Preparation method of gallium-copper alloy modified super-hydrophobic SEBS film

Abstract

The invention relates to the technical field of biological materials, and discloses a preparation method of a gallium-copper alloy modified super-hydrophobic SEBS (styrene-ethylene-butylene-styrene) membrane, which comprises the following specific steps: step 1, preparing a super-hydrophobic SEBS membrane; 2, liquid metal is added into a dispersing agent, ultrasonic treatment is carried out, and gallium particle suspension liquid is obtained; soaking the super-hydrophobic SEBS membrane in the gallium particle suspension, and drying the super-hydrophobic SEBS membrane to obtain a gallium coating modified SEBS membrane; the liquid metal is any one of gallium, gallium-indium alloy or gallium-indium-tin alloy; and step 3, soaking the SEBS membrane modified by the gallium coating in a copper ion solution, taking out the SEBS membrane, cleaning, and drying to obtain the super-hydrophobic SEBS membrane modified by the gallium-copper alloy. According to the invention, liquid metal (GaLM) particles are used as a copper carrier, and the gallium-copper alloy is modified on the super-hydrophobic SEBS film, so that the film is endowed with a stable structure, has dual functions of efficiently sterilizing and inhibiting bacterial adhesion, and has a relatively wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of biomaterials, and in particular to a method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS film. Background Art

[0002] It is crucial to explore alternative non-antibiotic approaches and multiple comprehensive antimicrobial strategies to effectively combat bacterial resistance.

[0003] Superhydrophobic antibacterial surfaces in nature can be divided into antibacterial adhesion and bactericidal. Antibacterial adhesion inhibits bacterial adhesion through superhydrophobic surfaces, and bactericidal properties refer to the micro / nanostructure on its surface that can pierce or stretch bacterial cells to kill them. Many organisms in nature exhibit good antifouling and antibacterial surface properties, such as the surface of lotus leaves, dragonfly wings, and lizard skin. These natural surfaces have inspired researchers to design and develop liquid-repellent and antibacterial surface materials. Therefore, combining the superhydrophobic structural characteristics of the material surface to construct a self-cleaning antibacterial surface has gradually become a research focus for solving bacterial infections.

[0004] The application of metal ions as antimicrobial agents in the field of antibacterial has attracted widespread attention. Copper ions have highly efficient antibacterial properties and have been used for a range of applications for thousands of years. It is worth noting that liquid metals (mainly gallium and gallium-based alloys), as a new type of antibacterial material, are increasingly being used in biomedical fields such as drug delivery, neural connection and tumor treatment due to their high fluidity, excellent thermal conductivity, low cytotoxicity and biocompatibility. Previous studies have demonstrated that Ga exhibits moderate antibacterial activity against a variety of pathogens, and Ga 3+ It has a unique mechanism of action that disrupts bacterial iron metabolism, thereby reducing the development of bacterial resistance, making it a potential alternative to traditional antibiotics to achieve effective sterilization. Summary of the invention

[0005] Purpose of the invention: In view of the problems existing in the prior art, the present invention provides a method for preparing a super-hydrophobic SEBS membrane modified with a gallium-copper alloy. Liquid metal (GaLM) particles are used as a carrier of copper. By modifying the gallium-copper alloy on the super-hydrophobic SEBS membrane, the membrane is given a stable structure and has the dual functions of highly efficient sterilization and inhibition of bacterial adhesion, which has a relatively broad application prospect.

[0006] Technical solution: The present invention provides a method for preparing a super-hydrophobic SEBS film modified by a gallium-copper alloy, comprising the following steps: Step 1, preparing a super-hydrophobic SEBS membrane; Step 2: adding liquid metal to a dispersant, ultrasonicating, and obtaining a gallium particle suspension; then immersing the superhydrophobic SEBS membrane in the gallium particle suspension, and drying, to obtain a gallium-coated SEBS membrane; the liquid metal is any one of gallium, gallium-indium alloy, or gallium-indium-tin alloy; Step 3: soak the SEBS membrane modified with the gallium coating in a copper ion solution, take it out, wash it, and dry it to obtain a super-hydrophobic SEBS membrane modified with a gallium-copper alloy.

