Oleophylic and hydrophobic oiling coating based on molecular chain winding as well as preparation method and application of oleophylic and hydrophobic oiling coating

Abstract

The invention discloses an oleophylic and hydrophobic oiling coating based on molecular chain winding as well as a preparation method and application of the oleophylic and hydrophobic oiling coating. The preparation method comprises the following steps: S1, soaking a substrate in a silane coupling agent solution, taking out the substrate, and reacting at 100-120 DEG C for 10-60 minutes to obtain a substrate of which the surface is modified with a silane coupling agent; s2, soaking the substrate in a reaction type polydimethylsiloxane solution, and reacting for 6-12 hours at 20-60 DEG C, so that the reaction type polydimethylsiloxane is used as a connecting center to connect the isocyanate groups of any two silane coupling agents to form a molecular lock structure; s3, soaking the substrate obtained in the step S2 in a dimethyl siloxane prepolymer solution, carrying out an ultrasonic reaction for 10-30 minutes so as to enable a polymer molecular chain formed by the dimethyl siloxane prepolymer solution to generate topological winding with a molecular lock structure under ultrasonic induction, and after ultrasonic treatment is finished, taking out the substrate in a spin-coating or lifting manner to form a bottom coating; and S4, putting the substrate obtained in the step S3 into a vacuum drying oven for drying, and then soaking the substrate in an oily solvent.

Description

Technical Field

[0001] The present invention relates to the fields of chemistry, chemical engineering, and functional materials technology, and more specifically, to an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement, and a preparation method and application thereof. Background Art

[0002] Liquid-injectable coatings with lubricating properties are of great significance in fields such as biomedicine. By modifying the surface of implants or medical catheters with lipophilic and hydrophobic coatings, the adhesion of biological fluids including blood, sweat, tears, wound exudates, etc. can be prevented, thus avoiding secondary damage caused by removal. Although the existing superhydrophobic coating technology has made certain progress in anti-fouling, self-cleaning and anti-blood adhesion, the following major problems still exist: 1) Insufficient durability: Some superhydrophobic coatings rely on the physical properties of micro-nano structures. After experiencing mechanical or environmental stresses such as tape stripping, scratching, ultrasonic cleaning or high-temperature treatment, their micro-nano structures are easily damaged, resulting in a decrease in hydrophobicity, affecting long-term performance; 2) Biocompatibility issues: Existing superhydrophobic coatings often use fluorine-containing compounds as surface modifiers. Although they can effectively reduce surface energy and improve hydrophobicity, some fluorine-containing materials may have poor biocompatibility, potential toxicity or environmental pollution risks in medical applications; 3) Limited coating adhesion and substrate adaptability: Current superhydrophobic coatings have poor adhesion on certain substrate materials (such as metals, inorganic materials and certain organic polymer materials) and are prone to peeling or degradation, affecting the stability of the coating and its practical application range. 4) Lack of broad adaptability to biofluids: Some existing superhydrophobic coatings may lose their hydrophobicity in biofluid environments such as blood, wound exudate, sweat, and tears due to the adsorption of proteins or other biomolecules, affecting their anti-pollution performance.

[0003] Hydrogels are typical water-based coatings. In recent years, researchers have achieved strong adhesion between hydrogels and substrates by introducing photoinitiators, thermal initiators, and adhesion layers onto the surface. However, hydrogels are typically prepared through free radical polymerization or polycondensation, methods that are unsuitable for oily polymers and their corresponding media, such as polydimethylsiloxane (PDMS), which undergoes hydrosilylation. This significantly limits the preparation and use of oily polymer coatings.

