A method for preparing an anti-sticking nano-coating based on molecular brush grafting technology

The molecular brush grafting technology is used to form an anti-adhesion coating with a nanometer thickness on the surface of the substrate, which solves the problems of substrate limitations and complex preparation processes in the existing technology, and realizes simple and mild preparation under normal conditions, which is suitable for industrial applications.

CN118879199BActive Publication Date: 2025-10-10DALIAN UNIV OF TECH
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Patent Information

Application Number
CN202410968516.9
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-07-19
Publication Date
2025-10-10
Estimated Expiration
2044-07-19

AI Technical Summary

Technical Problem

The existing preparation process of non-adhesion coatings has problems such as substrate limitations, complex preparation process, harsh preparation conditions and large coating thickness, making it difficult to achieve simple and gentle preparation of anti-adhesion coatings with nanometer-level thickness.

Method used

Using molecular brush grafting technology, the anti-adhesion polymer is dissolved in an organic solvent and coated on a clean, dry substrate. The anti-adhesion polymer is grafted onto the surface of the substrate through hydrogen bonding, complexation and π-π bonds to form an anti-adhesion coating with a nanometer thickness.

Benefits of technology

It has achieved the goal of preparing an anti-adhesion coating with nanometer thickness through a simple process under conventional conditions without being restricted by the substrate, solving the problems of substrate limitations, complex preparation process and harsh conditions in the existing technology, and is suitable for industrial production.

✦ Generated by Eureka AI based on patent content.

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Patent Text Reader

Abstract

The application belongs to the technical field of nano coating preparation, and provides a method for preparing an anti-adhesion nano coating based on a molecular brush grafting technology, wherein an anti-adhesion polymer solution is coated on a clean and dry substrate, the anti-adhesion polymer is grafted on the surface of the substrate through actions including hydrogen bonds, complexation and pi-pi bonds, after complete evaporation of an organic solvent, the anti-adhesion polymer not stably combined with the substrate is removed through cleaning, and thus an anti-adhesion nano coating is formed on the surface of the substrate. The anti-adhesion polymer is formed by reacting an organic silicon molecule with an adhesion agent, and the adhesion agent is a compound with a hydroxyl group and an amine group on a benzene ring. The application can realize simple and mild preparation of an anti-adhesion coating with a nano-level thickness without limitation of the substrate.
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Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of nano-coating preparation, and relates to a method for preparing an anti-adhesion nano-coating based on a molecular brush grafting technique. BACKGROUND

[0002] The adhesion of contaminants on the surface will cause loss to actual production and life and even threaten personal safety. In the field of energy, the deposition of particulate contaminants and the accumulation of ice and snow on solar photovoltaic panels will block the propagation of sunlight, causing the utilization rate of sunlight to decrease, resulting in the reduction of photovoltaic power generation efficiency; the wind turbine blades will lose 10% to 30% of the power generation capacity every year due to the ice and snow on the surface, and in severe cases, the wind turbine will even collapse, causing economic losses. In the field of transportation, the icing on the surface of the aircraft wing will cause the loss of lift and increase the risk of crashing. As can be seen, the non-adhesion surface plays a crucial role in liquid transportation, anti-fouling and ice deposition suppression and many other fields.

[0003] The non-adhesion surface usually needs to have liquid repellency. Since the proposal of Young's equation in the 17th century, people have developed various anti-adhesion surfaces, i.e. liquid repellent surfaces, based on the principle of biological simulation and surface interface regulation technology. At present, the development of advanced liquid repellent technology has experienced several stages, from the air-structure lubrication (Superhydrophobic surface, SHS) in 1996, the air-Re-entrant structure (Superomniphobic surface, SOS) in 2007, the liquid-structure lubrication (Liquid infused surface, LIS) in 2011, the air-Double Re-entrant structure (Superomniphobic surface, SOS) in 2014, to the chemical grafting liquid lubrication (Liquid-like surface, LLS) in 2016. Overall, the strategies to reduce the adhesion of the surface mainly include regulating the surface geometry and chemical surface modification, and the essence is to change the phase interface between the object and the substrate to achieve liquid repellency and anti-adhesion effect. However, the superhydrophobic surface based on micro-texture still has challenges in practical application in some fields due to its inherent limitations. For example, in a low-temperature or high-humidity environment, water vapor or small droplets will condense or even freeze in the micro-texture, thereby causing the failure of the superhydrophobic structure. In addition, when a liquid with low surface tension flows on the structure surface or a droplet hits the surface, it is easy to enter the micro-texture and cause the failure of the hydrophobic structure. The liquid infusion surface based on liquid lubrication will lose the lubricating liquid when the adhering object is detached, and also has the problem of evaporation of the lubricating liquid, and when the lubricating liquid is consumed, the non-adhesion property of the surface will also fail.

[0004] Although anti-adhesion technology has made some progress, the preparation process of non-adhesion coatings still faces the following challenges: (1) Substrate limitations. For example, LLS relies on the active sites on the substrate surface and requires pretreatment of the substrate. In order to accelerate the preparation of the coating, high temperature and acid or base catalysis are often required, which will cause corrosion of the metal substrate. (2) Complex preparation process. For example, traditional super-hydrophobic surfaces often require secondary modification with low surface energy molecules to achieve super-hydrophobicity. For example, the structures of re-entrant and doble re-entrant are complex, and the preparation process is cumbersome and difficult to achieve rapid preparation. For example, LIS requires two stages: structural molding and liquid infusion. (3) Harsh preparation conditions: For example, the use of chemical modification strategies often requires specific conditions, such as high temperature, vacuum environment, ultraviolet light irradiation, etc. (4) Long preparation time: For example, the immersion method for preparing LLS requires 12 hours or even 48 hours to complete the preparation of molecular brush coatings. (5) Large coating thickness: Except for LLS, which can achieve the preparation of non-adhesive coatings with nanometer thickness, existing methods are difficult to achieve the preparation of nano-anti-adhesive coatings. The large coating thickness will make it impossible to use in some precision fields. Therefore, if a preparation technology for anti-adhesive nano-coatings that is not restricted by substrates, has a simple preparation process and mild preparation conditions can be developed, it will be of great significance to extend the service life and safety of components, improve energy utilization, expand applications in precision fields, and reduce risks. Summary of the Invention

[0005] In response to the above-mentioned problems existing in the existing preparation process of non-adhesive coatings, the present invention provides a method for preparing anti-adhesive nanocoatings based on molecular brush grafting technology, so as to achieve the simple and gentle preparation of anti-adhesive coatings with nanometer thickness without being restricted by the substrate.

