CN114344950B - Super-hydrophilic-super-oleophobic surface stable in air-water-oil and preparation method and application thereof - Google Patents
Super-hydrophilic-super-oleophobic surface stable in air-water-oil and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophilic-super-oleophobic surface stable in air-water-oil and a preparation method and application thereof. The material of the super-hydrophilic-super-oleophobic surface stable in air-water-oil is obtained by spraying dispersion liquid of nano-micron particles on a substrate; the nano-micron particles are methacrylic acid/hydroxyethyl methacrylate composite nano-micron particles, and are modified as follows: the fluorine compound is used for modifying the nano-micron particles. According to the invention, after the nano-micron particles are sprayed on the substrate material, the surface of the material has stable super-hydrophilicity-super-lipophobicity. The surface of the invention can be used in air, water and oil, and the oil-water separation can be realized by directly identifying oil and water without any pretreatment operation. The invention provides a new way for the preparation of the super-wetting material and the oil-water separation.
Description
Technical Field
The invention relates to a super-hydrophilic-super-oleophobic surface stable in air-water-oil and a preparation method and application thereof, belonging to the technical field of oil-water separation materials.
Background
Over the last 20 years, researchers developed nearly 64 types of super-wetting surfaces based on four basic wetting phenomena (hydrophilic, oleophilic, hydrophobic and oleophobic) (fig. 1 a). Most super-wetted surfaces need to remain stable in their self-wetting state under ideal conditions. The surface maintaining a stable super-wet state in a multi-phase environment of air, water, oil, etc. is not easily subject to environmental restrictions, is easy to store, and has a significant advantage in industrial applications.
Particularly, the super-hydrophilic-super-oleophobic surface can block oil stains, water with lower viscosity can be selectively separated in the oil-water separation process, high-viscosity oil can be effectively prevented from blocking a pore channel, and the super-hydrophilic-super-oleophobic surface has positive significance for oil-water separation and antifouling fabrics. However, the preparation difficulty of the surface is high, the use condition is single, and the storage environment is harsh, which is mainly reflected in that: according to the theory of young's equation, oleophobic surfaces with very low surface free energy also tend to be hydrophobic, and surfaces consisting of a single material cannot have a superhydrophilic-superoleophobic wetting state. In order to solve the problems, the existing preparation method of the super-hydrophilic-super-oleophobic surface needs to form a water film in an aqueous environment to realize the underwater oleophobic effect, and needs to be pre-wetted by water to induce the recombination of surface groups to realize the hydrophilic-oleophobic effect. However, these improved methods still cannot get rid of the limitation of using in water or pretreatment operations such as water wetting, and how to prepare superhydrophilic-superoleophobic surfaces that remain stable in air, water and oil is a challenge today.
The back shell of the nano-budworm has a plurality of hydrophilic protrusions (with high surface free energy chemical groups) and wax-like hydrophobic grooves (with low surface free energy chemical groups), the hydrophilic protrusion structure can capture scarce water vapor from desert air, and collected water drops can be conveyed to the head of the budworm along the hydrophobic grooves for drinking (fig. 1 b). Therefore, the surface constructed by two different surface free energy chemical groups can combine two opposite wetting states of hydrophilic and hydrophobic, and can maintain stability for a long time. Therefore, there is a need to provide an air and water/oil amphibious superhydrophilic-superoleophobic surface based on a nano-budworm structure.
Disclosure of Invention
The object of the present invention is to provide a superhydrophilic-superoleophobic surface stable in air, water, oil, which surface shows excellent and stable superhydrophilic-superoleophobic properties in air, water, oil, allowing an efficient separation of oil-water mixtures and oil-in-water emulsions without any pre-treatment.
