Super-slippery antibacterial coating material and preparation method and application thereof

Abstract

The application provides a super-smooth antibacterial coating material and a preparation method and application thereof, relates to the technical field of medical implant materials, and comprises the following steps: S1, pretreating silver nanoparticles and polyethylene glycol respectively; S2, placing the pretreated silver nanoparticles in a first solvent to obtain a silver nanoparticle solution, and then adding a silane reagent and a catalyst to generate a silanization reaction and obtain activated silver nanoparticles; S3, placing a hydrophilic monomer in a second solvent, and then adding the activated silver nanoparticles to obtain a silver nanoparticle-modified hydrophilic monomer; S4, placing the pretreated polyethylene glycol and an activating agent in a third solvent to perform an activation treatment and obtain an activated polyethylene glycol solution; and S5, placing the silver nanoparticle-modified hydrophilic monomer in the activated polyethylene glycol solution to obtain the super-smooth antibacterial coating material. When the super-smooth antibacterial coating material is coated on the surface of a silica gel urinary catheter, the lubricity and antibacterial property of the urinary catheter are significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical implant materials, in particular to a super-slippery antibacterial coating material and a preparation method and application thereof. BACKGROUND

[0002] Latex urinary catheters are widely used in clinical practice due to their elasticity and comfort, but there are still some problems to be solved. These problems mainly involve the antibacterial properties, biocompatibility and lubricity of latex urinary catheters.

[0003] Firstly, although silicone urinary catheters are widely used in the medical field, their antibacterial properties have certain limitations. Although silicone materials have good tissue compatibility and durability, making them one of the preferred materials for long-term indwelling urinary catheters, their surfaces are prone to become a breeding ground for bacteria, resulting in relatively poor antibacterial properties. Bacteria can accumulate in large numbers on the surface of silicone urinary catheters, forming biofilms and secreting polysaccharide matrix, fibrin and lipoprotein, etc. fibrous cross-linked substances, further weakening the effect of antibiotics. This not only increases the risk of urinary tract infection, but also can cause a series of complications, such as urethral mucosa damage, urethral stricture and stone formation, etc.

[0004] Secondly, the lubricity of existing latex urinary catheters is relatively poor, which can cause pain and discomfort to patients during insertion and removal of the catheter, and even can cause urethral damage. The insertion and removal of the catheter requires a certain amount of force, and a catheter with poor lubricity will increase the friction between the catheter and the urethral wall, causing pain and discomfort to the patient. For some patients with urethral stricture or sensitivity, this pain and discomfort can be more severe. In addition, poor lubricity also increases the friction between the catheter and the urethral wall, increasing the risk of urinary tract infection. The urethra is a sensitive mucosal tissue, and long-term friction can cause damage to the urethral mucosa, providing an opportunity for bacterial invasion and proliferation.

[0005] Therefore, the antibacterial properties, biocompatibility and lubricity of existing latex urinary catheters need to be solved. SUMMARY

[0006] The purpose of the present application is to provide a super-slippery antibacterial coating material and a preparation method and application thereof. The present application realizes the efficient connection of chemical bonds between silver nanoparticles and polyethylene glycol (PEG) and specific hydrophilic monomers by activating the surface of silver nanoparticles, thereby designing a new coating material with super-slippery and antibacterial properties. When the super-slippery antibacterial coating material is coated on the surface of a silicone urinary catheter, the lubricity and antibacterial properties of the catheter are significantly improved.

[0007] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0008] The application provides a preparation method of super-smooth antibacterial coating material, comprising the following steps:

[0009] S1: pretreating silver nanoparticles and polyethylene glycol respectively;

[0010] S2: placing the pretreated silver nanoparticles in a first solvent, stirring, obtaining a silver nanoparticle solution, adding a silane reagent and a catalyst, continuing to stir, and performing a silanization reaction to obtain activated silver nanoparticles;

[0011] S3: placing a hydrophilic monomer in a second solvent, stirring, adding the activated silver nanoparticles, and continuing to stir to obtain a silver nanoparticle-modified hydrophilic monomer;

[0012] S4: placing the pretreated polyethylene glycol and an activating agent in a third solvent, performing an activation treatment, and obtaining an activated polyethylene glycol solution;

[0013] S5: placing the silver nanoparticle-modified hydrophilic monomer in the activated polyethylene glycol solution, stirring, and obtaining the super-smooth antibacterial coating material.

[0014] Further, in the above technical solution, the pretreatment of the silver nanoparticles in step S1 comprises:

[0015] dispersing the silver nanoparticles in ultrapure water, performing ultrasonic treatment and centrifugal treatment, discarding the supernatant, and repeating the cleaning for 1-3 times to obtain the pretreated silver nanoparticles;

[0016] wherein the centrifugal treatment is performed at a speed of 12000-15000 rpm for 10-30 min;

[0017] and / or, the particle size of the silver nanoparticles is 10-100 nm;

[0018] and / or, in step S1, the pretreatment of the polyethylene glycol comprises:

[0019] placing the polyethylene glycol in a drying agent for drying, filtering after the drying is completed, and obtaining the pretreated polyethylene glycol;

[0020] wherein the drying agent is anhydrous magnesium sulfate or anhydrous sodium sulfate;

[0021] the addition amount of the drying agent is 2-5 times the mass of the polyethylene glycol;

[0022] the drying time is 10-20 h;

[0023] and / or, the number average molecular weight of the polyethylene glycol is 300-400.

