Super-lubricity antibacterial coating material as well as preparation method and application thereof

Abstract

The invention provides a super-lubricity antibacterial coating material and a preparation method and application thereof, and relates to the technical field of medical implant materials, and the preparation method comprises the following steps: S1, respectively pretreating silver nanoparticles and polyethylene glycol; s2, the pretreated silver nanoparticles are placed in a first solvent, a silver nanoparticle solution is obtained, then a silane reagent and a catalyst are added, a silanization reaction is carried out, and activated silver nanoparticles are obtained; 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, putting the pretreated polyethylene glycol and an activating agent into a third solvent, and carrying out activating treatment to obtain an activated polyethylene glycol solution; and S5, putting the hydrophilic monomer modified by the silver nanoparticles into the activated polyethylene glycol solution to obtain the super-lubricity antibacterial coating material. When the surface of a silica gel catheter is coated with the super-lubricity antibacterial coating material, the lubricity and antibacterial property of the catheter are remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of medical implant materials, and in particular to an ultra-slip antibacterial coating material and a preparation method and application thereof. Background Art

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

[0003] First, although silicone catheters are widely used in the medical field, their antibacterial properties have certain limitations. Although silicone material has good tissue compatibility and durability, making it one of the preferred materials for long-term indwelling catheters, its surface easily becomes a breeding ground for bacteria, resulting in relatively poor antibacterial properties. Bacteria can gather in large numbers on the surface of silicone catheters to form biofilms and secrete cellulose-like cross-links such as polysaccharide matrix, fibrin and lipoprotein, further weakening the effect of antibiotics. This not only increases the risk of urinary tract infection, but may also cause a series of complications, such as urethral mucosal damage, urethral stenosis and stone formation.

[0004] Secondly, the lubricity of existing latex catheters is relatively poor, which may cause pain and discomfort to patients when inserting and removing the catheter, and may even 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 stenosis or sensitivity, this pain and discomfort may be more severe. In addition, poor lubricity will also increase 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 may cause damage to the urethral mucosa, providing an opportunity for bacterial invasion and reproduction.

[0005] Therefore, the antibacterial, biocompatibility and lubricity problems of existing latex catheters need to be solved urgently. Summary of the invention

[0006] The purpose of the present invention is to provide an ultra-slip antibacterial coating material and a preparation method and application thereof. The present invention activates the surface of silver nanoparticles to achieve efficient chemical bond connection between these nanoparticles and polyethylene glycol (PEG) and specific hydrophilic monomers, thereby designing a new coating material with both ultra-slip and antibacterial properties. When the ultra-slip antibacterial coating material is coated on the surface of a silicone catheter, the lubricity and antibacterial properties of the catheter are significantly improved.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] The present invention provides a method for preparing an ultra-slip antibacterial coating material, comprising the following steps:

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

[0010] 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 cause a silanization reaction to obtain activated silver nanoparticles;

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

[0012] S4: placing the pretreated polyethylene glycol and the activator in a third solvent for activation treatment to obtain an activated polyethylene glycol solution;

[0013] S5: placing the hydrophilic monomer modified with silver nanoparticles in an activated polyethylene glycol solution and stirring the solution to obtain an ultra-slippery antibacterial coating material.

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

[0015] Dispersing silver nanoparticles in ultrapure water, performing ultrasonic treatment and centrifugation, discarding the supernatant, and repeatedly washing 1-3 times to obtain pretreated silver nanoparticles;

[0016] The centrifugal speed is 12000-15000rpm, and the centrifugal time is 10-30min;

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

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

[0019] The polyethylene glycol is placed in a desiccant for drying, and after drying, it is filtered to obtain the pretreated polyethylene glycol;

[0020] Wherein, the desiccant is anhydrous magnesium sulfate or anhydrous sodium sulfate;

[0021] The amount of desiccant added is 2-5 times the mass of polyethylene glycol;

[0022] Drying time is 10-20h;