The material with the super-hydrophilic-super-oleophobic surface stable in air-water-oil provided by the invention is obtained by spraying a dispersion liquid of nano-micro particles with high surface free energy chemical groups and low surface free energy chemical groups onto a substrate;
the spraying thickness has no special requirement and is generally 10-100 mu m;
the substrate can be glass, paperboard, metal plate, plastic plate or the like;
the nano-micron particles are methacrylic acid/hydroxyethyl methacrylate composite nano-micron particles;
the nano-micron particles are modified as follows:
and modifying the nano-micron particles by adopting a fluorine compound to obtain the nano-micron particles with high surface free energy chemical groups and low surface free energy chemical groups, wherein the particle size of the nano-micron particles is 30-100 nm.
Preferably, before spraying, preparing a glue film on the substrate, preferably spraying with Super75 adhesive sticker of 3M company to form the glue film (the spraying time is preferably 5 s);
preparing the dispersion liquid by adopting ethanol, wherein the mass concentration of the nano-micron particles with the high surface free energy chemical groups and the low surface free energy chemical groups in the dispersion liquid is 0.1-10%;
the spraying conditions were as follows:
the working distance is 10-15 cm;
the pressure is 0.1-0.5 MPa.
Specifically, the fluorine compound may be perfluorooctanoic acid;
the modification is carried out according to the following steps:
dispersing the nano-micron particles into the ethanol solution of the perfluorooctanoic acid, stirring for 1-24 hours at room temperature, and drying to obtain the nano-micron particles with high surface free energy chemical groups and low surface free energy chemical groups;
in the ethanol solution, the molar concentration of the perfluorooctanoic acid is 100-200 mM.
The methacrylic acid/hydroxyethyl methacrylate composite nano-micron particles are prepared according to the following method:
adding a water phase containing sodium methacrylate and hydroxyethyl methacrylate into an oil phase containing an emulsifier, and sequentially carrying out emulsification and reaction to obtain the water-soluble acrylate emulsion;
adding the aqueous phase under stirring;
the water phase contains potassium persulfate and N, N-methylene-bisacrylamide, and the concentrations of the potassium persulfate and the N, N-methylene-bisacrylamide have no special requirements and can be adjusted within a proper range;
specifically, emulsifying for 10-60 min under the condition of stirring;
reacting for 1-4 h at 25-70 ℃ under the condition of stirring.
The molar ratio of the sodium methacrylate to the hydroxyethyl methacrylate may be 1:0.3 to 0.4;
the emulsifier can be span 80 and/or tween 60;
the solvent of the oil phase may be number 10 white oil.
The stable super-hydrophilic-super-oleophobic surface is prepared by adopting nano-micro particles containing high-surface free energy chemical groups and low-surface free energy groups through spraying, can be used in air, water and oil, does not need any pretreatment operation, directly identifies oil and water, realizes quick oil-water mixture/emulsion separation, and has positive practical significance for preparation, use and storage of the super-hydrophilic-super-oleophobic surface.
The super-hydrophilic-super-oleophobic surface prepared by utilizing different surface free energy chemical groups and capable of being stable in air, water and oil is provided by the invention, wherein nano-micron particles are synthesized by methacrylic acid/hydroxyethyl methacrylate, the surface has higher surface free energy, and after the modification of perfluorooctanoic acid, the surface of the nano-micron particles has both high surface free energy chemical groups and low surface free energy chemical groups. After the nano-micron particle particles are sprayed on the base material, the surface of the material has stable super-hydrophilic-super-oleophobic property. The surface of the invention can be used in air, water and oil, and the oil-water separation can be realized by directly identifying oil and water without any pretreatment operation. The invention provides a new way for the preparation of the super-wetting material and the oil-water separation.
Drawings
Fig. 1a is a schematic diagram of 64 types of super-wetting surfaces developed in recent years, and fig. 1b is a schematic diagram of water collection by nano-budworm.
FIG. 2 is a scanning electron micrograph of the nano-micro particles prepared in example 1 of the present invention.
Fig. 3 is a graph showing the state of wetting of water droplets (deionized water, blue dyed by methylene blue) and oil droplets (n-hexadecane, red dyed by sudan iii) on glass, kraft paper, metal, and teflon surfaces and on the surface after coating of nano-micro particles prepared in example 1.