[0024] Further, in the above technical solution, the silanization reaction in step S2 comprises:

[0025] pH value is 4-6, reaction temperature is 30-40℃, reaction time is 12-24h;

[0026] And / or, the silane reagent includes one or more of 3-aminopropyltriethoxysilane, gamma-aminopropyltriethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, N-beta-(aminoethyl)-gamma-aminopropylmethyldimethoxysilane or gamma-aminopropylmethyldiethoxysilane;

[0027] And / or, the first solvent includes one or more of anhydrous ethanol, acetone, acetone or dimethyl sulfoxide;

[0028] And / or, the catalyst includes one or more of acetic acid, citric acid, formic acid or tartaric acid;

[0029] And / or, step S2 further includes: after the silanization reaction, centrifuging the siloxane reaction mixture, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times and then centrifuging, discarding the supernatant, and obtaining the activated silver nanoparticles;

[0030] Wherein, the centrifugal speed is 12000-15000rpm, and the centrifugal time is 10-30min;

[0031] And / or, the mass ratio of the pretreated silver nanoparticles, the silane reagent, the catalyst and the first solvent is 1:(5-10):(0.01-0.1):(10-15).

[0032] Further, in the above technical solution, in step S3, the reaction temperature is 30-50℃, and the reaction time is 1-6h;

[0033] And / or, the hydrophilic monomer includes one or more of acrylic acid, methacrylic acid, methyl acrylate, acrylic anhydride, ethyl acrylate;

[0034] And / or, the second solvent includes one or more of anhydrous ethanol, acetone or dimethyl sulfoxide;

[0035] And / or, step S3 further includes: centrifuging the mixed solution after the reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times and then centrifuging, and discarding the supernatant;

[0036] Wherein, the centrifugal speed is 12000-15000rpm, and the centrifugal time is 10-30min;

[0037] And / or, the mass ratio of the activated silver nanoparticles, the hydrophilic monomer and the second solvent is 1:(5-10):(5-15).

[0038] Further, on the basis of the above technical solutions, in step S4, the activation treatment comprises:

[0039] The activation temperature is 20-30 DEG C, the activation time is 1-5h, and the protective atmosphere comprises nitrogen or argon;

[0040] And / or, the first activation agent comprises N-hydroxysuccinimide or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide;

[0041] And / or, the third solvent comprises one or more of anhydrous ethanol, acetone or dimethyl sulfoxide;

[0042] And / or, the mass ratio of the pretreated polyethylene glycol, the first activation agent and the third solvent is 1:(1-6):(5-15).

[0043] Further, on the basis of the above technical solutions, in step S5, the reaction temperature is 20-30 DEG C, and the reaction time is 6-10h;

[0044] And / or, in step S5, after the esterification reaction, the following steps are further included:

[0045] The mixed solution after the reaction is centrifuged, washed and dried to obtain the super-smooth antibacterial coating material;

[0046] Wherein, the centrifugal speed is 12000-15000rpm, and the centrifugal time is 10-30min;

[0047] The washing is 1-3 times using ultrapure water;

[0048] The drying temperature is 40-60 DEG C, and the drying time is 10-24h.

[0049] The application also provides a super-smooth antibacterial coating material prepared by the preparation method of the super-smooth antibacterial coating material.

[0050] The application also provides a super-smooth antibacterial coating material prepared by the preparation method of the super-smooth antibacterial coating material or the application of the super-smooth antibacterial coating material, which can be used for preparing a super-smooth antibacterial silica gel urinary catheter.

[0051] Further, on the basis of the above technical solutions, the preparation of the super-smooth antibacterial silica gel urinary catheter comprises the following steps:

[0052] (1) The super-smooth antibacterial coating material is placed in a fourth solvent and ball milled to obtain a super-smooth antibacterial coating slurry;

[0053] (2) The silica gel urinary catheter is immersed in a second activation agent for activation;

[0054] (3) the activated silica gel catheter is cleaned, immersed in the super-smooth antibacterial coating slurry for 60-70s, slowly taken out, placed in a sealed container with humidity of 80-100%, dried at a temperature of 50-70 DEG C for 25-35min, repeated for 2-4 times, and then the super-smooth antibacterial silica gel catheter is obtained by placing the coated catheter in a sealed container with humidity of 80-100% at 45-55 DEG C for 15-24h.

[0055] Further, on the basis of the above technical solutions, the fourth solvent includes one or more of ethanol, acetone and methanol.

[0056] And / or, the mass ratio of the fourth solvent to the super-smooth antibacterial coating material is (1-1.5):1.

[0057] And / or, the rotation speed of the ball mill is 100-200rpm, and the ball milling time is 10-30min.

[0058] And / or, the second activator is a silane coupling agent solution, and the silane coupling agent includes one or more of methyltrimethoxysilane, ethyltrimethoxysilane or aminopropyltriethoxysilane.

[0059] And / or, the activation temperature is 20-30 DEG C, and the activation time is 1-3min.

[0060] The super-smooth antibacterial coating material provided by the application and the preparation method and application thereof have the following beneficial effects:

[0061] 1. The application realizes efficient connection of chemical bonds between the silver nanoparticles and polyethylene glycol (PEG) and specific hydrophilic monomers by activating the surface of the silver nanoparticles, thereby designing a new coating material with super-smooth and antibacterial properties.

[0062] 2、The application can make silver nanoparticles connect with hydrophilic monomers such as acrylic acid and its derivatives through the introduction of amino groups on the surface of silver nanoparticles, and can form a firm chemical bond with the ester group in the special activated polyethylene glycol molecule. The antibacterial properties of silver nanoparticles and the excellent lubricating and hydrophilic properties of acrylic acid and its derivatives and activated polyethylene glycol are connected through the chemical bond in the amino group or the hydrophilic monomer such as acrylic acid and its derivatives, and a new composite material with efficient antibacterial and excellent lubricating properties is constructed. DETAILED DESCRIPTION

[0063] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. It should be apparent to those skilled in the art that the embodiments are only used to help understand the present application, and should not be regarded as a specific limitation on the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should fall within the scope of protection of the present application. The process parameters not specified in the following embodiments are usually according to the conventional conditions.