[0006] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology comprises the following steps:

[0008] (1) dissolving an anti-adhesion polymer in an organic solvent to obtain an anti-adhesion polymer solution; the preparation method of the anti-adhesion polymer is as follows:

[0009] Under stirring and protective gas protection, the adhesive solution is added dropwise to the organosilicon molecule solution, the molar ratio of the organosilicon molecule to the adhesive is controlled to be 1:(0.05-5), and the mixture is fully reacted at 0-100°C. The unreacted raw materials and solvent are removed, and the mixture is dried to obtain an anti-adhesion polymer; the adhesive is a compound having hydroxyl and amine groups on the benzene ring;

[0010] (2) The anti-adhesion polymer solution is coated on a clean, dry substrate, and the anti-adhesion polymer is grafted onto the surface of the substrate through actions including hydrogen bonding, complexation, and π-π bonding. After the organic solvent is completely evaporated, the anti-adhesion polymer that is not stably bonded to the substrate is washed away, thereby forming an anti-adhesion nanocoating on the surface of the substrate.

[0011] In the above technical solution, the organic silicon molecules are R1-Si(CH3)2-O-Si(CH3)2-R1, R2-Si(CH3)2-O-Si-(CH3)3, H2N(CH2)3Si[O(CH2) n (CH3)3]3 or poly[dimethylsiloxane-co-(3-aminopropyl)methylsiloxane], wherein R1 is -(CH2)3NH2, -OH, -(CH2)3COOH or -CH(O)CH-, and R2 is -(CH2)3O(CH2)2OH, -(CH2)3COOH or -(CH2)3OCH2CH(O)CH).

[0012] Furthermore, in the above technical solution, the H2N(CH2)3Si[O(CH2) n In (CH3)3]3, n=0 or 1.

[0013] In the above technical solution, the adhesive includes any one of dopamine hydrochloride, 6-hydroxydopamine and 3-hydroxy-4-methoxyphenethylamine.

[0014] In the above technical solution, the organosilicon molecule solution is formed by dissolving organosilicon molecules in dichloromethane, and the concentration of the organosilicon molecule solution is preferably 0.01 to 0.2 mmol / mL; the adhesive solution is formed by dissolving an adhesive in N,N-dimethylformamide, and the concentration of the adhesive solution is preferably 0.01 to 1 mmol / mL. The adhesive solution is preferably prepared using N,N-dimethylformamide from which oxygen has been removed; before the adhesive solution is added dropwise to the organosilicon molecule solution, it is preferably to remove oxygen from the organosilicon molecule solution.

[0015] In the above technical solution, in step (1), when preparing the anti-adhesion polymer, a chain extender solution may be added dropwise to the organosilicon molecule solution. That is, in step (1), when preparing the anti-adhesion polymer, the adhesive solution and the chain extender solution are added dropwise to the organosilicon molecule solution under stirring and protective gas protection, and the mixture is fully reacted at 0-100°C. Unreacted raw materials and solvent are removed, and the mixture is dried to obtain the anti-adhesion polymer. Preferably, the molar ratio of the organosilicon molecule to the chain extender is controlled to be 1:(1-5).

[0016] In the above technical solution, whether to use the chain extender mainly depends on the specific structure of the organic silicon molecule. When the organic silicon molecule is R2-Si(CH3)2-O-Si-(CH3)3, the chain extender does not need to be used; when the organic silicon molecule is H2N(CH2)3Si[O(CH2) n (CH3)3]3 or poly[di-methyl siloxane-co-(3-amino propyl) methyl siloxane], the chain extender needs to be used; when the organic silicon molecule is R1-Si(CH3)2-O-Si(CH3)2-R1, the chain extender can be used or not used. In actual application, whether to add the chain extender can be determined according to the structure of the organic silicon molecule and the actual application requirement.

[0017] In the above technical solution, the chain extender is a common chain extender used in the preparation of the organic silicon polymer in the prior art. For example, the feasible chain extender includes one or a combination of 4,4'-methylene bis(phenyl isocyanate), 4,4'-diisocyanate dicyclohexyl methane D, isophthalimide, isophorone diisocyanate, and toluene diisocyanate.

[0018] In the above technical solution, the chain extender solution is formed by dissolving the chain extender in N,N-dimethylformamide, and the concentration of the chain extender solution is preferably 0.1-1 mmol / mL. The chain extender solution is preferably prepared by using N,N-dimethylformamide from which oxygen is removed.

[0019] In the above technical solution, the protective gas is a non-reactive gas that does not react with the adhesion agent / organic silicon molecule system and the adhesion agent / organic silicon molecule / chain extender system in the process of preparing the anti-adhesion high molecule. The protective gas can be an inert gas or nitrogen.

[0020] In the above technical solution, in step (1) in the preparation of the anti-adhesion high molecule, a catalyst for promoting the synthesis of the organic silicon polymer can be added to the organic silicon molecule solution. The catalyst includes at least one of triethylamine, 4-N,N-dimethylpyridine, trimethylamine, and dibutyltin dilaurate. Generally, the catalyst is added in an amount such that the molar ratio of the catalyst to the organic silicon molecule is 1:(2-3).