FIG. 4 is the contact angle of n-hexadecane, n-dodecane, n-octane, kerosene, QHD crude, SZ crude, and PL crude in air on the coating surface.
FIG. 5 is the contact angle of n-hexadecane, n-dodecane, n-octane, kerosene, QHD crude, SZ crude, and PL crude in water on the coating surface.
Fig. 6 is a graph showing the wetting time of water droplets on the coating surface in n-hexadecane, n-dodecane, n-octane, and liquid paraffin.
FIG. 7 shows the surface of the nano-micro particles, the cover glass, the aluminum sheets, the iron sheets and the polytetrafluoroethylene
And
fig. 8 is a scanning electron micrograph of a wire mesh before and after coating with the nano-and micro-sized particles of the present invention.
FIG. 9 is a photograph of a process for separating oil and water mixture by using a wire coated with nano-micro particles of the present invention.
Fig. 10 shows the separation efficiency and flux of the wire netting coated with nano-micro particles of the present invention for separating n-hexadecane-water, liquid paraffin-water, and engine oil-water mixtures.
Fig. 11 is an optical microscope photograph of wire separation spray coated wire separation water/n-hexadecane, water/liquid paraffin, water/motor oil emulsion before and after coating with nano-micron particles of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The materials, reagents, etc. used in the following examples are as follows:
perfluorooctanoic acid (95%) was purchased from Sigma-Aldrich. Absolute ethanol (99.8 percent or more), sodium dodecyl benzene sulfonate (98 percent), 10# white oil, span 80 (pharmaceutical grade), tween 60 (100 percent), sodium methacrylate (99 percent), hydroxyethyl methacrylate (99 percent), N-methylene bisacrylamide (97 percent) and potassium persulfate (99.5 percent) are purchased from Aladdin Biotechnology Ltd, N-hexadecane (> 99.5 percent), N-dodecane (> 99 percent), liquid paraffin, octane (> 99 percent), heptane (> 99 percent), kerosene (boiling point temperature 18.9-250.4 percent), engine oil, glass slide glass, aluminum (4 mm X20 mm), iron (2 mm X20 mm), polytetrafluoroethylene (PTFE, 2mm X20 mm), wire netting (1000 mesh) and kraft paper are purchased from Maxlin Biotechnology Ltd. Spray type Super75 adhesive was purchased from 3M company.
In the following examples, the contact angle and the sliding angle are defined by a Tracker equipped with a tilting platform TM High temperature high pressure system (TECLIS Scientific) determination: carefully drop water/oil (5 μ Ι _ drop) on the surface, and obtain the static contact angle by averaging the measurements at five positions on each surface.
In the examples described below, the microstructure of the samples was characterized after covering them with a thin layer of sputtered gold using a scanning electron microscope (SEM; cold field emission System model Hitachi S-4800).
The viscosities of the oils used in the following examples are shown in table 1:
TABLE 1 viscosity of different types of oils
Example 1 preparation of Nanoparticulate particles with high and Low surface free energy chemical groups
1. Preparation of nano-micro particles of high surface free energy chemical groups
Preparing an oil phase: 10# white oil: 68g of a mixture; the span 80:8.4g; tween 60:3.6g, and stirring uniformly to obtain an oil phase.
Water phase: 10g of deionized water; sodium methacrylate: 5.7g; hydroxyethyl methacrylate (HEMA) 3.6g; n, N-methylenebisacrylamide: 0.5g; potassium persulfate: 0.2g, stirred well to obtain an aqueous phase.
Gradually adding water phase dropwise into the oil phase under high speed stirring at 20000rpm, and after dropwise adding, maintaining high speed stirring at 20000rpm for 10min to obtain stable water-in-oil emulsion. The water-in-oil emulsion was placed in a three-necked flask, stirred at 800rpm and reacted at 65 ℃ for 2 hours.
After the reaction is finished, washing and filtering the reaction solution for three times by using ethanol to obtain nano-micron particles with high surface free energy chemical groups on the surface, and recording the nano-micron particles as follows: H-SFE MS.