[0064] The endpoints of the ranges and any values disclosed in the present application are not limited to the precise values stated. The ranges or values should be interpreted as being approximate. For numeric values, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to form one or more new numeric ranges, which should be considered as being specifically disclosed in the present application.

[0065] According to the first aspect of the present application, a preparation method of super-smooth antibacterial coating material is provided, comprising the following steps:

[0066] S1: pretreating silver nanoparticles and polyethylene glycol respectively;

[0067] S2: placing the pretreated silver nanoparticles in a first solvent, stirring to obtain a silver nanoparticle solution, then adding a silane reagent and a catalyst, and continuing to stir to occur a silanization reaction to obtain activated silver nanoparticles;

[0068] S3: placing a hydrophilic monomer in a second solvent, stirring, then adding the activated silver nanoparticles, and continuing to stir to obtain a silver nanoparticle modified hydrophilic monomer;

[0069] S4: placing the pretreated polyethylene glycol and an activating agent in a third solvent, and performing an activation treatment to obtain an activated polyethylene glycol solution;

[0070] S5: Put the silver nanoparticle modified hydrophilic monomer into the activated polyethylene glycol solution and stir to obtain the super-smooth antibacterial coating material.

[0071] Specifically, the present application realizes the efficient connection between the silver nanoparticles and polyethylene glycol (PEG) and specific hydrophilic monomers through the activation treatment of the surface of the silver nanoparticles, thereby designing a new coating material with super-smooth and antibacterial properties. In the activation process, the surface of the silver nanoparticles is endowed with high reactivity, so that they can chemically react with PEG and hydrophilic monomers to form stable and dense chemical bond connection. When the super-smooth antibacterial coating material is coated on the surface of the silica catheter, its excellent lubricity and antibacterial property are fully exerted. The improvement of lubricity makes the catheterization process smoother, reducing the pain and discomfort of the patient; and the enhancement of antibacterial property effectively protects the health of the patient's urinary system and reduces the complications caused by the use of catheter.

[0072] As an optional embodiment of the present application, in step S1, the pretreatment of the silver nanoparticles includes:

[0073] The silver nanoparticles are dispersed in ultrapure water and subjected to ultrasonic treatment to obtain a uniform dispersion solution, and then the silver nanoparticles are separated from the solution by centrifugal treatment, the supernatant is discarded, and the washing is repeated 1-3 times to ensure the removal of impurities in the silver nanoparticles;

[0074] The centrifugal speed is 12000-15000 rpm and the centrifugal time is 10-30 min; during the centrifugal process, the larger centrifugal force can precipitate the silver nanoparticles to the bottom of the centrifugal tube faster, however, too high centrifugal force may cause aggregation or damage of the silver nanoparticles;

[0075] And / or, the particle size of the silver nanoparticles is 10-100 nm;

[0076] And / or, in step S1, the pretreatment of the polyethylene glycol includes:

[0077] The polyethylene glycol is placed in a drying agent for drying to remove the water therein and improve its purity and stability;

[0078] The drying agent is anhydrous magnesium sulfate or anhydrous sodium sulfate; the addition amount of the drying agent is 2-5 times the mass of the polyethylene glycol; the drying time is 10-20 h; after drying, the pretreated polyethylene glycol is obtained by filtration;

[0079] And / or, the number average molecular weight of the polyethylene glycol is 300-400, such as PEG320, PEG340, PEG360, PEG380, etc.

[0080] Specifically, polyethylene glycol molecular chain is rich in hydrophilic ethylene glycol units, which endow PEG with excellent water retention and lubricating properties. When polyethylene glycol is skillfully applied to the surface of the silicone urinary catheter, it can form a continuous, uniform and durable lubricating coating. This lubricating coating not only effectively reduces the friction coefficient between the silicone urinary catheter and the urethral tissue, making the catheterization process smoother and unobstructed, but also greatly reduces the risk of urethral injury and infection caused by friction. The lubricating effect of polyethylene glycol is derived from its strong water absorption capacity, which can rapidly absorb water and swell when in contact with urine or body fluids, forming a smooth protective film that ensures the smooth insertion and removal of the urinary catheter and guarantees the comfort of the patient. In addition, the polyethylene glycol coating has good biocompatibility and stability, and is less likely to cause allergic reactions or rejection, ensuring the safety of use. It not only significantly improves the lubricity of the silicone urinary catheter, but also prolongs its service life to some extent, reducing the inconvenience and pain to patients caused by frequent replacement of the urinary catheter. The number average molecular weight of polyethylene glycol is limited to 300-400 in the present invention because they are usually liquid at room temperature, easy to apply and distribute, have good water solubility, low toxicity, low irritation, and good lubricity. Higher molecular weight PEG, such as PEG 1000, PEG 1500, PEG 2000, etc., although also has good lubricity, but they are usually solid or semi-solid at room temperature, need to be heated to melt before use, in addition, high molecular weight PEG liquid may cause irritation to the skin or mucosa.