[0021] In the above technical solution, in step (1) in the preparation of the anti-adhesion high molecule, the reaction is preferably controlled at 0-100°C for 4-8 h.

[0022] In the above technical solution, in the anti-adhesion high molecule solution in step (1), the concentration of the anti-adhesion high molecule is preferably 5-100 μg / mL.

[0023] In the above technical solution, the coating method in step (2) includes spraying, brushing, or soaking.

[0024] In the above technical solution, in step (2), when the anti-adhesion polymer solution is applied to a clean, dry substrate, the anti-adhesion polymer solution is controlled to completely cover the portion of the clean, dry substrate on which the anti-adhesion nanocoating is to be prepared. For example, when the coating method is spraying or brushing, the anti-adhesion polymer solution is sprayed or brushed onto the portion of the clean, dry substrate on which the anti-adhesion nanocoating is to be prepared, so that the anti-adhesion polymer solution completely covers the portion of the anti-adhesion nanocoating to be prepared. For another example, when the coating method is immersion, the portion of the clean, dry substrate on which the anti-adhesion nanocoating is to be prepared is completely immersed in the anti-adhesion polymer solution for 5 to 60 seconds.

[0025] In the above technical solution, the substrate is an organic material substrate, an inorganic material substrate or a metal substrate. For example, the material of the substrate can be aluminum, copper, stainless steel, gold, silicon, glass, polyurethane, etc.

[0026] In the above technical solution, the thickness of the anti-adhesion nanocoating formed on the surface of the substrate in step (2) is related to the molecular weight of the anti-adhesion polymer and has nothing to do with other factors. The thickness of the anti-adhesion nanocoating is at the nanometer level, and the thickness of the coating is usually not more than 1000 nm. The specific coating thickness can be determined according to actual application requirements. Furthermore, the thickness of the coating is generally between 20 and 200 nm. For example, the thickness of the coating can be between 20 and 50 nm.

[0027] In the above technical solution, the clean and dry substrate refers to a substrate that is ultrasonically cleaned with deionized water, ethanol and acetone in sequence to remove organic pollutants and solid particles on the surface of the substrate, and then dried.

[0028] In the above technical solution, when using deionized water, ethanol and acetone to ultrasonically clean the substrate, it is preferred to control the ultrasonic cleaning time to be 10 to 300 seconds.

[0029] In the above technical solution, in step (2), acetone or toluene can be used to clean and remove the anti-adhesion polymer that is not stably bonded to the substrate.

[0030] The present invention is confirmed by experiments:

[0031] The thickness of the anti-adhesion coating prepared by the method of the present invention is at the nanometer level, which can effectively improve the anti-adhesion effect of the substrate without affecting the surface morphology and light transmittance of the substrate. The anti-adhesion nanocoating prepared by the method of the present invention has excellent stability and still maintains excellent liquid repellency after long-term immersion in organic solvents. The method of the present invention is not limited by the material of the substrate and can be used to prepare anti-adhesion nanocoatings on organic substrates and inorganic substrates, such as aluminum, copper, stainless steel, gold, silicon, glass, polyurethane and the like. The method of the present invention achieves rapid preparation of anti-adhesion nanocoatings through simple processes, such as spraying, brushing and immersion.

[0032] Compared with the prior art, the technical solution of the present invention can produce the following beneficial technical effects:

[0033] 1. The present invention provides a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology. A phenol-terminated organosilicon polymer is used as the anti-adhesion polymer. A solution of the anti-adhesion polymer is applied to a clean, dry substrate. The anti-adhesion polymer is grafted onto the substrate surface through interactions including hydrogen bonding, complexation, and π-π bonding. After the organic solvent has completely evaporated, any anti-adhesion polymer not stably bonded to the substrate is removed by washing, thereby forming an anti-adhesion nanocoating on the substrate surface. The method is not limited by substrates, features a simple preparation process, requires a short processing time, operates under mild conditions, and achieves a coating thickness on the nanometer scale. This method effectively addresses the issues of existing methods for preparing non-adhesion coatings, such as substrate limitations, complex preparation processes, and demanding processing conditions.

[0034] 2. The method of the present invention has low requirements for instruments, reagents and process conditions. No special instruments or expensive equipment are required. The anti-adhesion nanocoating can be prepared under conventional operating conditions. Therefore, the present invention is suitable for promotion and application under existing simple process conditions and is easy to achieve industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the H-NMR spectrum of the anti-adhesion polymer prepared in Example 1.

[0036] Figure 2 These are the light transmittance test results of the glass substrate in Example 1 before and after modification with the anti-adhesion nanocoating.

[0037] Figure 3 These are the ice shear force test results of the glass substrate in Example 1 before and after modification with the anti-adhesion nanocoating.

[0038] Figure 4 This is the liquid repellency test result of the coated aluminum substrate in Example 2 after being immersed in toluene for 24 hours.

[0039] Figure 5 304 stainless steel substrate before and after modification with the anti-adhesion nanocoating in Example 3.

[0040] Figure 6 These are the water drop contact angle test results of the 316 stainless steel substrate in Example 4 before and after modification with the anti-adhesion nanocoating.

[0041] Figure 7 These are the coating thickness test results of the silicon substrate in Example 5 before and after modification with the anti-adhesion nanocoating.

[0042] Figure 8 These are atomic force microscope images of the silicon substrate in Example 6 before and after modification with the anti-adhesion nanocoating.

[0043] Figure 9 FTIR spectrum of the silicon substrate after modification of the anti-adhesion nanocoating in Example 6.

[0044] Figure 10 These are the test results of the liquid repellency of the polyurethane substrate in Example 7 before and after modification with the anti-adhesion nanocoating.

[0045] Figure 11 This is the stability test result of the anti-adhesion nanocoating on the gold substrate in Example 8. DETAILED DESCRIPTION

[0046] The following examples further illustrate the method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology provided by the present invention. It should be noted that the following examples are intended only to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Based on the above disclosure, non-essential improvements and adjustments made by persons skilled in the art to implement the present invention remain within the scope of protection of the present invention.

