阅读说明：本技术 一种高耐久性亲水涂层的制备方法 (Preparation method of high-durability 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,具体涉及一种高耐久性亲水涂层及其制备方法。高耐久性亲水涂层为双层涂层体系,采用光固化工艺,其中底层涂层中光固化树脂采用环氧大豆油丙烯酸酯,面层涂层中光固化树脂采用聚氨酯丙烯酸酯,两层通过化学键和分子间作用力牢牢结合成一个完整的复合涂层,使整个涂层既具有亲水润滑功能,又具有可靠的牢固性。高耐久性亲水涂层制备方法包括以下步骤：器械表面处理、配制底层涂料、配制面层涂料、制备亲水涂层、和亲水涂层后处理。(The invention belongs to the technical field of high polymer materials, and particularly relates to a high-durability hydrophilic coating and a preparation method thereof. The high-durability hydrophilic coating is a double-layer coating system and adopts a photocuring process, wherein the photocuring resin in the bottom layer coating adopts epoxy soybean oil acrylate, the photocuring resin in the surface layer coating adopts polyurethane acrylate, and the two layers are firmly combined into a complete composite coating through chemical bonds and intermolecular force, so that the whole coating has a hydrophilic lubricating function and reliable firmness. The preparation method of the high-durability hydrophilic coating comprises the following steps: surface treatment of instruments, preparation of primer, preparation of surface coating, preparation of hydrophilic coating and post-treatment of hydrophilic coating.)

1. A high-durability hydrophilic coating and a preparation method thereof are 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 primer: adding the epoxy soybean oil acrylate prepolymer, the reactive diluent, the photoinitiator and the auxiliary agent into a container, and stirring at room temperature for 20-60 min to obtain the primer; the mass ratio of the epoxidized soybean oil acrylate prepolymer to the reactive diluent is 1 (0.1-10), and the mass of the photoinitiator is 0.1-5 wt% of the total mass of the primer; the mass of the auxiliary agent is 0 wt% -30 wt% of the total mass of the low-layer coating;

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

(4) preparing a hydrophilic coating: coating the bottom layer coating on the surface of a clean instrument, and carrying out photocuring to obtain a bottom layer coating; coating the surface layer coating on the surface of the bottom layer coating, and carrying out photocuring to obtain a surface layer coating, thereby obtaining an initial product with a hydrophilic coating;

(5) and (3) post-treatment of the hydrophilic coating: and (3) placing the device with the hydrophilic coating initial product in water, soaking for 30-60 min at room temperature, taking out and drying to obtain the device with the hydrophilic coating with high durability.

2. The method for preparing a hydrophilic coating with high durability according to claim 1, wherein: 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.

3. The method for preparing a hydrophilic coating with high durability according to claim 1, wherein: the hydrophilic polymer is one or more of polyvinylpyrrolidone, poly (N-2-hydroxypropyl) methacrylamide, polyacrylamide, alginic acid, hyaluronic acid and chitosan; the auxiliary agent is one or more of a flatting agent and a dispersing agent.

4. The method for preparing a hydrophilic coating with high durability according to claim 1, wherein: 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 phosphonic acid ethyl ester, 1-hydroxy-cyclohexyl-phenyl ketone, 4-phenyl benzophenone, 4-chlorine benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and benzoin dimethyl ether.

5. The method for preparing a hydrophilic coating with high durability as claimed in claim 1, wherein the epoxy soybean oil acrylate prepolymer is prepared by the steps of: adding epoxidized soybean oil into a reaction vessel, stirring and heating to 70-90 ℃, gradually adding a mixture of acrylic acid, a catalyst I and a polymerization inhibitor which are prepared according to a certain proportion, controlling the dropping 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 first catalyst is 0.1-5 wt% of epoxidized soybean oil.

6. The method for preparing a hydrophilic coating with high durability according to claim 1, wherein: the epoxidized soybean oil is epoxidized mixed unsaturated fatty ester and fatty acid, mainly comprises linoleic acid, oleic acid, palmitic acid and stearic acid, and each molecule contains 3-4 epoxy groups.

7. The method for preparing a hydrophilic coating with high durability according to claim 1, wherein: 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.

8. The method for preparing the hydrophilic coating with high durability as claimed in claim 1, wherein the preparation of the urethane acrylate prepolymer comprises the following steps: adding diisocyanate and hydroxyethyl methacrylate into a reaction vessel, heating to 25-50 ℃, stirring for reaction for 1-3 h to obtain an intermediate product, heating to 45-70 ℃, adding a catalyst II and polytetrahydrofuran diol, and reacting for 5-15 h to obtain a polyurethane acrylate prepolymer; the second catalyst is one or more of dibutyltin dilaurate and stannous octoate, and the mass of the second catalyst is 1-3 wt% of that of the polytetrahydrofuran diol; the mass ratio of the diisocyanate to the hydroxyethyl methacrylate to the polytetrahydrofuran diol is 1 (0.9-1.1) to 0.45-0.55; the number average molecular weight of the polytetrahydrofuran diol is 2000 plus or minus 50.

