阅读说明：本技术 一种超疏水导电皮革及其制备方法 (Super-hydrophobic conductive leather and preparation method thereof ) 是由 鲍艳 郭茹月 郑茜 许佳琛 张文博 刘超 祝茜 于 2021-11-09 设计创作，主要内容包括：本发明公开了一种超疏水导电皮革及其制备方法,属于智能型皮革制品和柔性电子皮肤技术领域。采用分散聚合法,制备带正电的聚苯乙烯微球；以聚苯乙烯微球为模板,通过正负电荷间的静电吸引作用,在其表面包覆带负电的碳化钛纳米片,利用刻蚀剂对模板进行部分去除,得到两亲性碳化钛纳米片,以皮革为过滤器对两亲性碳化钛纳米片分散液进行过滤,烘干后即得到超疏水导电皮革。两亲性碳化钛纳米片的亲疏水作用力驱使其以亲水端朝下、疏水端朝上的方式在皮革表面定向排布,相互接触的碳化钛纳米片为皮革提供导电性能,其上的疏水链段为皮革提供超疏水所需的低表面能,两者协同作用,同步实现皮革制品的疏水和导电性能。(The invention discloses super-hydrophobic conductive leather and a preparation method thereof, and belongs to the technical field of intelligent leather products and flexible electronic skins. Preparing positively charged polystyrene microspheres by a dispersion polymerization method; the preparation method comprises the steps of coating negatively charged titanium carbide nanosheets on the surfaces of polystyrene microspheres serving as templates through electrostatic attraction between positive charges and negative charges, removing part of the templates by using an etching agent to obtain amphiphilic titanium carbide nanosheets, filtering amphiphilic titanium carbide nanosheet dispersion liquid by using leather as a filter, and drying to obtain the super-hydrophobic conductive leather. The amphiphilic titanium carbide nanosheets are driven to be directionally arranged on the surface of the leather in a manner that the hydrophilic ends face downwards and the hydrophobic ends face upwards by the hydrophilic acting force of the amphiphilic titanium carbide nanosheets, the titanium carbide nanosheets which are in contact with each other provide conductivity for the leather, the hydrophobic chain segments on the titanium carbide nanosheets provide low surface energy required by super-hydrophobicity for the leather, and the hydrophobic end segments and the hydrophobic chain segments cooperate to synchronously realize the hydrophobicity and the conductivity of the leather product.)

1. The preparation method of the super-hydrophobic conductive leather is characterized by comprising the following steps:

step 1) preparing polystyrene microspheres;

step 2) mixing the polystyrene microspheres, deionized water and a titanium carbide solution, and after reaction, sequentially washing and drying to obtain polystyrene @ titanium carbide microspheres;

step 3) adding the polystyrene @ titanium carbide microspheres into an etching agent for etching, and sequentially washing and drying after etching to obtain amphiphilic titanium carbide nanosheets;

and 4) mixing the amphiphilic titanium carbide nanosheets with deionized water to obtain amphiphilic titanium carbide nanosheet dispersion liquid, then performing suction filtration on the amphiphilic titanium carbide nanosheet dispersion liquid by taking leather as a filter, and drying to obtain the super-hydrophobic conductive leather.

2. The method for preparing the superhydrophobic conductive leather according to claim 1, wherein in the step 1), the method for preparing the polystyrene microspheres comprises the following steps:

preparing a polyvinylpyrrolidone solution, mixing the polyvinylpyrrolidone solution, styrene and azobisisobutyronitrile, heating for reaction, and sequentially centrifuging, washing and drying a reaction product to obtain the polystyrene microsphere.

3. The preparation method of the superhydrophobic conductive leather according to claim 2, wherein in the polyvinylpyrrolidone solution, the solvent is a mixed solution of absolute ethyl alcohol and deionized water, and the volume ratio of the absolute ethyl alcohol to the deionized water is (75-95): (5-25);

the feeding ratio of the polyvinylpyrrolidone to the solvent is (2.3-3.5) g: (80-120) mL;

the mass ratio of the polyvinylpyrrolidone to the styrene to the azobisisobutyronitrile is (2.3-3.5): (10-18): (0.15-0.25).