[0007] Furthermore, in step 1, the specific preparation method of the super-hydrophobic SEBS membrane is: S1. The SEBS powder is dissolved in a good solvent, and then a poor solvent is added and mixed, and stirred to obtain a mixed solution; S2. The mixed solution is coated on the surface of the substrate material. After the good solvent evaporates, the membrane is placed in an alcohol solution for ultrasonic treatment and dried to obtain a superhydrophobic SEBS membrane.

[0008] Further, in S1, the good solvent is any one of toluene, xylene or cyclohexane; In S1, the poor solvent is any one of cyclohexanol, n-decanol or diethylene glycol; In S2, the alcohol solution is any one of ethanol, n-butanol or propanol.

[0009] Further, in S1, the mass volume ratio of the SEBS powder to the good solvent is 10:1-1:10; In S1, the volume ratio of the good solvent to the poor solvent is 1:3-10:3.

[0010] Preferably, in S1, the specific conditions of the stirring are: stirring temperature is 20-35°C, stirring speed is 100-400r / min, and stirring time is 1-4h; In S2, the specific conditions of the volatilization are: volatilization temperature is 20-35°C, and volatilization time is 3-24 h; In S2, the specific conditions of the ultrasound are: the ultrasound temperature is 20-35°C, and the ultrasound time is 10-30min; In S2, the specific conditions of the drying are: drying temperature is 30-40°C, and drying time is 12-48h.

[0011] Furthermore, in step 2, the concentration of the gallium particle suspension is 0.1%-1%.

[0012] Furthermore, in step 2, the dispersant is any one of anhydrous ethanol, ultrapure water or a mixed solution of anhydrous ethanol and ultrapure water in a ratio of 1:1.

[0013] Furthermore, in step three, the copper ion solution is any one of copper chloride solution, copper sulfate solution or copper nitrate solution, and the concentration of the copper ion solution is 0.1-1 M.

[0014] Preferably, in step three, the soaking time is 1-12 h.

[0015] Preferably, in step three, the specific conditions of the drying are: drying temperature is 50-75° C., and drying time is 3-6 hours.

[0016] The synthesis idea and principle of the gallium-copper alloy-modified super-hydrophobic SEBS membrane prepared by the present invention are as follows: Although copper ions have highly effective antibacterial properties, they have high cytotoxicity and low adhesion to SEBS membranes. According to the Mott-Cabrera theory, electron transfer causes the metal to spontaneously form a layer of natural oxide about 3 nm thick on the surface. Since the oxide layer is very thin, the liquid metal as an electron donor and the Cu ions as an electron acceptor are 2+ There is a significant difference in the standard reduction potential between them. Therefore, under the influence of the standard reduction potential relative to the standard hydrogen electrode, a thermodynamic spontaneous reaction will occur on the surface of the GaLM oxide, and the copper particles will form a strong metallic bond with the oxide surface, resulting in the formation of Cu crystals and adhesion to the surface of the GaLM oxide. Therefore, the present invention creatively utilizes the excellent adhesion ability of the gallium particles wrapped by the oxide layer, uses it as an adhesion layer between Cu and the superhydrophobic SEBS film, and forms copper micron crystals on the surface of the GaLM oxide. On the one hand, the formation of copper micron crystals significantly reduces copper toxicity, improves biocompatibility, and reduces inflammation; on the other hand, the excellent adhesion ability of the gallium particles wrapped by the oxide layer can achieve a firm bond between Cu and the superhydrophobic SEBS film; in addition, Ga 3+ It also has a certain antibacterial effect on a variety of bacteria. 3+ With Cu 2+ Double-layer modification of superhydrophobic SEBS membrane realizes Ga 3+ and Cu 2+ The super-hydrophobic structure of SEBS membrane can also prevent or limit the contact between bacteria and the surface of SEBS membrane, further preventing the formation of bacterial biofilm, thereby reducing bacterial adhesion. Therefore, the super-hydrophobic SEBS membrane modified with gallium-copper alloy prepared by the present invention achieves excellent antibacterial performance and biocompatibility.