[0004] In addition to chemical bonds, chain segment entanglement is also an effective molecular interaction. This effect does not require specific reactive functional groups to achieve considerable strength. Professor Suo Zhigang's team used very little water, cross-linkers and initiators to prepare hydrogel precursor solutions, synthesized polyacrylamide hydrogels with densely entangled chain segments, and pointed out that when the number of entanglements far exceeds the number of cross-links, the hydrogel elastomer becomes stronger and tougher. In addition, they strongly connected two polymer networks (such as biological tissues and hydrogels) through topological bonding. At the molecular level, this new layer of polymer network is like a "suture line", which "sews" the original two layers of network together at the molecular scale. This adhesive that can form topological bonding is called a topological adhesive. However, topological sutures are still limited to hydrogels and biological tissues, and there are still few reports on the exploration of oily networks. Summary of the Invention

[0005] To address these issues, the first objective of the present invention is to provide a method for preparing an oleophilic, hydrophobic, oil-injected coating based on molecular chain entanglement. This method utilizes a chemically bonded, molecularly locked structure to form a stable base layer, combined with ultrasound-induced molecular chain topological entanglement to improve the coating's structural stability and durability, enabling it to withstand multiple mechanical insults (such as scraping, ultrasonic cleaning, and tape stripping) while maintaining stable hydrophobic properties.

[0006] A second object of the present invention is to provide an oleophilic and hydrophobic oil-injected coating.

[0007] The third object of the present invention is to provide an application of an oleophilic and hydrophobic oil-injected coating in the preparation of flexible wearable materials and biomedical devices.

[0008] In order to achieve the above first object, the present invention adopts the following technical solutions:

[0009] The present invention discloses a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement, comprising the following steps:

[0010] S1. Soaking the substrate in a silane coupling agent solution having a mass fraction of 0.98-8.3 wt% for 8-24 h, taking it out and cleaning it, and reacting it at 100-120° C. for 10-60 min to obtain a substrate with a surface modified with a silane coupling agent;

[0011] S2. Soaking the substrate of the surface-modified silane coupling agent in a reactive polydimethylsiloxane solution and reacting it at 20-60° C. for 6-12 hours, so that the reactive polydimethylsiloxane acts as a linking center to link any two isocyanate groups of the silane coupling agent to form a molecular lock structure;

[0012] S3, immersing the substrate obtained in step S2 in a dimethylsiloxane prepolymer solution, and ultrasonically reacting the solution for 10 to 30 minutes, so that the polymer molecular chains formed by the dimethylsiloxane prepolymer solution are topologically entangled with the molecular lock structure under ultrasonic induction. After the ultrasonication is completed, the substrate is removed by spin coating or pulling to form a primer layer;

[0013] S4. Place the substrate obtained in step S3 in a vacuum drying oven to dry, and then soak it in an oily solvent for 10 to 60 minutes to obtain the oleophilic and hydrophobic oil-injected coating.

[0014] Furthermore, the silane coupling agent structure contains an isocyanate group, which is selected from one or more of isocyanatepropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate.

[0015] Furthermore, the molecular weight of the reactive polydimethylsiloxane is 1000 to 10000; illustratively, the molecular weight can be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, etc.

[0016] Furthermore, the reactive polydimethylsiloxane is selected from one or more of amino-terminated polydimethylsiloxane, hydroxy-terminated polydimethylsiloxane, and carboxyl-terminated polydimethylsiloxane.

[0017] Furthermore, the mass concentration of the reactive polydimethylsiloxane solution is 1 / 6 to 5 / 6, that is, the mass ratio of the reactive polydimethylsiloxane to the solvent dispersing the reactive polydimethylsiloxane is 5:1 to 1:5.

[0018] Furthermore, the two raw materials, dimethylsiloxane and cross-linking agent, in the dimethylsiloxane prepolymer liquid are both commercially available products. Generally, the dimethylsiloxane and cross-linking agent are prepared in a mass ratio of 10:1 to obtain the dimethylsiloxane prepolymer liquid.

[0019] Furthermore, the oily solvent is selected from one or more of dimethyl silicone oil, mineral oil, liquid paraffin, vegetable oil, and alkane, and has a viscosity of 10 to 1000 mPa·s.

[0020] Furthermore, the spin coating speed is 1000 to 10000 rpm.

[0021] Furthermore, the pulling speed is 5 to 200 μm / s.

