Preparation method of antibacterial material as well as product and application of antibacterial material

Abstract

The invention discloses a novel antibacterial material as well as a preparation method, a product and application thereof. The preparation method comprises the following steps: dissolving long-chain alkylamine in an alcohol solution, and marking as a solution A; respectively dissolving zinc nitrate and sodium hydroxide in deionized water, and marking as a solution B; slowly dropwise adding the solution B into the solution A, reacting at normal pressure and low temperature of 0-40 DEG C for 2-30 hours, centrifuging a product, washing with an alcoholic solution for 3-5 times, and drying in a drying oven at the temperature of 60-80 DEG C to obtain a product C; dispersing C into deionized water, uniformly stirring, slowly adding 0.5-1 mmol of a silver salt solution into the solution, and magnetically stirring for 1-2 hours to obtain D; and slowly adding D into a 1M sodium borohydride solution, dipping for 60-90 minutes, centrifuging, and drying in a vacuum oven at 60-80 DEG C for 6-10 hours to obtain the final antibacterial material. The antibacterial material prepared by the invention has a double-effect antibacterial function, and the antibacterial agent prepared by the invention has an excellent antibacterial effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of materials, and relates to a novel antibacterial material, and also relates to a preparation method and application thereof. BACKGROUND

[0002] Various catheters are often used in medical treatment to achieve the purpose of replacing control of certain functions of the human body. For example, urinary catheters, tracheal intubation tubes, central venous catheters, PICC tubes, intracanal cannulas, ventricular drainage tubes, three-lumen two-cuff tubes, and closed thoracic drainage tubes. There are dozens of organic polymer materials used in medical plastic products, which are used in products with different properties for different purposes. And the medical catheter material for achieving the purpose of replacing control of certain functions of the human body is mostly biomedical material. Biomedical material refers to a class of materials with special properties, special functions, used in medical health fields such as human organs, surgical repair, physiotherapy rehabilitation, diagnosis, examination and treatment of diseases, and does not cause adverse effects on human tissues and blood.

[0003] In order to improve the antibacterial performance of medical catheters, researchers in the field have developed a variety of new biomedical materials. The invention with publication number CN118240242A provides a preparation method of nano-zinc oxide antibacterial master batch, its product and application. The preparation steps of the nano-zinc oxide antibacterial master batch include: dissolving long-chain alkylamine in an alcohol solution, marked as solution A; dissolving a soluble zinc salt in deionized water, marked as solution B; slowly adding solution B to solution A and reacting for 2-30 hours, centrifuging, washing and drying the product to obtain nano-zinc oxide; uniformly dispersing nano-zinc oxide and a dispersing agent in a glycol solution at high speed to form a uniform dispersion liquid, so that the nano-zinc oxide is added in the form of the dispersion liquid and esterification reaction is carried out; using the above obtained glycol dispersion liquid and terephthalic acid as monomers, adding a catalyst to prepare polyester through esterification and polycondensation reaction, and the obtained polyester is extruded, granulated and dried to obtain nano-zinc oxide polyester antibacterial master batch.

[0004] The invention with publication number CN113273580A discloses a preparation method of an antibacterial agent, comprising the following steps: (1) mixing and dispersing copper nitrate, deionized water, isopropyl alcohol and sodium borohydride to form dispersion liquid A; (2) adding an ammonia solution to the dispersion liquid A to carry out a precipitation reaction, then filtering, drying and calcining to obtain nano-copper particles; (3) taking cerium nitrate, pyromellitic acid, N,N-dimethylformamide, yttrium nitrate and nano-copper particles to react; (4) washing, solid-liquid separating and drying the product obtained in step (3), and calcining at high temperature to obtain the antibacterial agent. The invention prepares the antibacterial agent of core-shell particles with nano-copper as the core and the composite material of cerium dioxide and yttrium trioxide as the shell. The new antibacterial agent has good dispersibility, and the antibacterial performance is better than that of a single antibacterial agent, which can provide good antibacterial effect for thermoplastic plastics.