2. Nano-micron particle modified by perfluorooctanoic acid and having high surface free energy chemical group
Under magnetic stirring at 1000rpm, H-SFE MS particles (3.0 g) were gradually dispersed in an anhydrous ethanol solution (100mM, 20mL) of perfluorooctanoic acid, and stirred for 24 hours. This solution is called LH-SFE MS dispersion. After drying the mixture in vacuo, nano-micro particles with surfaces rich in high and low surface free energy chemical groups were obtained, recorded as: LH-SFE MS.
The scanning electron micrograph of the nano-micron particles prepared in this example is shown in fig. 2, and it can be seen that the nano-micron particles are in a regular spherical shape, the particle size is between 30 nm and 90nm, and the agglomerate aggregates thereof form a nano-micron multilevel coarse structure.
Example 2 preparation of Superhydrophilic-Superoleophobic surface Stable in air-Water-oil
A clean and dry piece of glass slide was exposed to a Super75 adhesive mist for about 3 seconds to form a glue film having a thickness of about 10 μm. LH-SFE MS dispersion (ethanol, 3 wt%) (2 mL) was sprayed onto glass slides by an air spray device (SIBONGD HD-134) at a working distance of 15cm and a working pressure of 0.2MPa, at a coating thickness of 50 μm. And (3) putting the glass slide carrying the coating in a thermostat with the temperature of 70 ℃ for 24 hours, and then completely evaporating the solvent to obtain the super-hydrophilic-super-oleophobic surface stable in air-water-oil.
As shown in fig. 3, water droplets (deionized water, blue dyed by methylene blue) and oil droplets (n-hexadecane, red dyed by sudan iii) exhibited rapid wetting behavior on the surface of glass sheet, kraft paper, which was not coated with the above-mentioned polymer particles, and the red oil droplets spread over a wider range than the blue droplets, indicating that the surface of glass and kraft paper had strong lipophilicity. On the metal sheet which is not coated with the polymer particles, water drops do not spread obviously, and the spreading range of the oil drops is larger and more uniform, which shows that the surface of the metal sheet has weaker hydrophilicity and stronger lipophilicity. On the surface of the polytetrafluoroethylene which is not coated with the nano-micron particles, no water drop or oil drop is spread, and the surface of the polytetrafluoroethylene has hydrophobic and oleophobic properties. When glass, kraft paper, metal and polytetrafluoroethylene surfaces are coated with the above-mentioned nano-micro particles, the wetting behavior of water and oil droplets on these surfaces is completely different from the original state of the uncoated nano-micro particles without any pretreatment. The water droplets spread rapidly on these surfaces, while the droplets still appear spherical. This indicates that the above-described nano-micro particles can change the surface of glass, kraft paper, metal and polytetrafluoroethylene into an excellent super hydrophilic-super oleophobic state, and that this super wetting state is not affected by the original wettability of the substrate material.
The slide coated with the above-mentioned nano-micro particles was placed in air, under water and under oil, and the oil drop contact angle or water drop wetting time was measured. As shown in fig. 4, the contact angles of n-hexadecane, n-dodecane, n-octane, kerosene, QHD crude oil, SZ crude oil, and PL crude oil on the coating surface were about 150 ° as measured by the sitting drop method in air. As shown in fig. 5, the contact angle of n-hexadecane, n-dodecane, n-octane, kerosene, QHD crude oil, SZ crude oil, and PL crude oil on the coating surface was about 165 ° when the coating was placed in deionized water by the pendant drop method. As shown in fig. 6, the water droplets in n-hexadecane, n-dodecane, n-octane, and liquid paraffin completely spread on the coating surface within about 10 seconds. The higher the viscosity of the oil, the greater the resistance of the water droplets to the oil, and the longer the wetting time, and the water droplets had a wetting time of 10.12s in liquid paraffin having a viscosity of 40.21mPa · s. These results show that coatings coated with the above-described nano-micro particles can have stable superhydrophilic-superoleophobic properties in air, water, oil without any pretreatment. The coating has direct and quick oil repellency, and has potential application prospects in the aspects of oil-water separation and oil stain resistance.
