WO2021097667A1 - Biomedical material surface polymer-based coating - Google Patents

Abstract

Disclosed is a biomedical material surface polymer-based coating, comprising the following components in parts by mass: 2-5 parts of tetraethoxysilane, 40-60 parts of pure water, 0.5-2 parts of glacial acetic acid, 0.5-2 parts of silane coupling agent, 0.1-0.5 part of nano titanium dioxide, and 0.5-1 part of nano silver. By adding nano titanium dioxide and nano silver, the coating has good antibacterial and protective properties.

Description

Polymer-based coating on the surface of biomedical material Technical field

The invention relates to the technical field of polymer materials, in particular to a polymer-based coating on the surface of biomedical materials.

Background technique

The medical surface coating material is a medical surface composite material composed of a group material as a matrix and a layer of homogenous or heterogeneous film formed on its surface by a certain process technology. Its function is to improve the biological properties of the substrate surface, or to block the dissolution and diffusion of substrate ions to the surrounding tissues, or to improve the physical and chemical properties such as wear resistance and insulation of the substrate surface. The most widely used is to add to the civil metal material substrate. For coating bioceramic coatings, plasma spraying, vapor deposition, ion sputtering, immersion, sintering, electrophoresis and pyrolysis can be used for coating preparation. The first two methods are most suitable. Coating materials are mainly used to manufacture artificial bones, joint sockets, joint heads, artificial tooth roots, artificial heart valves, etc.; it can also be used as an insulating layer for wires of electrical implant devices and surface coatings for guiding wires of cardiovascular catheters. Existing coating materials generally only have a single performance, such as protection, antibacterial, and anticoagulant properties, and cannot have multiple properties at the same time to improve the performance of medical materials. Therefore, there is a need to provide a polymer-based coating on the surface of biomedical materials.

Summary of the invention

In order to overcome the defects in the prior art, a polymer-based coating on the surface of biomedical materials is provided.

The present invention is realized through the following schemes:

A polymer-based coating on the surface of biomedical materials, in parts by mass, the base coating includes 2-5 parts of ethyl orthosilicate, 40-60 parts of pure water, 0.5-2 parts of glacial acetic acid, and silane coupling 0.5-2 parts of coupling agent, 0.1-0.5 parts of nano titanium dioxide, 0.5-1 parts of nano silver.

The nano titanium dioxide is prepared by a method including the following steps:

Weigh the raw materials: Weigh the raw materials according to the following parts by weight, 4-6 parts of butyl titanate, 10-30 parts of anhydrous ethanol, 0.5-2 parts of glacial acetic acid, 0.5-2 parts of ultrapure water, concentrated nitric acid 1- 3 copies;

Prepare solution a: At 15-25°C, drop butyl titanate into 10-20 parts of absolute ethanol at a constant rate of 40-60 drops/min, and then add 0.5-2 parts of glacial acetic acid to obtain solution a;

Prepare solution b: mix 0.5-2 parts of ultrapure water and 5-10 parts of absolute ethanol, and then gradually add concentrated nitric acid to obtain solution b with pH=2-3;

Preparation: Drop the solution a into solution b at a constant speed of 30-50 drops/min, stir at a constant speed for 0.5-1h until a transparent gel appears, and then put it in a muffle furnace and heat it up to 300-600℃ for 0.5 -1h, grinding to obtain the nano titanium dioxide.

The average particle size of the nano titanium dioxide is 5-15 nm, and the specific surface area is 80-115 m ² /g.

The average particle size of the nano silver is 20-30 nm, and the specific surface area is 70-90 m ² /g.

The beneficial effects of the present invention are:

1. The polymer-based coating on the surface of a biomedical material of the present invention uses nano-silver. On the one hand, nano-silver particles have a large specific surface area and high surface energy, so that they have strong surface activity and super adsorption ability, so it is helpful Corrupted oxygen atoms, oxygen free radicals, alkane molecules, etc. have a strong capture ability, which can effectively protect materials from bacteria. On the other hand, silver ions react with the organic matter in bacteria to effectively kill bacteria, thereby Achieve antibacterial and bactericidal effects.