[0081] As an optional embodiment of the present application, in step S2, the silanization reaction comprises:

[0082] The pH value is 4-6 (such as 4, 5, 6), and the pH value will affect the charge state of the silver nanoparticle surface and the activation effect of the silane reagent on the silver nanoparticle; the reaction temperature is 30-40℃, and the reaction time is 12-24h;

[0083] And / or, the silane reagent comprises one or more of 3-aminopropyl triethoxysilane, γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane or γ-aminopropyl methyl diethoxysilane;

[0084] Specifically, the present application uses the silane reagent as described above, which is an aminated silane coupling agent. By introducing amino groups to the surface of silver nanoparticles through the aminated silane coupling agent, not only can the dispersibility and stability of silver nanoparticles be improved to prevent them from agglomerating or precipitating in solution, but also rich active sites are provided for silver nanoparticles, improving the biocompatibility and catalytic activity of silver nanoparticles.

[0085] And / or, the first solvent comprises one or more of anhydrous ethanol, acetone or dimethyl sulfoxide;

[0086] And / or, the catalyst comprises one or more of acetic acid, citric acid, formic acid or tartaric acid;

[0087] And / or, step S2 further comprises, after the silanization reaction: centrifuging the siloxane reaction mixture, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times and then centrifuging, discarding the supernatant, and obtaining the activated silver nanoparticles;

[0088] Wherein, the centrifugal speed is 12000-15000 rpm, and the centrifugal time is 10-30 min;

[0089] And / or, the mass ratio of the pretreated silver nanoparticles, silane reagent, catalyst and first solvent is 1:(5-10):(0.01-0.1):(10-15), such as 1:5:0.05:12, 1:6:0.07:13, 1:7:0.08:14, 1:8:0.07:11, 1:9:0.09:12, etc.

[0090] As an optional embodiment of the present application, in step S3, the amino groups in the activated silver nanoparticles and the carboxyl groups, ester groups or anhydride groups in the hydrophilic monomers form new chemical bonds, so that the silver nanoparticles are modified on the hydrophilic monomers. The reaction temperature of this process is 30-50℃, and the reaction time is 1-6h;

[0091] And / or, the hydrophilic monomer comprises one or more of acrylic acid, methacrylic acid, methyl acrylate, acrylic anhydride, ethyl acrylate;

[0092] Specifically, acrylic acid and its derivatives have active chemical properties and strong corrosiveness. In the production process of the silica catheter, after acrylic acid and its derivatives are introduced onto the surface of the silica catheter, a hydrophilic lubricating coating with excellent lubricating performance is formed. This hydrophilic lubricating coating can significantly reduce the friction and damage of the silica catheter with the body tissue during insertion and removal, thereby reducing the risk of infection. When the coating comes into contact with aqueous liquid, the high molecular compounds in it can quickly absorb water to form a hydrophilic gel layer. This gel layer not only has good lubricating effect, but also has certain stability and is not easy to fall off. Compared with traditional lubricants, the hydrophilic lubricating coating prepared from acrylic acid and its derivatives has higher safety and effectiveness. They are not easily absorbed by the human body and are not easily adhered to the urethra, thereby avoiding the occurrence of adverse reactions such as urethral stenosis. At the same time, this coating can significantly improve the resistance and tear strength of the silica catheter, prolonging its service life.

[0093] And / or, the second solvent comprises one or more of anhydrous ethanol, acetone or dimethyl sulfoxide;

[0094] And / or, in step S3, further comprising: centrifuging the mixed solution after reaction, discarding the supernatant, and washing the precipitate with ultrapure water for 1-3 times and then centrifuging, discarding the supernatant;

[0095] Wherein, the centrifugal speed is 12000-15000 rpm, and the centrifugal time is 10-30 min;

[0096] And / or, the mass ratio of the activated silver nanoparticles, the hydrophilic monomer and the second solvent is 1:(5-10):(5-15).

[0097] As an optional embodiment of the present application, in step S4, after the polyethylene glycol is activated, the terminal hydroxyl group is converted into a reactive ester group, and the activation treatment comprises:

[0098] The activation temperature is 20-30℃, the activation time is 1-5h, and the protective atmosphere comprises nitrogen or argon;

[0099] And / or, the first activator comprises N-hydroxysuccinimide or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide;

[0100] And / or, the third solvent comprises one or more of anhydrous ethanol, acetone or dimethyl sulfoxide;

[0101] And / or, the mass ratio of the pretreated polyethylene glycol, the first activator and the third solvent is 1:(1-6):(5-15).

[0102] As an optional embodiment of the present application, in step S5, the activated polyethylene glycol reacts with the amino group on the surface of the silver nanoparticles to form an amide bond (-CONH-), thereby connecting the PEG to the surface of the silver nanoparticles. The activated polyethylene glycol can also react with the carboxyl group, anhydride group, etc. in acrylic acid and its derivatives, realizing the close connection between polyethylene glycol, silver nanoparticles and hydrophilic monomers. The reaction temperature of this process is 20-30℃, and the reaction time is 6-10h;

[0103] And / or, in step S5, further comprising the following steps:

[0104] Centrifuging, washing and drying the mixed solution after reaction to obtain a super-smooth antibacterial coating material;

[0105] Wherein, the centrifugal speed is 12000-15000 rpm, and the centrifugal time is 10-30 min;

[0106] The washing is washing 1-3 times with ultrapure water;

[0107] The temperature for drying is 40-60°C, and the drying time is 10-24h.

[0108] According to a second aspect of the present application, there is provided a super- slippery antibacterial coating material prepared by the method for preparing a super- slippery antibacterial coating material as described above.

[0109] According to a third aspect of the present application, there is provided a use of the super- slippery antibacterial coating material as described above, for preparing a super- slippery antibacterial silicone catheter.

