阅读说明：本技术 一种具有光催化和油水分离性能的超疏水柔性织物及其制备方法和应用 (Super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances and preparation method and application thereof ) 是由 刘恩周 赵月梅 樊君 胡晓云 白雪 何玉东 贺春良 于 2019-10-16 设计创作，主要内容包括：本发明提供了一种具有光催化和油水分离性能的超疏水柔性织物及其制备方法和应用,属于污水处理技术领域。本发明通过在柔性织物表面负载光催化材料和疏水组分,能够使柔性织物兼具光催化和超疏水油水分离性能,其中,光催化材料在可见光照射下对污水中的有机污染物具有良好的光降解效果；疏水组分成膜性好,能够在柔性织物表面形成疏水涂层。同时,本发明提供的制备方法简单,易于操作,光催化材料可以先负载于柔性织物表面,也可以与疏水组分同时负载在柔性织物表面。实施例结果表明,本发明所得超疏水柔性织物的表面水接触角可达164°,且能在2h内实现可见光下亚甲基蓝的降解。(The invention provides a super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, and a preparation method and application thereof, and belongs to the technical field of sewage treatment. According to the invention, the photocatalytic material and the hydrophobic component are loaded on the surface of the flexible fabric, so that the flexible fabric has both photocatalytic and super-hydrophobic oil-water separation performances, wherein the photocatalytic material has a good photodegradation effect on organic pollutants in sewage under the irradiation of visible light; the hydrophobic component has good film forming property and can form a hydrophobic coating on the surface of the flexible fabric. Meanwhile, the preparation method provided by the invention is simple and easy to operate, and the photocatalytic material can be loaded on the surface of the flexible fabric firstly or can be loaded on the surface of the flexible fabric together with the hydrophobic component. The example result shows that the surface water contact angle of the super-hydrophobic flexible fabric obtained by the invention can reach 164 degrees, and the degradation of methylene blue under visible light can be realized within 2 h.)

1. A preparation method of a super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances is characterized by comprising the following steps:

(1) mixing a photocatalytic material with water, and performing ultrasonic treatment to obtain a photocatalytic material dispersion liquid;

(2) placing the flexible fabric into the photocatalytic material dispersion liquid, and sequentially carrying out sealing heating treatment and drying to obtain the flexible fabric loaded with the photocatalytic material;

(3) mixing polydimethylsiloxane, tetraethoxysilane, catalyst and solvent to obtain hydrophobic solution;

(4) placing the flexible fabric loaded with the photocatalytic material in the hydrophobic solution, and sequentially carrying out sealing heating treatment and drying to obtain a super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances;

or comprises the following steps:

(a) mixing polydimethylsiloxane, tetraethoxysilane, catalyst, solvent and photocatalytic material to obtain hydrophobic solution containing the photocatalytic material;

(b) and placing the flexible fabric in the hydrophobic solution containing the photocatalytic material, and sequentially carrying out sealing heating treatment and drying to obtain the super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances.

2. The production method according to claim 1, wherein the photocatalytic material is red phosphorus and/or bismuth tungstate; the flexible fabric is a polyester fabric; the ratio of the mass of the photocatalytic material to the area of the flexible fabric is (0.006-0.016) g:1cm²。

3. The preparation method according to claim 1, wherein the temperature of the sealing heat treatment in the step (2) is 130 to 160 ℃ and the time is 8 to 12 hours.

4. The method of claim 1, wherein the catalyst in step (3) and step (a) is independently di-n-octyltin dilaurate and/or dibutyltin dilaurate, and the solvent is independently at least one of n-hexane, cyclohexane, and ethanol.

5. The production method according to claim 1 or 4, characterized in that the amounts of polydimethylsiloxane, tetraethoxysilane, catalyst and solvent used in the step (3) and the step (a) are, independently, 1g: (1-5) g: (0.1-0.2) g:60 mL.