[0047] Example 1

[0048] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0049] (1) Preparation of anti-adhesion polymers

[0050] ① Dissolve the organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -(CH2)3NH2, and this organosilicon molecule is referred to as NH2-PDMS-NH2) with a molecular weight of 27,000 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.05 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 10 minutes to expel air from the organosilicon solution. Simultaneously, stir the organosilicon solution using a magnetic stirrer.

[0051] Nitrogen was bubbled through N,N-dimethylformamide (DMF) for 10 minutes to expel air. The chain extender, 4,4′-methylenebis(phenylisocyanate) (MDI), was dissolved in DMF to obtain a 0.33 mmol / mL MDI solution. Nitrogen was bubbled through DMF for 10 minutes to expel air. Dopamine hydrochloride (DOPA) was then dissolved in DMF to obtain a 0.0167 mmol / L DOPA solution.

[0052] ② Under stirring, nitrogen protection and ice bath conditions, the MDI solution was added dropwise to a three-necked round-bottom flask containing the organosilicon molecular solution, and then the dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the reaction was carried out under stirring, nitrogen protection and ice bath conditions for 4 hours. The resulting reaction product was repeatedly washed with deionized water, then dried at 30°C using a vacuum rotary evaporator, and then dried in an oven to obtain an anti-adhesion polymer.

[0053] In this step, the amounts of the organosilicon molecule solution, the MDI solution, and the dopamine hydrochloride solution are controlled so that the molar ratio of the organosilicon molecule, the MDI, and the dopamine hydrochloride is 1:1:0.05.

[0054] The structural formula of the phenol-terminated organosilicon polymer prepared in this step is as follows:

[0055]

[0056] The NMR hydrogen spectrum of the anti-adhesion polymer prepared in this step is as follows Figure 1 As shown, Figure 1 Among them, d (δ3.18ppm), e (δ1.56ppm), f (δ0.6ppm), g (δ0.25ppm) and h (δ0.13ppm) belong to the organic silicon molecule NH2-PDMS-NH2, a (δ7.36ppm), b (δ7.03ppm) and c (δ3.8ppm) belong to the chain extender MDI, and i, j and k (δ6.72ppm) belong to DOPA, which indicates that DOPA, MDI and NH2-PDMS-NH2 participated in the reaction, and the integral ratio of MDI and DOPA was 25:1.

[0057] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 5 μg / mL.

[0058] (3) The glass substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the glass substrate, and then blown dry with N2 to obtain a clean and dry glass substrate.

[0059] The anti-adhesion polymer solution is sprayed onto a clean, dry glass substrate to completely cover the glass substrate. The anti-adhesion polymer is grafted onto the surface of the glass substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the glass substrate is rinsed with toluene to remove the anti-adhesion polymer, thereby forming an anti-adhesion nanocoating on the surface of the glass substrate.

[0060] The light transmittance test was conducted on the glass substrate used in this embodiment and the glass substrate with the anti-adhesion nano coating formed on the surface. The results are as follows: Figure 2 As shown by Figure 2 It can be seen that the transmittance curves of the glass substrate and the glass substrate with the anti-adhesion nanocoating formed on the surface are basically the same, that is, after the anti-adhesion nanocoating is modified, the transmittance is almost unchanged, indicating that the formed anti-adhesion nanocoating is very thin.

[0061] The ice shear force of the glass substrate used in this embodiment and the glass substrate with the anti-adhesion nano coating formed on the surface was measured by an ice shear force device. The results are as follows: Figure 3 As shown in Figures (a) and (b). Figure 3 It can be seen that the ice shear force of the glass substrate used in this embodiment is 57.7 N, and the ice shear force of the glass substrate with the anti-adhesion nanocoating formed on the surface is 5.6 N. Therefore, it can be seen that the surface of the glass substrate with the anti-adhesion nanocoating formed on the surface exhibits extremely low adhesion to ice, showing ice repellency.

[0062] Example 2

[0063] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0064] (1) Preparation of anti-adhesion polymers

[0065] ① Dissolve an organosilicon molecule (R1-Si(CH3)2-O-Si(CH3)2-R1) (where R1 is -(CH2)3COOH) with a molecular weight of 50,000 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.03 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and introduce nitrogen gas for 5 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0066] Nitrogen was bubbled through DMF for 5 minutes to expel air, and then the chain extender 4,4′-diisocyanate dicyclohexylmethane (HMDI) was dissolved in DMF to obtain an HMDI solution with an HMDI concentration of 1 mmol / mL. Nitrogen was bubbled through DMF for 5 minutes to expel air, and then dopamine hydrochloride was dissolved in DMF to obtain a 0.1 mmol / L dopamine hydrochloride solution.

[0067] ② The HMDI solution was added dropwise to a three-necked round-bottom flask containing an organosilicon molecule solution, and the dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the catalyst triethylamine was added and reacted under nitrogen protection and condensation reflux at 90°C for 6 hours. The resulting reaction product was repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 60°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0068] In this step, the amounts of the organosilicon molecule solution, HMDI solution and dopamine hydrochloride solution are controlled so that the molar ratio of the organosilicon molecules, HMDI and dopamine hydrochloride is 1:1:0.1; and the amount of triethylamine added is controlled so that the molar ratio of triethylamine to the organosilicon molecules is 1:1.5.

[0069] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 10 μg / mL.

[0070] (3) The aluminum substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the aluminum substrate, and then dried with N2 to obtain a clean and dry aluminum substrate.

[0071] The anti-adhesion polymer solution is sprayed onto a clean, dry aluminum substrate to completely cover the aluminum substrate. The anti-adhesion polymer is grafted onto the surface of the aluminum substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the aluminum substrate is removed by rinsing with acetone, thereby forming an anti-adhesion nanocoating on the surface of the aluminum substrate.