4. The method for preparing superhydrophobic conductive leather according to claim 2,

the conditions for the heating reaction were: the temperature is 70-85 ℃, and the time is 10-20 h;

before heating reaction, mixing and stirring the polyvinylpyrrolidone solution, the styrene and the azobisisobutyronitrile for 30-50 min;

the drying conditions were: and (4) performing vacuum environment at the temperature of 30-60 ℃ for 4-8 h.

5. The method for preparing the superhydrophobic conductive leather according to claim 1, wherein in the step 2), the feeding ratio of the polystyrene microspheres, the deionized water and the titanium carbide solution during mixing is (0.25-0.45) g: (80-150) mL: (150-230) mL;

the concentration of the titanium carbide solution is 0.8-1.3 mg/mL.

6. The method for preparing the superhydrophobic conductive leather according to claim 1, wherein in the step 3), the etchant is any one of tetrahydrofuran, toluene, N 'N' -dimethylformamide, chloroform, dichloromethane and acetone;

the feeding ratio of the polystyrene @ titanium carbide microspheres to the etching agent is (0.3-0.6) g: (30-60) mL.

7. The method for preparing superhydrophobic conductive leather according to claim 1,

in the step 2), firstly, mixing polystyrene microspheres and deionized water, performing ultrasonic treatment for 20-40 min, then adding a titanium carbide solution, stirring at room temperature for 4-8 h, and then performing vacuum drying at 30-60 ℃ for 4-8 h;

in the step 3), the reaction conditions of mixing the polystyrene @ titanium carbide microspheres and the etching agent are as follows: the temperature is 35-55 ℃, the time is 20-40 h, and then vacuum drying is carried out for 4-8 h at the temperature of 30-60 ℃;

in the step 4), the drying conditions are as follows: and (3) performing vacuum environment at 40-70 ℃ for 6-10 h.

8. The preparation method of the superhydrophobic conductive leather according to claim 1, wherein in the amphiphilic titanium carbide nanosheet dispersion, the feeding ratio of the amphiphilic titanium carbide nanosheets to deionized water is (20-40) mg: 20 mL;

the sizing rate of the amphiphilic titanium carbide nanosheet dispersion liquid on the surface of the leather is 0.2-0.5 mg/cm²。

9. The super-hydrophobic conductive leather obtained by the preparation method of any one of claims 1 to 8 is characterized in that the water contact angle of the super-hydrophobic conductive leather is 159-163 degrees; the resistivity is 140-160 omega/sq.

Technical Field

The invention belongs to the technical field of intelligent leather products and flexible electronic skins, and relates to super-hydrophobic conductive leather and a preparation method thereof.

Background

The skin serves as a surface covering for the human body, provides a physical barrier for protecting internal organs, and has a neural network for sensing external environmental stimuli such as temperature, vibration, pressure, and the like. Electronic skin is an artificial skin that mimics the function of human skin. In recent years, driven by autonomous artificial intelligence, medical diagnosis, bionic artificial limbs, and the like, development of electronic skins capable of understanding, simulating, and even surpassing human skins has become a hot point of research.

Leather is a traditional natural material derived from animal skin, inherits the complex structure of skin, which makes it a potential candidate material for manufacturing high-performance electronic skin. The main function of electronic skin is to sense external stimuli and then convert the external stimuli into analog electronic signals, while the traditional leather has skin-like elasticity but its sensing ability is in a deprived state. Therefore, good electrical conductivity is essential for leather-based electronic skins in order to restore the original perception of leather. Titanium carbide nanosheets, as a novel two-dimensional material, have the advantages of high conductivity, excellent mechanical properties, controllable manufacturing cost and the like, and therefore have wide application in the fields of energy storage equipment, electromagnetic shielding, sensors and the like.

In addition, in practical applications, the harsh environment containing water, microbes, or acids/bases/salts can interfere with the stability of the leather-based electronic skin during operation, resulting in unstable conductivity and electronic sensing, thereby shortening the service life of the leather-based electronic skin.