Example 3 Studies of the mechanism of a Superhydrophilic-Superoleophobic surface stabilized in air-Water-oil
Surface free energy (gamma) of solid surface sv ) Is a dispersion component (gamma) sv d ) And a non-dispersive component (gamma) sv p ) And (4) summing. These two components are subjected to dispersive forces and dipole hydrogen bonding, respectively. The water is affected by both dipole hydrogen bonds and dispersion forces, and the dispersion component of the non-polar solvent is negligible. According to equations (S1) and (S2), the oleophobic and hydrophilic surfaces must have a large surface free energy (γ) sv ) And a smaller dispersion component (gamma) sv d ). In order to confirm the relationship between the surface energy and the wetting behavior, the data calculated by the equation (S3) are plotted in fig. 7 and table 2.
TABLE 2 surface free energy component of various surfaces
Gamma for iron, aluminum and glass slides sv A value lower than the surface tension (gamma) of water water ＝72.8mN·m -1 ) And γ sv d Higher than the surface tension (gamma) of n-hexadecane hexadecane ＝22.3mN·m -1 ). This confirms that in fig. 3, the contact angle of the n-hexadecane droplet on iron, aluminum and glass slides is smaller than that of water. Gamma of Polytetrafluoroethylene (PTFE) sv And gamma sv d This also demonstrates its unique hydrophobic and oleophobic properties, below the surface tension of water and hexadecane. Gamma on LH-SFE MS surface sv Is significantly higher than the surface tension of water, and gamma sv d Lower than the surface tension (20-40 mN.m) of n-hexadecane and most organic solvents -1 ). Therefore, the surface of the LH-SFE MS has larger surface free energy and smaller dispersion component due to two chemical groups rich in the surface of the LH-SFE MS, wherein the surface free energy is promoted by the sodium carboxylate group and the hydroxyl group on the surface of the LH-SFE MS to attract water molecules, so that the wetting of water is accelerated. The long fluorocarbon chain of perfluorooctanoic acid effectively reduces the surface free energy, which has a repulsive effect on oil molecules and hinders the wetting of oil.
When the LH-SFE MS coating is submerged in water, water molecules will first diffuse into the surface and form a water film. Due to the protection of the water film, the LH-SFE MS coating still has stable super oleophobic property under water. When the LH-SFE MCC coating is submerged in oil, the coating surface forms a layer of air cushion against oil molecule contact and intrusion due to the superoleophobic properties. The air cushion on the surface of the coating also provides a wetting space for the water droplets. However, due to the limited viscosity of the oil phase and the volume of the air cushion, the water droplets spread more slowly under the oil than in air.
Example 4 separation of oil-water mixture and oil-in-water emulsion with Superhydrophilic-Superoleophobic wire
1. Preparing the wire netting loaded with LH-SFE MS nano-micron particles
A piece of clean and dry 1000 mesh wire was exposed to a Super75 adhesive mist for about 3s to form a film, and a LH-SFE MS dispersion (ethanol, 3 wt%) (2 mL) was sprayed onto the wire by an air spraying device (SIBONGD HD-134) at a working distance of 15cm and a working air pressure of 0.2 MPa. And (3) putting the wire mesh loaded with the nano-micron particles into a thermostat with the temperature of 70 ℃ for 24 hours, and completely evaporating the solvent to obtain the super-hydrophilic-super-oleophobic wire mesh stable in air-water-oil.
The scanning electron micrograph of the LH-SFE MS nano-micron particle loaded wire mesh prepared in this example is shown in fig. 8. Compared with the photo before coating the polymer, the wire gauze loaded with LH-SFE MS nano-micron particles is gathered with a large number of nano-micron multilevel protruding structures.
2. Preparation of oil-in-water emulsions and oil-water separation process
60mL of deionized water, 40mL of oil and 0.5g of sodium dodecyl benzene sulfonate are mixed, magnetized and stirred for 4 hours to prepare a stable oil-in-water emulsion.