[0072] The aluminum substrate with the anti-adhesion nanocoating formed on its surface (coated aluminum substrate) was immersed in toluene for 24 hours, and the liquid repellency of the anti-adhesion nanocoating on its surface was tested. 5 μL of hexadecane was dropped onto the coated aluminum substrate after immersion, and the movement of the hexadecane droplet on the coated aluminum substrate was observed and recorded using a camera. The results are shown in FIG. Figure 4 As shown. Figure 4 It can be seen that the hexadecane droplets can slide smoothly on the coated aluminum substrate without any trace of droplet retention. This shows that the coating has a good anti-fouling effect on the one hand, and on the other hand, it shows that the coating has excellent stability.

[0073] Example 3

[0074] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0075] (1) Preparation of anti-adhesion polymers

[0076] ① Dissolve an organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -OH) with a molecular weight of 10,000 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.013 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 15 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0077] Nitrogen was bubbled through DMF for 15 minutes to expel air, and then the chain extender 4,4′-methylenebis(phenyl isocyanate) (MDI) and toluene diisocyanate (TDI) were dissolved in DMF to obtain an MDI-TDI mixture with an MDI concentration of 0.2 mmol / mL and a TDI concentration of 0.2 mmol / mL. Nitrogen was bubbled through DMF for 15 minutes to expel air, and then 6-hydroxydopamine was dissolved in DMF to obtain a 0.04 mmol / L 6-hydroxydopamine solution.

[0078] ② The MDI-TDI mixed solution was added dropwise to a three-necked round-bottom flask containing an organosilicon molecular solution, and the 6-hydroxydopamine solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, catalysts triethylamine and dibutyltin dilaurate were added, and the mixture was reacted under nitrogen protection and condensation reflux at 100°C for 8 hours. The resulting reaction product was repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 50°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0079] In this step, the amounts of the organosilicon molecule solution, the MDI-TDI mixed solution, and the 6-hydroxydopamine solution are controlled so that the molar ratio of the organosilicon molecules, MDI, TDI, and 6-hydroxydopamine is 2:1:1:0.2; and the amounts of triethylamine and dibutyltin dilaurate added are controlled so that the molar ratio of triethylamine, dibutyltin dilaurate, and the organosilicon molecules is 1:1:1.

[0080] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 30 μg / mL.

[0081] (3) The 304 stainless steel substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the 304 stainless steel substrate, and then dried with N2 to obtain a clean and dry 304 stainless steel substrate.

[0082] The anti-adhesion polymer solution is brush-coated on a clean, dry 304 stainless steel substrate to completely cover the 304 stainless steel substrate. The anti-adhesion polymer is grafted onto the surface of the 304 stainless steel substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the 304 stainless steel substrate is rinsed with acetone to remove the anti-adhesion polymer, thereby forming an anti-adhesion nanocoating on the surface of the 304 stainless steel substrate.

[0083] The 304 stainless steel substrate used in this embodiment and the 304 stainless steel substrate with an anti-adhesion nano-coating formed on its surface were tested by scanning electron microscopy. The results are as follows: Figure 5 As shown in Figures (a) and (b), Figure 5 It can be seen that after the surface of the 304 stainless steel substrate is modified with the anti-adhesion nano coating, no corrosion spots appear on the 304 stainless steel substrate, indicating that the anti-adhesion nano coating is suitable for modifying the surface of the metal substrate.

[0084] Example 4

[0085] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0086] (1) Preparation of anti-adhesion polymers

[0087] ① Dissolve an 800 g / mol organosilicon molecule, R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -CH(O)CH-), in dichloromethane to obtain a 0.1 mmol / mL organosilicon solution. Place the organosilicon solution in a three-necked round-bottom flask and introduce nitrogen gas for 5 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0088] Nitrogen was bubbled through DMF for 5 minutes to expel air, and then the chain extenders isophorone diisocyanate (IPDI) and 4,4′-methylenebis(phenylisocyanate) (MDI) were dissolved in DMF to obtain an IPDI-MDI mixture with an IPDI and MDI concentration of 0.167 mmol / mL each. Nitrogen was bubbled through DMF for 5 minutes to expel air, and then 3-hydroxy-4-methoxyphenethylamine was dissolved in DMF to obtain a 0.33 mmol / L 3-hydroxy-4-methoxyphenethylamine solution.

[0089] ② The IPDI-MDI mixture was added dropwise to a three-necked round-bottom flask containing an organosilicon molecule solution, and the 3-hydroxy-4-methoxyphenylethylamine solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the catalyst triethylamine was added and reacted under nitrogen protection and condensation reflux at 80°C for 8 hours. The resulting reaction product was repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 45°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0090] In this step, the amounts of the organosilicon molecule solution, the IPDI-MDI mixed solution, and the 3-hydroxy-4-methoxyphenethylamine solution are controlled so that the molar ratio of the organosilicon molecules, IPDI, MDI, and 3-hydroxy-4-methoxyphenethylamine is 1:0.5:0.5:0.6; and the amount of triethylamine added is controlled so that the molar ratio of triethylamine to the organosilicon molecules is 1:2.5.

[0091] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 10 μg / mL.

[0092] (3) The 316 stainless steel substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the 316 stainless steel substrate, and then dried with N2 to obtain a clean and dry 316 stainless steel substrate.

[0093] The anti-adhesion polymer solution is sprayed on a clean, dry 316 stainless steel substrate to completely cover the 316 stainless steel substrate. The anti-adhesion polymer is grafted onto the surface of the 316 stainless steel substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the 316 stainless steel substrate is removed by rinsing with acetone, thereby forming an anti-adhesion nanocoating on the surface of the 316 stainless steel substrate.