6. The preparation method according to claim 1, wherein the ratio of the volume of the hydrophobic solution to the area of the flexible fabric loaded with the photocatalytic material in the step (4) is (1.2-1.6) mL:1cm²(ii) a The ratio of the volume of the hydrophobic solution containing the photocatalytic material to the area of the flexible fabric in the step (b) is (1.2-1.6) mL:1cm²。

7. The method according to claim 1, wherein the temperature of the sealing heat treatment in the step (4) and the step (b) is independently 100 to 120 ℃ and the time is independently 8 to 16 hours.

8. The method according to claim 1, wherein the hydrophobic solution in the step (3) and the hydrophobic solution containing the photocatalytic material in the step (a) independently further comprise paraffin and/or SiO₂。

9. The super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances prepared by the preparation method of any one of claims 1 to 8.

10. The use of the superhydrophobic flexible fabric having photocatalytic and oil-water separation properties of claim 9 in sewage treatment.

Technical Field

The invention relates to the technical field of sewage treatment, in particular to a super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, and a preparation method and application thereof.

Background

The photocatalysis technology is one of effective ways for solving the problems of energy shortage and environmental pollution at present, and has good application prospects in the fields of light energy conversion, air purification, sterilization, disinfection, self-cleaning and the like. The development of high-performance photocatalysts is still the focus of research in the field of photocatalysis. Most semiconductor photocatalysts are limited by their band structure, e.g. TiO₂、ZnO、ZnS、SrTiO₃And the like, can only absorb and utilize ultraviolet light, so that the utilization rate of sunlight is low; visible light catalysts having visible light response, e.g. g-C₃N₄、CdS、Ag₃PO₄、Bi₂WO₆P, etc., although having a high light energy utilization efficiency, they are mainly present in powder form, although having a high specific surfaceThe area and the mass and heat transfer performance are good, but the problems of easy agglomeration, difficult recovery, serious loss, easy secondary pollution and the like exist, and the large-scale application is difficult. Currently, the development of photocatalytic materials in the form of thin films having practical value is one of the research hotspots in this field.

Considering that most industrial sewage contains oil stain and toxic and harmful pollutants, the development of an oil-water separation and pollutant purification integrated technology is undoubtedly beneficial to improving the environmental treatment capability and reducing the production cost. Patent CN201711109397.8 discloses a titanium dioxide/cotton fabric with super-hydrophobic and self-cleaning functions, but only using ultraviolet light, and TiO₂The oxidation performance is strong (the position of a valence band is positive), and organic components in the hydrophobic coating can be degraded, so that the stability of the hydrophobic coating is influenced. Patent CN201710894467.9 discloses a super-hydrophobic visible light photocatalytic self-cleaning coating and a preparation method thereof, but the preparation method is complex, and the composite material exists in a microsphere form, so that the problems of recycling and the like cannot be overcome. The literature (Journal of Materials Chemistry A,2015,3: 16958-16945) adopts a screen deposition technique to prepare a PDMS modified CdS thin film on a glass surface, but the thin film cannot realize oil-water separation.

Disclosure of Invention

In view of the above, the present invention aims to provide a super-hydrophobic flexible fabric with photocatalytic and oil-water separation properties, a preparation method and an application thereof, wherein the method is simple to operate and low in cost, and the obtained super-hydrophobic flexible fabric has both photocatalytic and oil-water separation properties and is good in self-cleaning ability.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, which comprises the following steps:

(1) mixing a photocatalytic material with water, and performing ultrasonic treatment to obtain a photocatalytic material dispersion liquid;

(2) placing the flexible fabric into the photocatalytic material dispersion liquid, and sequentially carrying out sealing heating treatment and drying to obtain the flexible fabric loaded with the photocatalytic material;

(3) mixing polydimethylsiloxane, tetraethoxysilane, catalyst and solvent to obtain hydrophobic solution;

(4) placing the flexible fabric loaded with the photocatalytic material in the hydrophobic solution, and sequentially carrying out sealing heating treatment and drying to obtain a super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances;

or comprises the following steps:

(a) mixing polydimethylsiloxane, tetraethoxysilane, catalyst, solvent and photocatalytic material to obtain hydrophobic solution containing the photocatalytic material;

(b) and placing the flexible fabric in the hydrophobic solution containing the photocatalytic material, and sequentially carrying out sealing heating treatment and drying to obtain the super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances.