The separation of the oil-water mixture as shown in fig. 9, a prepared piece of LH-SFE MS nano-micron particle wire mesh was first installed in the separation device, and then an immiscible liquid of 80mL oil and 80mL water was poured into the separation device, which was driven by gravity only and did not require any pre-treatment.
Separation of oil-in-water emulsion as shown in fig. 11, two prepared wires of LH-SFE MS nano-micron particles were installed in a separation device, and then 30mL of the oil-in-water emulsion was poured into the separation device, which was driven by gravity only and did not require any pretreatment.
As shown in fig. 9, when the mixture is poured out of the beaker, the oil will first contact the surface of the wire due to the lower density of the oil on top of the oil water mixture. For the previously reported superhydrophilic-superoleophobic surfaces, the membrane must first be wetted with water or otherwise pretreated, otherwise oil droplets will penetrate through the wire mesh and no oil-water separation can be achieved. By virtue of the stable super-hydrophilic-super-oleophobic characteristics in air, water and oil, the iron wire mesh loaded with LH-SFE MS nano-micron particles can keep the water and oil passing resistance when oil drops contact the surface for the first time. As shown in FIG. 10, the iron wire net loaded with LH-SFE MS nano-micron particles can effectively separate high-viscosity oil-water mixtures, and the separation efficiency exceeds 98%. The excellent performance is that the oil drops are not easy to adhere to the surface and block pore channels due to stable super-oleophobic performance in a gas-liquid environment, so that the separation process is not influenced by the viscosity of the oil. The wire separation flux was about 2000 L.m for oils of different viscosities under the influence of gravity alone -2 ·h -1 。
As shown in fig. 11, the LH-SFE MS nano-microparticle loaded wire mesh has better separation ability for oil-in-water emulsions than the wire mesh without any modification. After the liquid paraffin-water emulsion and the engine oil-water emulsion pass through the LH-SFE MS membrane, the quantity and the content of micron-sized oil drops in the filtrate are also obviously reduced. The separation efficiencies of the n-hexadecane-water emulsion, the liquid paraffin-water emulsion and the engine oil-water emulsion were 97.40%, 97.00% and 96.80%, respectively. This shows that the LH-SFE MS nano-micron particle loaded wire mesh can separate the emulsion of high viscosity oil with high efficiency.
Claims (10)
1. A material with a super-hydrophilic-super-oleophobic surface stable in air-water-oil is obtained by spraying a dispersion of nano-micron particles onto a substrate;
the nano-micron particles are methacrylic acid/hydroxyethyl methacrylate composite nano-micron particles;
the nano-micron particles are modified as follows:
and modifying the nano-micron particles by adopting a fluorine compound to obtain the nano-micron particles with high surface free energy chemical groups and low surface free energy chemical groups.
2. The material of claim 1, wherein: the substrate is glass, a paperboard, a metal plate, a plastic plate or a wire mesh.
3. The material according to claim 1 or 2, characterized in that: before spraying, preparing a glue film on the substrate;
preparing the dispersion liquid by adopting ethanol;
the spraying conditions were as follows:
the working distance is 10-15 cm;
the pressure is 0.1-0.5 MPa.
4. The material of claim 3, wherein: the fluorine compound is perfluorooctanoic acid.
5. The material of claim 4, wherein: the modification is carried out according to the following steps:
dispersing the nano-micron particles into the ethanol solution of the perfluorooctanoic acid, stirring for 1-24 h at room temperature, and drying to obtain the nano-micron particles with the chemical groups with high surface free energy and the chemical groups with low surface free energy.
6. The material of claim 5, wherein: the methacrylic acid/hydroxyethyl methacrylate composite nano-micron particles are prepared according to the following method:
adding a water phase containing sodium methacrylate and hydroxyethyl methacrylate into an oil phase containing an emulsifier, and sequentially carrying out emulsification and reaction to obtain the water-soluble acrylate emulsion;
adding the aqueous phase under stirring;
the water phase contains potassium persulfate and N, N-methylene-bisacrylamide.