[0005] With the development of medical technology and the emergence of new and complex medical requirements from patients, the development of more biocompatible, antibacterial, and self-cleaning medical catheter materials has become a long-term research topic. Summary of the Invention

[0006] The purpose of this invention is to provide a novel antibacterial material with excellent biocompatibility and good antibacterial and self-cleaning properties.

[0007] Another object of the present invention is to provide a method for preparing a novel antibacterial material.

[0008] Another object of the present invention is to provide an application of the above-mentioned product.

[0009] The objective of this invention is achieved through the following solution.

[0010] In a first aspect, the present invention provides a method for preparing a novel antibacterial material, the specific steps of which are as follows: (1) Dissolve long-chain alkylamines in alcohol solution to a concentration of 5-100 g / L and label it as solution A.

[0011] (2) Dissolve zinc nitrate and sodium hydroxide in deionized water respectively, so that their molar ratio is 1:2-1:7, and label it as solution B.

[0012] (3) Slowly add solution B to solution A, react at normal pressure and low temperature of 0-40 °C for 2-30 h, centrifuge the product, wash it with alcohol solution 3-5 times, and dry it in an oven at 60-80 °C to obtain product C.

[0013] (4) Disperse C in deionized water and stir until homogeneous. Then slowly add 0.5-1 mmol of silver salt solution to the solution and stir magnetically for 1-2 h to obtain D.

[0014] (5) Slowly add D to 1 M sodium borohydride solution, soak for 60-90 min, centrifuge, and dry in a vacuum oven at 60-80℃ for 6-10 h to obtain the final antibacterial material.

[0015] Preferably, the long-chain alkylamine described in the above preparation method is one or a combination of decaamine, dodecylamine, or similar alkylamine.

[0016] Preferably, the alcohol used in the above preparation method is one or a combination of methanol, ethanol, or propanol. More preferably, the alcohol used in steps (1) and (3) is the same.

[0017] Preferably, the silver salt mentioned in the above preparation method is one or a combination of silver acetate, silver nitrate, or silver citrate.

[0018] In step (1), the long-chain alkylamine is dissolved in the alcohol solution, and it should be fully dissolved. Preferably, the concentration is 5 to 10 g / L. More preferably, the concentration is 6 to 9 g / L, for example, 7 or 8 g / L.

[0019] In step (2), zinc nitrate and sodium hydroxide are prepared into an aqueous solution. Preferably, the mass ratio of zinc nitrate to sodium hydroxide can be selected from 0.7 to 1.8, more preferably, the mass ratio is 0.72 to 1.06. In a preferred embodiment of the invention, 4.91 g of zinc nitrate and 2.73 g of sodium hydroxide are dissolved in deionized water, and in another preferred embodiment, 2.85 g of zinc nitrate and 3.98 g of sodium hydroxide are dissolved in deionized water to form solution B.

[0020] In step (3), the low-temperature reaction can also be carried out in a constant temperature chamber. Preferably, the temperature does not exceed 20 °C, for example, the temperature is 2 to 20 °C. Preferably, the reaction time is 15 to 20 h.

[0021] In step (4), the concentration of the silver salt solution is preferably 0.5-0.75 mmol.

[0022] In step (5), take an appropriate amount of sodium borohydride solution as usual. 1M refers to 1 mol / L, and the volume of sodium borohydride solution is usually no less than that of solution D.

[0023] In step (5), the immersion time shall be no less than 40 min, preferably 60-80 min. Drying shall be carried out under vacuum conditions, and the drying time is preferably 6-8 h.

[0024] Preferably, the equipment used in the preparation method of the present invention is conventional equipment, such as an oven for drying, a centrifuge with appropriate speed and radius for centrifugation, etc.

[0025] Secondly, the present invention provides a novel antibacterial material, which can be prepared according to any of the methods described above.

[0026] Thirdly, the present invention provides the application of the above-mentioned antibacterial materials.

[0027] This invention provides a novel antibacterial material as an antibacterial agent in the preparation of plastic masterbatch and then in the preparation of PP plastic sheets.