[0017] Beneficial effect: Compared with the prior art, the gallium-copper alloy-modified super-hydrophobic SEBS membrane prepared by the present invention is modified with gallium-copper alloy on the super-hydrophobic SEBS membrane, liquid metal (GaLM) particles are used as copper carriers, and Cu is replaced by an electric substitution process. 2+While being converted into Cu crystals, Ga particles wrapped by the oxide layer are used as an adhesion layer between Cu and the super-hydrophobic SEBS film. The method of the invention is simple and easy to implement, has a simple process, and fully utilizes the preparation advantages of the super-hydrophobic surface structure and the current displacement reaction process. The prepared gallium-copper alloy-modified super-hydrophobic SEBS film has a stable structure, has the dual functions of efficient sterilization and inhibition of bacterial adhesion, and is not easy to produce bacterial resistance. It has a vital impact on improving the antibacterial properties of medical biomaterials, avoiding bacterial infection and the health of patients, and has a relatively broad application prospect. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 Scanning electron microscope images of the samples of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Implementation Example 1 prepared in the present invention; Figure 2 The surface wettability measurement results of the samples of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Implementation Example 1 prepared in the present invention; Figure 3 The antibacterial effect diagram of the samples of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Embodiment 1 prepared by the present invention on Escherichia coli and Staphylococcus aureus; Figure 4 The bacterial adhesion morphology results on the surfaces of the samples of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Implementation Example 1 prepared in the present invention. DETAILED DESCRIPTION

[0019] The present invention is described in detail below in conjunction with the embodiments.

[0020] Implementation 1: Dissolve SEBS powder in xylene solution to form a 10 wt% SEBS xylene solution. Use a pipette to draw 12 ml of the solution into a beaker, then add 9 ml of n-decanol and stir at 30 °C for 2 h. After the solution is mixed evenly, coat it on a glass plate. After the xylene is completely evaporated, place the membrane in ethanol to ultrasonically remove the n-decanol and place it in a vacuum drying oven to complete the preparation of the superhydrophobic SEBS membrane. Cut the prepared membrane into 1×1 cm 2 The pieces were ultrasonically cleaned with water and ethanol respectively, and dried for later use.

[0021] 30 µl of liquid metal gallium was added to 15 ml of ethanol, and the solution was ultrasonicated for 10-30 min using an ultrasonic crusher to form a gallium (Ga) particle suspension. The reserved superhydrophobic SEBS membrane was then immersed in the gallium particle suspension for 10 min, and quickly placed in an oven to evaporate the solvent, so that the gallium particles were deposited on the membrane surface to form a metal coating. Copper sulfate pentahydrate was dissolved in water to form a solution with a concentration of 1 M. The SEBS membrane containing the metal coating was immersed in the copper sulfate solution, taken out after 3 h, the residual solution was rinsed off with deionized water, and dried in an oven to complete the preparation of the superhydrophobic SEBS membrane modified with gallium-copper alloy.

[0022] The gallium-copper alloy-modified super-hydrophobic SEBS membrane sample prepared in this embodiment was subjected to an antibacterial test. Using the plate count method, the sterilization rates for Escherichia coli and Staphylococcus aureus were both above 90%. The results are shown in Table 1.

[0023] Implementation 2: Dissolve SEBS powder in xylene solution to form a 10 wt% SEBS xylene solution. Use a pipette to draw 12 ml of the solution into a beaker, then add 9 ml of n-decanol and stir at 30 °C for 2 h. After the solution is mixed evenly, coat it on a glass plate. After the xylene is completely evaporated, place the membrane in ethanol to ultrasonically remove the n-decanol and place it in a vacuum drying oven to complete the preparation of the superhydrophobic SEBS membrane. Cut the prepared membrane into 1×1 cm 2 The pieces were ultrasonically cleaned with water and ethanol respectively, and dried for later use.

[0024] 30 µl of eutectic gallium indium was added to 15 ml of ethanol, and the solution was ultrasonicated for 10-30 minutes using an ultrasonic crusher to form a gallium (Ga) particle suspension. The reserved superhydrophobic SEBS membrane was then immersed in the gallium particle suspension for 10 minutes, and quickly placed in an oven to evaporate the solvent, so that the gallium particles were deposited on the membrane surface to form a metal coating. Copper sulfate pentahydrate was dissolved in water to form a solution with a concentration of 1 M. The SEBS membrane containing the metal coating was immersed in the copper sulfate solution, taken out after 3 hours, the residual solution was rinsed off with deionized water, and dried in an oven to achieve the preparation of the superhydrophobic SEBS membrane modified with gallium-copper alloy.

[0025] The gallium-copper alloy-modified super-hydrophobic SEBS membrane sample prepared in this embodiment was subjected to an antibacterial test. Using the plate count method, the sterilization rates for Escherichia coli and Staphylococcus aureus were both above 93%. The results are shown in Table 1.