[0110] As an optional embodiment of the present application, the method for preparing a super- slippery antibacterial silicone catheter comprises the following steps:

[0111] (1) placing the super-slippery antibacterial coating material in a fourth solvent, and performing ball milling to obtain a super-slippery antibacterial coating slurry;

[0112] (2) immersing the silicone catheter in a second activating agent for activation;

[0113] (3) immersing the activated silicone catheter in the super-slippery antibacterial coating slurry for 60-70s, slowly taking it out, placing it in a sealed container with a humidity of 80-100%, and drying at a temperature of 50-70°C for 25-35min, repeating 2-4 times, and then taking out the silicone catheter coated with the super-slippery antibacterial coating, placing it in a sealed container with a humidity of 80-100%, and placing it at a temperature of 45-55°C for 15-24h to obtain a super-slippery antibacterial silicone catheter.

[0114] Specifically, the activation of the silane coupling agent with pure silica gel is to utilize the hydrolytic functional groups in the silane coupling agent to chemically react with the silicon hydroxyl groups on the surface of the silica gel, forming siloxane bonds and introducing organic functional groups on the surface of the silica gel. This activation process aims to improve the bonding strength of the silica gel, improve the compatibility with organic materials, enhance the durability, and adjust the surface properties, so that the silica gel has better performance and stability in specific applications. In this way, a uniform organic film is formed on the surface of the activated silica gel, thereby improving the bonding ability of the silica gel with other materials and its own physical and chemical properties.

[0115] As an optional embodiment of the present application, the fourth solvent comprises one or more of ethanol, acetone, and methanol;

[0116] And / or, the mass ratio of the fourth solvent to the super-slippery antibacterial coating material is (1-1.5): 1;

[0117] And / or, the rotation speed of the ball milling is 100-200rpm, and the ball milling time is 10-30min;

[0118] And / or, the second activator is a silane coupling agent solution, the silane coupling agent including one or more of methyltrimethoxysilane, ethyltrimethoxysilane or aminopropyltriethoxysilane;

[0119] And / or, the activation temperature is 20-30℃, and the activation time is 1-3min.

[0120] The application will be further described in detail below in combination with specific examples and comparative examples.

[0121] The silver nanoparticles, polyethylene glycol and the like used in the application are all commercially available products.

[0122] Example 1

[0123] Preparation of super-slippery antibacterial coating material:

[0124] S1: Pretreatment of silver nanoparticles (particle size 100nm) and polyethylene glycol (PEG350) respectively;

[0125] The pretreatment of silver nanoparticles includes:

[0126] The silver nanoparticles are dispersed in ultrapure water, ultrasonic treatment and centrifugal treatment are performed, after the supernatant is discarded, the pretreated silver nanoparticles are obtained by repeating the cleaning for 1-3 times;

[0127] The rotation speed is 12000rpm, and the centrifugal time is 30min.

[0128] The pretreatment of polyethylene glycol includes:

[0129] The polyethylene glycol is dried in anhydrous magnesium sulfate for 15h, and the pretreated polyethylene glycol is obtained after filtration;

[0130] The addition amount of anhydrous magnesium sulfate is 3 times of the mass of the polyethylene glycol.

[0131] S2: The pretreated silver nanoparticles are placed in acetone, stirring is performed, the pH value is adjusted to 5, 3-aminopropyltriethoxysilane and acetic acid are added, stirring is continued, silanization reaction occurs at a temperature of 40℃ for 24h, the siloxane reaction mixture is centrifuged, the supernatant is discarded, the precipitate is cleaned with ultrapure water for 1-3 times and then centrifuged, the supernatant is discarded, and the activated silver nanoparticles are obtained.

[0132] The mass ratio of the pretreated silver nanoparticles, 3-aminopropyltriethoxysilane, acetic acid and acetone is 1:8:0.05:13.

[0133] The rotation speed of centrifugation is 12000rpm, and the centrifugal time is 30min.

[0134] S3: Put the acrylic acid into acetone, stir, then add the activated silver nanoparticles, continue to stir, react at a temperature of 30 DEG C for 6h, centrifuge the mixed solution after reaction, discard the supernatant, wash the precipitate with ultrapure water 1-3 times and then centrifuge, discard the supernatant, and obtain the silver nanoparticle modified hydrophilic monomer;

[0135] The mass ratio of the activated silver nanoparticles, the acrylic acid and the acetone is 1:8:10;

[0136] The centrifugal speed is 12000 rpm, and the centrifugal time is 30 min.

[0137] S4: Put the pretreated polyethylene glycol and N-hydroxysuccinimide into acetone, maintain an argon atmosphere, activate at a temperature of 25 DEG C for 2h, and obtain an activated polyethylene glycol solution;

[0138] The mass ratio of the pretreated polyethylene glycol, the N-hydroxysuccinimide and the acetone is 1:4:6.

[0139] S5: Put the silver nanoparticle modified hydrophilic monomer into the activated polyethylene glycol solution, stir at a temperature of 20 DEG C for 8h, then centrifuge, wash and dry to obtain the super-smooth antibacterial coating material;

[0140] The centrifugal speed is 12000 rpm, and the centrifugal time is 30 min.

[0141] The washing is washing 1-3 times with ultrapure water;

[0142] The drying temperature is 50 DEG C, and the drying time is 24h.

[0143] Preparation of the super-smooth antibacterial silica gel urinary catheter:

[0144] (1) Put the super-smooth antibacterial coating material into acetone, ball mill to obtain a super-smooth antibacterial coating slurry;

[0145] The mass ratio of the acetone and the super-smooth antibacterial coating material is 1:1;

[0146] The ball milling speed is 150 rpm, and the ball milling time is 30 min.

[0147] (2) Dip the silica gel urinary catheter into an ethyl trimethoxysilane solution for activation;

[0148] The activation temperature is 25 DEG C, and the activation time is 2 min.