[0022] Furthermore, the substrate includes but is not limited to metal (such as stainless steel, titanium alloy, etc.), glass, ceramic, polymer materials (such as polydimethylsiloxane PMMA, PTFE, etc.), etc.

[0023] In order to achieve the above second purpose, the present invention adopts the following technical solutions:

[0024] The present invention discloses an oleophilic and hydrophobic oil-injection coating, which is prepared by the above-mentioned preparation method.

[0025] In order to achieve the third object, the present invention adopts the following technical solutions:

[0026] The present invention discloses an application of the oleophilic and hydrophobic oil-injected coating in the preparation of flexible wearable materials and biomedical devices.

[0027] The beneficial effects of the present invention are as follows:

[0028] The present invention proposes an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology and its preparation method. Compared with existing super-hydrophobic coating technology, it has significant advantages in stability, biocompatibility, substrate adaptability and anti-adhesion ability of biological fluids:

[0029] 1) Improved durability to ensure long-term stable hydrophobic performance.

[0030] The present invention enhances the stability of the coating through chemical bonding of the "molecular lock" structure, and combines it with ultrasound-induced topological entanglement of the molecular chains to effectively improve the mechanical durability and adhesion of the coating. As a result, the oleophilic and hydrophobic oil-injected coating of the present invention can still maintain excellent hydrophobic properties after long-term use and mechanical damage, has stronger mechanical durability, can withstand mechanical damage such as scratching, tape stripping, and ultrasonic cleaning, and maintains stable hydrophobicity over a long period of time. It is suitable for medical devices and antifouling coating applications that require frequent cleaning or long-term use. In addition, the size of the molecular lock structure can be changed by adjusting the molecular weight of the reactive polydimethylsiloxane. By regulating the ultrasonic conditions, the degree of topological entanglement between the polymer molecular chain and the molecular lock structure can be improved, thereby affecting the mechanical durability and adhesion of the coating.

[0031] 2) It does not contain fluorine compounds, which improves biocompatibility.

[0032] The raw materials used in this invention are all non-toxic polymer materials and do not contain any fluorine-containing components, ensuring biological safety. Therefore, the lipophilic and hydrophobic oil-injected coating of the present invention is non-toxic to cells and the blood environment, making it more suitable for the surfaces of medical devices such as surgical instruments, catheters, and artificial joints.

[0033] 3) Wider substrate adaptability and improved coating adhesion.

[0034] The present invention utilizes "molecular lock" chemical bonding + molecular chain topological entanglement technology to significantly enhance the adhesion of the coating to different substrates, making it applicable to a variety of materials, including but not limited to metals, glass, ceramics, polymer materials, and other substrates. Based on this characteristic, the oleophilic and hydrophobic oil-injected coating of the present invention is more suitable for different types of medical devices and industrial applications, enhancing its practical value.

[0035] 4) Wide adaptability to various biological fluids.

[0036] The lipophilic, hydrophobic, oil-injected coating of the present invention achieves highly effective lyophobicity against biological fluids such as blood, sweat, tears, and wound exudate by optimizing its molecular chain structure, ensuring excellent anti-contamination capabilities even in complex biological environments. Furthermore, the lipophilic, hydrophobic, oil-injected coating of the present invention effectively reduces the adhesion of biological fluids such as blood, lowering contamination risks and improving the safety and usability of medical devices.

[0037] In summary, the present invention develops a low-cost, low-energy, biofriendly, durable and widely applicable oleophilic and hydrophobic coating and its preparation method through innovative molecular chain winding technology, providing a high-performance solution for the medical, industrial and anti-fouling fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The process flow chart for preparing oleophilic and hydrophobic oil-injected coatings is shown.

[0039] Figure 2 The scanning electron microscope images of the cross section of the coating of Example 1 before and after immersion in dimethyl silicone oil during the coating preparation process are shown.

[0040] Figure 3 The contact angle change diagram of Example 1 during the hydrophobic change test is shown. DETAILED DESCRIPTION

[0041] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and drawings. Those skilled in the art should understand that the following specific description is illustrative rather than restrictive and should not be used to limit the scope of protection of the present invention.