[0026] Implementation 3: Dissolve SEBS powder in xylene solution to form a 10 wt% SEBS xylene solution. Use a pipette to draw 12 ml of the solution into a beaker, then add 9 ml of n-decanol and stir at 30 °C for 2 h. After the solution is mixed evenly, coat it on a glass plate. After the xylene is completely evaporated, place the membrane in ethanol to ultrasonically remove the n-decanol and place it in a vacuum drying oven to complete the preparation of the superhydrophobic SEBS membrane. Cut the prepared membrane into 1×1 cm 2 The pieces were ultrasonically cleaned with water and ethanol respectively, and dried for later use.

[0027] 30 µl of gallium-indium-tin alloy was added to 15 ml of ethanol, and the solution was ultrasonicated for 10-30 min using an ultrasonic crusher to form a gallium (Ga) particle suspension. The reserved superhydrophobic SEBS membrane was then soaked in the gallium particle suspension for 10 min, and quickly placed in an oven to evaporate the solvent, so that the gallium particles were deposited on the membrane surface to form a metal coating. Copper sulfate pentahydrate was dissolved in water to form a solution with a concentration of 1 M. The SEBS membrane containing the metal coating was soaked in the copper sulfate solution, taken out after 3 h, the residual solution was rinsed off with deionized water, and dried in an oven to achieve the preparation of a superhydrophobic SEBS membrane modified with gallium-copper alloy.

[0028] The gallium-copper alloy-modified super-hydrophobic SEBS membrane sample prepared in this embodiment was subjected to an antibacterial test. Using the plate count method, the sterilization rates for Escherichia coli and Staphylococcus aureus were both above 93%. The results are shown in Table 1.

[0029] Comparative Example 1: Dissolve SEBS powder in xylene solution to form a 10 wt% SEBS xylene solution. After the solution is mixed evenly, apply it on a glass plate. After the xylene is completely evaporated, soak the glass plate in water until the SEBS film can be gently removed from the glass plate. Cut the prepared SEBS film into 1×1 cm 2 The pieces were ultrasonically cleaned with water and ethanol respectively, and dried for later use.

[0030] The samples prepared in this comparative example were subjected to antibacterial tests. Using the plate count method, it was found that there was no obvious bactericidal effect on Escherichia coli and Staphylococcus aureus. The results are shown in Table 1.

[0031] Comparative Example 2: Dissolve SEBS powder in xylene solution to form a 10 wt% SEBS xylene solution. Use a pipette to draw 12 ml of the solution into a beaker, then add 9 ml of n-decanol and stir at 30 °C for 2 h. After the solution is mixed evenly, coat it on a glass plate. After the xylene is completely evaporated, place the membrane in ethanol to ultrasonically remove the n-decanol and place it in a vacuum drying oven to complete the preparation of the superhydrophobic SEBS membrane. Cut the prepared membrane into 1×1 cm2 The pieces were ultrasonically cleaned with water and ethanol respectively, and dried for later use.

[0032] The samples prepared in this comparative example were subjected to antibacterial tests. Using the plate count method, it was found that there was no obvious bactericidal effect on Escherichia coli and Staphylococcus aureus. The results are shown in Table 1.

[0033] Comparative Example 3: Dissolve SEBS powder in xylene solution to form a 10 wt% SEBS xylene solution. Use a pipette to draw 12 ml of the solution into a beaker, then add 9 ml of n-decanol and stir at 30 °C for 2 h. After the solution is mixed evenly, coat it on a glass plate. After the xylene is completely evaporated, place the membrane in ethanol to ultrasonically remove the n-decanol and place it in a vacuum drying oven to complete the preparation of the superhydrophobic SEBS membrane. Cut the prepared membrane into 1×1 cm 2 The pieces were ultrasonically cleaned with water and ethanol respectively, and dried for later use.

[0034] 30 µl of liquid metal gallium was added to 15 ml of ethanol, and the solution was ultrasonicated for 10-30 min using an ultrasonic crusher to form a gallium (Ga) particle suspension. The reserved superhydrophobic SEBS membrane was then immersed in the gallium particle suspension for 10 min and quickly placed in an oven to evaporate the solvent, so that the gallium particles were deposited on the membrane surface to form a metal coating.