[0094] The wetting properties of the 316 stainless steel substrate and the 316 stainless steel substrate with an anti-adhesion nanocoating formed on its surface were characterized using a contact angle meter. The results were as follows: Figure 6 As shown in Figures (a) and (b), Figure 6It can be seen that the surface of the 316 stainless steel substrate is relatively hydrophilic, with a water droplet contact angle of 58.6°. After the surface of the 304 stainless steel substrate is modified with an anti-adhesion nanocoating, the water droplet contact angle is 104.7°, showing a relatively hydrophobic state.

[0095] Example 5

[0096] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0097] (1) The preparation method of the anti-adhesion polymer is the same as that of Example 4. The anti-adhesion polymer is dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 50 μg / mL.

[0098] (2) The copper substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the copper substrate, and then dried with N2 to obtain a clean and dry copper substrate.

[0099] A clean, dry copper substrate is immersed in an anti-adhesion polymer solution for 5 to 10 seconds. During the immersion process, the anti-adhesion polymer is grafted onto the surface of the copper substrate through actions including hydrogen bonding, complexation, and π-π bonding. After the immersion is completed, the copper substrate is removed. After the acetone is completely evaporated, toluene is used to rinse to remove the anti-adhesion polymer that is not stably bonded to the copper substrate, thereby forming an anti-adhesion nanocoating on the surface of the copper substrate.

[0100] The coating thickness on the silicon substrate and the copper substrate with the anti-adhesion coating formed on the surface thereof used in this embodiment was measured by ellipsometer. The results are as follows: Figure 7 As shown by Figure 7 It can be seen that the coating thickness on the copper substrate with the anti-adhesion coating formed on the surface is 21.65 nm.

[0101] Example 6

[0102] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0103] (1) Preparation of anti-adhesion polymers

[0104] ① Dissolve the organosilicon molecule poly[dimethylsiloxane-co-(3-aminopropyl)methylsiloxane] with a molecular weight of 209.39 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.1 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 15 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0105] Nitrogen was bubbled through DMF for 15 minutes to expel air, and then the chain extender 4,4′-methylenebis(phenylisocyanate) (MDI) was dissolved in DMF to obtain a 1 mmol / mL MDI solution. Nitrogen was bubbled through DMF for 15 minutes to expel air, and then dopamine hydrochloride was dissolved in DMF to obtain a 1 mmol / L dopamine hydrochloride solution.

[0106] ② Under stirring, nitrogen protection and ice bath conditions, the MDI solution was added dropwise to a three-necked round-bottom flask containing the organosilicon molecular solution, and then the dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the reaction was carried out under stirring, nitrogen protection and ice bath conditions for 5 hours. The resulting reaction product was repeatedly washed with deionized water, then dried at 50°C using a vacuum rotary evaporator, and then dried in an oven to obtain an anti-adhesion polymer.

[0107] In this step, the amounts of the organosilicon molecule solution, the MDI solution, and the dopamine hydrochloride solution are controlled so that the molar ratio of the organosilicon molecule, the MDI, and the dopamine hydrochloride is 1:5:5.

[0108] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 50 μg / mL.

[0109] (3) The silicon substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the silicon substrate, and then dried with N2 to obtain a clean and dry silicon substrate.

[0110] The anti-adhesion polymer solution is brush-coated on a clean, dry silicon substrate to completely cover the silicon substrate. The anti-adhesion polymer is grafted onto the surface of the silicon substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the silicon substrate is rinsed with toluene to remove the anti-adhesion polymer, thereby forming an anti-adhesion nanocoating on the surface of the silicon substrate.

[0111] The silicon substrate used in this embodiment and the silicon substrate with an anti-adhesion nano-coating formed on its surface were tested by atomic force microscope. The results are as follows: Figure 8 As shown in Figures (a) and (b), Figure 8 It can be seen that the surface roughness Ra of the silicon substrate is 0.52nm, and the surface roughness Ra of the silicon substrate modified with the anti-adhesion nano coating is 0.63nm. The difference in surface roughness between the two is not obvious, and both are smooth surfaces. The silicon substrate with the anti-adhesion nano coating was tested by Fourier transform infrared spectroscopy, and the results are as follows Figure 9 As shown, Figure 9 The coating is shown to have Si-O-Si, Si-CH3, Si-(CH3)2 and CH bonds.

[0112] Example 7

[0113] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0114] (1) Preparation of anti-adhesion polymers

[0115] ① Dissolve the organosilicon molecule (3-aminopropyl)triethoxysilane (i.e., H2N(CH2)3Si(OC2H5)3) with a molecular weight of 191.34 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.2 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 10 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0116] Nitrogen was bubbled through DMF for 10 minutes to expel air, and then the chain extender isophorone diisocyanate (IPDI) was dissolved in DMF to obtain a 1 mmol / mL IPDI solution. Nitrogen was bubbled through DMF for 10 minutes to expel air, and then dopamine hydrochloride was dissolved in DMF to obtain a 0.5 mmol / L dopamine hydrochloride solution.

[0117] ② Under stirring, nitrogen protection and ice bath conditions, the IPDI solution was added dropwise to a three-necked round-bottom flask containing the organosilicon molecule solution, and then the dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the reaction was carried out under stirring, nitrogen protection and ice bath conditions for 6 hours. The resulting reaction product was repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 35°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0118] In this step, the amounts of the organosilicon molecule solution, the IPDI solution, and the dopamine hydrochloride solution are controlled so that the molar ratio of the organosilicon molecule, IPDI, and dopamine hydrochloride is 1:1:0.5.

[0119] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 10 μg / mL.

[0120] (2) The tubular polyurethane substrate was ultrasonically cleaned using deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the polyurethane substrate, and then dried using N2 to obtain a clean and dry polyurethane substrate.