[0042] Example 1

[0043] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0044] (1) Use anhydrous ethanol, acetone and deionized water to separate the glass pieces (2×7cm 2) Clean it by ultrasonic cleaning for 30 minutes, dry it in a 50°C oven for 1 hour, and treat it with a plasma cleaner in high power mode for 10 minutes.

[0045] (2) The glass slide was immersed in a pre-prepared 1.9% TEPI (triethoxypropylsilane) solution for 12 h, and then washed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 min to obtain a glass slide with surface modified with TEPI.

[0046] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS solution in acetone, soak the glass sheet obtained in step (2) in the amino-terminated PDMS solution (molecular weight 4000), heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure (see Figure 1 After removal, the sample was washed with acetone and dried under nitrogen at room temperature.

[0047] (4) The glass sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to crosslinker was 10:1, commercially available, Dow Corning 184), and reacted under 100% power ultrasound for 30 min, so that the molecular chains formed by PDMS and the crosslinker were topologically entangled with the molecular lock structure under ultrasound induction (see Figure 1 In step IV), the film was vertically pulled at a speed of 100 μm / s to form a film, and then placed in an oven at 60° C. overnight to form a primer layer.

[0048] (5) After removing the primer layer, immerse it in dimethyl silicone oil with a viscosity of 10 mPa·s for 30 minutes. Then, an oleophilic and hydrophobic oil-filled coating is obtained on the surface of the glass sheet.

[0049] Figure 2 Scanning electron micrographs of a cross-section of the coating are shown before and after immersion in dimethyl silicone oil during coating preparation. After immersion, the coating thickness increases, and the morphology exhibits the characteristic wrinkled morphology of an oily solution, demonstrating that the dimethyl silicone oil has penetrated the three-dimensional network of polydimethylsiloxane (PDMS).

[0050] The prepared coating was subjected to the following treatments to test its hydrophobicity changes. The final hydrophobicity effect was found to have no significant change (see Figure 3 ), including the advancing and retarding contact angles of water on the surface, showed no statistically significant differences:

[0051] (i) The coating was subjected to 200 repeated tape application and stripping cycles at room temperature;

[0052] (ii) subjecting the coating to continuous sonication at room temperature for 24 hours;

[0053] (iii) placing the coating in a constant temperature drying oven at 120° for 72 hours;

[0054] (iv) Scratching the coating surface with a surgical pad at room temperature.

[0055] Example 2

[0056] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0057] (1) Use anhydrous ethanol, acetone and deionized water to separate the glass pieces (2×2cm 2 ) Clean it by ultrasonic cleaning for 30 minutes, dry it in a 50°C oven for 1 hour, and treat it with a plasma cleaner in high power mode for 10 minutes.

[0058] (2) The glass slide was placed in a pre-prepared 1.9% TEPI solution and soaked for 12 h. After being taken out, it was rinsed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 min to obtain a glass slide with surface modified with TEPI.

[0059] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS (molecular weight 4000) solution in acetone. Immerse the glass slide obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the slide and rinse with acetone, then dry under nitrogen at room temperature.

[0060] (4) The glass sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to the crosslinker was 10:1, commercially available, Dow Corning 184), and reacted under 100% power ultrasound for 30 minutes so that the molecular chains formed by the PDMS and the crosslinker were topologically entangled with the molecular lock structure under ultrasound induction. The glass sheet was spin-coated at a speed of 3000 rpm and then placed in an oven at 60°C overnight to form a primer layer.

[0061] (5) After removing the primer layer, immerse it in dimethyl silicone oil with a viscosity of 10 mPa·s for 30 minutes. Then, an oleophilic and hydrophobic oil-filled coating is obtained on the surface of the glass sheet.

[0062] The hydrophobicity change test results are the same as those in Example 1.

[0063] Example 3

[0064] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0065] (1) NiTi alloy sheets (2×2 cm) were washed with anhydrous ethanol, acetone and deionized water respectively. 2 ) Clean it by ultrasonic cleaning for 30 minutes, dry it in a 50°C oven for 1 hour, and treat it with a plasma cleaner in high power mode for 10 minutes.