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

[0024] Further, based on the above technical solution, in step S2, the silanization reaction includes:

[0025] The pH value is 4-6, the reaction temperature is 30-40°C, and the reaction time is 12-24h;

[0026] and / or, the silane reagent comprises one or more of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane or γ-aminopropylmethyldiethoxysilane;

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

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

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

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

[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, on the basis of the above technical solution, in step S3, the reaction temperature is 30-50°C, and the reaction time is 1-6h;

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

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

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

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

[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 solution, in step S4, the activation treatment includes:

[0039] The activation temperature is 20-30°C; the activation time is 1-5h; the protective atmosphere includes nitrogen or argon;

[0040] and / or, the first activator 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 activator and the third solvent is 1:(1-6):(5-15).

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

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

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

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

[0047] Cleaning is done by using ultrapure water 1-3 times;

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

[0049] The present invention also provides an ultra-slip antibacterial coating material prepared by the method for preparing the ultra-slip antibacterial coating material as described above.

[0050] The present invention also provides a super-slip antibacterial coating material prepared by the preparation method of the super-slip antibacterial coating material as described above or an application of the super-slip antibacterial coating material as described above, which can be used to prepare a super-slip antibacterial silicone catheter.

[0051] Further, on the basis of the above technical solution, the preparation of the super-smooth antibacterial silicone catheter includes the following steps:

[0052] (1) placing the super-slippery antibacterial coating material in a fourth solvent and performing ball milling to obtain a super-slippery antibacterial coating slurry;

[0053] (2) immersing the silicone urinary catheter in a second activating agent for activation;

[0054] (3) After cleaning the activated silicone catheter, immerse it in the super-slip antibacterial coating slurry for 60-70 seconds, slowly take it out and place it in a sealed container with a humidity of 80-100%, dry it at 50-70°C for 25-35 minutes, repeat 2-4 times, take out the catheter coated with the super-slip antibacterial coating, place it in a sealed container with a humidity of 80-100%, and place it at 45-55°C for 15-24 hours to obtain a super-slip antibacterial silicone catheter.

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

[0056] and / or, the mass ratio of the fourth solvent to the ultra-slippery antibacterial coating material is (1-1.5):1;

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

[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°C and the activation time is 1-3 min.

[0060] The present invention provides an ultra-slip antibacterial coating material and a preparation method and application thereof, and the beneficial effects are as follows:

[0061] 1. The present invention activates the surface of silver nanoparticles to achieve efficient chemical bond connection between these nanoparticles and polyethylene glycol (PEG) and specific hydrophilic monomers, thereby designing a new coating material with both super-slip and antibacterial properties; during the activation process, the surface of the silver nanoparticles is endowed with high reactivity, allowing them to chemically react with PEG and hydrophilic monomers to form stable and dense chemical bond connections. When this super-slip antibacterial coating material is coated on the surface of a silicone catheter, its excellent lubricity and antibacterial properties are fully exerted. The improvement in lubricity makes the catheterization process smoother and reduces the pain and discomfort of the patient; while the enhancement of antibacterial properties effectively protects the health of the patient's urinary system and reduces complications caused by the use of a catheter.

[0062] 2. The present invention introduces amino groups on the surface of silver nanoparticles, so that the silver nanoparticles can establish a stable chemical bond connection with hydrophilic monomers such as acrylic acid and its derivatives, and realize a strong chemical bond with the ester group in the specially activated polyethylene glycol molecule. The chemical bonds in hydrophilic monomers such as amino groups or acrylic acid and its derivatives are used as bridges to cleverly connect the antibacterial properties of silver nanoparticles with the excellent lubrication and hydrophilic properties of acrylic acid and its derivatives and activated polyethylene glycol, thus constructing a new composite material with both high-efficiency antibacterial and excellent lubrication properties. DETAILED DESCRIPTION

[0063] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. The process parameters of the following embodiments that do not specify specific conditions are usually based on conventional conditions.