[0028] The content of antibacterial agent in PP plastic is determined according to actual needs, usually 0.1%-1%, preferably 0.1%-0.3%, by weight percentage.

[0029] Novel antibacterial materials, antibacterial agents, or antibacterial plastics exhibit excellent antibacterial properties. In this embodiment of the invention, antibacterial testing was performed using the ISO 22196:2011 (E) method. Results showed significant inhibitory effects against common bacteria, including Staphylococcus aureus and Escherichia coli. The antibacterial activity value against Staphylococcus aureus ATCC6538P was greater than 4.5, and the antibacterial activity value against Escherichia coli ATCC8739 was greater than 4.3.

[0030] This invention discloses a novel antibacterial material and its preparation method, which possesses excellent antibacterial properties. It can be used as a component or antibacterial agent in various medical materials, including various catheters frequently used in medicine, such as urinary catheters, endotracheal tubes, central venous catheters, PICC lines, intraductal cannulas, ventricular drainage tubes, three-lumen two-balloon tubes, closed chest drainage tubes, etc., and has applications in medical and healthcare fields such as human organ repair, surgical repair, physical therapy and rehabilitation, diagnosis, examination, and treatment of diseases.

[0031] In the description of this application, the terms "comprising," "including," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a reference structure" does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0032] It should be noted that in this article, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Detailed Implementation

[0033] The technical solution will be clearly and completely described below through embodiments of this application. Obviously, the described embodiments are only some preferred embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of this application.

[0034] Example 1 This embodiment provides an antibacterial material, prepared according to the following steps: (1) Dissolve decaamine in methanol solution to a concentration of 5 g / L, and label it as solution A; (2) Dissolve 4.91g of zinc nitrate and 2.73g of sodium hydroxide in deionized water and label the solution as solution B; (3) Slowly add solution B to solution A, react at normal pressure and low temperature 0 ℃ for 30 h, centrifuge the product, wash it three times with methanol solution, and dry it in an oven at 60 ℃ to obtain product C; (4) Disperse C in deionized water and stir until homogeneous. Then slowly add 0.5 mmol silver nitrate solution to the solution and stir magnetically for 1 h to obtain D; (5) Add D slowly to 1 M sodium borohydride solution, soak for 60 min, centrifuge, and dry in a vacuum oven at 80 °C for 6 h to obtain the final product.

[0035] The sample obtained in this example was used as an antibacterial agent to prepare plastic masterbatch, and then PP plastic sheets were prepared. The antibacterial agent content in the PP plastic was 0.1%. The antibacterial properties were determined using the ISO22196:2011(E) method. The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P was greater than 4.7, and the antibacterial activity value against Escherichia coli ATCC8739 was greater than 4.3.

[0036] Example 2 This embodiment provides a second antibacterial material, which is prepared according to the following steps: (1) Dissolve dodecylamine in an ethanol solution to a concentration of 10 g / L, and label it as solution A; (2) Dissolve 2.85g of zinc nitrate and 3.98g of sodium hydroxide in deionized water, and label the solution as solution B; (3) Slowly add solution B to solution A, react at normal pressure and low temperature of 10 °C for 20 h, centrifuge the product, wash it 5 times with ethanol solution, and dry it in an oven at 80 °C to obtain product C; (4) Disperse C in deionized water and stir until homogeneous. Then slowly add 0.75 mmol silver nitrate solution to the solution and stir magnetically for 1 h to obtain D; (5) Add D slowly to 1 M sodium borohydride solution, soak for 80 min, centrifuge, and dry in a vacuum oven at 80 °C for 8 h to obtain the final product.

[0037] The sample obtained in this example was used as an antibacterial agent to prepare plastic masterbatch, and then PP plastic sheets were prepared. The antibacterial agent content in the PP plastic was 0.3%. The antibacterial properties were determined using the ISO22196:2011(E) method. The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P was greater than 5.4, and the antibacterial activity value against Escherichia coli ATCC8739 was greater than 4.8.