Preferably, the photocatalytic material is red phosphorus and/or bismuth tungstate; the flexible fabric is a polyester fabric; the ratio of the mass of the photocatalytic material to the area of the flexible fabric is (0.006-0.016) g:1cm²。

Preferably, the temperature of the sealing and heating treatment in the step (2) is 130-160 ℃, and the time is 8-12 hours.

Preferably, the catalyst in step (3) and step (a) is independently di-n-octyltin dilaurate and/or dibutyltin dilaurate, and the solvent is independently at least one of n-hexane, cyclohexane and ethanol.

Preferably, the dosage ratio of the polydimethylsiloxane, the tetraethoxysilane, the catalyst and the solvent in the step (3) and the step (a) is independently 1g, (1-5) g, (0.1-0.2) g and 60 mL.

Preferably, the ratio of the volume of the hydrophobic solution to the area of the flexible fabric loaded with the photocatalytic material in the step (4) is (1.2-1.6) mL:1cm²(ii) a The ratio of the volume of the hydrophobic solution containing the photocatalytic material to the area of the flexible fabric in the step (b) is (1.2-1.6) mL:1cm²。

Preferably, the temperature of the sealing and heating treatment in the step (4) and the step (b) is independently 100-120 ℃, and the time is independently 8-16 h.

Preferably, the hydrophobic solution in step (3) and the hydrophobic solution containing the photocatalytic material in step (a) independently further comprise paraffin and/or SiO₂。

The invention provides application of the super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances prepared by the preparation method in sewage treatment.

The invention also provides the super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances

The invention provides a preparation method of a super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, the invention can enable the flexible fabric to have photocatalysis and super-hydrophobic oil-water separation performances by loading a photocatalysis material and a hydrophobic component on the surface of the flexible fabric, wherein the photocatalysis material has a good photodegradation effect on organic pollutants in sewage under the irradiation of visible light; the hydrophobic component has good film forming property, can form a hydrophobic coating on the surface of the flexible fabric, has excellent oil-water separation performance, and can remove dust, oil stains and the like on the surface by means of water drop sliding and a photocatalysis process, thereby realizing the self-cleaning effect. Meanwhile, the preparation method provided by the invention is simple and easy to operate, and the photocatalytic material can be loaded on the surface of the flexible fabric firstly or can be loaded on the surface of the flexible fabric together with the hydrophobic component. The surface water contact angle of the super-hydrophobic flexible fabric obtained by the invention can reach 164 degrees, and the degradation of methylene blue under visible light can be realized within 2 h.

Drawings

FIG. 1 is a water drop contact object diagram of the super-hydrophobic flexible fabric obtained in example 1;

FIG. 2 is a contact angle test chart of the superhydrophobic flexible fabric obtained in example 1;

FIG. 3 is a graph showing the fluorescence intensity of methylene blue solution in example 1 at different irradiation times of visible light;

FIG. 4 is a water drop contact object diagram of the super-hydrophobic flexible fabric obtained in example 2;

FIG. 5 is a contact angle test chart of the superhydrophobic flexible fabric obtained in example 2;

FIG. 6 is a graph showing the fluorescence intensity of methylene blue solution in example 2 at different irradiation times of visible light.

Detailed Description

The invention provides a preparation method of a super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, which comprises the following steps:

(1) mixing a photocatalytic material with water, and performing ultrasonic treatment to obtain a photocatalytic material dispersion liquid;

(2) placing the flexible fabric into the photocatalytic material dispersion liquid, and sequentially carrying out sealing heating treatment and drying to obtain the flexible fabric loaded with the photocatalytic material;

(3) mixing polydimethylsiloxane, tetraethoxysilane, catalyst and solvent to obtain hydrophobic solution;

(4) and placing the flexible fabric loaded with the photocatalytic material in the hydrophobic solution, and sequentially carrying out sealing heating treatment and drying to obtain the super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances.