[0064] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0065] According to a first aspect of the present invention, there is provided a method for preparing an ultra-slip antibacterial coating material, comprising the following steps:

[0066] S1: pretreatment of 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 cause a silanization reaction to obtain activated silver nanoparticles;

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

[0069] S4: placing the pretreated polyethylene glycol and the activator in a third solvent for activation treatment to obtain an activated polyethylene glycol solution;

[0070] S5: placing the hydrophilic monomer modified with silver nanoparticles in an activated polyethylene glycol solution and stirring the solution to obtain an ultra-slippery antibacterial coating material.

[0071] Specifically, the present invention activates the surface of silver nanoparticles to achieve efficient chemical bond connection between these nanoparticles and polyethylene glycol (PEG) and specific hydrophilic monomers, thereby designing a new coating material with both super-slip and antibacterial properties; during the activation process, the surface of the silver nanoparticles is endowed with high reactivity, allowing them to chemically react with PEG and hydrophilic monomers to form stable and dense chemical bond connections. When this super-slip antibacterial coating material is coated on the surface of a silicone catheter, its excellent lubricity and antibacterial properties are fully exerted. The improvement in lubricity makes the catheterization process smoother and reduces the pain and discomfort of the patient; while the enhancement of antibacterial properties effectively protects the health of the patient's urinary system and reduces complications caused by the use of a catheter.

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

[0073] Dispersing silver nanoparticles in ultrapure water, performing ultrasonic treatment to obtain a uniform dispersion, separating the silver nanoparticles from the solution by centrifugation, discarding the supernatant, and repeating washing 1-3 times to ensure that impurities in the silver nanoparticles are removed;

[0074] The centrifugal treatment speed is 12000-15000rpm, and the centrifugal time is 10-30min. During the centrifugal process, a larger centrifugal force can precipitate the silver nanoparticles to the bottom of the centrifuge tube more quickly. However, too high a centrifugal force may cause the silver nanoparticles to aggregate or be damaged.

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

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

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

[0078] The desiccant is anhydrous magnesium sulfate or anhydrous sodium sulfate; the amount of the desiccant added is 2-5 times the mass of the polyethylene glycol; the drying time is 10-20 hours; after drying, filtering is performed to obtain the pretreated polyethylene glycol;

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

[0080] Specifically, the polyethylene glycol molecular chain is rich in hydrophilic ethylene glycol units, which give PEG excellent water retention and lubrication properties. When polyethylene glycol is cleverly applied to the surface of a silicone catheter, it can form a continuous, uniform and durable lubricating coating. This lubricating coating can not only effectively reduce the friction coefficient between the silicone catheter and the urethral tissue, making the catheterization process smoother and more unobstructed, but also greatly reduce the risk of urethral damage and infection caused by friction. The lubricating effect of polyethylene glycol comes from its strong water absorption capacity. It can quickly absorb water and swell when in contact with urine or body fluids to form a smooth protective film. This protective film ensures the smooth insertion and removal of the catheter and the comfort of the patient. In addition, the polyethylene glycol coating also has good biocompatibility and stability, is not easy to cause allergic reactions or rejection reactions, and ensures the safety of use. It can not only significantly improve the lubricity of silicone catheters, but also extend their service life to a certain extent, reducing the inconvenience and pain caused to patients by frequent replacement of catheters. The present invention limits the number average molecular weight of polyethylene glycol to 300-400 because they are usually liquid at room temperature, easy to apply and distribute, and have good water solubility, low toxicity, low irritation and good lubricity. Although PEG with higher molecular weight, such as PEG 1000, PEG 1500, PEG 2000, etc., also have good lubricity, they are usually solid or semi-solid at room temperature and need to be heated and melted before use. In addition, high molecular weight PEG liquid may irritate the skin or mucous membrane.

