drops on one side surface of the hydrophilic-oleophobic layer of the fabric. The results show that water droplets can only be transported from the side of the hydrophobic-oleophobic layer to the side of the hydrophilic-oleophobic layer and cannot reach the hydrophobic-oleophobic side from the side of the hydrophilic-oleophobic layer (in FIG. 3b5-b6, no water droplets are below the fabric), i.e. water droplets cannot be transported from the side of the hydrophilic-oleophobic layer to the side of the hydrophobic-oleophobic layer, and the time for water droplets to reach the side of the hydrophilic-oleophobic layer through the side of the hydrophobic-oleophobic layer of the fabric is 12.5 +/-0.5 s.
And (3) performing a hexadecane contact angle test on the polyester fabric treated in the step (4), wherein fig. 4a and b are results of the hexadecane contact angle test of one side surface of the fabric hydrophilic-oleophobic layer and one side surface of the hydrophobic-oleophobic layer respectively, and the results show that the contact angles of hexadecane on one side of the fabric hydrophilic-oleophobic layer and one side of the hydrophobic-oleophobic layer are 143.4 +/-4.8 degrees and 150.8 +/-4.0 degrees respectively.
The polyester fabric treated in the step (4) is subjected to a water transportation behavior test in hexadecane, and the results of the water transportation behavior test in hexadecane of water drops on one side surface of the hydrophobic-oleophobic layer of the fabric are shown in FIGS. 5a1-a3, and the results of the water transportation behavior test in hexadecane of water drops on one side surface of the hydrophilic-oleophobic layer of the fabric are shown in FIGS. 5b1-b 3. The results show that in hexadecane, water droplets can only be transported from the hydrophobic-oleophobic layer to the hydrophilic-oleophobic layer, but not from the hydrophilic-oleophobic layer to the hydrophobic-oleophobic layer.
Example 3
A preparation method of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type fabric comprises the following specific steps:
(1) adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into a mixed solution of hydrophilic monomers methacrylic acid, POSS acrylate and perfluorohexyl ethyl acrylate, wherein the mass ratio of the methacrylic acid to the POSS acrylate is 50:1, and the mass ratio of the methacrylic acid to the perfluorohexyl ethyl acrylate is 5:2, and stirring at 25 ℃ for 10min to obtain a modified monomer solution. And (2) mixing the solution with acetone serving as a solvent in a volume ratio of 3:1, and stirring at 25 ℃ for 10min to obtain a hydrophilic-oleophobic modified solution, wherein the photoinitiator accounts for 3 wt% of the total mass of the modified monomer solution.
(2) Soaking 5cm × 5cm polyester fabric in hydrophilic-oleophobic modified solution for 1-10min, removing excessive solution, and irradiating in UV photocuring instrument with irradiation intensity of 50mW/cm for 30min2And obtaining the hydrophilic-oleophobic polyester fabric.
(3) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into perfluorohexyl ethyl acrylate, POSS acrylate and hydrophobic SiO2Obtaining a modified monomer solution in the mixed solution, wherein the mass ratio of the perfluorohexyl ethyl acrylate to the POSS acrylate is 150:1, and hydrophobic SiO is2The mass of the perfluorohexyl ethyl acrylate is 3 percent of the total mass of the POSS acrylate. And mixing acetone serving as a solvent with the solution in a volume ratio of 2:1, and stirring at 25 ℃ for 10min to obtain a hydrophobic-oleophobic modified solution, wherein the 2-hydroxy-2-methyl-1-phenyl-1-acetone accounts for 3 wt% of the total mass of the modified monomer solution.
(4) Fixing the hydrophilic-oleophobic polyester fabric obtained in the step 2 on a paperboard, placing the paperboard at a position 15cm away from a spray gun, spraying a hydrophobic-oleophobic modified solution, placing the spraying side in a UV (ultraviolet) photocuring instrument, and irradiating for 30min at an irradiation intensity of 50mW/cm2The sprayed side hydrophobic-oil-repellent layer is 15mg/m after illumination2。
And (3) carrying out a contact angle test on the polyester fabric treated in the step (4) to obtain the following results: water drops can be transported only from one side of the hydrophobic-oleophobic layer to one side of the hydrophilic-oleophobic layer and cannot be transported from one side of the hydrophilic-oleophobic layer to one side of the hydrophobic-oleophobic layer, and the time for the water drops to reach one side of the hydrophilic-oleophobic layer through one side of the hydrophobic-oleophobic layer of the fabric is 33.2 +/-2.5 seconds. The contact angles of hexadecane on one side of the fabric hydrophilic-oleophobic layer and one side of the fabric hydrophobic-oleophobic layer are respectively 151.9 +/-6.0 degrees and 150 +/-6.8 degrees. In hexadecane, water droplets can be transported from the hydrophobic-oleophobic layer side to the hydrophilic-oleophobic layer side, but cannot be transported from the hydrophilic-oleophobic layer side to the hydrophobic-oleophobic layer side.
Example 4
A preparation method of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type fabric comprises the following specific steps:
(1) adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into a mixed solution of hydrophilic monomers methacrylic acid, POSS acrylate and perfluorohexyl ethyl acrylate, wherein the mass ratio of the methacrylic acid to the POSS acrylate is 50:1, and the mass ratio of the methacrylic acid to the perfluorohexyl ethyl acrylate is 1:1, and stirring at 25 ℃ for 10min to obtain a modified monomer solution. And (2) mixing the solution with acetone serving as a solvent in a volume ratio of 3:1, and stirring at 25 ℃ for 10min to obtain a hydrophilic-oleophobic modified solution, wherein the photoinitiator accounts for 3 wt% of the total mass of the modified monomer solution.
