阅读说明：本技术 一种光固化亲水涂层的制备方法 (Preparation method of photocuring hydrophilic coating ) 是由 聂智军 裘雅红 黄海生 王利明 于 2021-10-11 设计创作，主要内容包括：本发明属于高分子材料技术领域,具体涉及一种光固化亲水涂层的制备方法,光固化亲水涂层包括环氧大豆油丙烯酸酯预聚物或聚氨酯丙烯酸酯预聚物、活性稀释剂、光引发剂、亲水聚合物和助剂。光固化亲水涂层具有半互穿网络结构,环氧大豆油丙烯酸酯预聚物或聚氨酯丙烯酸酯亲水涂层经光固化形成网络结构,亲水聚合物以分子缠结的方式分散于交联网络空隙,使亲水涂层既具有亲水润滑功能,又具有可靠的牢固性。(The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a photocuring hydrophilic coating. The photocuring hydrophilic coating has a semi-interpenetrating network structure, the epoxidized soybean oil acrylate prepolymer or the polyurethane acrylate hydrophilic coating forms a network structure through photocuring, and the hydrophilic polymer is dispersed in cross-linked network gaps in a molecular entanglement manner, so that the hydrophilic coating has a hydrophilic lubricating function and reliable firmness.)

1. A preparation method of a photocuring hydrophilic coating is characterized in that the preparation of the hydrophilic coating comprises the following steps:

(1) treating the surface of the instrument: carrying out ultrasonic cleaning on the surface of the instrument, and treating the surface of the instrument by adopting nitrogen, ammonia or oxygen plasma after cleaning;

(2) preparing a hydrophilic coating: adding the prepolymer, the reactive diluent, the photoinitiator, the hydrophilic polymer and the auxiliary agent into a container, and stirring at room temperature for 20-60 min to obtain the hydrophilic coating; the prepolymer is a polyurethane acrylate prepolymer or an epoxidized soybean oil acrylate prepolymer, and the mass ratio of the prepolymer to the hydrophilic polymer to the reactive diluent is 1: (0.1-10), wherein the mass of the photoinitiator is 0.1-5 wt% of that of the hydrophilic coating, and the mass of the auxiliary agent is 0-30 wt% of the total mass of the hydrophilic coating;

(3) preparing a hydrophilic coating: coating a hydrophilic coating on the surface of an instrument, and carrying out photocuring to obtain a hydrophilic coating;

(4) and (3) post-treatment of the hydrophilic coating: and (4) placing the instrument treated in the step (3) in water, soaking at room temperature for 30-90 min, and drying after soaking to obtain the instrument with the super-smooth hydrophilic coating.

2. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the hydrophilic polymer is one or more of polyvinylpyrrolidone, poly (N-2-hydroxypropyl) methacrylamide, polyacrylamide, alginic acid, hyaluronic acid and chitosan, and the auxiliary agent is one or more of a flatting agent and a dispersing agent

3. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the active diluent is one or more of glycidyl methacrylate, polyethylene glycol diacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dipropylene glycol diacrylate, allyl alcohol glycidyl ether and triethylene glycol divinyl ether.

4. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the photoinitiator is one or more of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl phenylpropanone, benzophenone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, 2,4, 6-trimethyl benzoyl ethyl phosphonate, 1-hydroxy-cyclohexyl-phenyl ketone, 4-phenyl benzophenone, 4-chloro benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and benzoin dimethyl ether.

5. The method for preparing a photo-curable hydrophilic coating according to claim 1, wherein the step of preparing the epoxy soybean oil acrylate prepolymer comprises: adding a certain amount of epoxidized soybean oil into a reaction vessel, stirring and heating to 70-90 ℃, gradually dropwise adding an acrylic acid-catalyst-polymerization inhibitor mixture prepared according to a certain proportion, controlling the dropwise adding speed, heating to 90-120 ℃, stirring and reacting for 3-12 h to obtain an epoxidized soybean oil acrylate prepolymer; the mass ratio of the epoxidized soybean oil to the acrylic acid is 1 (3-5); the first catalyst is one or more of N, N-dimethylaniline, N-dimethylbenzylamine, triethylamine and triphenylphosphine, and the content of the first catalyst is 0.1-5 wt% of that of the epoxidized soybean oil; the polymerization inhibitor is one or more of hydroquinone and p-methoxyphenol, and the content of the polymerization inhibitor is 0.01 wt% -1 wt% of that of the epoxidized soybean oil.

6. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the epoxidized soybean oil is epoxidized mixed unsaturated fatty ester and fatty acid, the main components are linoleic acid, oleic acid, palmitic acid and stearic acid, and each molecule contains 3-4 epoxy groups.

7. The method for preparing a photo-curable hydrophilic coating according to claim 1, wherein the preparation of the urethane acrylate prepolymer comprises the following steps: adding a cyclic carbonate compound, an amine compound and a catalyst II into a reaction vessel under the inert gas, heating to 50-150 ℃, and stirring for reacting for 5-48 h; the mass ratio of the cyclic carbonate compound to the amine compound is 1 (0.01-1); the second catalyst is cesium carbonate, and the addition amount of the second catalyst is 0.01-0.1% of the total mass of the cyclic carbonate compounds.

8. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the cyclic carbonate compound is one or more of ethylene carbonate, propylene carbonate acrylate and propylene carbonate methacrylate.

9. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the amine compound is one or more of ethylenediamine, hexanediamine, decanediamine, p-phenylenediamine, isophorone diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and polyether amine.

10. The method of claim 1, wherein the step of forming the photocurable hydrophilic coating comprises: the photocuring is one or more of ultraviolet photocuring and LED photocuring, and the photocuring time is 0.5-5 min.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a photocuring hydrophilic coating.

Background

The interventional diagnosis and treatment technology is a series of technologies for introducing specific instruments such as a puncture needle, a catheter, a guide wire and the like into a human body through natural pores or tiny wounds of the human body to carry out minimally invasive treatment. Compared with the traditional medical technology, the interventional diagnosis and treatment has the advantages of low wound, small treatment risk, low treatment cost and the like, and is widely popularized and applied clinically. Currently, most interventional devices are made of hydrophobic materials, such as polyvinyl chloride, polyurethane, silicone rubber, and the like. Although they have excellent mechanical properties and biocompatibility, they are too hydrophobic, and have a large friction force against tissues when being introduced into a human body, so that epithelial tissues such as urethra, blood vessel wall and respiratory tract are easily damaged, pain or burning sensation is generated to patients, and complicated inflammation is easily caused after bacteria are adsorbed. Therefore, it is necessary to perform a surface lubrication treatment on the interventional instrument.

The hydrophilic coating can well solve the problem of friction between the interventional device and human tissues. Through forming the stable hydrophilic polymer coating of one deck on intervention apparatus surface, in the water environment, hydrophilic polymer absorbs a large amount of moisture, forms a hydration layer, greatly reduces the coefficient of friction between intervention apparatus and the human tissue, reduces the damage to the human tissue, improves the convenience of doctor's operation and the travelling comfort of disease simultaneously. Since the interventional device is moved and stays in the body for a certain time. Thus, in addition to high hydrophilic lubricity, hydrophilic coatings on interventional devices must also be robust and stable, i.e., the coating will not fall off after repeated rubbing and maintain a good balance of properties.

At first, researchers directly coat hydrophilic polymers on the surface of medical instruments, the hydrophilic polymers are adhered to the surface of materials through intermolecular forces, the adhesion force is weak, and the coating is easy to fall off and cannot meet the use requirements of the medical instruments. The conventional hydrophilic coating is usually a mixture comprising hydrophilic polymer, oligomer, reactive diluent, auxiliary agent and other components, and a thermosetting process is generally adopted, namely a thermosetting coating is coated on the surface of a device and is placed in a higher temperature environment, so that reactive groups in a thermosetting coating liquid react, a solvent volatilizes, and finally the film is cured on the surface of the device to form a film. The thermocuring process is simple, basically only needs leaching and drying, but has more obvious defects, such as longer reaction time; the high temperature affects the performance of the instrument material and accelerates the migration of the small molecular auxiliary agent; heating and curing lead to poor controllability of the production process and poor stability of the coating. The photocuring process can be rapidly cured at normal temperature, and can overcome the defect of thermocuring, so that the application of photocuring in hydrophilic coatings is more and more paid attention by researchers.