[0149] (3) The activated silicone catheter is cleaned and immersed in the super-slippery antibacterial coating slurry for 65 s, slowly taken out and placed in a sealed container with a humidity of 100% and dried at 60°C for 30 min. The process is repeated 2-4 times. The super-slippery antibacterial silicone catheter is obtained by placing the coated catheter in a sealed container with a humidity of 100% and placing it at 50°C for 24 h.

[0150] Example 2

[0151] Preparation of super-slippery antibacterial coating material:

[0152] S1: Pretreatment of silver nanoparticles (particle size 50 nm) and polyethylene glycol (PEG300);

[0153] The pretreatment of silver nanoparticles includes:

[0154] The silver nanoparticles are dispersed in ultrapure water, ultrasonic treatment and centrifugal treatment are performed, and after discarding the supernatant, the pretreated silver nanoparticles are obtained by repeating the cleaning process 1-3 times;

[0155] The centrifugal speed is 12000 rpm and the centrifugal time is 30 min.

[0156] The pretreatment of polyethylene glycol includes:

[0157] The polyethylene glycol is dried in anhydrous magnesium sulfate for 20 h, and after drying, the pretreated polyethylene glycol is obtained by filtering;

[0158] The amount of anhydrous magnesium sulfate added is 3 times the mass of the polyethylene glycol.

[0159] S2: The pretreated silver nanoparticles are placed in anhydrous ethanol and stirred, the pH value is adjusted to 6, γ-aminopropyl triethoxysilane and citric acid are added, and the stirring is continued. The silanization reaction occurs at a temperature of 35°C for 20 h. The siloxane reaction mixture is centrifuged, the supernatant is discarded, and the precipitate is washed with ultrapure water 1-3 times and then centrifuged. The supernatant is discarded, and the activated silver nanoparticles are obtained.

[0160] The mass ratio of pretreated silver nanoparticles, γ-aminopropyl triethoxysilane, citric acid and anhydrous ethanol is 1:6:0.02:10.

[0161] The centrifugal speed is 12000 rpm and the centrifugal time is 30 min.

[0162] S3: The methyl acrylate is placed in anhydrous ethanol and stirred, and then the activated silver nanoparticles are added and stirring is continued, and the reaction is carried out at a temperature of 40 DEG C for 4 h, and then the mixed solution after the reaction is centrifuged, the supernatant is discarded, and the precipitate is washed with ultrapure water for 1-3 times and then centrifuged, the supernatant is discarded, and the silver nanoparticle modified hydrophilic monomer is obtained;

[0163] The mass ratio of the activated silver nanoparticles, the methyl acrylate and the anhydrous ethanol is 1:5:8.

[0164] The centrifugal speed is 12000 rpm, and the centrifugal time is 30 min.

[0165] S4: The pretreated polyethylene glycol and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide are placed in anhydrous ethanol, and an activation treatment is carried out under a nitrogen atmosphere at a temperature of 25 DEG C for 3 h, and the activated polyethylene glycol solution is obtained.

[0166] The mass ratio of the pretreated polyethylene glycol, the 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and the anhydrous ethanol is 1:3:5.

[0167] S5: The silver nanoparticle modified hydrophilic monomer is placed in the activated polyethylene glycol solution and stirred at a temperature of 30 DEG C for 8 h, and then the super-smooth antibacterial coating material is obtained through centrifugation, washing and drying.

[0168] The centrifugal speed is 12000 rpm, and the centrifugal time is 30 min.

[0169] The washing is carried out by using ultrapure water for 1-3 times.

[0170] The drying temperature is 40 DEG C, and the drying time is 24 h.

[0171] Preparation of the super-smooth antibacterial silica gel urinary catheter:

[0172] (1) The super-smooth antibacterial coating material is placed in ethanol and ball milled to obtain a super-smooth antibacterial coating slurry.

[0173] The mass ratio of the ethanol and the super-smooth antibacterial coating material is 1.5:1.

[0174] The ball milling speed is 150 rpm, and the ball milling time is 20 min.

[0175] (2) The silica gel urinary catheter is immersed in a methyltrimethoxysilane solution for activation.

[0176] The activation temperature is 25 DEG C, and the activation time is 2 min.

[0177] (3) The activated silica gel urinary catheter is cleaned and immersed in the super-smooth antibacterial coating slurry for 65 s, slowly taken out and placed in a sealed container with a humidity of 100% and dried at a temperature of 60°C for 30 min. The process is repeated 2-4 times, and then the super-smooth antibacterial coating is coated on the urinary catheter, which is placed in a sealed container with a humidity of 100% and placed at 50°C for 24 h to obtain a super-smooth antibacterial silica gel urinary catheter.

[0178] Example 3

[0179] Preparation of super-smooth antibacterial coating material:

[0180] S1: The silver nanoparticles with a particle size of 80 nm and polyethylene glycol (PEG400) are pretreated respectively.

[0181] The pretreatment of silver nanoparticles includes:

[0182] The silver nanoparticles are dispersed in ultrapure water, ultrasonic treatment and centrifugal treatment are performed, and after the supernatant is discarded, the pretreated silver nanoparticles are obtained by repeating the cleaning process 1-3 times;

[0183] The centrifugal speed is 12000 rpm, and the centrifugal time is 30 min.

[0184] The pretreatment of polyethylene glycol includes:

[0185] The polyethylene glycol is dried in anhydrous sodium sulfate for 15 h, and after drying, the pretreated polyethylene glycol is obtained by filtering.

[0186] The amount of anhydrous sodium sulfate added is 3 times the mass of the polyethylene glycol.