[0038] Example 3 This embodiment provides a third antibacterial material, prepared according to the following steps: (1) Dissolve decaamine in an ethanol solution to a concentration of 5 g / L, and label it as solution A; (2) Dissolve 3.463g of zinc nitrate and 4.93g of sodium hydroxide in deionized water, and label the solution as solution B; (3) Slowly add solution B to solution A, react at normal pressure and low temperature of 20 °C for 15 h, centrifuge the product, wash it 5 times with ethanol solution, and dry it in an oven at 80 °C to obtain product C; (4) Disperse C in deionized water and stir until homogeneous. Then slowly add 1 mmol of silver nitrate solution to the solution and stir magnetically for 1 h to obtain D; (5) Add D slowly to 1 M sodium borohydride solution, soak for 80 min, centrifuge, and dry in a vacuum oven at 60 °C for 10 h to obtain the final product.

[0039] The sample obtained in this example was used as an antibacterial agent to prepare plastic masterbatch, and then PP plastic sheets were prepared. The antibacterial agent content in the PP plastic was 1%. The antibacterial properties were determined using the ISO22196:2011(E) method. The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P was greater than 5.7, and the antibacterial activity value against Escherichia coli ATCC8739 was greater than 5.2.

[0040] The embodiments described above are merely specific implementations of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be conceived by those skilled in the art within the scope of the technology disclosed in this application without creative effort should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of protection of the claims in this application.

Claims

1. A method for preparing an antibacterial material, characterized in that, Includes the following steps: (1) Dissolve long-chain alkylamines in an alcohol solution to a concentration of 5–100 g / L, and label it as solution A; (2) Dissolve zinc nitrate and sodium hydroxide in deionized water respectively, so that their molar ratio is 1:2-1:7, and label it as solution B; (3) Slowly add solution B to solution A, react at normal pressure and low temperature (0-40 °C) for 2-30 h, centrifuge the product, wash it 3-5 times with alcohol solution, and dry it at 60-80 °C to obtain product C; (4) Disperse C in deionized water and stir until homogeneous. Then slowly add 0.5-1 mmol of silver salt solution to the solution and stir magnetically for 1-2 h to obtain D; (5) Slowly add D to 1 M sodium borohydride solution, soak for 60-90 min, centrifuge, and dry under vacuum at 60-80 ℃ for 6-10 h to obtain the final antibacterial material; The long-chain alkylamine is one of decaamine, dodecylamine, or a combination thereof.

2. The method for preparing the antibacterial material according to claim 1, characterized in that, The alcohol used in steps (1) and (3) is the same.

3. The method for preparing the antibacterial material according to claim 1, characterized in that, The alcohol is one or a combination of methanol, ethanol, or propanol.

4. The method for preparing the antibacterial material according to claim 1, characterized in that, The silver salt is one or a combination of silver acetate, silver nitrate, or silver citrate.

5. The method for preparing the antibacterial material according to claim 1, characterized in that, Drying is completed using an oven.

6. The method for preparing the antibacterial material according to claim 1, characterized in that, In step (1), the long-chain alkylamine is dissolved in an alcohol solution to achieve a concentration of 5–10 g / L; In step (2), the mass ratio of zinc nitrate to sodium hydroxide is 0.7-1.8; In step (3), the temperature of the low-temperature reaction is 2-20 °C, and the reaction time is 15-20 h; In step (4), the concentration of the silver salt solution is 0.5-0.75 mmol; In step (5), the impregnation time is 60-80 min and the vacuum drying time is 6-8 h.

7. An antibacterial material, characterized in that, It is obtained by the preparation method according to any one of claims 1-6.

8. The application of the antibacterial material according to claim 7, wherein the antibacterial material according to claim 7 is used as an antibacterial agent.

9. The application according to claim 8, characterized in that, The application of the antibacterial material according to claim 7 in the preparation of plastic masterbatch or plastic sheet, wherein the antibacterial agent content in the plastic is 0.1%-1% by weight.