Disclosure of Invention

The invention aims to overcome the defects that the conductivity and electronic sensing of leather-based electronic skin in a severe environment are unstable in the prior art, and provides super-hydrophobic conductive leather and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:

a preparation method of super-hydrophobic conductive leather comprises the following steps:

step 1) preparing polystyrene microspheres;

step 2) mixing the polystyrene microspheres, deionized water and a titanium carbide solution, and after reaction, sequentially washing and drying to obtain polystyrene @ titanium carbide microspheres;

step 3) adding the polystyrene @ titanium carbide microspheres into an etching agent for etching, and sequentially washing and drying after etching to obtain amphiphilic titanium carbide nanosheets;

and 4) mixing the amphiphilic titanium carbide nanosheets with deionized water to obtain amphiphilic titanium carbide nanosheet dispersion liquid, then performing suction filtration on the amphiphilic titanium carbide nanosheet dispersion liquid by taking leather as a filter, and drying to obtain the super-hydrophobic conductive leather.

Preferably, in step 1), the preparation method of the polystyrene microsphere comprises:

preparing a polyvinylpyrrolidone solution, mixing the polyvinylpyrrolidone solution, styrene and azobisisobutyronitrile, heating for reaction, and sequentially centrifuging, washing and drying a reaction product to obtain the polystyrene microsphere.

Preferably, in the polyvinylpyrrolidone solution, the solvent is a mixed solution of absolute ethyl alcohol and deionized water, and the volume ratio of the absolute ethyl alcohol to the deionized water is (75-95): (5-25);

the feeding ratio of the polyvinylpyrrolidone to the solvent is (2.3-3.5) g: (80-120) mL;

the mass ratio of the polyvinylpyrrolidone to the styrene to the azobisisobutyronitrile is (2.3-3.5): (10-18): (0.15-0.25).

Preferably, the conditions of the heating reaction are: the temperature is 70-85 ℃, and the time is 10-20 h;

before heating reaction, mixing and stirring the polyvinylpyrrolidone solution, the styrene and the azobisisobutyronitrile for 30-50 min;

the drying conditions were: and (4) performing vacuum environment at the temperature of 30-60 ℃ for 4-8 h.

Preferably, in the step 2), the feeding ratio of the polystyrene microspheres, the deionized water and the titanium carbide solution during mixing is (0.25-0.45) g: (80-150) mL: (150-230) mL;

the concentration of the titanium carbide solution is 0.8-1.3 mg/mL.

Preferably, in step 3), the etchant is any one of tetrahydrofuran, toluene, N' -dimethylformamide, chloroform, dichloromethane and acetone.

The feeding ratio of the polystyrene @ titanium carbide microspheres to the etching agent is (0.3-0.6) g: (30-60) mL.

Preferably, in the step 2), firstly, mixing the polystyrene microspheres and deionized water, performing ultrasonic treatment for 20-40 min, then adding a titanium carbide solution, stirring at room temperature for 4-8 h, and then performing vacuum drying at 30-60 ℃ for 4-8 h;

in the step 3), the reaction conditions of mixing the polystyrene @ titanium carbide microspheres and the etching agent are as follows: the temperature is 35-55 ℃, the time is 20-40 h, and then vacuum drying is carried out for 4-8 h at the temperature of 30-60 ℃;

in the step 4), the drying conditions are as follows: and (3) performing vacuum environment at 40-70 ℃ for 6-10 h.

Preferably, in the amphiphilic titanium carbide nanosheet dispersion, the feeding ratio of the amphiphilic titanium carbide nanosheets to the deionized water is (20-40) mg: 20 mL;

the sizing rate of the amphiphilic titanium carbide nanosheet dispersion liquid on the surface of the leather is 0.2-0.5 mg/cm²。