The invention mixes the photocatalysis material with water, and obtains the photocatalysis material dispersion liquid after ultrasonic treatment. In the present invention, the photocatalytic material is preferably red phosphorus and/or bismuth tungstate, and the particle size of the photocatalytic material is preferably <1 μm. In the invention, the volume ratio of the mass of the photocatalytic material to water is preferably (0.2-2) g: 500mL, more preferably at a concentration of 1g: 500 mL; the frequency of the ultrasonic wave is preferably 20KHz, the power is preferably 300-800W, more preferably 300W, 400W, 500W, 600W, 700W or 800W, and the time is preferably 10 h. The invention changes the grain diameter of the photocatalysis material into nanometer grade by ultrasonic.

After the photocatalytic material dispersion liquid is obtained, the flexible fabric is placed in the photocatalytic material dispersion liquid, and sealing, heating and drying are sequentially carried out to obtain the photocatalytic material loaded flexible fabric. In the invention, the flexible fabric is preferably a polyester fabric, and the polyester fabric is flexible and wear-resistant, has rich pore channels and is uniformly distributed, thereby being beneficial to the load of a photocatalytic material and a hydrophobic component; before the sealing and heating treatment, the flexible fabric is preferably subjected to washing and drying treatment to remove stains on the surface of the flexible fabric. In the present inventionThe mass to area ratio of the photocatalytic material to the flexible fabric is preferably 0.006 g:1cm². According to the invention, the photocatalytic material dispersion liquid and the flexible fabric are preferably placed in a sealed container for sealing and heating treatment, the temperature of the sealing and heating treatment is preferably 130-160 ℃, more preferably 140-150 ℃, the time is preferably 8-12 h, more preferably 9-11 h, the temperature and the pressure in the sealed container can be increased, and the adhesion of a hydrophobic component on the surface of the fabric is facilitated. The invention preferably cools and washes the flexible fabric after the sealing and heating treatment, and then dries the fabric; the washing detergent is preferably water; the present invention does not require any particular manner of cooling and washing, and cooling and washing means well known to those skilled in the art may be used.

The invention mixes polydimethylsiloxane, tetraethoxysilane, catalyst and solvent to obtain hydrophobic solution. In the present invention, the catalyst is preferably di-n-octyltin dilaurate and/or dibutyltin dilaurate, more preferably di-n-octyltin dilaurate or dibutyltin dilaurate, and the solvent is preferably at least one of n-hexane, cyclohexane and ethanol, more preferably n-hexane, cyclohexane or ethanol; the dosage ratio of the polydimethylsiloxane, the ethyl orthosilicate, the catalyst and the solvent is preferably 1g: (1-5) g: (0.1-0.2) g:60mL, more preferably 1g: 2 g: 0.1 g:60 mL. In the invention, the mixing mode is preferably stirring mixing, and the mixing temperature is preferably 40-60 ℃, and more preferably 50 ℃. During the stirring and mixing process, polydimethylsiloxane and tetraethoxysilane are subjected to polymerization reaction to generate a long-chain cross-linked reticular polymer, and the polymer has good hydrophobic property.

After the hydrophobic solution is obtained, the flexible fabric loaded with the photocatalytic material is placed in the hydrophobic solution, and sealing, heating and drying are sequentially carried out to obtain the super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances. In the invention, the ratio of the volume of the hydrophobic solution to the area of the flexible fabric loaded with the photocatalytic material is preferably (1.2-1.6) mL:1cm². The hydrophobic solution and the flexible fabric are preferably placed in a sealed containerAnd (3) carrying out sealing and heating treatment, wherein the sealing and heating treatment temperature is preferably 100-120 ℃, more preferably 110 ℃, and the time is preferably 12 h. During sealing and heating treatment, the long-chain cross-linked network polymer in the hydrophobic solution can form a hydrophobic coating on the surface of the flexible fabric, so that the flexible fabric has excellent oil-water separation performance, and dust, oil stains and the like on the surface can be removed by means of water drop sliding and a photocatalysis process, so that a self-cleaning effect is realized. The invention preferably cools and washes the flexible fabric after the sealing and heating treatment, and then dries the fabric; the present invention does not require any particular manner of cooling and washing, and cooling and washing means well known to those skilled in the art may be used.