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

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

[0083] and / or, the silane reagent comprises one or more of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane or γ-aminopropylmethyldiethoxysilane;

[0084] Specifically, the present invention adopts the silane reagents as described above, which are all aminated silane coupling agents. The amino groups are introduced into the surface of silver nanoparticles through the aminated silane coupling agents, which can not only improve the dispersibility and stability of the silver nanoparticles and prevent them from agglomerating or precipitating in the solution, but also provide abundant active sites for the silver nanoparticles, thereby improving the biocompatibility and catalytic activity of the 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 mixture after the siloxane reaction, discarding the supernatant, washing the precipitate with ultrapure water for 1-3 times and then centrifuging again, discarding the supernatant, and obtaining activated silver nanoparticles;

[0088] 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, the silane reagent, the catalyst and the 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 invention, in step S3, the amino groups in the silver nanoparticles and the carboxyl groups, ester groups or anhydride groups in the hydrophilic monomers are activated to form new chemical bonds, so that the silver nanoparticles are modified on the hydrophilic monomers. The reaction temperature of this process is 30-50° C. and the reaction time is 1-6 hours.

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

[0092] Specifically, acrylic acid and its derivatives have active chemical properties and strong corrosiveness. During the production process of silicone catheters, acrylic acid and its derivatives are introduced into the surface of silicone catheters to form a hydrophilic lubricating coating with excellent lubricating properties. This hydrophilic lubricating coating can significantly reduce the friction and damage between the silicone catheter and the body tissue during insertion and removal, thereby reducing the risk of infection. When the coating comes into contact with an aqueous liquid, the polymer compounds therein will quickly absorb water to form a hydrophilic gel layer, which not only has a good lubricating effect, but also can maintain a 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 easy to adhere to the urethra, thereby avoiding the occurrence of adverse reactions such as urethral stenosis. At the same time, this coating can also significantly improve the tolerance and tear strength of silicone catheters and extend their service life.

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

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

[0095] 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 invention, in step S4, after the polyethylene glycol is activated, its terminal hydroxyl group is converted into an active ester group, and the activation treatment includes:

[0098] The activation temperature is 20-30°C; the activation time is 1-5h; the protective atmosphere includes 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 invention, in step S5, the activated polyethylene glycol undergoes an amidation reaction with the amino groups 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 may also react with the carboxyl group, anhydride group, etc. in acrylic acid and its derivatives, thereby achieving a tight connection between the polyethylene glycol, the silver nanoparticles, and the hydrophilic monomer. The reaction temperature of this process is 20-30° C., and the reaction time is 6-10 hours.

[0103] And / or, step S5 also includes the following steps:

[0104] The mixed solution after the reaction is centrifuged, washed, and dried to obtain an ultra-slippery antibacterial coating material;

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

[0106] Cleaning is done by using ultrapure water 1-3 times;

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

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

[0109] According to a third aspect of the present invention, there is provided an application of the super-slippery antibacterial coating material as described above, which can be used to prepare a super-slippery antibacterial silicone catheter.

[0110] As an optional embodiment of the present invention, the preparation of an ultra-smooth 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 urinary catheter in a second activating agent for activation;

[0113] (3) Immerse the activated silicone catheter in the super-slip antibacterial coating slurry for 60-70 seconds, slowly take it out and place it in a sealed container with a humidity of 80-100%, dry it at 50-70°C for 25-35 minutes, repeat 2-4 times, take out the catheter coated with the super-slip antibacterial coating and place it in a sealed container with a humidity of 80-100%, and place it at 45-55°C for 15-24 hours to obtain a super-slip antibacterial silicone catheter.

[0114] Specifically, the use of silane coupling agents and pure silica gel for activation is to use the hydrolyzable functional groups in the silane coupling agent to react chemically with the silanol groups on the surface of the silica gel to form siloxane bonds and introduce organic functional groups on the surface of the silica gel. This activation process is intended to increase the bonding strength of the silica gel, improve its compatibility with organic materials, enhance its durability, and adjust its surface properties so that it 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 ability of the silica gel to combine with other materials and its own physical and chemical properties.