According to the super-hydrophobic conductive leather obtained by the preparation method, the water contact angle of the super-hydrophobic conductive leather is 159-163 degrees; the resistivity is 140-160 omega/sq.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a preparation method of super-hydrophobic conductive leather, which adopts a dispersion polymerization method to prepare positively charged polystyrene microspheres; the preparation method comprises the steps of coating negatively charged titanium carbide nanosheets on the surfaces of polystyrene microspheres serving as templates through electrostatic attraction between positive charges and negative charges, removing part of the templates by using an etching agent to obtain amphiphilic titanium carbide nanosheets, filtering amphiphilic titanium carbide nanosheet dispersion liquid by using leather as a filter, and drying to obtain the super-hydrophobic conductive leather. The invention adopts a template method and a subsequent dissolving process to prepare amphiphilic titanium carbide nanosheets with hydrophilic titanium carbide on one side and hydrophobic residual polystyrene chain segments on the other side. The titanium carbide nanosheet has the advantages of excellent conductivity, high specific surface area, hydrophilic surface, rich surface oxygen-containing functional groups and the like, and provides a hydrophilic side and conductivity for the amphiphilic titanium carbide nanosheet; the polystyrene microspheres are used as templates and tightly combined with one side of the titanium carbide nanosheets, the spherical structure is damaged in the subsequent template removing process, the residual polystyrene chain segments are selectively grafted on one side of the titanium carbide nanosheets and provide hydrophobicity for the amphiphilic titanium carbide nanosheets, and finally the hydrophilic/hydrophobic performance of the amphiphilic titanium carbide nanosheets is realized. The amphiphilic titanium carbide nanosheet obtained by the preparation method disclosed by the invention is hundreds of nanometers to several micrometers in size, the square resistance is about 2.26 omega/sq, and meanwhile, compared with the original titanium carbide nanosheet, the amphiphilic titanium carbide nanosheet can be stably distributed on an oil/water emulsion interface and has a certain emulsifying property, so that the hydrophilic/hydrophobic properties of the amphiphilic titanium carbide nanosheet are proved. The preparation process is simple, easy to realize, the preparation device is easy to build, the cost is low, and the preparation device is suitable for large-scale industrial use. The manufacturing process of the super-hydrophobic conductive leather is simple and easy to realize, the preparation device is easy to build, low in cost, universal and expandable, and the super-hydrophobic conductive leather is matched with the leather making and dyeing process of the traditional leather industry.

Furthermore, the mixing ratio of the polystyrene microspheres to the titanium carbide nanosheets determines the number of adsorption layers of the titanium carbide nanosheets on the surfaces of the polystyrene microspheres. The proper proportion of the titanium carbide nano-sheets is the key for the titanium carbide nano-sheets to be uniformly adsorbed on the surface of the polystyrene microsphere in a single-layer mode, and only the innermost titanium carbide nano-sheets are completely fixed on the surface of the polystyrene microsphere, so that an amphiphilic structure is formed in the subsequent template dissolving process. And the excessive titanium carbide nanosheets can be overlapped on the surfaces of the polystyrene microspheres, and only completely hydrophilic titanium carbide nanosheets can be formed after the template is removed.

Furthermore, tetrahydrofuran, toluene, N' -dimethylformamide, chloroform, dichloromethane or acetone are used as an etching agent, and the reaction conditions in the etching process determine the hydrophobic property of the amphiphilic titanium carbide nanosheet. Proper etching conditions are the key for ensuring that the amphiphilic titanium carbide nanosheets are formed and have a super-hydrophobic effect. When the etching degree is insufficient, the polystyrene microspheres are still spherical, so that the titanium carbide layer on the surface cannot be separated. And excessive etching can lead to excessive removal of the polystyrene chain segment selectively grafted on one side of the titanium carbide nanosheet, thereby affecting the superhydrophobic performance of the amphiphilic titanium carbide nanosheet.

The invention also discloses super-hydrophobic conductive leather prepared based on the method. The amphiphilic titanium carbide nanosheets are compounded with leather, hydrophilic titanium carbide and hydrophobic residual polystyrene chain segments are arranged on one side of each amphiphilic titanium carbide nanosheet, the amphiphilic titanium carbide nanosheets are driven to be directionally arranged on the surface of the leather in a manner that hydrophilic ends face downwards and hydrophobic ends face upwards by hydrophilic acting force, the mutually contacted titanium carbide nanosheets provide conductivity for the leather, the hydrophobic chain segments on the amphiphilic titanium carbide nanosheets provide low surface energy required by super-hydrophobicity for the leather, and the hydrophobic and conductivity of the leather product are synchronously realized through synergistic effect of the hydrophilic titanium carbide nanosheets and the hydrophobic residual polystyrene chain segments. Compared with the original leather, the super-hydrophobic conductive leather prepared by the preparation method has the square resistance reduced to 140.28 omega/sq, can emit light when being connected into a closed loop, and has the water contact angle increased to 161.3 degrees. Through reasonable design, the leather can be reused, and even has the characteristics exceeding the characteristics of real skin, so that a new platform is provided for realizing multifunctional electronic skin.