[0066] (2) The alloy sheet was placed in a pre-prepared 1.9% TEPI solution and soaked for 12 hours. After being taken out, it was rinsed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 minutes to obtain an alloy sheet with surface modified with TEPI.

[0067] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS (molecular weight 4000) solution in acetone. Immerse the alloy sheet obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the sheet and rinse with acetone, then dry it under nitrogen at room temperature.

[0068] (4) The alloy sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to the cross-linking agent was 10:1), and reacted under 100% power ultrasound for 30 minutes so that the molecular chains formed by PDMS and the cross-linking agent were topologically entangled with the molecular lock structure under ultrasound induction. The alloy sheet was spin-coated at a speed of 3000 rpm and then placed in an oven at 60°C overnight to form a primer layer.

[0069] (5) After removing the primer coating, immerse it in 10 mPa·s dimethyl silicone oil for 30 min. Then, an oleophilic and hydrophobic oil-filled coating can be obtained on the surface of the nickel-titanium alloy.

[0070] The hydrophobicity change test results are the same as those in Example 1.

[0071] Example 4

[0072] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0073] (1) NiTi alloy sheets (2×7 cm) were washed with anhydrous ethanol, acetone and deionized water respectively. 2 ) Clean it by ultrasonic cleaning for 30 minutes, dry it in a 50°C oven for 1 hour, and treat it with a plasma cleaner in high power mode for 10 minutes.

[0074] (2) The alloy sheet was placed in a pre-prepared 1.9% TEPI solution and soaked for 12 hours. After being taken out, it was rinsed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 minutes to obtain an alloy sheet with surface modified with TEPI.

[0075] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS (molecular weight 4000) solution in acetone. Immerse the alloy sheet obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the sheet and rinse with acetone, then dry it under nitrogen at room temperature.

[0076] (4) The alloy sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS and cross-linking agent was 10:1), and reacted under 100% power ultrasound for 30 minutes, so that the molecular chains formed by PDMS and the cross-linking agent were topologically entangled with the molecular lock structure under ultrasonic induction, and vertically pulled into a film at a speed of 100 μm / s, and then placed in a 60°C oven overnight to form a primer layer.

[0077] (5) After removing the primer coating, immerse it in 10 mPa·s dimethyl silicone oil for 30 min. Then, an oleophilic and hydrophobic oil-filled coating can be obtained on the surface of the nickel-titanium alloy.

[0078] The hydrophobicity change test results are the same as those in Example 1.

[0079] Example 5

[0080] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0081] (1) Use anhydrous ethanol, acetone and deionized water to separate the polytetrafluoroethylene sheet (2×7cm 2 ) Clean it by ultrasonic cleaning for 30 minutes, dry it in a 50°C oven for 1 hour, and treat it with a plasma cleaner in high power mode for 10 minutes.

[0082] (2) The polytetrafluoroethylene sheet was immersed in a pre-prepared 1.9% TEPI solution for 12 h, washed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 min to obtain a polytetrafluoroethylene sheet with surface modified with TEPI.

[0083] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS (molecular weight 4000) solution in acetone. Immerse the polytetrafluoroethylene sheet obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the sheet and rinse with acetone, then dry it under nitrogen at room temperature.

[0084] (4) The polytetrafluoroethylene sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to the crosslinker was 10:1), and reacted under 100% power ultrasound for 30 minutes, so that the molecular chains formed by the PDMS and the crosslinker were topologically entangled with the molecular lock structure under ultrasound induction, and vertically pulled at a speed of 100 μm / s to form a film, and then placed in a 60°C oven overnight to form a primer layer.

[0085] (5) After removing the primer layer, immerse it in 200 mPa·s dimethyl silicone oil for 30 min. Then, an oleophilic and hydrophobic oil-injected coating can be obtained on the polytetrafluoroethylene surface.

[0086] The hydrophobicity change test results are the same as those in Example 1.