9. The method of claim 8, wherein the hydrophilic coating has a high durability, comprising: the diisocyanate is one or more of 1, 6-hexamethylene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate.

10. The method for preparing a hydrophilic coating with high durability according to claim 1, wherein: the photocuring is one or more of ultraviolet photocuring and LED photocuring, the photocuring time of the bottom layer is 0.5-3 min, and the photocuring time of the surface layer is 1-5 min.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a high-durability 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.

Hydrophilic coatings are generally mixtures of hydrophilic polymers, oligomers, reactive diluents, adjuvants, and the like, and generally employ a thermal curing process in which a thermal curing coating is applied to the surface of a device, placed in a relatively high temperature environment, the reactive groups in the thermal curing coating react, the solvent volatilizes, and finally the coating cures to a film on the surface of the device. 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 highly durable hydrophilic coating and a method for preparing the same.

Disclosure of Invention

The present invention is directed to a high durability hydrophilic coating and a method for preparing the same, which solves the above problems of the prior art.

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

a preparation method of a high-durability 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 primer: adding the epoxy soybean oil acrylate prepolymer, the reactive diluent, the photoinitiator and the auxiliary agent into a container, and stirring at room temperature for 20-60 min to obtain the primer; the mass ratio of the epoxidized soybean oil acrylate prepolymer to the reactive diluent is 1 (0.1-10), and the mass of the photoinitiator is 0.1-5 wt% of the total mass of the primer; the mass of the auxiliary agent is 0 wt% -30 wt% of the total mass of the surface layer coating;

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

(4) preparing a hydrophilic coating: coating the bottom layer coating on the surface of a clean instrument, and carrying out photocuring to obtain a bottom layer coating; coating the surface layer coating on the surface of the bottom layer coating, and carrying out photocuring to obtain a surface layer coating, thereby obtaining an initial product with a hydrophilic coating;

(5) and (3) post-treatment of the hydrophilic coating: and (3) placing the apparatus with the initial hydrophilic coating in water, soaking for 30-60 min at room temperature, taking out and drying to obtain the hydrophilic coating with high durability.

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

preferably, the photoinitiator is one or more of 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphosphonate, 1-hydroxy-cyclohexyl-phenyl ketone, 4-phenyl benzophenone, 4-chlorobenzophenone and 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 epoxidized soybean oil into a reaction vessel, stirring and heating to 70-90 ℃, gradually adding a mixture of acrylic acid, a catalyst I and a polymerization inhibitor which are prepared according to a certain proportion, controlling the dropping 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 first catalyst is 0.1-5 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 to 4 epoxy groups.

Preferably, 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.

Preferably, the preparation of the urethane acrylate prepolymer comprises the following steps: adding diisocyanate and hydroxyethyl methacrylate into a reaction vessel, heating to 25-50 ℃, stirring for reaction for 1-3 h to obtain an intermediate product, heating to 45-70 ℃, adding a catalyst II and polytetrahydrofuran diol, and reacting for 5-15 h to obtain a polyurethane acrylate prepolymer; the second catalyst is one or more of dibutyltin dilaurate and stannous octoate, and the mass of the second catalyst is 1-3 wt% of that of the polytetrahydrofuran diol; the mass ratio of the diisocyanate to the hydroxyethyl methacrylate to the polytetrahydrofuran diol is 1 (0.9-1.1) to 0.45-0.55; the number average molecular weight of the polytetrahydrofuran diol is 2000 +/-50;

preferably, the diisocyanate is one or more of 1, 6-hexamethylene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate.

Preferably, the photocuring is one or more of ultraviolet photocuring and LED photocuring, the photocuring time of the bottom layer is 0.5-3 min, and the photocuring time of the surface layer is 1-5 min.

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

(1) according to the preparation method of the high-durability hydrophilic coating, the photo-curing process is adopted, and compared with the thermal curing process, the photo-curing process 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) according to the preparation method of the high-durability hydrophilic coating, the hydrophilic coating is a double-layer system, the bottom coating is used as a connecting layer and has a dense cross-linked network structure, so that the hydrophilic coating can be firmly combined with an instrument and can also provide bonding cross-linked points for a surface layer; the surface layer coating is a hydrophilic functional layer and has a semi-interpenetrating network structure, and the hydrophilic polymer is dispersed in cross-linked network gaps in a molecular entanglement mode. Compared with a single-layer coating system, the double-layer coating system can better balance the lubricating property and the firmness of the coating;

(3) according to the preparation method of the high-durability hydrophilic coating provided by the invention, the hydrophilic coating is a bi-component curing system, the light-cured resin in the bottom coating adopts the epoxy soybean oil acrylate, and compared with the traditional bisphenol A type glycidyl ether epoxy acrylate, the epoxy soybean oil acrylate can obviously improve the flexibility of the coating while maintaining the advantages of high curing speed, high adhesive force, good chemical resistance and the like. The light-cured resin in the surface layer coating adopts polyurethane acrylate, so that the wear resistance and flexibility of the coating can be further improved. The two layers are firmly combined into a complete composite coating through chemical bonds and intermolecular force, so that the whole coating has a hydrophilic lubricating function and reliable firmness.

