CN117599254A - Method for preparing super-lubrication antibacterial medical catheter coating in one step - Google Patents

Abstract

The invention discloses a one-step method for preparing a super-lubricant antibacterial medical catheter coating. Using direct dip coating and heat curing, a super-lubricant antibacterial coating with an interpenetrating polymer network structure was obtained. By bonding the modified hyperbranched polylysine containing double bonds inside the substrate network, it is more firmly combined in the coating and has an efficient and broad-spectrum antibacterial effect. The present invention only needs to immerse the catheter base material in a coating containing both lubricating and antibacterial substances, thereby imparting significant lubricating and antibacterial properties to the catheter. The operation is simple and easy, and the one-step dip coating method is conducive to large-scale production.

Description

A one-step method for preparing super-lubricant antibacterial medical catheter coating

Technical field

The invention relates to a one-step method for preparing a super-lubricating antibacterial medical catheter coating, and belongs to the field of medical materials.

Background technique

Medical catheters, as an integral part of modern medicine, have greatly improved the quality of medical care in preventing, treating and alleviating diseases. According to incomplete statistics, the amount of medical catheters imported into my country each year exceeds 150 million yuan, and the annual use of medical catheters accounts for 8.7% of the total amount of medical devices. As a necessary tool for implantation treatment, the large-scale import of medical catheters has also greatly affected the development of medical science in our country.

The most commonly used medical catheter materials are silicone rubber, polyvinyl chloride, and polyurethane. Most of these materials have hydrophobic surfaces and high friction during insertion, which can lead to various complications during clinical use. Moreover, the catheter itself is not biologically active, making it difficult to inhibit persistent infection caused by local wounds at the access site. Therefore, building a lubricating and antibacterial coating on the surface of medical catheters can effectively reduce tissue damage, kill bacteria, and reduce tissue infection.

At present, the commonly used methods for surface lubrication or hydrophilic modification of medical catheters mainly include silane coupling agent grafting method, swelling embedding initiator method and direct coating method. The silane coupling agent grafting method requires plasma treatment of the substrate, heating and solidification, and then grafting a lubricating layer. It has limitations such as complex processes, uneven coatings, and easy damage to the surface morphology of the substrate. The swelling embedded initiator method is to first swell the oil-soluble initiator on the polymer substrate, and then graft the lubricating monomer on the surface interface through the water-soluble initiator in the solution. Most of the substrates treated by this method are polymerized in the solution, which is wasteful. Raw materials and high costs are issues; the direct coating method is to directly solidify the coating on the catheter to form a film. The coating obtained by this method is easy to fall off and the monomer is easy to remain. Therefore, it is necessary to develop a universal medical catheter preparation method that is simple, easy to produce in batches and can be lubricated for a long time.

In recent years, biocides such as pharmaceuticals, metal ions, and quaternary ammonium salts have been used to produce antibacterial coatings, but there are still many shortcomings. Antibiotics and other drugs often do not have broad-spectrum bactericidal activity. Coated catheters are usually inefficient in inhibiting biofilm formation and are prone to drug resistance. Metal antibacterial agents are commonly used such as silver, copper or zinc. However, antibacterial metals The continuous precipitation and accumulation of ions will destroy the microenvironmental balance of surrounding tissues, causing problems such as cytotoxicity and poor biocompatibility; quaternary ammonium salt disinfectants are inefficient disinfectants and cannot kill fungi, tuberculosis bacilli, and hydrophilic viruses. It has many incompatible incompatibilities with microorganisms such as bacterial spores and is relatively expensive. Therefore, there is a lack of a safe, efficient, broad-spectrum antibacterial, stable performance, non-biotoxic, low-cost, non-drug-resistant antibacterial coating material and efficient preparation method.

Contents of the invention

The object of the present invention is to provide a one-step method for preparing a super-lubricant antibacterial medical catheter coating in view of the shortcomings of the existing technology. Using direct dip coating and heat curing, a super-lubricant antibacterial coating with an interpenetrating polymer network structure was obtained. By bonding the modified hyperbranched polylysine containing double bonds inside the substrate network, a coating with broad-spectrum antibacterial properties, stable performance, strong bonding, and non-toxicity is obtained. This method is simple, time-saving, and has excellent results.

The technical solutions adopted by the present invention are as follows:

A method for preparing a super-lubricant antibacterial medical catheter coating in one step, the method comprising:

The cleaned medical catheter is dip-coated into the super-lubricant antibacterial coating. After being taken out and cured by heating, it is rinsed with water and dried to obtain a super-lubricant antibacterial coating with an interpenetrating polymer network structure. The super-lubricating antibacterial coating includes the following weight components: 15-20 parts of hydrophilic monomer, 5-10 parts of lubricating polymer, 3-5 parts of modified hyperbranched polylysine, and 0.1 part of cross-linking agent -0.5 parts, 0.5-1 parts of initiator, 45-70 parts of organic reagents, 20-40 parts of deionized water.