Drawings

Fig. 1 shows TEM photographs (a) and FT-IR spectra (b) of amphiphilic titanium carbide nanoplates prepared in example 1.

FIG. 2 is a photograph showing the appearance of a stabilized oil/water emulsion of the original titanium carbide nanoplates (a) and the amphiphilic titanium carbide nanoplates (B) prepared in example 1 (oil phase: styrene; water phase: aqueous rhodamine B solution; oil phase: water phase: 1:7 w/w).

Fig. 3 is a photograph of the appearance of the original leather (a) and the superhydrophobic-conductive leather (b) prepared in example 1.

Fig. 4 is a water contact angle of the original leather (a) and the superhydrophobic-conductive leather (b) prepared in example 1.

Fig. 5 is a photograph of the original leather (a) and the superhydrophobic-conductive leather (b) prepared in example 1, which are connected into a closed circuit.

Detailed Description

The invention is described in further detail below with reference to the accompanying drawings:

in order to avoid electronic sensing interference and prolong the service life, constructing a super-hydrophobic structure on the surface of the leather-based electronic skin is an ideal choice for resisting liquid interference.

Example 1

A preparation method of amphiphilic titanium carbide nanosheets comprises the following steps:

(1) dissolving 2.5g of polyvinylpyrrolidone in a mixed solution of 75mL of anhydrous ethanol and 21mL of deionized water, stirring at 130rpm at room temperature, then adding 12g of styrene and 0.19g of azobisisobutyronitrile into the mixed solution under a nitrogen environment, stirring for 35min, carrying out heat preservation reaction at 85 ℃ for 17h, centrifuging and washing the product, and carrying out vacuum drying at 45 ℃ for 5h to obtain the polystyrene microsphere.

(2) Adding 0.32g of polystyrene microspheres into 120mL of deionized water, carrying out ultrasonic dispersion for 22min, then adding 165mL of titanium carbide aqueous dispersion with the concentration of 1.1mg/mL, stirring at 400rpm for 5h at room temperature, centrifuging and washing the product, and carrying out vacuum drying at 30 ℃ for 5h to obtain the polystyrene @ titanium carbide microspheres.

(3) Adding 0.4g of polystyrene @ titanium carbide microspheres into 35mL of tetrahydrofuran, magnetically stirring at 51 ℃ and 410rpm for 35h, centrifuging and washing a product, and drying in vacuum at 35 ℃ for 6h to obtain the amphiphilic titanium carbide nanosheet.

Preparing the super-hydrophobic conductive leather based on the method:

(4) adding 25mg of amphiphilic titanium carbide nanosheet into 20mL of deionized water, ultrasonically dispersing for 26min, and then performing suction filtration on a dispersion liquid of the amphiphilic titanium carbide nanosheet by using leather as a filter, wherein the sizing amount of the amphiphilic titanium carbide nanosheet is 0.3mg/cm²And vacuum drying at 47 ℃ for 10h to obtain the super-hydrophobic conductive leather.

Example 2

A preparation method of amphiphilic titanium carbide nanosheets comprises the following steps:

(1) dissolving 3.3g of polyvinylpyrrolidone in a mixed solution of 82mL of anhydrous ethanol and 10mL of deionized water, stirring at 100rpm at room temperature, then adding 18g of styrene and 0.15g of azobisisobutyronitrile into the mixed solution under a nitrogen environment, stirring for 50min, carrying out heat preservation reaction at 81 ℃ for 20h, centrifuging and washing the product, and carrying out vacuum drying at 50 ℃ for 4h to obtain the polystyrene microsphere.

(2) Adding 0.25g of polystyrene microspheres into 150mL of deionized water, carrying out ultrasonic dispersion for 34min, then adding 190mL of titanium carbide aqueous dispersion with the concentration of 0.9mg/mL, stirring at 310rpm for 8h at room temperature, centrifuging and washing the product, and carrying out vacuum drying at 55 ℃ for 7h to obtain the polystyrene @ titanium carbide microspheres.

(3) Adding 0.3g of polystyrene @ titanium carbide microspheres into 60mL of N ', N' -dimethylformamide, magnetically stirring at 35 ℃ and 500rpm for 26h, centrifuging and washing a product, and drying in vacuum at 60 ℃ for 5h to obtain the amphiphilic titanium carbide nanosheet.