[0087] Example 6

[0088] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0089] (1) Use anhydrous ethanol, acetone and deionized water to separate the polytetrafluoroethylene sheet (2×2cm 2 ) Ultrasonic cleaning for 30 minutes, drying in a 50°C oven for 1 hour, and plasma cleaning for 10 minutes at high power mode;

[0090] (2) The polytetrafluoroethylene sheet was immersed in a pre-prepared 1.9% TEPI solution for 12 h, washed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 min to obtain a polytetrafluoroethylene sheet with surface modified with TEPI.

[0091] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS (molecular weight 4000) solution in acetone. Immerse the polytetrafluoroethylene sheet obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the sheet and rinse with acetone, then dry it under nitrogen at room temperature.

[0092] (4) The polytetrafluoroethylene sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to the crosslinker was 10:1), and reacted under 100% power ultrasound for 30 minutes so that the molecular chains formed by the PDMS and the crosslinker were topologically entangled with the molecular lock structure under ultrasound induction. The sheet was spin-coated at a speed of 3000 rpm and then placed in an oven at 60°C overnight to form a primer layer.

[0093] (5) After removing the primer layer, immerse it in 100 mPa·s dimethyl silicone oil for 30 min. Then, an oleophilic and hydrophobic oil-injected coating can be obtained on the polytetrafluoroethylene surface.

[0094] The hydrophobicity change test results are the same as those in Example 1.

[0095] Example 7

[0096] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0097] (1) A glass sheet (40 mm * 20 mm * 2 mm) was ultrasonically cleaned with anhydrous ethanol, acetone, and deionized water for 30 min, dried in a 50°C oven for 1 hour, and treated with a plasma cleaner at high power mode for 10 min.

[0098] (2) The glass slide was placed in a pre-prepared 1.9% TEPI solution and soaked for 12 h. After being taken out, it was rinsed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 min to obtain a glass slide with surface modified with TEPI.

[0099] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS solution (the molecular weight of the amino-terminated PDMS is 1000, 3000, 4000, or 5000) in acetone. Immerse the glass slide obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the slide and rinse with acetone, then dry under nitrogen at room temperature.

[0100] (4) The glass sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to cross-linker was 10:1), and reacted under 100% power ultrasound for 30 minutes, so that the molecular chains formed by PDMS and the cross-linker were topologically entangled with the molecular lock structure under ultrasound induction, and vertically pulled at a speed of 100 μm / s to form a film. Then, two quartz sheets were clamped around the film and glued together with an overlapping length of about 1 cm. The film was clamped with a clamp and placed flat in an oven at 80°C overnight.

[0101] (5) The maximum shear adhesion force between two quartz plates was measured using a tensile tester. The adhesion forces of samples prepared from amino-terminated PDMS with molecular weights of 1000, 3000, 4000, and 5000 were 55.98 ± 4.03 N / cm 2 , 74.79±1.79N / cm 2 、85.26±3.12N / cm 2 、117.62±5.64N / cm2 .

[0102] (6) After removing the primer layer, immerse it in dimethyl silicone oil with a viscosity of 10 mPa·s for 30 minutes. Then, an oleophilic and hydrophobic oil-filled coating is obtained on the surface of the glass sheet.

[0103] The hydrophobicity change test results are the same as those in Example 1.

[0104] Example 8

[0105] This example provides a method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement technology. Figure 1 As shown, the following steps are included:

[0106] (1) A glass sheet (40 mm * 20 mm * 2 mm) was ultrasonically cleaned with anhydrous ethanol, acetone, and deionized water for 30 min, dried in a 50°C oven for 1 hour, and treated with a plasma cleaner at high power mode for 10 min.

[0107] (2) The glass slide was placed in a pre-prepared 1.9% TEPI solution and soaked for 12 h. After being taken out, it was rinsed with toluene and acetone respectively, dried with nitrogen at room temperature, and placed in an oven at 120°C for 30 min to obtain a glass slide with surface modified with TEPI.