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

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

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

[0118] 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;

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

[0120] The present invention will be further described in detail below with reference to specific embodiments and comparative examples.

[0121] The silver nanoparticles, polyethylene glycol, etc. used in the present invention are all commercially available products.

[0122] Example 1

[0123] Preparation of super-slip antibacterial coating materials:

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

[0125] Pretreatment of silver nanoparticles includes:

[0126] Dispersing silver nanoparticles in ultrapure water, performing ultrasonic treatment and centrifugation, discarding the supernatant, and repeatedly washing 1-3 times to obtain pretreated silver nanoparticles;

[0127] Among them, the rotation speed is 12000rpm and the centrifugation time is 30min;

[0128] Pretreatment of polyethylene glycol includes:

[0129] The polyethylene glycol was placed in anhydrous magnesium sulfate and dried for 15 hours, and after drying, it was filtered to obtain the pretreated polyethylene glycol;

[0130] Among them, the addition amount of anhydrous magnesium sulfate is 3 times the mass of polyethylene glycol;

[0131] S2: placing the pretreated silver nanoparticles in acetone, stirring, adjusting the pH value to 5, then adding 3-aminopropyltriethoxysilane and acetic acid, continuing to stir, and causing silanization reaction at a temperature of 40° C. for 24 hours, centrifuging the mixture after the siloxane reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times, and then centrifuging again, discarding the supernatant, and obtaining activated silver nanoparticles;

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

[0133] The centrifugal speed was 12000 rpm and the centrifugal time was 30 min.

[0134] S3: placing acrylic acid in acetone, stirring, then adding activated silver nanoparticles, continuing to stir, reacting at 30°C for 6 hours, centrifuging the mixed solution after the reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times, and then centrifuging again, discarding the supernatant, to obtain a hydrophilic monomer modified with silver nanoparticles;

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

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

[0137] S4: placing the pretreated polyethylene glycol and N-hydroxysuccinimide in acetone, maintaining an argon atmosphere, at a temperature of 25° C., and performing an activation treatment for 2 hours to obtain an activated polyethylene glycol solution;

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

[0139] S5: placing the hydrophilic monomer modified with silver nanoparticles in an activated polyethylene glycol solution, stirring at a temperature of 20° C. for 8 h, and then centrifuging, washing, and drying to obtain an ultra-slippery antibacterial coating material;

[0140] Among them, the centrifugal speed is 12000rpm, and the centrifugal time is 30min;

[0141] Cleaning is done by using ultrapure water 1-3 times;

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

[0143] Preparation of super-smooth antibacterial silicone catheter:

[0144] (1) placing the super-slip antibacterial coating material in acetone and performing ball milling to obtain a super-slip antibacterial coating slurry;

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

[0146] The ball milling speed was 150 rpm and the ball milling time was 30 min;

[0147] (2) immersing the silicone urinary catheter in an ethyltrimethoxysilane solution for activation;

[0148] Among them, the activation temperature is 25°C and the activation time is 2min;

[0149] (3) After cleaning the activated silicone catheter, immerse it in the super-slip antibacterial coating slurry for 65 seconds, slowly take it out and place it in a sealed container with a humidity of 100%, dry it at 60°C for 30 minutes, repeat 2-4 times, take out the catheter coated with the super-slip antibacterial coating, place it in a sealed container with a humidity of 100%, and place it at 50°C for 24 hours to obtain a super-slip antibacterial silicone catheter.