Preparing the super-hydrophobic conductive leather based on the method:

(4) adding 32mg of amphiphilic titanium carbide nanosheet into 20mL of deionized water, ultrasonically dispersing for 30min, and then performing suction filtration on a dispersion liquid of the amphiphilic titanium carbide nanosheet by taking leather as a filter, wherein the sizing amount of the amphiphilic titanium carbide nanosheet is 0.2mg/cm²And vacuum drying at 58 ℃ for 8h to obtain the super-hydrophobic conductive leather.

Example 3

A preparation method of amphiphilic titanium carbide nanosheets comprises the following steps:

(1) dissolving 2.7g of polyvinylpyrrolidone in a mixed solution of 78mL of anhydrous ethanol and 25mL of deionized water, stirring at 140rpm at room temperature, then adding 15g of styrene and 0.20g of azobisisobutyronitrile into the mixed solution under a nitrogen environment, stirring for 40min, carrying out heat preservation reaction at 70 ℃ for 13h, centrifuging and washing the product, and carrying out vacuum drying at 30 ℃ for 6h to obtain the polystyrene microsphere.

(2) Adding 0.43g of polystyrene microspheres into 80mL of deionized water, carrying out ultrasonic dispersion for 40min, then adding 220mL of titanium carbide aqueous dispersion with the concentration of 1.2mg/mL, stirring at 370rpm for 6h at room temperature, centrifuging and washing the product, and carrying out vacuum drying at 50 ℃ for 8h to obtain the polystyrene @ titanium carbide microspheres.

(3) Adding 0.5g of polystyrene @ titanium carbide microspheres into 45mL of acetone, magnetically stirring at 55 ℃ and 260rpm for 37h, centrifuging and washing the product, and drying in vacuum at 55 ℃ for 7h to obtain the amphiphilic titanium carbide nanosheet.

Preparing the super-hydrophobic conductive leather based on the method:

(4) adding 40mg of amphiphilic titanium carbide nanosheet into 20mL of deionized water, ultrasonically dispersing for 18min, and then performing suction filtration on a dispersion liquid of the amphiphilic titanium carbide nanosheet by taking leather as a filter, wherein the sizing amount of the amphiphilic titanium carbide nanosheet is 0.5mg/cm²And vacuum drying at 63 ℃ for 6h to obtain the super-hydrophobic conductive leather.

Example 4

A preparation method of amphiphilic titanium carbide nanosheets comprises the following steps:

(1) dissolving 3.5g of polyvinylpyrrolidone in a mixed solution of 90mL of anhydrous ethanol and 5mL of deionized water, stirring at 120rpm at room temperature, then adding 10g of styrene and 0.25g of azobisisobutyronitrile into the mixed solution under a nitrogen environment, stirring for 45min, carrying out heat preservation reaction at 78 ℃ for 10h, centrifuging and washing the product, and carrying out vacuum drying at 35 ℃ for 8h to obtain the polystyrene microsphere.

(2) Adding 0.29g of polystyrene microspheres into 135mL of deionized water, carrying out ultrasonic dispersion for 37min, then adding 180mL of titanium carbide aqueous dispersion with the concentration of 0.8mg/mL, stirring at 330rpm for 6h at room temperature, centrifuging and washing the product, and carrying out vacuum drying at 60 ℃ for 6h to obtain the polystyrene @ titanium carbide microspheres.

(3) Adding 0.4g of polystyrene @ titanium carbide microspheres into 55mL of toluene, magnetically stirring at 37 ℃ and 450rpm for 40h, centrifuging and washing the product, and drying in vacuum at 40 ℃ for 8h to obtain the amphiphilic titanium carbide nanosheet.

Preparing the super-hydrophobic conductive leather based on the method:

(4) adding 20mg of amphiphilic titanium carbide nanosheets into 20mL of deionized water, ultrasonically dispersing for 27min, then, taking leather as a filter, carrying out suction filtration on the dispersion liquid of the amphiphilic titanium carbide nanosheets,the sizing amount of the amphiphilic titanium carbide nanosheet is 0.2mg/cm²And vacuum drying at 40 ℃ for 9h to obtain the super-hydrophobic conductive leather.