For the above reasons, it is desirable to provide a method for preparing a photocurable hydrophilic coating.

Disclosure of Invention

The present invention aims to provide a method for preparing a photo-curing hydrophilic coating, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of a photocuring hydrophilic coating comprises the following steps:

(1) treating the surface of the instrument: carrying out ultrasonic cleaning on the surface of the instrument, and treating the surface of the instrument by adopting nitrogen, ammonia or oxygen plasma after cleaning;

(2) preparing a hydrophilic coating: adding the prepolymer, the reactive diluent, the photoinitiator, the hydrophilic polymer and the auxiliary agent into a container, and stirring at room temperature for 20-60 min to obtain the hydrophilic coating; the prepolymer is a polyurethane acrylate prepolymer or an epoxidized soybean oil acrylate prepolymer, and the mass ratio of the prepolymer to the hydrophilic polymer to the reactive diluent is 1: (0.1-10), wherein the mass of the photoinitiator is 0.1-5 wt% of that of the hydrophilic coating;

(3) preparing a hydrophilic coating: coating a hydrophilic coating on the surface of an instrument, and carrying out photocuring to obtain a hydrophilic coating;

(4) and (3) post-treatment of the hydrophilic coating: and (4) placing the instrument treated in the step (3) in water, soaking at room temperature for 30-90 min, and drying after soaking to obtain the instrument with the super-smooth hydrophilic coating.

Preferably, the hydrophilic polymer is one or more of polyvinylpyrrolidone, poly (N-2-hydroxypropyl) methacrylamide, polyacrylamide, alginic acid, hyaluronic acid and chitosan.

Preferably, the reactive diluent is one or more of glycidyl methacrylate, polyethylene glycol diacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dipropylene glycol diacrylate, allyl alcohol glycidyl ether and triethylene glycol divinyl ether.

Preferably, the photoinitiator is one or more of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphosphonate, 1-hydroxy-cyclohexyl-phenyl ketone, 4-phenyl benzophenone, 4-chlorobenzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone and benzoin bismethyl ether.

Preferably, the auxiliary agent is one or more of a leveling agent and a dispersing agent.

Preferably, the preparation step of the epoxidized soybean oil acrylate prepolymer comprises the following steps: adding a certain amount of epoxidized soybean oil into a reaction vessel, stirring and heating to 70-90 ℃, gradually dropwise adding an acrylic acid-catalyst-polymerization inhibitor mixture prepared according to a certain proportion, controlling the dropwise adding speed, heating to 90-120 ℃, stirring and reacting for 3-12 h to obtain an epoxidized soybean oil acrylate prepolymer; the mass ratio of the epoxidized soybean oil to the acrylic acid is 1 (3-5); the first catalyst is one or more of N, N-dimethylaniline, N-dimethylbenzylamine, triethylamine and triphenylphosphine, and the content of the first catalyst is 0.1-5 wt% of that of the epoxidized soybean oil; the polymerization inhibitor is one or more of hydroquinone and p-methoxyphenol, and the polymerization inhibitor is 0.01 wt% -1 wt% of epoxidized soybean oil.

Preferably, the epoxidized soybean oil is an epoxidized mixed unsaturated fatty ester and fatty acid, the main components are linoleic acid, oleic acid, palmitic acid and stearic acid, and each molecule contains 3-4 epoxy groups.

Preferably, the preparation of the urethane acrylate prepolymer comprises the following steps: adding a cyclic carbonate compound, an amine compound and a catalyst II into a reaction vessel under the inert gas, heating to 50-150 ℃, and stirring for reacting for 5-48 h; the mass ratio of the cyclic carbonate compound to the amine compound is 1 (0.01-1); the second catalyst is cesium carbonate, and the addition amount of the second catalyst is 0.01-0.1% of the total mass of the cyclic carbonate compounds.