[0150] Example 2

[0151] Preparation of super-slip antibacterial coating materials:

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

[0153] Pretreatment of silver nanoparticles includes:

[0154] Dispersing silver nanoparticles in ultrapure water, performing ultrasonic treatment and centrifugation, discarding the supernatant, and repeatedly washing 1-3 times to obtain pretreated silver nanoparticles;

[0155] Among them, the centrifugal speed is 12000rpm, and the centrifugal time is 30min;

[0156] Pretreatment of polyethylene glycol includes:

[0157] The polyethylene glycol is placed in anhydrous magnesium sulfate and dried for 20 hours, and after drying, it is filtered to obtain the pretreated polyethylene glycol;

[0158] Among them, the addition amount of anhydrous magnesium sulfate is 3 times the mass of polyethylene glycol;

[0159] S2: placing the pretreated silver nanoparticles in anhydrous ethanol, stirring, adjusting the pH value to 6, adding γ-aminopropyltriethoxysilane and citric acid, continuing to stir, and causing silanization reaction at 35°C for 20 hours, centrifuging the mixture after the siloxane reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times and then centrifuging again, discarding the supernatant, and obtaining activated silver nanoparticles;

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

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

[0162] S3: Methyl acrylate is placed in anhydrous ethanol, stirred, and activated silver nanoparticles are added, and the mixture is stirred continuously, and the mixture is reacted at 40°C for 4 hours. The mixed solution after the reaction is centrifuged, and the supernatant is discarded. The precipitate is washed with ultrapure water for 1-3 times and then centrifuged again, and the supernatant is discarded to obtain a hydrophilic monomer modified with silver nanoparticles;

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

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

[0165] S4: placing the pretreated polyethylene glycol and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide in anhydrous ethanol, maintaining a nitrogen atmosphere, and performing an activation treatment at a temperature of 25° C. for 3 hours to obtain an activated polyethylene glycol solution;

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

[0167] S5: placing the hydrophilic monomer modified with silver nanoparticles in an activated polyethylene glycol solution, stirring at 30° C. for 8 h, and then centrifuging, washing, and drying to obtain an ultra-slippery antibacterial coating material;

[0168] Among them, the centrifugal speed is 12000rpm, and the centrifugal time is 30min;

[0169] Cleaning is done by using ultrapure water 1-3 times;

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

[0171] Preparation of super-smooth antibacterial silicone catheter:

[0172] (1) placing the super-slip antibacterial coating material in ethanol and performing ball milling to obtain a super-slip antibacterial coating slurry;

[0173] The mass ratio of ethanol to the super-slippery antibacterial coating material is 1.5:1;

[0174] The ball milling speed was 150 rpm and the ball milling time was 20 min;

[0175] (2) immersing the silicone urinary catheter in a methyltrimethoxysilane solution for activation;

[0176] Among them, the activation temperature is 25°C and the activation time is 2min;

[0177] (3) After cleaning the activated silicone catheter, immerse it in the super-slip antibacterial coating slurry for 65 seconds, slowly take it out and place it in a sealed container with a humidity of 100%, dry it at 60°C for 30 minutes, repeat 2-4 times, take out the catheter coated with the super-slip antibacterial coating, place it in a sealed container with a humidity of 100%, and place it at 50°C for 24 hours to obtain a super-slip antibacterial silicone catheter.

[0178] Example 3

[0179] Preparation of super-slip antibacterial coating materials:

[0180] S1: Pretreatment of silver nanoparticles with a particle size of 80 nm and polyethylene glycol (PEG400) respectively;

[0181] Pretreatment of silver nanoparticles includes:

[0182] Dispersing silver nanoparticles in ultrapure water, performing ultrasonic treatment and centrifugation, discarding the supernatant, and repeatedly washing 1-3 times to obtain pretreated silver nanoparticles;

[0183] Among them, the centrifugal speed is 12000rpm, and the centrifugal time is 30min;

[0184] Pretreatment of polyethylene glycol includes:

[0185] The polyethylene glycol was placed in anhydrous sodium sulfate for drying for 15 hours, and after drying, it was filtered to obtain the pretreated polyethylene glycol;

[0186] Among them, the amount of anhydrous sodium sulfate added is 3 times the mass of polyethylene glycol;