Example 5

A preparation method of amphiphilic titanium carbide nanosheets comprises the following steps:

(1) dissolving 2.3g of polyvinylpyrrolidone into a mixed solution of 83mL of anhydrous ethanol and 18mL of deionized water, stirring at 170rpm at room temperature, then adding 14g of styrene and 0.23g of azobisisobutyronitrile into the mixed solution under a nitrogen environment, stirring for 30min, carrying out heat preservation reaction at 83 ℃ for 18h, centrifuging and washing a product, and carrying out vacuum drying at 55 ℃ for 7h to obtain the polystyrene microsphere.

(2) Adding 0.45g of polystyrene microspheres into 115mL of deionized water, carrying out ultrasonic dispersion for 20min, then adding 150mL of titanium carbide aqueous dispersion with the concentration of 1.0mg/mL, stirring at 230rpm for 4h at room temperature, centrifuging and washing the product, and carrying out vacuum drying at 35 ℃ for 5h to obtain the polystyrene @ titanium carbide microspheres.

(3) Adding 0.5g of polystyrene @ titanium carbide microspheres into 30mL of dichloromethane, magnetically stirring at 50 ℃ and 420rpm for 32h, centrifuging and washing the product, and drying in vacuum at 45 ℃ for 4h to obtain the amphiphilic titanium carbide nanosheet.

Preparing the super-hydrophobic conductive leather based on the method:

(4) adding 29mg of amphiphilic titanium carbide nanosheet into 20mL of deionized water, ultrasonically dispersing for 22min, and then performing suction filtration on a dispersion liquid of the amphiphilic titanium carbide nanosheet by using leather as a filter, wherein the sizing amount of the amphiphilic titanium carbide nanosheet is 0.4mg/cm²And vacuum drying at 45 ℃ for 7h to obtain the super-hydrophobic conductive leather.

Example 6

A preparation method of amphiphilic titanium carbide nanosheets comprises the following steps:

(1) dissolving 3.0g of polyvinylpyrrolidone in a mixed solution of 95mL of anhydrous ethanol and 10mL of deionized water, stirring at 110rpm at room temperature, then adding 17g of styrene and 0.18g of azobisisobutyronitrile into the mixed solution under a nitrogen environment, stirring for 40min, carrying out heat preservation reaction at 75 ℃ for 15h, centrifuging and washing the product, and carrying out vacuum drying at 60 ℃ for 6h to obtain the polystyrene microsphere.

(2) Adding 0.33g of polystyrene microspheres into 90mL of deionized water, carrying out ultrasonic dispersion for 32min, then adding 230mL of titanium carbide aqueous dispersion with the concentration of 1.3mg/mL, stirring at 200rpm for 5h at room temperature, centrifuging and washing the product, and carrying out vacuum drying at 40 ℃ for 4h to obtain the polystyrene @ titanium carbide microspheres.

(3) Adding 0.6g of polystyrene @ titanium carbide microspheres into 40mL of chloroform, magnetically stirring at 40 ℃ and 250rpm for 20h, centrifuging and washing a product, and drying in vacuum at 30 ℃ for 5h to obtain the amphiphilic titanium carbide nanosheet.

Preparing the super-hydrophobic conductive leather based on the method:

(4) adding 35mg of amphiphilic titanium carbide nanosheet into 20mL of deionized water, ultrasonically dispersing for 15min, and then performing suction filtration on a dispersion liquid of the amphiphilic titanium carbide nanosheet by taking leather as a filter, wherein the sizing amount of the amphiphilic titanium carbide nanosheet is 0.3mg/cm²And drying for 8 hours at 70 ℃ in vacuum to obtain the super-hydrophobic conductive leather.

The results of the research on the hydrophobicity and the conductivity of the superhydrophobic conductive leather prepared in the above example are shown in table 1.

TABLE 1 hydrophobic and conductive Properties of the superhydrophobic conductive leather prepared in each example

As can be seen from Table 1, the super-hydrophobic conductive leather prepared by the invention has excellent super-hydrophobic performance, the contact angles of the super-hydrophobic conductive leather and water are all larger than 150 degrees, the conductivity is good, and small bulbs can be lightened.