[0035] Next, the measurement and characterization results of the samples of Implementation Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are analyzed: Escherichia coli and Staphylococcus aureus were selected as experimental strains for the in vitro antibacterial experiment. The revived bacteria were placed in a liquid culture medium and shaken overnight on a 37°C constant temperature shaker. The samples of Implementation Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 were placed in a 24-well plate and sterilized under ultraviolet light for 30 minutes. Then, 200µL of diluted bacterial solution was added to the surface of the sample, and then 400µL of PBS solution was added respectively. After the well plate was placed in a shaker at 37°C for 6 hours, 100 μL of bacterial solution was taken for plating, and the number of bacterial colonies was observed after placing it in a 37°C constant temperature incubator overnight.

[0036] Escherichia coli and Staphylococcus aureus were selected as experimental strains for the bacterial adhesion experiment. The revived bacteria were placed in a liquid culture medium and shaken overnight at a constant temperature of 37°C. The samples of Implementation Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 were placed in a 24-well plate, sterilized under ultraviolet light for 30 minutes, and 50 µL of the diluted bacterial solution was added to the sample surface and placed in a shaker for incubation at 37°C for 6 hours; after the incubation, the sample surface was slowly washed 3 times with a sterilized PBS buffer solution to remove bacteria that were not adhered to the surface. Then, a PBS solution containing 2.5wt% glutaraldehyde was used to fix the sample at room temperature overnight. After fixation, the sample surface was repeatedly washed 3 times with a PBS buffer solution to remove excess glutaraldehyde solution, and then 1 ml of 10%, 30%, 50%, 70%, 90%, and 100% ethanol solution was used in turn to perform gradient dehydration on the sample, with each gradient dehydration lasting 15 minutes. The treated samples were placed in a vacuum drying oven at 37°C and dried overnight. Scanning electron microscopy (SEM) was used to observe the surface morphology of the dried samples to analyze the bacterial adhesion.

[0037] The scanning electron microscope image of the super hydrophobic SEBS film sample prepared by the present invention is as follows: Figure 1 As shown, Figure 1 (A) is the original SEBS membrane. It can be seen that the surface of the unmodified SEBS is smooth. Figure 1 (B) The surface of SEBS after film formation regulated by mixed solvent is composed of interconnected bead-like SEBS. The rough surface morphology formed on the sample surface enables the film to achieve surface superhydrophobic properties. Figure 1 (C) is a super-hydrophobic SEBS film modified with a gallium coating. A layer of relatively smooth spherical gallium particles of various sizes wrapped in an oxide layer, namely liquid metal (GaLM) particles, is covered on the surface of the original super-hydrophobic structure. Figure 1 (D) is the rough morphology of the gallium-copper alloy surface with a spike-like structure grown on the surface of the gallium coating. It can be seen that Cu crystals are formed and attached to the surface of the GaLM oxide.

[0038] The surface wettability measurement results of the samples prepared in Embodiment 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 of the present invention are as follows: Figure 2 As shown, the droplet volume is controlled by software to be 5µL. In order to ensure the stability of the measurement results, multiple measurements were taken and the average value of the data was taken as the final result. Figure 2It can be seen that the contact angle of the SEBS sample surface is 104.2°. The 4-6 µm SEBS beads on the surface of the superhydrophobic SEBS membrane greatly increase the roughness of the SEBS membrane surface, allowing more air to enter the gaps between the beads inside the membrane, causing the static water contact angle on its surface to increase to 157.4°. The sample modified with gallium coating maintains the original superhydrophobic structure of the surface, with a water contact angle of 152.8°. The water contact angle of the superhydrophobic SEBS membrane sample modified with gallium-copper alloy is 155.3°. The pointed alloy structure increases the roughness of the gallium coating surface, making the contact angle of its surface larger, thus showing superhydrophobicity.

[0039] The antibacterial plating results and plate colony statistics of the samples prepared in Embodiment 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 of the present invention are as follows: Figure 3 As shown in Table 1. The results show that more colonies can be seen on the surface of the original SEBS membrane and the superhydrophobic SEBS membrane, and the antibacterial effect on Escherichia coli and coccus aureus is weak. The bacterial colonies on the surface of the superhydrophobic SEBS membrane sample modified by the gallium coating began to decrease, indicating that gallium ions have a moderate antibacterial effect on bacteria. The sterilization rate of the surface of the superhydrophobic SEBS membrane sample modified by gallium-copper alloy is greater than 99%, indicating that on the one hand, the pointed morphology of the gallium-copper alloy shows good physical structure bactericidal activity, and on the other hand, the synergistic antibacterial effect of gallium ions and copper ions further improves the antibacterial performance.