[0187] S2: placing the pretreated silver nanoparticles in dimethyl sulfoxide, stirring, adjusting the pH value to 4, then adding N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and tartaric acid, continuing to stir, and causing silanization reaction at a temperature of 40° C. for 14 hours, centrifuging the mixture after the siloxane reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times, and then centrifuging again, discarding the supernatant, and obtaining activated silver nanoparticles;

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

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

[0190] S3: placing acrylic anhydride in dimethyl sulfoxide, stirring, then adding activated silver nanoparticles, continuing to stir, reacting at a temperature of 50° C. for 3 hours, centrifuging the mixed solution after the reaction, discarding the supernatant, washing the precipitate with ultrapure water 1-3 times, and then centrifuging again, discarding the supernatant, to obtain a hydrophilic monomer modified with silver nanoparticles;

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

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

[0193] S4: placing the pretreated polyethylene glycol and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide in dimethyl sulfoxide, maintaining a nitrogen atmosphere, and performing an activation treatment at a temperature of 25° C. for 5 hours to 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: placing the hydrophilic monomer modified with silver nanoparticles in an activated polyethylene glycol solution, stirring at a temperature of 25° C. for 8 hours, and then centrifuging, washing, and drying to obtain an ultra-slippery antibacterial coating material;

[0196] Among them, the centrifugal speed is 12000rpm, and the centrifugal time is 30min;

[0197] Cleaning is done by using ultrapure water 1-3 times;

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

[0199] Preparation of super-smooth antibacterial silicone catheter:

[0200] (1) placing the super-slip antibacterial coating material in ethanol and performing ball milling to obtain a super-slip antibacterial coating slurry;

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

[0202] The ball milling speed was 150 rpm and the ball milling time was 20 min;

[0203] (2) immersing the silicone urinary catheter in an aminopropyltriethoxysilane solution for activation;

[0204] Among them, the activation temperature is 25°C and the activation time is 2min;

[0205] (3) After cleaning the activated silicone catheter, immerse it in the super-slip antibacterial coating slurry for 65 seconds, slowly take it out and place it in a sealed container with a humidity of 100%, dry it at 60°C for 30 minutes, repeat 2-4 times, take out the catheter coated with the super-slip antibacterial coating, place it in a sealed container with a humidity of 100%, and place it at 50°C for 24 hours to obtain a super-slip antibacterial silicone catheter.

[0206] Comparative Example 1

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

[0208] Comparative Example 2

[0209] The difference between this comparative example and Example 1 is that in step S2, vinyltriethoxysilane is used as the silane reagent to perform silanization treatment on the silver nanoparticles, and the remaining operating steps and technical parameters are the same as those in Example 1.

[0210] Performance Testing

[0211] The antibacterial properties of the super-slip antibacterial silicone catheters obtained in Examples 1-3 and Comparative Examples 1-2 against Escherichia coli, Enterobacter faecalis and Candida albicans were tested according to standard ISO22196-2011; the sliding friction of the super-slip antibacterial silicone catheter surface was tested according to YY / T1536-2017.

[0212] Performance data

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

[0214]

[0215] It can be seen from Table 1 that compared with Example 1, since the number average molecular weight of the polyethylene glycol used in Comparative Example 1 is 2000 and the activation temperature is relatively high, the activator N-hydroxysuccinimide evaporates faster, thereby affecting the activation of the polyethylene glycol and ultimately affecting the lubricity of the super-slip antibacterial coating.

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

[0217] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an ultra-slip antibacterial coating material, characterized in that: The steps include: S1: pretreatment of silver nanoparticles and polyethylene glycol respectively; 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 cause a silanization reaction to obtain activated silver nanoparticles; S3: placing the hydrophilic monomer in a second solvent, stirring, then adding activated silver nanoparticles, and continuing to stir to obtain a hydrophilic monomer modified with silver nanoparticles; S4: placing the pretreated polyethylene glycol and the activator in a third solvent for activation treatment to obtain an activated polyethylene glycol solution; S5: placing the hydrophilic monomer modified with silver nanoparticles in an activated polyethylene glycol solution and stirring the solution to obtain an ultra-slippery antibacterial coating material.