2. The polymer-based coating on the surface of a biomedical material of the present invention adopts nano-titanium dioxide to form a deadly protective layer on the surface of medical materials, which can effectively prevent the penetration of corrosive media and provide good protection for medical materials, thereby achieving protection The role of anti-corrosion.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments:

A polymer-based coating on the surface of a biomedical material, in parts by mass, the base coating includes 2-5 parts of ethyl orthosilicate, 40-60 parts of pure water, 0.5-2 parts of glacial acetic acid, and silane coupling 0.5-2 parts of coupling agent, 0.1-0.5 parts of nano titanium dioxide, 0.5-1 parts of nano silver.

The nano titanium dioxide is prepared by a method including the following steps:

Weigh the raw materials: Weigh the raw materials according to the following parts by weight, 4-6 parts of butyl titanate, 10-30 parts of anhydrous ethanol, 0.5-2 parts of glacial acetic acid, 0.5-2 parts of ultrapure water, concentrated nitric acid 1- 3 copies;

Prepare solution a: At 15-25°C, drop butyl titanate into 10-20 parts of absolute ethanol at a constant rate of 40-60 drops/min, and then add 0.5-2 parts of glacial acetic acid to obtain solution a;

Prepare solution b: mix 0.5-2 parts of ultrapure water and 5-10 parts of absolute ethanol, and then gradually add concentrated nitric acid to obtain solution b with pH=2-3;

Preparation: Drop the solution a into solution b at a constant speed of 30-50 drops/min, stir at a constant speed for 0.5-1h until a transparent gel appears, and then put it in a muffle furnace and heat it up to 300-600℃ for 0.5 -1h, grinding to obtain the nano titanium dioxide.

The average particle size of the nano titanium dioxide is 5-15 nm, and the specific surface area is 80-115 m ² /g.

The average particle size of the nano silver is 20-30 nm, and the specific surface area is 70-90 m ² /g.

The application will be further elaborated below in conjunction with specific embodiments.

Comparative example 1

A polymer-based coating on the surface of a biomedical material, in parts by mass, the base coating includes 3.5 parts of ethyl orthosilicate, 50 parts of pure water, 1 part of glacial acetic acid, 1 part of silane coupling agent, nanometer 0.1 part of titanium dioxide and 0 part of nano-silver.

Comparative example 2

A polymer-based coating on the surface of a biomedical material, in parts by mass, the base coating includes 3.5 parts of ethyl orthosilicate, 50 parts of pure water, 1 part of glacial acetic acid, 1 part of silane coupling agent, nanometer 0 parts of titanium dioxide and 0.5 parts of nano-silver.

Example 1

A polymer-based coating on the surface of a biomedical material, in parts by mass, the base coating includes 3.5 parts of ethyl orthosilicate, 50 parts of pure water, 1 part of glacial acetic acid, 1 part of silane coupling agent, nanometer 0.1 part of titanium dioxide and 0.5 part of nano-silver.

The nano titanium dioxide is prepared by a method including the following steps:

Weigh the raw materials: Weigh the raw materials according to the following parts by weight: 5 parts of butyl titanate, 20 parts of anhydrous ethanol, 1 part of glacial acetic acid, 1 part of ultrapure water, 1.5 parts of concentrated nitric acid;

Prepare solution a: At 18°C, drop butyl titanate into 15 parts of absolute ethanol at a constant rate of 45 drops/min, and then add 1 part of glacial acetic acid to obtain solution a;

Prepare solution b: mix 1 part of ultrapure water and 5 parts of absolute ethanol, and then gradually add concentrated nitric acid to obtain solution b with pH=2-3;

Preparation: Drop the solution a into the solution b at a constant speed of 40 drops/min, stir at a constant speed for 0.5h until a transparent gel appears, dry it and put it in a muffle furnace and heat it up to 400°C for 1h, and grind to obtain the result. The nano-titanium dioxide.

The average particle size of the nano titanium dioxide is 10 nm, and the specific surface area is 85 m ² /g.

The average particle size of the nano silver is 25 nm, and the specific surface area is 75 m ² /g.