[0040] The samples prepared in this comparative example were subjected to antibacterial tests. Using the plate count method, it was found that only moderate bactericidal effects were present against Escherichia coli and Staphylococcus aureus. The results are shown in Table 1.

[0041]

[0042] By comparing the sterilization test results of comparative examples 1-3 with those of embodiments 1-3, it can be seen that the super-hydrophobic SEBS film modified with gallium-copper alloy prepared by the present invention can significantly improve its antibacterial performance.

[0043] The bacterial adhesion morphology results of the samples prepared in Embodiment 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are as follows: Figure 4 The results show that the surface of the original SEBS membrane has more Escherichia coli and Staphylococcus aureus adhered, while the superhydrophobic SEBS membrane and the surfaces of the samples of Comparative Example 3 and Implementation Example 1 prepared on this basis hardly have the two bacteria adhered. The superhydrophobic structure is not conducive to the adhesion and proliferation of bacteria. The results show that the superhydrophobic SEBS membrane modified with gallium-copper alloy has good anti-bacterial adhesion ability.

[0044] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a super-hydrophobic SEBS membrane modified with a gallium-copper alloy, characterized in that: The following steps are involved: Step 1, preparing a super-hydrophobic SEBS membrane; Step 2: adding liquid metal to a dispersant, and ultrasonicating to obtain a gallium particle suspension; then immersing the super-hydrophobic SEBS membrane in the gallium particle suspension, and drying to obtain a gallium-coated SEBS membrane; The liquid metal is any one of gallium, gallium-indium alloy or gallium-indium-tin alloy; Step 3: soak the SEBS membrane modified with the gallium coating in a copper ion solution, take it out, wash it, and dry it to obtain a super-hydrophobic SEBS membrane modified with a gallium-copper alloy.

2. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS membrane according to claim 1, characterized in that: In step 1, the specific preparation method of the super-hydrophobic SEBS membrane is: S1. The SEBS powder is dissolved in a good solvent, and then a poor solvent is added and mixed, and stirred to obtain a mixed solution; S2. The mixed solution is coated on the surface of the substrate material. After the good solvent evaporates, the membrane is placed in an alcohol solution for ultrasonic treatment and dried to obtain a superhydrophobic SEBS membrane.

3. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS film according to claim 2, characterized in that: In S1, the good solvent is any one of toluene, xylene or cyclohexane; In S1, the poor solvent is any one of cyclohexanol, n-decanol or diethylene glycol; In S2, the alcohol solution is any one of ethanol, n-butanol or propanol.

4. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS film according to claim 2, characterized in that: In S1, the mass volume ratio of the SEBS powder to the good solvent is 10:1-1:10; In S1, the volume ratio of the good solvent to the poor solvent is 1:3-10:

3.

5. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS film according to claim 2, characterized in that: In S1, the specific conditions of the stirring are: stirring temperature is 20-35°C, stirring speed is 100-400 r / min, and stirring time is 1-4h; In S2, the specific conditions of the volatilization are: volatilization temperature is 20-35°C, and volatilization time is 3-24 h; In S2, the specific conditions of the ultrasound are: the ultrasound temperature is 20-35°C, and the ultrasound time is 10-30min; In S2, the specific conditions of the drying are: drying temperature is 30-40°C, and drying time is 12-48h.

6. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS membrane according to claim 1, characterized in that: In step 2, the concentration of the gallium particle suspension is 0.1%-1%.

7. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS membrane according to claim 1, characterized in that: In step 2, the dispersant is any one of anhydrous ethanol, ultrapure water or a mixed solution of anhydrous ethanol and ultrapure water in a ratio of 1:

1.

8. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS membrane according to claim 1, characterized in that: In step 3, the copper ion solution is any one of copper chloride solution, copper sulfate solution or copper nitrate solution, and the concentration of the copper ion solution is 0.1-1 M.

9. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS membrane according to claim 1, characterized in that: In step three, the soaking time is 1-12 h.

10. The method for preparing a gallium-copper alloy-modified super-hydrophobic SEBS membrane according to claim 1, characterized in that: In step 3, the specific conditions of the drying are: drying temperature is 50-75° C., and drying time is 3-6 h.

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