2. The method for preparing the super-slip antibacterial coating material according to claim 1, characterized in that: In step S1, the pretreatment of silver nanoparticles includes: Dispersing silver nanoparticles in ultrapure water, performing ultrasonic treatment and centrifugation, discarding the supernatant, and repeatedly washing 1-3 times to obtain pretreated silver nanoparticles; The centrifugal speed is 12000-15000rpm, and the centrifugal time is 10-30min; and / or, the particle size of the silver nanoparticles is 10-100 nm; And / or, in step S1, the pretreatment of polyethylene glycol comprises: The polyethylene glycol is placed in a desiccant for drying, and after drying, it is filtered to obtain the pretreated polyethylene glycol; Wherein, the desiccant is anhydrous magnesium sulfate or anhydrous sodium sulfate; The amount of desiccant added is 2-5 times the mass of polyethylene glycol; Drying time is 10-20h; And / or, the number average molecular weight of the polyethylene glycol is 300-400.

3. The method for preparing the super-slip antibacterial coating material according to claim 1, characterized in that: In step S2, the silanization reaction comprises: The pH value is 4-6, the reaction temperature is 30-40°C, and the reaction time is 12-24h; and / or, the silane reagent comprises one or more of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane or γ-aminopropylmethyldiethoxysilane; and / or, the first solvent comprises one or more of anhydrous ethanol, acetone, 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 further comprises, after the silanization reaction, centrifuging the mixture after the siloxane reaction, discarding the supernatant, washing the precipitate with ultrapure water for 1-3 times and then centrifuging again, discarding the supernatant, and obtaining activated silver nanoparticles; The centrifugal speed is 12000-15000 rpm, and the centrifugal time is 10-30 min; 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).

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

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

6. The method for preparing the super-slip antibacterial coating material according to claim 1, characterized in that: In step S5, the reaction temperature is 20-30°C and the reaction time is 6-10h; And / or, in step S5, the esterification reaction further comprises the following steps: The mixed solution after the reaction is centrifuged, washed, and dried to obtain an ultra-slippery antibacterial coating material; Wherein, the centrifugal speed is 12000-15000rpm, and the centrifugal time is 10-30min; Cleaning is done by using ultrapure water 1-3 times; The drying temperature is 40-60°C and the drying time is 10-24h.

7. An ultra-slip antibacterial coating material obtained by the method for preparing an ultra-slip antibacterial coating material as described in any one of claims 1 to 6.

8. An application of the super-slip antibacterial coating material prepared by the method for preparing the super-slip antibacterial coating material according to any one of claims 1 to 6 or the super-slip antibacterial coating material according to claim 7, characterized in that: It can be used to prepare super-smooth antibacterial silicone catheters.

9. The use according to claim 8, characterized in that: The preparation of the super-smooth antibacterial silicone catheter includes the following steps: (1) placing the super-slippery antibacterial coating material in a fourth solvent and performing ball milling to obtain a super-slippery antibacterial coating slurry; (2) immersing the silicone urinary catheter in a second activating agent for activation; (3) After cleaning the activated silicone catheter, immerse it in the super-slip antibacterial coating slurry for 60-70 seconds, slowly take it out and place it in a sealed container with a humidity of 80-100%, dry it at 50-70°C for 25-35 minutes, repeat 2-4 times, take out the catheter coated with the super-slip antibacterial coating, place it in a sealed container with a humidity of 80-100%, and place it at 45-55°C for 15-24 hours to obtain a super-slip antibacterial silicone catheter.

10. The use 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 ultra-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, and the silane coupling agent includes one or more of methyltrimethoxysilane, ethyltrimethoxysilane or aminopropyltriethoxysilane; And / or, the activation temperature is 20-30°C and the activation time is 1-3 min.

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