7. The material of claim 6, wherein: emulsifying for 10-60 min under the condition of stirring;
reacting for 0.5-4 h at 25-80 ℃ under the condition of stirring.
8. The material of claim 7, wherein: the molar ratio of the sodium methacrylate to the hydroxyethyl methacrylate is 1:0.3 to 0.4.
9. The material of claim 8, wherein: the emulsifier is span 80 and/or tween 60;
the solvent of the oil phase is No. 10 white oil.
10. Use of a material according to any of claims 1 to 9 for separating oil and water mixtures and oil-in-water emulsions,
the material is used in air, water and/or oil.
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Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1285992A (en) * | 1988-09-28 | 1992-06-25 | Ciba-Geigy Ag | Molded polymers with hydrophilic surfaces, and process for making them |
| CN100434447C (en) * | 2005-09-09 | 2008-11-19 | 中国科学院理化技术研究所 | Nanometer and micron water-soluble microgel reservoir oil material and preparation method thereof |
| US8454836B2 (en) * | 2005-09-15 | 2013-06-04 | The University Of Akron | Method for removing water from an organic liquid |
| US8658707B2 (en) * | 2009-03-24 | 2014-02-25 | W. L. Gore & Associates, Inc. | Expandable functional TFE copolymer fine powder, the expanded functional products obtained therefrom and reaction of the expanded products |
| US20110184088A1 (en) * | 2010-01-27 | 2011-07-28 | Basf Se | Coating materials comprising composite particles |
| CN102304204B (en) * | 2011-05-20 | 2014-09-10 | 中科院广州化学有限公司 | Fluorine-containing bi-functional microspheres and application thereof |
| EP2883892B1 (en) * | 2012-08-10 | 2017-10-04 | Tohoku University | Organic-inorganic composite particles, dispersion liquid containing same, resin composition containing same, and method for producing organic-inorganic composite particles |
| CN103611426A (en) * | 2013-11-15 | 2014-03-05 | 天津工业大学 | Continuous ultraviolet radiation modification device of hydrophilic hollow fibrous membrane and preparation method of continuous ultraviolet radiation modification device |
| CN108117662B (en) * | 2017-11-30 | 2020-07-21 | 中国科学院兰州化学物理研究所 | Method for preparing hydrophilic lubricating coating on surface of material |
| CN108191040B (en) * | 2017-12-18 | 2019-01-22 | 北京桑德环境工程有限公司 | A kind of high-intensitive carrier material and preparation method thereof for sewage treatment |
| CN109173345B (en) * | 2018-09-21 | 2019-10-11 | 西安科技大学 | A kind of preparation method and applications of the super-amphiphobic material with pH responsiveness |
| CN109364528B (en) * | 2018-12-11 | 2021-02-12 | 哈尔滨工程大学 | Multi-level structure oil-water separation material with pH responsiveness and preparation method thereof |
| CN110354823A (en) * | 2019-07-10 | 2019-10-22 | 丽水学院 | A kind of novel quaternization cyclodextrin polyurethane copolymer material and preparation method thereof |
| CN110655607B (en) * | 2019-11-01 | 2021-08-24 | 苏州大学 | Porous polymer with oleophobic property and pH responsiveness, preparation and application thereof |
| CN112552532A (en) * | 2020-12-08 | 2021-03-26 | 上海视互力商贸有限公司 | Blue-light-proof and ultraviolet-resistant hydrogel contact lens and preparation method thereof |
| CN112717710B (en) * | 2020-12-11 | 2023-03-14 | 武汉理工大学 | Air super-oleophobic and super-hydrophilic film and preparation method and application thereof |
| CN113230901B (en) * | 2021-06-24 | 2022-04-19 | 浙江工业大学 | Super-amphiphilic/submerged super-amphiphobic PAN composite membrane for emulsion separation, and preparation method and application thereof |
| CN113387592B (en) * | 2021-07-19 | 2022-04-05 | 中国石油大学(北京) | Underwater super-oleophobic composite coating on glass surface and preparation method thereof |
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