[0187] S2: The pretreated silver nanoparticles are placed in dimethyl sulfoxide, stirred, and the pH value is adjusted to 4. N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane and tartaric acid are added, and the stirring is continued. The silanization reaction occurs at a temperature of 40°C for 14 h. The siloxane reaction mixture is centrifuged, the supernatant is discarded, and the precipitate is washed with ultrapure water 1-3 times and then centrifuged. The supernatant is discarded, and the activated silver nanoparticles are obtained.

[0188] The mass ratio of the pretreated silver nanoparticles, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, tartaric acid and dimethyl sulfoxide is 1:7:0.05:12.

[0189] The centrifugal speed is 12000 rpm, and the centrifugal time is 30 min.

[0190] S3: Put acrylic anhydride in dimethyl sulfoxide, stir, then add activated silver nanoparticles, continue to stir, react at a temperature of 50°C for 3h, centrifuge the mixed solution after reaction, discard the supernatant, wash the precipitate with ultrapure water 1-3 times and then centrifuge, discard the supernatant, and obtain silver nanoparticle modified hydrophilic monomers;

[0191] The mass ratio of the activated silver nanoparticles, acrylic anhydride and dimethyl sulfoxide is 1:10:15;

[0192] The centrifugal speed is 12000rpm, and the centrifugal time is 30min.

[0193] S4: Put the pretreated polyethylene glycol and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide in dimethyl sulfoxide, maintain a nitrogen atmosphere, activate at a temperature of 25°C for 5h, and obtain an activated polyethylene glycol solution;

[0194] The mass ratio of the pretreated polyethylene glycol, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and dimethyl sulfoxide is 1:6:10.

[0195] S5: Put the silver nanoparticle modified hydrophilic monomers in the activated polyethylene glycol solution, stir at a temperature of 25°C for 8h, then centrifuge, wash and dry to obtain a super-slippery antibacterial coating material;

[0196] The centrifugal speed is 12000rpm, and the centrifugal time is 30min.

[0197] The washing is washing 1-3 times with ultrapure water;

[0198] The drying temperature is 60°C, and the drying time is 15h.

[0199] Preparation of a super-slippery antibacterial silica gel urinary catheter:

[0200] (1) Put the super-slippery antibacterial coating material in ethanol, ball mill to obtain a super-slippery antibacterial coating slurry;

[0201] The mass ratio of ethanol to super-slippery antibacterial coating material is 1.5:1;

[0202] The ball milling speed is 150rpm, and the ball milling time is 20min.

[0203] (2) Soak the silica gel urinary catheter in an aminopropyl triethoxysilane solution for activation;

[0204] The activation temperature is 25°C, and the activation time is 2min.

[0205] (3) The activated silicone catheter is cleaned and immersed in the super-smooth antibacterial coating slurry for 65 s, slowly taken out and placed in a sealed container with a humidity of 100% and dried at a temperature of 60°C for 30 min. The process is repeated 2-4 times. The super-smooth antibacterial silicone catheter coated with the super-smooth antibacterial coating is taken out and placed in a sealed container with a humidity of 100% and placed at 50°C for 24 h to obtain the super-smooth antibacterial silicone catheter.

[0206] Comparative Example 1

[0207] The difference between the present comparative example and Example 1 is that the number average molecular weight of the polyethylene glycol used is 2000 and the activation temperature in step S4 is 65°C. The remaining operation steps and technical parameters are the same as those in Example 1.

[0208] Comparative Example 2

[0209] The difference between the present comparative example and Example 1 is that the vinyl triethoxysilane is used as the silane reagent in step S2 to silanize the silver nanoparticles. The remaining operation steps and technical parameters are the same as those in Example 1.

[0210] Performance Test

[0211] The super-smooth antibacterial silicone catheters obtained in Examples 1-3 and Comparative Examples 1-2 are tested for antibacterial performance on E. coli, Enterococcus faecalis and Candida albicans on the surface of the silicone catheter according to the standard ISO22196-2011, and the sliding friction force of the super-smooth antibacterial silicone catheter surface is tested according to YY / T1536-2017.

[0212] Effect Data

[0213] Table 1: Comparison of antibacterial performance and sliding friction force of the super-smooth antibacterial silicone catheters prepared in Examples 1-3 and Comparative Examples 1-2

[0214]

[0215] As can be seen from Table 1, compared with Example 1, the number average molecular weight of the polyethylene glycol used in Comparative Example 1 is 2000 and the activation temperature is higher, which leads to faster volatilization of the activating agent N-hydroxysuccinimide, thereby affecting the activation of the polyethylene glycol and ultimately affecting the lubricity of the super-smooth antibacterial coating.

[0216] As can be seen from Table 1, compared with Example 1, the vinyl triethoxysilane is used as the silane reagent in step S2 of Comparative Example 2, which does not contain an amino group, affecting the connection of the silver nanoparticles with the hydrophilic monomer and the polyethylene glycol, and ultimately affecting the antibacterial property and lubricity of the super-smooth antibacterial coating.

[0217] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions recorded in the above embodiments can be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a super-slippery antibacterial coating material, characterized in that, Includes the following steps: S1: Pretreatment of silver nanoparticles and polyethylene glycol respectively; Among them, the number average molecular weight of polyethylene glycol is 300-400; S2: The pretreated silver nanoparticles are placed in the first solvent and stirred to obtain a silver nanoparticle solution. Then, silane reagent and catalyst are added and stirred continuously to induce a silanization reaction and obtain activated silver nanoparticles. The silane reagent includes one or more of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane or γ-aminopropylmethyldiethoxysilane; S3: Place the hydrophilic monomer in the second solvent, stir, then add activated silver nanoparticles, and continue stirring to obtain a hydrophilic monomer modified with silver nanoparticles. S4: Place the pretreated polyethylene glycol and the first activator in the third solvent for activation treatment to obtain an activated polyethylene glycol solution; S5: The hydrophilic monomer modified with silver nanoparticles is placed in an activated polyethylene glycol solution and stirred to obtain an ultra-slippery antibacterial coating material.