Preferably, the cyclic carbonate compound is one or more of ethylene carbonate, propylene carbonate acrylate and propylene carbonate methacrylate.

Preferably, the amine compound is one or more of ethylenediamine, hexanediamine, decanediamine, p-phenylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyetheramine.

Preferably, the photocuring is one or more of ultraviolet photocuring and LED photocuring, and the photocuring time is 0.5-5 min.

Compared with the prior art, the invention has the beneficial effects that:

(1) compared with a thermal curing process, the photo-curing hydrophilic coating provided by the invention has the advantages of short curing time, low curing temperature and the like, and is more beneficial to production and risk control of medical instruments;

(2) the photocuring hydrophilic coating provided by the invention has a semi-interpenetrating network structure, an acrylate prepolymer forms a network structure through photocuring, and a hydrophilic polymer is dispersed in cross-linked network gaps in a molecular entanglement manner; compared with the direct coating of hydrophilic polymers, the hydrophilic coating with the semi-interpenetrating network structure can greatly improve the firmness of the coating;

(3) the invention provides a preparation method of a photocuring hydrophilic coating, and related epoxy acrylate resin is epoxy soybean oil acrylate; compared with the traditional bisphenol A type glycidyl ether epoxy acrylate, the epoxy soybean oil acrylate has longer molecular chain and moderate crosslinking density, and can obviously improve the flexibility of the coating, thereby greatly improving the cracking and falling-off phenomenon of the coating on the surface of a medical instrument;

(4) according to the preparation method of the photocuring hydrophilic coating, the polyurethane acrylate prepolymer adopts a non-isocyanate synthesis route, so that the biocompatibility risk caused by excessive residual isocyanate is avoided.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Adding 100g of epoxidized soybean oil into a reaction vessel, heating to 80 ℃, gradually adding a mixture of acrylic acid, N-dimethylaniline and hydroquinone which are prepared according to a certain proportion, controlling the dropping speed, heating to 100 ℃, and stirring for 5 hours to react to obtain the epoxidized soybean oil acrylate prepolymer. The mass ratio of the epoxidized soybean oil to the acrylic acid is 1: 3; the N, N-dimethylaniline accounts for 0.5 percent of the weight of the epoxidized soybean oil, and the hydroquinone accounts for 0.05 percent of the weight of the epoxidized soybean oil.

Adding the epoxy soybean oil acrylate prepolymer, the polyethylene glycol diacrylate, the 4-phenyl benzophenone, the polyvinylpyrrolidone and the hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyvinylpyrrolidone to the polyethylene glycol diacrylate is 1:2:5, and the mass of the 4-phenyl benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting nitrogen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 2

Adding 100g of epoxidized soybean oil into a reaction vessel, heating to 70 ℃, gradually adding a mixture of acrylic acid, N-dimethylaniline and hydroquinone which are prepared according to a certain proportion, controlling the dropping speed, heating to 110 ℃, and stirring for reacting for 5 hours to obtain the epoxidized soybean oil acrylate prepolymer. The mass ratio of the epoxidized soybean oil to the acrylic acid is 1: 3; the N, N-dimethylaniline accounts for 0.5 percent of the weight of the epoxidized soybean oil, and the hydroquinone accounts for 0.5 percent of the weight of the epoxidized soybean oil.

Adding the epoxy soybean oil acrylate prepolymer, the dipropylene glycol diacrylate, the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, the polyvinylpyrrolidone and the hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyvinylpyrrolidone to the dipropylene glycol diacrylate is 1:3:5, and the mass of the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting nitrogen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 3

Adding 100g of epoxidized soybean oil into a reaction vessel, heating to 80 ℃, gradually adding a mixture of acrylic acid, triethylamine and hydroquinone which are prepared according to a certain proportion, controlling the dropping speed, heating to 90 ℃, and stirring for reacting for 8 hours to obtain the epoxidized soybean oil acrylate prepolymer. The mass ratio of the epoxidized soybean oil to the acrylic acid is 1: 3; the triethylamine accounts for 0.1 percent of the weight of the epoxidized soybean oil, and the hydroquinone accounts for 0.5 percent of the weight of the epoxidized soybean oil.