Further, the medical catheter material is at least one of polyurethane, polyvinyl chloride, silicone rubber, and latex.

Further, the hydrophilic monomer is selected from one or more of acrylamide, N-vinylpyrrolidone, hydroxyethyl methacrylate, and N-hydroxymethylacrylamide.

Further, the lubricating polymer is selected from one or more of polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol.

Furthermore, the modified hyperbranched polylysine refers to being soaked in a modifier to make it contain double bonds. The modifier is one or more of (meth)acrylic anhydride and glycidyl (meth)acrylate aqueous solution. The solution concentration is 1-1.5wt%, the temperature is 37°C, and the soaking time is 4-6 hours.

Further, the cross-linking agent is one or more of N,N-methylenebisacrylamide or ethylene glycol dimethacrylamide.

Further, the initiator is a thermal initiator, selected from at least one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, and persulfate.

Further, the organic reagent is one or more of ethanol, isopropyl alcohol, ethylene glycol, and propanol.

Further, the heating and curing temperature is 60-90°C, and the curing time is 3-9 hours.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention provides a method for preparing a super-lubricant antibacterial medical catheter coating. The one-step dip coating and solidification preparation process avoids the problem of waste of raw materials. The process is simple, simple to operate, low in cost, good in repeatability, and can be quickly realized. Preparation of ultralubricant antimicrobial coatings.

2. The present invention provides a one-step method for preparing a super-lubricant antibacterial medical catheter coating. The antibacterial agent contained is hyperbranched polylysine, which can destroy bacterial cell membranes and DNA and increase the level of reactive oxygen species in bacterial cells. The mechanism plays an efficient and broad-spectrum antibacterial and bactericidal effect.

3. The present invention provides a one-step method for preparing a super-lubricant antibacterial medical catheter coating. By bonding modified hyperbranched polylysine with double bonds inside the network, it avoids the need for antibacterial agents due to low content. Insufficient effect or problems such as cytotoxicity caused by the precipitation and accumulation of antibacterial agents have achieved an efficient and stable sterilization effect.

Description of drawings

In order to make the purpose, technical solution and beneficial effects of the present invention clearer, the present invention provides the following drawings for Embodiment 1:

Figure 1 is a comparison of the appearance morphology of the lubricated antibacterial modified medical catheter prepared by the present invention and the original medical catheter without coating;

Figure 2 is a schematic diagram of the coated catheter prepared by the present invention;

Figure 3 is a plate colony diagram of the original medical catheter without coating;

Figure 4 is a colony diagram of a flat plate coated with a lubricating antibacterial coating prepared by the present invention;

Figure 5 is a friction coefficient curve chart of the lubricated antibacterial modified medical catheter prepared by the present invention and the original medical catheter without coating tested for 30 cycles underwater;

Figure 6 is a ¹ H-NMR spectrum of modified hyperbranched polylysine at different modifier concentrations in the present invention.

Detailed ways

The technical solutions of the present invention will be further described below with reference to examples, but these examples are not intended to limit the present invention.

Example 1

Dissolve hyperbranched polylysine and glycidyl methacrylate in 4g of water to prepare a 1wt% solution, and react at 37°C for 4 hours. Continue to add 1.5g hydroxyethyl methacrylate, 1g polyacrylamide, 0.01g ethylene glycol dimethylacrylamide, 0.05g azobisisobutyronitrile and 4.5g ethanol, stir evenly to obtain a lubricating antibacterial coating. Soak the polyurethane catheter in the above coating, lift it up after dipping and place it in a 60°C oven for 4 hours. Take out the catheter, soak it in ultrapure water for 1 hour, rinse it three times, and dry it to obtain a coated medical catheter. The appearance is shown in Figure 1. The appearance and morphology of the coated medical catheter are consistent with those of the catheter before modification. Figure 2 is a schematic diagram of the coated catheter prepared by the present invention. By bonding the modified hyperbranched polylysine with double bonds inside the network, the effects of insufficient antibacterial agents due to low content or precipitation and accumulation of antibacterial agents are avoided. issues such as cytotoxicity. The antibacterial method refers to GB/T 31402-2015. Since the contact area of the catheter is small and difficult to test, the same process is used to prepare a super-lubricant antibacterial coating on the sheet. Figure 3 is a colony diagram of a flat plate without a lubricating antibacterial coating; Figure 4 is a colony diagram of a flat plate coated with a lubricating antibacterial coating. From the comparison of the number of colonies in Figures 3 and 4, it can be seen that the super lubricating antibacterial coating disclosed in the present invention It has excellent antibacterial properties and can inhibit bacterial colonization on the catheter surface. Figure 5 is a friction coefficient curve chart of the lubricated antibacterial modified medical catheter and the original medical catheter tested 30 times underwater. From the results, it can be seen that the friction coefficient of the coated catheter prepared by the present invention is 0.029, while The friction coefficient of the unmodified catheter is 1.625. The coating prepared by the present invention can significantly reduce the friction coefficient and has super-lubricity properties; at the same time, the friction coefficient of the disclosed super-lubricity antibacterial coating is almost unchanged in 30 cycle friction tests. , indicating that there is almost no shedding of the coating and no degradation in lubricity. Figure 6 is a ¹ H-NMR spectrum of modified hyperbranched polylysine at different modifier concentrations in the present invention. In Figure 6, the peak positions of the vinyl methacrylate group appear at δ=6.2-6 and 5.8-5.6ppm, and the peak positions of the N-CH ₂ group in glycidyl methacrylate appear at δ=3.2-3.6ppm, -CH ₃ group peak appears at δ=1.8ppm. As the added amount of glycidyl methacrylate increases, the above peaks have a significant increasing trend, proving that the double bonds are successfully grafted on hyperbranched polylysine. The above data illustrates the successful production of superlubricant and antibacterial coatings by the method of this invention.