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 1, 6-hexamethylene diisocyanate, hydroxyethyl methacrylate and an antioxidant into a reaction vessel, heating to 50 ℃, and stirring for reacting for 3 hours to obtain an intermediate product; heating to 60 ℃; and adding dibutyltin dilaurate and polytetrahydrofuran diol, and reacting for 10h to obtain the urethane acrylate prepolymer. The mass ratio of 1, 6-hexamethylene diisocyanate, hydroxyethyl methacrylate and polytetrahydrofuran diol is 1:1.1: 0.55.

Adding the epoxy soybean oil acrylate prepolymer, the polyethylene glycol diacrylate and the 4-phenyl benzophenone into a container, and stirring at room temperature for 30min to obtain a primer, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyethylene glycol diacrylate is 1:2, and the mass of the 4-phenyl benzophenone is 3 wt% of the total mass of the primer; adding a polyurethane acrylate prepolymer, polyvinylpyrrolidone, glycidyl methacrylate and 4-phenyl benzophenone into a container, and stirring at room temperature for 30min to obtain the surface layer coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyvinylpyrrolidone to the glycidyl methacrylate is 1:2:2, and the mass of the 4-phenyl benzophenone is 3 wt% of the total mass of the surface layer 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. Then coating the bottom coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain a bottom coating; coating the surface layer coating on the surface of the obtained bottom coating, and curing for 3min by using ultraviolet light to obtain a face coating; and (3) placing the instrument in water, soaking for 30min at room temperature, taking out and drying 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 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 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 1, 6-hexamethylene diisocyanate, hydroxyethyl methacrylate and an antioxidant into a reaction vessel, heating to 45 ℃, and stirring for reacting for 3 hours to obtain an intermediate product; heating to 70 ℃; and adding dibutyltin dilaurate and polytetrahydrofuran diol, and reacting for 10h to obtain the urethane acrylate prepolymer. The mass ratio of 1, 6-hexamethylene diisocyanate, hydroxyethyl methacrylate and polytetrahydrofuran diol is 1:1: 0.5.

Adding the epoxy soybean oil acrylate prepolymer, triethylene glycol divinyl ether and 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone into a container, and stirring at room temperature for 50min to obtain a primer, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the triethylene glycol divinyl ether is 1:5, and the mass of the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone is 3 wt% of the total mass of the primer; adding a polyurethane acrylate prepolymer, polyvinylpyrrolidone, glycidyl methacrylate and 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone into a container, and stirring at room temperature for 50min to obtain a surface layer coating, wherein the mass ratio of the polyurethane acrylate prepolymer, the polyvinylpyrrolidone and the glycidyl methacrylate is 1:2:5, and the mass of the 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone is 3 wt% of the total mass of the surface layer 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. Then coating the bottom coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain a bottom coating; coating the surface layer coating on the surface of the obtained bottom coating, and curing for 3min by using ultraviolet light to obtain a face coating; and (3) placing the instrument in water, soaking for 60min at room temperature, taking out and drying 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 100 ℃, and stirring for reaction 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 triethylamine 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 4,4' -diphenylmethane diisocyanate, hydroxyethyl methacrylate and an antioxidant into a reaction vessel, heating to 60 ℃, and stirring for reacting for 3 hours to obtain an intermediate product; heating to 80 ℃; and adding dibutyltin dilaurate and polytetrahydrofuran diol, and reacting for 12h to obtain the urethane acrylate prepolymer. The mass ratio of 4,4' -diphenylmethane diisocyanate, hydroxyethyl methacrylate and polytetrahydrofuran diol is 1:1.1: 0.55.