[0121] A clean, dry polyurethane substrate is immersed in an anti-adhesion polymer solution for 5 to 10 seconds. During the immersion process, the anti-adhesion polymer is grafted onto the surface of the polyurethane substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the immersion is complete, the polyurethane substrate is removed. After the acetone has completely evaporated, the anti-adhesion polymer that is not stably bonded to the polyurethane substrate is rinsed with acetone to remove it, thereby forming an anti-adhesion nanocoating on the surface of the polyurethane substrate.

[0122] The polyurethane substrate used in this example and the polyurethane substrate with an anti-adhesion nanocoating formed on the surface (coated polyurethane substrate) were tested for liquid repellency. 5 μL of hexadecane was dropped onto the polyurethane substrate and the coated polyurethane substrate, respectively. The movement of the hexadecane droplets on the surfaces of the two was observed and recorded using a camera. The results are shown in FIG. Figure 10 As shown. Figure 10 As shown in Figure (a), the surface of the polyurethane substrate is lipophilic, and the hexadecane droplets leave a large number of marks on the tube wall. Figure 10 As shown in Figure (b), the hexadecane droplet can slide smoothly on the coated polyurethane substrate, and the shape of the droplet remains basically unchanged, showing an oleophobic state.

[0123] Example 8

[0124] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0125] (1) Preparation of anti-adhesion polymers

[0126] ① Dissolve the organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -(CH2)3COOH) with a molecular weight of 50,000 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.03 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 5 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0127] Nitrogen gas was bubbled into DMF for 5 min to expel air therein, and then dopamine hydrochloride was dissolved in DMF to obtain a 0.06 mmol / L dopamine hydrochloride solution.

[0128] ② The dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was complete, the catalyst triethylamine was added and the mixture was reacted for 6 hours under nitrogen protection and condensation reflux at 90°C. The resulting reaction product was repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 60°C, and then dried in an oven to obtain the final product, a phenol-terminated organosilicon polymer.

[0129] In this step, the amounts of the organosilicon molecule solution and the dopamine hydrochloride solution are controlled so that the molar ratio of the organosilicon molecules to the dopamine hydrochloride is 1:2; and the amount of triethylamine added is controlled so that the molar ratio of triethylamine to the organosilicon molecules is 1:1.5.

[0130] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 30 μg / mL.

[0131] (3) The gold substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the gold substrate, and then blown dry with N2 to obtain a clean and dry gold substrate.

[0132] The anti-adhesion polymer solution is brush-coated on a clean, dry gold substrate to completely cover the gold substrate. The anti-adhesion polymer is grafted onto the surface of the gold substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the gold substrate is removed by rinsing with acetone, thereby forming an anti-adhesion nanocoating on the surface of the gold substrate.

[0133] The stability of the coating on the gold substrate with anti-adhesion nanocoating formed on the surface was tested by quartz crystal microbalance. Figure 11 As shown by Figure 11 It can be seen that in the flowing sodium dodecyl sulfate solution, the frequency of the gold substrate hardly changes, indicating that the anti-adhesion polymer is firmly bonded to the surface of the gold substrate and exhibits excellent stability.

[0134] Example 9

[0135] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0136] (1) Preparation of anti-adhesion polymers

[0137] ① Dissolve the organosilicon molecule R2-Si(CH3)2-O-Si-(CH3)3 (where R2 is -(CH2)3OCH2CH(O)CH) with a molecular weight of 5000 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.1 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 10 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0138] Nitrogen gas was bubbled into DMF for 10 min to expel air therefrom, and then 6-hydroxydopamine was dissolved in DMF to obtain a 6-hydroxydopamine solution with a concentration of 0.67 mmol / mL.

[0139] ② Add the 6-hydroxydopamine solution dropwise to a three-necked round-bottom flask containing the organosilicon molecule solution. After the addition is complete, add the catalyst triethylamine and react for 8 hours under nitrogen protection and condensation reflux at 80°C. The resulting reaction product is repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 45°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0140] In this step, the amounts of the organosilicon molecule solution and the 6-hydroxydopamine solution are controlled so that the molar ratio of the organosilicon molecules to the 6-hydroxydopamine is 1:1; and the amount of triethylamine added is controlled so that the molar ratio of triethylamine to the organosilicon molecules is 1:1.5.

[0141] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 100 μg / mL.

[0142] (3) The glass substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the glass substrate, and then blown dry with N2 to obtain a clean and dry glass substrate.

[0143] The anti-adhesion polymer solution is sprayed onto a clean, dry glass substrate to completely cover the glass substrate. The anti-adhesion polymer is grafted onto the surface of the glass substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the glass substrate is removed by rinsing with acetone, thereby forming an anti-adhesion nanocoating on the surface of the glass substrate.

[0144] Example 10

[0145] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0146] (1) Preparation of anti-adhesion polymers

[0147] ① Dissolve the organosilicon molecule R2-Si(CH3)2-O-Si-(CH3)3 (where R2 is -(CH2)3COOH) with a molecular weight of 4500 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.1 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 20 minutes to expel air from the solution. Simultaneously, stir the solution with a magnetic stirrer.

[0148] Nitrogen gas was bubbled into DMF for 20 min to expel air therefrom, and then 3-hydroxy-4-methoxyphenethylamine was dissolved in DMF to obtain a 0.1 mmol / mL 3-hydroxy-4-methoxyphenethylamine solution.

[0149] ② Add the 3-hydroxy-4-methoxyphenethylamine solution dropwise to a three-necked round-bottom flask containing the organosilicon molecule solution. After the addition is complete, add the catalyst 4-N,N-dimethylpyridine and react under nitrogen protection and condensation reflux at 60°C for 6 hours. The resulting reaction product is repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 45°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0150] In this step, the amounts of the organosilicon molecule solution and the 3-hydroxy-4-methoxyphenethylamine solution are controlled so that the molar ratio of the organosilicon molecules to the 3-hydroxy-4-methoxyphenethylamine is 1:1; and the amount of 4-N,N-dimethylpyridine added is controlled so that the molar ratio of 4-N,N-dimethylpyridine to the organosilicon molecules is 1:3.