Example 2

This embodiment has many similarities with the first embodiment, and the similarities will not be repeated here. The differences are briefly described as follows:

A polymer-based coating on the surface of a biomedical material, in parts by mass, the base coating includes 3.5 parts of ethyl orthosilicate, 50 parts of pure water, 1 part of glacial acetic acid, 1 part of silane coupling agent, nanometer 0.3 parts of titanium dioxide and 0.7 parts of nano-silver.

Example 3

This embodiment has many similarities with the first embodiment, and the similarities will not be repeated here. The differences are briefly described as follows:

A polymer-based coating on the surface of a biomedical material, in parts by mass, the base coating includes 3.5 parts of ethyl orthosilicate, 50 parts of pure water, 1 part of glacial acetic acid, 1 part of silane coupling agent, nanometer 0.5 part of titanium dioxide and 1.0 part of nano-silver.

The coating prepared in Example 1 to Example 3 and the coating prepared in Comparative Example 1 to Example 2 were magnetically stirred for 8 days to form a sol; the aluminum alloy test piece of the same size was polished with sandpaper until there were no obvious scratches. Then use alkaline washing-water washing-acid washing-water washing-alcohol washing-blow-drying; respectively immerse the processed aluminum sheet in each sol for 45 minutes, and carry out coating coverage by pulling method, and then carry out the corresponding test; Carrier quantitative sterilization test method to detect the killing effect on Staphylococcus aureus

Table 1 List of performance parameters of aluminum sheets made of coatings with different proportions

Sample serial number Corrosion potential V Impact strength kJ/m ² 24h average sterilization rate (%) Comparative example 1 -0.612 6.2 67.3 Comparative example 2 -0.708 5.3 86.1 Example 1 -0.543 7.5 88.3 Example 2 -0.503 7.9 91.2 Example 3 -0.472 8.1 94.6

The above test data shows that with the change in the mass fraction of nano-TiO2 in the base coating, the corrosion potential and impact strength of the aluminum sheet gradually increase, indicating that the coating has good protection and anti-corrosion properties; at the same time, with the quality of nano-silver in the coating As the score changes, the sterilization rate of the aluminum sheet gradually increases, indicating that the coating has a stable antibacterial effect.

Although the technical solutions of the present invention have been described and enumerated in more detail, it should be understood that for those skilled in the art, it is important for those skilled in the art to modify the above-mentioned embodiments or adopt equivalent alternatives. Obviously, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of the present invention.

Claims (4)

A polymer-based coating on the surface of a biomedical material, characterized in that: in parts by mass, the base coating comprises 2-5 parts of ethyl orthosilicate, 40-60 parts of pure water, and 0.5-2 parts of glacial acetic acid. Parts, 0.5-2 parts of silane coupling agent, 0.1-0.5 parts of nano-titanium dioxide, 0.5-1 parts of nano-silver. The polymer-based coating on the surface of a biomedical material according to claim 1, wherein the nano titanium dioxide is prepared by a method including the following steps: Weigh the raw materials: Weigh the raw materials according to the following parts by weight, 4-6 parts of butyl titanate, 10-30 parts of anhydrous ethanol, 0.5-2 parts of glacial acetic acid, 0.5-2 parts of ultrapure water, concentrated nitric acid 1- 3 copies; Prepare solution a: At 15-25°C, drop butyl titanate into 10-20 parts of absolute ethanol at a constant rate of 40-60 drops/min, and then add 0.5-2 parts of glacial acetic acid to obtain solution a; Prepare solution b: mix 0.5-2 parts of ultrapure water and 5-10 parts of absolute ethanol, and then gradually add concentrated nitric acid to obtain solution b with pH=2-3; Preparation: Drop the solution a into solution b at a constant speed of 30-50 drops/min, stir at a constant speed for 0.5-1h until a transparent gel appears, and then put it in a muffle furnace and heat it up to 300-600℃ for 0.5 -1h, grinding to obtain the nano titanium dioxide. The polymer-based coating on the surface of a biomedical material according to claim 1, wherein the average particle size of the nano titanium dioxide is 5-15 nm, and the specific surface area is 80-115 m ² /g. The polymer-based coating on the surface of a biomedical material according to claim 1, wherein the average particle size of the nano-silver is 20-30 nm, and the specific surface area is 70-90 m ² /g.