Adding the epoxy soybean oil acrylate prepolymer, allyl alcohol glycidyl ether, benzophenone, polyvinylpyrrolidone and hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyvinylpyrrolidone to the allyl alcohol glycidyl ether is 1:3:10, and the mass of the benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting oxygen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 4

And (2) adding 100g of epoxidized soybean oil into a reaction vessel, heating to 70 ℃, gradually adding a mixture of acrylic acid, triphenylphosphine and hydroquinone which are prepared according to a certain proportion, controlling the dropping rate, heating to 100 ℃, and stirring for reacting for 6 hours to obtain the epoxidized soybean oil acrylate prepolymer. The mass ratio of the epoxidized soybean oil to the acrylic acid is 1: 3; the triphenylphosphine accounts for 0.5 percent of the mass of the epoxidized soybean oil, and the hydroquinone accounts for 0.1 percent of the mass of the epoxidized soybean oil.

Adding the epoxy soybean oil acrylate prepolymer, the dipropylene glycol diacrylate, the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, the polyvinylpyrrolidone and the N-methyl pyrrolidone into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyvinylpyrrolidone to the dipropylene glycol diacrylate is 1:2:5, and the mass of the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting oxygen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 5

Adding 100g of epoxidized soybean oil into a reaction vessel, heating to 80 ℃, gradually adding a mixture of acrylic acid, triethylamine and p-methoxyphenol which are prepared according to a certain proportion, controlling the dropping speed, heating to 100 ℃, and stirring for reacting for 8 hours to obtain the epoxidized soybean oil acrylate prepolymer. The mass ratio of the epoxidized soybean oil to the acrylic acid is 1: 3; the triethylamine accounts for 0.5 percent of the mass of the epoxidized soybean oil, and the p-methoxyphenol accounts for 0.1 percent of the mass of the epoxidized soybean oil.

Adding the epoxy soybean oil acrylate prepolymer, the polyethylene glycol diacrylate, the benzophenone, the polyvinylpyrrolidone and the N-methyl pyrrolidone into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyvinylpyrrolidone to the polyethylene glycol diacrylate is 1:2:1, and the mass of the benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting ammonia low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 6

And (2) adding 100g of epoxidized soybean oil into a reaction container, heating to 80 ℃, gradually adding a mixture of acrylic acid, triphenylphosphine and p-methoxyphenol which are prepared according to a certain proportion, controlling the dropping rate, heating to 100 ℃, and stirring for reacting for 5 hours to obtain the epoxidized soybean oil acrylate prepolymer. The mass ratio of the epoxidized soybean oil to the acrylic acid is 1: 3; the triphenylphosphine accounts for 0.5 percent of the mass of the epoxidized soybean oil, and the p-methoxyphenol accounts for 0.05 percent of the mass of the epoxidized soybean oil.

Adding the epoxy soybean oil acrylate prepolymer, allyl alcohol glycidyl ether, 4-phenyl benzophenone, alginic acid and hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the alginic acid to the allyl alcohol glycidyl ether is 1:3:5, and the mass of the 4-phenyl benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting ammonia low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out LED photocuring for 3min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 7

Under the condition of nitrogen, adding ethylene carbonate, hexamethylene diamine and cesium carbonate into a reaction vessel, heating to 80 ℃, and stirring for reaction for 10 hours to obtain the urethane acrylate prepolymer. The mass ratio of ethylene carbonate to hexamethylene diamine is 1: 0.5; the cesium carbonate accounts for 0.01 percent of the ethylene carbonate by mass.

Adding the polyurethane acrylate prepolymer, the polyethylene glycol diacrylate, the 4-phenyl benzophenone, the polyvinylpyrrolidone and the hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyvinylpyrrolidone to the polyethylene glycol diacrylate is 1:2:10, and the mass of the 4-phenyl benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting nitrogen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 8

Under the condition of nitrogen, adding ethylene carbonate, isophorone diamine and cesium carbonate into a reaction container, heating to 80 ℃, and stirring for reaction for 10 hours to obtain the urethane acrylate prepolymer. The mass ratio of ethylene carbonate to isophorone diamine is 1: 0.5; the cesium carbonate accounts for 0.01 percent of the ethylene carbonate by mass.