Example 2

Dissolve hyperbranched polylysine and acrylic anhydride in 3g of water to prepare a 1.2wt% solution, and react at 37°C for 5 hours. Continue to add 1.5g acrylamide, 0.8g polyvinylpyrrolidone, 0.02g ethylene glycol dimethylacrylamide, 0.08g benzoyl peroxide and 5.5g isopropyl alcohol, stir evenly to obtain a lubricating antibacterial coating. Soak the polyvinyl chloride pipe in the above coating, lift it up after dipping and place it in an oven at 80°C for 5 hours. Take out the catheter, soak it in ultrapure water for 1 hour, rinse it three times, and dry it to obtain a medical catheter with both lubrication and antibacterial effects.

Example 3

Dissolve hyperbranched polylysine and glycidyl acrylate in 2g of water to prepare a 1.5wt% solution, and react at 37°C for 6 hours. Continue to add 1.5g N-vinylpyrrolidone, 0.5g polyethylene oxide, 0.04g N,N-methylenebisacrylamide, 0.1g ammonium persulfate and 7g ethylene glycol, stir evenly to obtain a lubricating antibacterial coating. Soak the silicone rubber catheter in the above coating, lift it up after dipping and place it in a 90°C oven for 8 hours. Take out the catheter, soak it in ultrapure water for 1 hour, rinse it three times, and dry it to obtain a medical catheter with both lubrication and antibacterial effects.

Claims (9)

1. The method for preparing the super-lubricating antibacterial medical catheter coating by one step is characterized by immersing the cleaned medical catheter into the super-lubricating antibacterial coating, taking out, heating for curing, washing with water and drying to obtain the super-lubricating antibacterial coating with an interpenetrating polymer network structure; the super-lubricating antibacterial coating comprises the following components in parts by weight: 15-20 parts of hydrophilic monomer, 5-10 parts of lubricating polymer, 3-5 parts of modified hyperbranched polylysine, 0.1-0.5 part of cross-linking agent, 0.5-1 part of initiator, 45-70 parts of organic reagent and 20-40 parts of deionized water.

2. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the medical catheter material is at least one of polyurethane, polyvinyl chloride, silicone rubber and latex.

3. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the hydrophilic monomer is one or more selected from the group consisting of acrylamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate and N-methylolacrylamide.

4. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the lubricating polymer is one or more selected from the group consisting of polyacrylamide, polyvinylpyrrolidone, polyethylene oxide and polyvinyl alcohol.

5. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the modified hyperbranched polylysine is prepared by soaking the hyperbranched polylysine in a modifier so that the hyperbranched polylysine contains double bonds; the modifier is one or more of (methyl) acrylic anhydride and (methyl) glycidyl acrylate aqueous solution, the concentration of the modifier solution is 1-1.5wt%, the temperature is 37 ℃, and the soaking time is 4-6h.

6. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the cross-linking agent is one or more of N, N-methylenebisacrylamide or ethylene glycol dimethacrylate.

7. The method for preparing the super-lubricating antibacterial medical catheter coating according to claim 1, wherein the initiator is a thermal initiator and is at least one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide and persulfates.

8. The method for preparing the super-lubricating antibacterial medical catheter coating according to claim 1, wherein the organic reagent is one or more of ethanol, isopropanol, ethylene glycol and propanol.

9. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the heating curing temperature is 60-90 ℃ and the curing time is 3-9h.