(2) Soaking 5cm × 5cm polyester fabric in hydrophilic-oleophobic modified solution for 1-10min, removing excessive solution, and irradiating in UV photocuring instrument with irradiation intensity of 50mW/cm for 30min2And obtaining the hydrophilic-oleophobic polyester fabric.
(3) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into perfluorohexyl ethyl acrylate, POSS acrylate and hydrophobic SiO2Obtaining a modified monomer solution in the mixed solution, wherein the mass ratio of the perfluorohexyl ethyl acrylate to the POSS acrylate is 150:1, and hydrophobic SiO is2The mass of the perfluorohexyl ethyl acrylate is 3 percent of the total mass of the POSS acrylate. And mixing acetone serving as a solvent with the solution in a volume ratio of 2:1, and stirring at 25 ℃ for 10min to obtain a hydrophobic-oleophobic modified solution, wherein the 2-hydroxy-2-methyl-1-phenyl-1-acetone accounts for 3 wt% of the total mass of the modified monomer solution.
(4) Fixing the hydrophilic-oleophobic polyester fabric obtained in the step 2 on a paperboard, placing the paperboard at a position 15cm away from a spray gun, spraying a hydrophobic-oleophobic modified solution, placing the spraying side in a UV (ultraviolet) photocuring instrument, and irradiating for 30min at an irradiation intensity of 50mW/cm2The sprayed side hydrophobic-oil-repellent layer is 5mg/m after illumination2。
And (3) carrying out a contact angle test on the polyester fabric treated in the step (4) to obtain the following results: water drops can be transported only from one side of the hydrophobic-oleophobic layer to one side of the hydrophilic-oleophobic layer and cannot be transported from one side of the hydrophilic-oleophobic layer to one side of the hydrophobic-oleophobic layer, and the time for the water drops to reach one side of the hydrophilic-oleophobic layer through one side of the hydrophobic-oleophobic layer of the fabric is 45.6 +/-2.5 seconds. The contact angles of hexadecane on one side of the fabric hydrophilic-oleophobic layer and one side of the fabric hydrophobic-oleophobic layer are 149.3 +/-4.8 degrees and 152 +/-3.7 degrees respectively. In hexadecane, water droplets can only be transported from the hydrophobic-oleophobic layer side to the hydrophilic-oleophobic layer side, but not from the hydrophilic-oleophobic layer side to the hydrophobic-oleophobic layer side.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material is characterized by comprising the following steps:
(1) attaching a hydrophilic-oleophobic modified solution to the outer surface of the substrate, wherein the hydrophilic-oleophobic modified solution comprises a hydrophilic monomer, a fluoroalkyl monomer, a cross-linking agent, a photoinitiator and an organic solvent, then polymerizing and cross-linking under the irradiation of ultraviolet light, and forming a hydrophilic-oleophobic layer on the outer surface of the substrate after the reaction is completed; the mass ratio of the hydrophilic monomer to the fluoroalkyl monomer is 10:1-1: 10;
(2) and (2) attaching a hydrophobic-oleophobic modified solution to the surface of one side of the base material treated in the step (1), wherein the hydrophobic-oleophobic modified solution comprises a fluoroalkyl monomer, a cross-linking agent, micro-nano particles, a photoinitiator and an organic solvent, then polymerizing and cross-linking under ultraviolet irradiation, and after complete reaction, forming a hydrophobic-oleophobic layer on the surface of one side of a hydrophilic-oleophobic layer to obtain the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material.
2. The method of claim 1, wherein: in the step (1), the hydrophilic monomer is any one or more of acrylic acid, methacrylic acid, acrylamide and methacrylamide.
3. The method of claim 1, wherein: in steps (1) and (2), the fluoroalkyl monomers are independently selected from compounds of the following general structural formula:
wherein R is hydrogen or methyl, m is an integer of 1 to 5, and n is an integer of 3 to 9.
4. The method of claim 1, wherein: in the steps (1) and (2), the crosslinking agent is independently selected from any one or more of polyethylene glycol diacrylate, N-carboxyethyl acrylamide, 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate and POSS acrylate.
5. The method of claim 1, wherein: in the steps (1) and (2), the photoinitiator is independently selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethylbenzoyl diphenylphosphine, a-dimethylbenzyl ketal, benzophenone, 1-hydroxycyclohexyl benzophenone and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide.
6. The method of claim 1, wherein: in the step (2), the loading amount of the hydrophobic-oleophobic coating on the surface of the substrate is 0.5-20mg/m2。
7. A double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material prepared by the preparation method of any one of claims 1-6, characterized in that: the oil-water repellent coating comprises a substrate, wherein the outer surface of the substrate is modified with the hydrophilic-oil repellent layer, and the surface of one side of the hydrophilic-oil repellent layer, which is far away from the substrate, is modified with the hydrophobic-oil repellent layer.
8. Use of the double-sided oleophobic superhydrophobic-superhydrophilic Janus-type material of claim 7 as a material for the directional transport of water in air and/or oil.
9. The use according to claim 8, wherein the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material is used as one or more of a one-way moisture-conductive material, a moisture-absorbing and quick-drying fabric, an oil-water separation material, a one-way water transport material in microfluidics and a one-way water transport material.
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