Taking example 1 as an example, a TEM photograph of the amphiphilic titanium carbide nanosheets prepared by the method is shown in fig. 1(a), titanium carbide nanosheets with uniform distribution can be clearly seen, and the titanium carbide nanosheets are provided with polystyrene distributed in a dotted mannerAn alkene chain segment, and figure 1(b) is an FT-IR spectrum of an amphiphilic titanium carbide nanosheet, and it can be seen that the original titanium carbide nanosheet is 600-500 cm^-1Has obvious characteristic peak corresponding to Ti-O bond; the amphiphilic titanium carbide nanosheets prepared in the embodiment 1 of the invention are 1448 cm, 1490 cm and 1597cm^-1C ═ C stretching vibration and 3026 and 3066cm^-1C-H stretching vibration of (B) illustrates the presence of benzene rings, 696 and 754cm^-1The C-H bending vibration shows that the benzene ring is mono-substituted, combining 2850 and 2922cm^-1Of (C is a-CH)₂Stretching vibration shows that the surfaces of the amphiphilic titanium carbide nanosheets are provided with polystyrene chain segments. Fig. 2 is a photograph of an oil/water emulsion stabilized by an original titanium carbide nanosheet and the amphiphilic titanium carbide nanosheet prepared in example 1, and it can be seen that in the oil/water emulsion stabilized by the original titanium carbide nanosheet, a distinct boundary line exists between oil and water before and after emulsification, and the original titanium carbide nanosheet is always distributed in the water phase, which is mainly caused by the hydrophilic surface and abundant surface oxygen-containing functional groups of the titanium carbide nanosheet; in the oil/water emulsion with stable amphiphilic titanium carbide nanosheets, the amphiphilic titanium carbide nanosheets are mainly distributed at an oil/water interface and can form an oil-in-water emulsion through emulsification, which shows that the amphiphilic titanium carbide nanosheets have hydrophilic/hydrophobic properties similar to those of a surfactant, and a polystyrene chain segment on one side of the titanium carbide nanosheets provides hydrophobicity for the amphiphilic titanium carbide nanosheets, so that the hydrophilic/hydrophobic properties of the amphiphilic titanium carbide nanosheets are finally realized. Fig. 3 is a photograph showing the appearance of the original leather (a) and the superhydrophobic and conductive leather (b) prepared in example 1, and it can be seen that the superhydrophobic and conductive leather has a significantly blackened appearance compared to the original leather because the surface is covered with a large amount of titanium carbide nanoplates. Fig. 4 shows water contact angles of the original leather (a) and the superhydrophobic conductive leather (b) prepared in example 1, and it can be seen that the contact angle of a water drop on the superhydrophobic conductive leather surface is significantly larger than that on the original leather surface, indicating that the preparation method of the present invention can significantly improve the hydrophobic property of leather. FIG. 5 is a photograph showing the original leather (a) and the superhydrophobic-conductive leather (b) prepared in example 1, which are connected into a closed circuit, and it can be seen that the original leather cannot light the small bulb, but the superhydrophobic-conductive leather prepared by the present invention can light the small bulb, indicating that it isHas excellent conductive performance.

The leather used in the examples of the present invention is any of cow leather, sheep leather, and pig leather.

In summary, the invention relates to a method for constructing super-hydrophobic conductive leather based on amphiphilic titanium carbide nanosheets, which comprises the steps of taking leather as a filter, and carrying out suction filtration on an aqueous dispersion of the amphiphilic titanium carbide nanosheets to prepare the super-hydrophobic conductive leather. Namely, the invention prepares the super-hydrophobic conductive leather through a simple suction filtration process. The amphiphilic titanium carbide nanosheets are driven to be directionally arranged on the surface of the leather in a manner that the hydrophilic ends face downwards and the hydrophobic ends face upwards by the hydrophilic acting force of the amphiphilic titanium carbide nanosheets, the titanium carbide nanosheets which are in contact with each other provide conductivity for the leather, the hydrophobic chain segments on the titanium carbide nanosheets provide low surface energy required by super-hydrophobicity for the leather, and the hydrophobic end segments and the hydrophobic chain segments cooperate to synchronously realize the hydrophobicity and the conductivity of the leather product. The invention compounds titanium carbide and leather, which can endow leather with good conductivity to restore the original perception capability of leather, even make the leather have the performance exceeding real skin.

The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.