2. The method for preparing the super-slippery antibacterial coating material according to claim 1, characterized in that, In step S1, the pretreatment of silver nanoparticles includes: Silver nanoparticles were dispersed in ultrapure water, subjected to ultrasonic treatment and centrifugation, and the supernatant was discarded. The washing process was repeated 1-3 times to obtain pretreated silver nanoparticles. The centrifugation speed was 12,000-15,000 rpm, and the centrifugation time was 10-30 min. And / or, the particle size of the silver nanoparticles is 10-100 nm; And / or, in step S1, the pretreatment of polyethylene glycol includes: Polyethylene glycol was placed in a desiccant and dried. After drying, it was filtered to obtain pretreated polyethylene glycol. The desiccant is anhydrous magnesium sulfate or anhydrous sodium sulfate; The amount of desiccant added is 2-5 times the mass of polyethylene glycol; The drying time is 10-20 hours.

3. The method for preparing the super-slippery antibacterial coating material according to claim 1, characterized in that, In step S2, the silanization reaction includes: The pH value is 4-6, the reaction temperature is 30-40℃, and the reaction time is 12-24h; And / or, the first solvent includes one or more of anhydrous ethanol, acetone, or dimethyl sulfoxide; And / or, the catalyst comprises one or more of acetic acid, citric acid, formic acid or tartaric acid; And / or, step S2 after the silanization reaction further includes: centrifuging the mixture after the silanization reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times and then centrifuging again, discarding the supernatant, to obtain activated silver nanoparticles. The centrifugation speed is 12000-15000 rpm, and the centrifugation time is 10-30 min; And / or, the mass ratio of the pretreated silver nanoparticles, silane reagent, catalyst and first solvent is 1:(5-10):(0.01-0.1):(10-15).

4. The method for preparing the super-slippery antibacterial coating material according to claim 1, characterized in that, In step S3, the reaction temperature is 30-50℃ and the reaction time is 1-6h; And / or, the hydrophilic monomer includes one or more of acrylic acid, methacrylic acid, methyl acrylate, acrylic anhydride, and ethyl acrylate; And / or, the second solvent includes one or more of anhydrous ethanol, acetone, or dimethyl sulfoxide; And / or, step S3 further includes: centrifuging the mixed solution after reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times and then centrifuging again, discarding the supernatant; The centrifugation speed is 12000-15000 rpm, and the centrifugation time is 10-30 min; And / or, the mass ratio of activated silver nanoparticles, hydrophilic monomers and second solvent is 1:(5-10):(5-15).

5. The method for preparing the super-slippery antibacterial coating material according to claim 1, characterized in that, In step S4, the activation process includes: The activation temperature is 20-30℃; the activation time is 1-5 hours; the protective atmosphere includes nitrogen or argon. And / or, the first activator includes N-hydroxysuccinimide or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide; And / or, the third solvent includes one or more of anhydrous ethanol, acetone, or dimethyl sulfoxide; And / or, the mass ratio of pretreated polyethylene glycol, first activator and third solvent is 1:(1-6):(5-15).

6. The method for preparing the super-slippery antibacterial coating material according to claim 1, characterized in that, In step S5, the reaction temperature is 20-30℃ and the reaction time is 6-10h; And / or, in step S5, the esterification reaction is followed by the following steps: The reacted mixture was centrifuged, washed, and dried to obtain an ultra-slippery antibacterial coating material. The centrifugation speed was 12,000-15,000 rpm, and the centrifugation time was 10-30 min. The cleaning process involves rinsing with ultrapure water 1-3 times. The drying temperature is 40-60℃, and the drying time is 10-24 hours.

7. An ultra-slippery antibacterial coating material prepared by the method of preparing ultra-slippery antibacterial coating material according to any one of claims 1-6.

8. The application of a super-slippery antibacterial coating material prepared by the method of any one of claims 1-6, or the super-slippery antibacterial coating material as described in claim 7, characterized in that, It can be used to prepare super-slippery antibacterial silicone urinary catheters.

9. The application according to claim 8, characterized in that, The preparation of an ultra-slippery antibacterial silicone urinary catheter includes the following steps: (1) The super-slippery antibacterial coating material is placed in the fourth solvent and ball-milled to obtain a super-slippery antibacterial coating slurry; (2) The silicone catheter is activated by immersing it in the second activator; (3) After cleaning the activated silicone catheter, immerse it in the super-slippery antibacterial coating slurry for 60-70 seconds, slowly remove it and place it in a sealed container with a humidity of 80-100%, dry it at 50-70℃ for 25-35 minutes, repeat 2-4 times, then remove the catheter coated with the super-slippery antibacterial coating and place it in a sealed container with a humidity of 80-100%, place it at 45-55℃ for 15-24 hours to obtain the super-slippery antibacterial silicone catheter.

10. The application according to claim 9, characterized in that, The fourth solvent includes one or more of ethanol, acetone, and methanol; And / or, the mass ratio of the fourth solvent to the super-slippery antibacterial coating material is (1-1.5):1; And / or, the ball milling speed is 100-200 rpm, and the ball milling time is 10-30 min; And / or, the second activator is a silane coupling agent solution, wherein the silane coupling agent includes one or more of methyltrimethoxysilane, ethyltrimethoxysilane or aminopropyltriethoxysilane; And / or, the activation temperature is 20-30℃, and the activation time is 1-3 min.

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