Or, the invention provides a preparation method of the super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, which comprises the following steps:

(a) mixing polydimethylsiloxane, tetraethoxysilane, catalyst, solvent and photocatalytic material to obtain hydrophobic solution containing the photocatalytic material;

(b) and placing the flexible fabric in the hydrophobic solution containing the photocatalytic material, and sequentially carrying out sealing heating treatment and drying to obtain the super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances.

The invention mixes polydimethylsiloxane, tetraethoxysilane, catalyst, solvent and photocatalytic material to obtain hydrophobic solution containing the photocatalytic material. In the present invention, the types of the photocatalytic material, the catalyst and the solvent, and the dosage ratio of the polydimethylsiloxane, the tetraethoxysilane, the catalyst and the solvent are the same as those in the above-mentioned scheme, and are not described herein again. In the present invention, the amount of the photocatalytic material is the same as the mass of the photocatalytic material and the area ratio of the flexible fabric in the step (2), and details are not repeated herein. In the present invention, the mixing is preferably performed by stirring; the temperature during mixing is preferably 40-60 ℃, and more preferably 50 ℃. According to the invention, the polydimethylsiloxane, the ethyl orthosilicate, the catalyst and the solvent are preferably firstly mixed and stirred, and then the photocatalytic material is added for secondary stirring and mixing. According to the invention, polydimethylsiloxane and tetraethoxysilane are subjected to polymerization reaction in the first mixing process to generate a long-chain cross-linked reticular polymer, the polymer has good hydrophobic property, and then a catalyst is added to ensure that raw materials are fully dispersed, and catalyst particles participate in the cross-linking reaction, so that the particles finally attached to the surface of the fabric fiber are not easy to fall off. In the invention, the time for the first mixing is preferably 2-4 h, more preferably 2h, and the time for the second mixing is preferably 12-24 h, more preferably 12-18 h.

After the hydrophobic solution containing the photocatalytic material is obtained, the flexible fabric is placed in the hydrophobic solution containing the photocatalytic material, and sealing, heating and drying are sequentially carried out to obtain the super-hydrophobic flexible fabric with photocatalytic and oil-water separation performances. In the present invention, the specific operation manner and conditions of the sealing heat treatment and drying are the same as those in the step (4), and are not described herein again.

In the present invention, the hydrophobic solution in the step (3) and the hydrophobic solution containing the photocatalytic material in the step (a) preferably further include paraffin and/or SiO₂The mass ratio of the paraffin to the polydimethylsiloxane is preferably (1.2-2.4): 1, more preferably (1.5 to 2.2): 1, most preferably 2: 1; the SiO₂The mass ratio of the polydimethylsiloxane to the polydimethylsiloxane is preferably (0.6-1.4): 1, more preferably (0.8 to 1.2): 1, most preferably 1.2: 1. in the present invention, the paraffin and SiO₂Loaded on the surface of flexible fabric, where paraffin is favorable for oil-water separation, SiO₂Has higher roughness, and is beneficial to improving the hydrophobic performance of the hydrophobic coating. The invention is directed to the paraffin wax and/or SiO₂The adding mode of (2) has no special requirements, and the mixture is directly added into the hydrophobic solution and stirred uniformly.

The invention provides the super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances, which is prepared by the preparation method. In the invention, the surface of the super-hydrophobic flexible fabric is loaded with the photocatalytic material and the hydrophobic coating, so that the super-hydrophobic flexible fabric has both photocatalytic performance and super-hydrophobic oil-water separation performance, has a good photodegradation effect on organic pollutants in sewage under visible light, and can remove dust, oil stains and the like on the surface by means of water drop sliding and a photocatalytic process, thereby realizing a self-cleaning effect.

The invention provides application of the super-hydrophobic flexible fabric with photocatalysis and oil-water separation performances in sewage treatment. The super-hydrophobic flexible fabric provided by the invention can degrade organic pollutants in sewage under visible light, and is more suitable for organic sewage containing oil stains because of good oil-water separation performance.

The following examples are provided to illustrate the super-hydrophobic flexible fabric with photocatalytic and oil-water separation properties, and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.