[0151] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 40 μg / mL.

[0152] (3) The glass substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the glass substrate, and then blown dry with N2 to obtain a clean and dry glass substrate.

[0153] The anti-adhesion polymer solution is sprayed onto a clean, dry glass substrate to completely cover the glass substrate. The anti-adhesion polymer is grafted onto the surface of the glass substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the glass substrate is removed by rinsing with acetone, thereby forming an anti-adhesion nanocoating on the surface of the glass substrate.

[0154] Example 11

[0155] In this embodiment, a method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology is provided, and the steps are as follows:

[0156] (1) Preparation of anti-adhesion polymers

[0157] ① Dissolve the organosilicon molecule R2-Si(CH3)2-O-Si-(CH3)3 (where R2 is -(CH2)3O(CH2)2OH) with a molecular weight of 5000 g / mol in dichloromethane to obtain an organosilicon solution with a concentration of 0.03 mmol / mL. Place the organosilicon solution in a three-necked round-bottom flask and bubble nitrogen through it for 20 minutes to expel air from the organosilicon molecules. Simultaneously, stir the organosilicon solution using a magnetic stirrer.

[0158] Nitrogen gas was bubbled into DMF for 10 min to expel air therefrom, and then dopamine hydrochloride was dissolved in DMF to obtain a 0.33 mmol / L dopamine hydrochloride solution.

[0159] ② Add the dopamine hydrochloride solution dropwise to a three-necked round-bottom flask containing the organosilicon molecule solution. After the addition is complete, add the catalyst triethylamine and react for 8 hours under nitrogen protection and condensation reflux at 80°C. The resulting reaction product is repeatedly washed with deionized water, then dried using a vacuum rotary evaporator at 40°C, and then dried in an oven to obtain an anti-adhesion polymer.

[0160] In this step, the amounts of the organosilicon molecule solution and the dopamine hydrochloride solution are controlled so that the molar ratio of the organosilicon molecules to the dopamine hydrochloride is 1:1, and the amount of triethylamine added is controlled so that the molar ratio of triethylamine to the organosilicon molecules is 1:1.

[0161] (2) The anti-adhesion polymer was dissolved in acetone to obtain an anti-adhesion polymer solution with a concentration of 30 μg / mL.

[0162] (3) The glass substrate was ultrasonically cleaned with deionized water, ethanol, and acetone in sequence to remove organic pollutants and solid particles on the surface of the glass substrate, and then blown dry with N2 to obtain a clean and dry glass substrate.

[0163] The anti-adhesion polymer solution is sprayed onto a clean, dry glass substrate to completely cover the glass substrate. The anti-adhesion polymer is grafted onto the surface of the glass substrate through interactions including hydrogen bonding, complexation, and π-π bonding. After the acetone is completely evaporated, the anti-adhesion polymer that is not stably bonded to the glass substrate is removed by rinsing with acetone, thereby forming an anti-adhesion nanocoating on the surface of the glass substrate.

Claims

1. A method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology, characterized in that: The following steps are involved: (1) dissolving an anti-adhesion polymer in an organic solvent to obtain an anti-adhesion polymer solution; the preparation method of the anti-adhesion polymer is as follows: Under stirring and protective gas protection, the adhesive solution is added dropwise to the organosilicon molecule solution, the molar ratio of the organosilicon molecule to the adhesive is controlled to be 1:(0.05-5), the mixture is fully reacted at 0-100°C, the unreacted raw materials and solvent are removed, and the mixture is dried to obtain an anti-adhesion polymer. The adhesive comprises any one of dopamine hydrochloride, 6-hydroxydopamine, and 3-hydroxy-4-methoxyphenylethylamine. The organosilicon molecule is R1-Si(CH3)2-O-Si(CH3)2-R1, R2-Si(CH3)2-O-Si-(CH3)3, H2N(CH2)3Si(OC2H5)3, or poly[dimethylsiloxane-co-(3-aminopropyl)methylsiloxane], R1 is -(CH2)3NH2, -OH, or -(CH2)3COOH, and R2 is -(CH2)3O(CH2)2OH or -(CH2)3COOH. (2) The anti-adhesion polymer solution is coated on a clean, dry substrate. The anti-adhesion polymer is grafted onto the surface of the substrate through actions including hydrogen bonding, complexation and π-π bonding. After the organic solvent is completely evaporated, the anti-adhesion polymer that is not stably bonded to the substrate is washed away, thereby forming an anti-adhesion nanocoating with a thickness of no more than 1000 nm on the surface of the substrate.

2. The method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology according to claim 1, characterized in that: In step (1), when preparing the anti-adhesion polymer, a chain extender solution is also added dropwise to the organosilicon molecule solution, and the molar ratio of the organosilicon molecule to the chain extender is controlled to be 1:(1-5).

3. The method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology according to claim 1, characterized in that: In step (1), when preparing the anti-adhesion polymer, a catalyst is added to the organic silicon molecule solution, wherein the catalyst includes at least one of triethylamine, 4-N,N-dimethylpyridine, trimethylamine and dibutyltin dilaurate.

4. The method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology according to claim 1, characterized in that: In step (1), when preparing the anti-adhesion polymer, the reaction time is controlled at 0-100°C for 4-8 hours.

5. The method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology according to any one of claims 1 to 4, characterized in that: In the anti-adhesion polymer solution of step (1), the concentration of the anti-adhesion polymer is 5-100 μg / mL.

6. The method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology according to any one of claims 1 to 4, characterized in that: The coating method in step (2) includes spraying, brushing or dipping.

7. The method for preparing an anti-adhesion nanocoating based on molecular brush grafting technology according to any one of claims 1 to 4, characterized in that: The substrate is an organic material substrate, an inorganic material substrate or a metal substrate.

Citation Information

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