[0108] (3) Prepare 100 mL of a 50.0 wt% amino-terminated PDMS (molecular weight 4000) solution in acetone. Immerse the glass slide obtained in step (2) in the amino-terminated PDMS solution, heat in a water bath, and react at 40°C for 8 h to chemically bond the amino-terminated PDMS and TEPI to form a molecular lock structure. Remove the slide and rinse with acetone, then dry under nitrogen at room temperature.

[0109] (4) The glass sheet obtained in step (3) was immersed in a PDMS prepolymer solution (the mass ratio of PDMS to the cross-linker was 10:1), and reacted under 100% power ultrasound for different times (0 min, 10 min, 20 min, 30 min, 40 min) so that the molecular chains formed by the PDMS and the cross-linker were topologically entangled with the molecular lock structure under ultrasonic induction. The film was vertically pulled at a speed of 100 μm / s to form a film. Then, two quartz sheets were clamped around the film and glued together with an overlapping length of about 1 cm. The film was clamped with a clip and placed flat in an oven at 80°C overnight.

[0110] (5) The maximum shear adhesion force between two quartz plates was measured using a tensile testing machine. The adhesion forces of samples prepared with different ultrasonic times (0 min, 10 min, 20 min, 30 min, and 40 min) were 39.79 ± 3.10 N / cm 2 、68.93±8.98N / cm 2、81.15±6.62N / cm 2 , 95.68±4.17N / cm 2 , 97.13±3.62N / cm 2 .

[0111] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A method for preparing an oleophilic and hydrophobic oil-injected coating based on molecular chain entanglement, characterized in that: The steps include: S1. Soaking the substrate in a silane coupling agent solution having a mass fraction of 0.98-8.3 wt% for 8-24 h, taking it out and cleaning it, and reacting it at 100-120° C. for 10-60 min to obtain a substrate with a surface modified with a silane coupling agent; S2. Soaking the substrate of the surface-modified silane coupling agent in a reactive polydimethylsiloxane solution and reacting it at 20-60° C. for 6-12 hours, so that the reactive polydimethylsiloxane acts as a linking center to link any two isocyanate groups of the silane coupling agent to form a molecular lock structure; S3, immersing the substrate obtained in step S2 in a dimethylsiloxane prepolymer solution, and ultrasonically reacting the solution for 10 to 30 minutes, so that the polymer molecular chains formed by the dimethylsiloxane prepolymer solution are topologically entangled with the molecular lock structure under ultrasonic induction. After the ultrasonication is completed, the substrate is removed by spin coating or pulling to form a primer layer; S4. Place the substrate obtained in step S3 in a vacuum drying oven to dry, and then soak it in an oily solvent for 10 to 60 minutes to obtain the oleophilic and hydrophobic oil-injected coating.

2. The preparation method according to claim 1, characterized in that The silane coupling agent is selected from one or more of isocyanatepropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate.

3. The preparation method according to claim 1, characterized in that The molecular weight of the reactive polydimethylsiloxane is 1,000 to 10,000.

4. The preparation method according to claim 1, characterized in that The reactive polydimethylsiloxane is selected from one or more of amino-terminated polydimethylsiloxane, hydroxy-terminated polydimethylsiloxane, and carboxyl-terminated polydimethylsiloxane.

5. The preparation method according to claim 1, characterized in that The mass concentration of the reactive polydimethylsiloxane solution is 1 / 6 to 5 / 6.

6. The preparation method according to claim 1, characterized in that The oily solvent is selected from one or more of dimethyl silicone oil, mineral oil, liquid paraffin, vegetable oil, and alkane, and has a viscosity of 10 to 1000 mPa·s.

7. The preparation method according to claim 1, characterized in that The spin coating speed is 1000-10000 rpm.

8. The preparation method according to claim 1, characterized in that The pulling speed is 5 to 200 μm / s.

9. An oleophilic and hydrophobic oil-injection coating, characterized in that: The preparation method is described in any one of claims 1 to 8.

10. Use of the oleophilic and hydrophobic oil-injected coating according to claim 9 in the preparation of flexible wearable materials and biomedical devices.

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