Adding a polyurethane acrylate prepolymer, dipropylene glycol diacrylate, 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, polyvinylpyrrolidone and hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyvinylpyrrolidone to the dipropylene glycol diacrylate is 1:3:8, and the mass of the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting nitrogen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 9

Under the condition of nitrogen, adding propylene carbonate acrylate, triethylene tetramine and cesium carbonate into a reaction vessel, heating to 100 ℃, and stirring for reaction for 12 hours to obtain the urethane acrylate prepolymer. The mass ratio of the propylene carbonate acrylate to the triethylene tetramine is 1: 0.5; the cesium carbonate accounts for 0.01 percent of the mass of the propylene carbonate acrylate.

Adding the polyurethane acrylate prepolymer, allyl alcohol glycidyl ether, benzophenone, polyvinylpyrrolidone and hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyvinylpyrrolidone to the allyl alcohol glycidyl ether is 1:3:10, and the mass of the benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting oxygen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 10

Under the condition of argon, adding propylene carbonate acrylate, isophorone diamine and cesium carbonate into a reaction container, heating to 100 ℃, and stirring for reaction for 12 hours to obtain a polyurethane acrylate prepolymer. The mass ratio of the propylene carbonate acrylate to the isophorone diamine is 1: 0.5; the cesium carbonate accounts for 0.02 percent of the mass of the propylene carbonate acrylate.

Adding a polyurethane acrylate prepolymer, dipropylene glycol diacrylate, 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, polyvinylpyrrolidone and N-methyl pyrrolidone into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyvinylpyrrolidone to the dipropylene glycol diacrylate is 1:2:5, and the mass of the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting oxygen low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 11

Under the condition of nitrogen, adding propylene carbonate methacrylate, triethylene tetramine and cesium carbonate into a reaction vessel, heating to 70 ℃, and stirring for reacting for 8 hours to obtain the urethane acrylate prepolymer. The mass ratio of the propylene carbonate methacrylate to the triethylene tetramine is 1: 0.5; 0.01 percent of the mass of the propylene carbonate methacrylate.

Adding the polyurethane acrylate prepolymer, polyethylene glycol diacrylate, benzophenone, polyvinylpyrrolidone and N-methyl pyrrolidone into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyvinylpyrrolidone to the polyethylene glycol diacrylate is 1:2:8, and the mass of the benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting ammonia low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Example 12

Under the condition of argon, adding propylene carbonate methacrylate, isophorone diamine and cesium carbonate into a reaction vessel, heating to 90 ℃, and stirring for reaction for 12 hours to obtain a polyurethane acrylate prepolymer. The mass ratio of the propylene carbonate methacrylate to the isophorone diamine is 1: 0.5; the cesium carbonate accounts for 0.01 percent of the mass of the propylene carbonate methacrylate.

Adding a polyurethane acrylate prepolymer, allyl alcohol glycidyl ether, 4-phenyl benzophenone, alginic acid and hydroxypropyl methyl cellulose into a container, and stirring at room temperature for 30min to obtain the hydrophilic coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the alginic acid to the allyl alcohol glycidyl ether is 1:3:5, and the mass of the 4-phenyl benzophenone is 1 wt% of the total mass of the coating.

Before coating the surface of the instrument, cleaning the instrument by adopting ultrasonic to remove oil stains on the surface of the instrument; and treating the surface of the instrument by adopting ammonia low-temperature plasma. And then coating the hydrophilic coating on the surface of the instrument, and carrying out LED photocuring for 3min to obtain the hydrophilic coating. Tests show that the hydrophilic coating has no cytotoxicity; the friction force in the water environment is reduced by more than 90%, and after repeated friction action, the hydrophilic coating can be completely kept, and the increase amplitude of the friction force is not more than 5%.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.