Adding the epoxy soybean oil acrylate prepolymer, polyethylene glycol diacrylate and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into a container, and stirring at room temperature for 30min to obtain a primer, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyethylene glycol diacrylate is 1:5, and the mass of the 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone is 3 wt% of the total mass of the primer; adding a polyurethane acrylate prepolymer, polyvinylpyrrolidone, allyl alcohol glycidyl ether and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into a container, and stirring at room temperature for 30min to obtain the surface layer coating, wherein the mass ratio of the polyurethane acrylate prepolymer, the polyvinylpyrrolidone and the allyl alcohol glycidyl ether is 1:3:5, and the mass of the 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone is 3 wt% of the total mass of the surface layer 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. Then coating the bottom coating on the surface of the instrument, and curing for 3min by using ultraviolet light to obtain a bottom coating; coating the surface layer coating on the surface of the obtained bottom coating, and curing for 5min by using ultraviolet light to obtain a face coating; and (3) placing the instrument in water, soaking for 30min at room temperature, taking out and drying 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 80 ℃, gradually adding a mixture of acrylic acid, triphenylphosphine and hydroquinone which are prepared according to a certain proportion, controlling the dropping speed, 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 1 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 4,4' -diphenylmethane diisocyanate, hydroxyethyl methacrylate and an antioxidant into a reaction vessel, heating to 50 ℃, and stirring for reacting for 3 hours to obtain an intermediate product; heating to 60 ℃; and adding stannous octoate and polytetrahydrofuran diol, and reacting for 12h to obtain the urethane acrylate prepolymer. The mass ratio of 4,4' -diphenylmethane diisocyanate, hydroxyethyl methacrylate and polytetrahydrofuran diol is 1:1: 0.5.

Adding the epoxy soybean oil acrylate prepolymer, the dipropylene glycol diacrylate and the 4-phenyl benzophenone into a container, and stirring at room temperature for 30min to obtain a primer, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the dipropylene glycol diacrylate is 1:3, and the mass of the benzoin dimethyl ether is 3 wt% of the total mass of the primer; adding a polyurethane acrylate prepolymer, polyacrylamide, glycidyl methacrylate and 4-phenyl benzophenone into a container, and stirring at room temperature for 30min to obtain the surface layer coating, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyacrylamide to the glycidyl methacrylate is 1:5:5, and the mass of benzoin dimethyl ether is 3 wt% of the total mass of the surface layer 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. Then coating the bottom coating on the surface of the instrument, and curing for 3min by using ultraviolet light to obtain a bottom coating; coating the surface layer coating on the surface of the obtained bottom coating, and curing for 5min by using ultraviolet light to obtain a face coating; and (3) placing the instrument in water, soaking for 30min at room temperature, taking out and drying 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 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 triethylamine accounts for 1 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 isophorone diisocyanate, hydroxyethyl methacrylate and an antioxidant into a reaction vessel, heating to 60 ℃, and stirring for reacting for 3 hours to obtain an intermediate product; heating to 80 ℃; and adding dibutyltin dilaurate and polytetrahydrofuran diol, and reacting for 10h to obtain the urethane acrylate prepolymer. The mass ratio of the isophorone diisocyanate, the hydroxyethyl methacrylate and the polytetrahydrofuran diol is 1:1.1: 0.55.

Adding the epoxy soybean oil acrylate prepolymer, the polyethylene glycol diacrylate and the 1-hydroxy-cyclohexyl-phenyl ketone into a container, and stirring at room temperature for 50min to obtain a primer, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyethylene glycol diacrylate is 1:6, and the mass of the 1-hydroxy-cyclohexyl-phenyl ketone is 3 wt% of the total mass of the primer; adding a polyurethane acrylate prepolymer, polyvinylpyrrolidone, glycidyl methacrylate and 1-hydroxy-cyclohexyl-phenyl ketone into a container, and stirring at room temperature for 50min to obtain the surface coating, wherein the mass ratio of the polyurethane acrylate prepolymer, the polyvinylpyrrolidone and the glycidyl methacrylate is 1:3:3, and the mass of the 1-hydroxy-cyclohexyl-phenyl ketone is 3 wt% of the total mass of the surface 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. Then coating the bottom coating on the surface of the instrument, and carrying out LED photocuring for 3min to obtain a bottom coating; coating the surface layer coating on the surface of the obtained bottom coating, and carrying out LED photocuring for 3min to obtain a face coating; and (3) placing the instrument in water, soaking for 30min at room temperature, taking out and drying 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 1 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 isophorone diisocyanate, hydroxyethyl methacrylate and an antioxidant into a reaction vessel, heating to 50 ℃, and stirring for reacting for 3 hours to obtain an intermediate product; heating to 60 ℃; and adding stannous octoate and polytetrahydrofuran diol, and reacting for 12h to obtain the urethane acrylate prepolymer. The mass ratio of the isophorone diisocyanate to the hydroxyethyl methacrylate to the polytetrahydrofuran diol is 1:1: 0.5.

Adding the epoxy soybean oil acrylate prepolymer, the polyethylene glycol diacrylate and the 4-phenyl benzophenone into a container, and stirring at room temperature for 50min to obtain a primer, wherein the mass ratio of the epoxy soybean oil acrylate prepolymer to the polyethylene glycol diacrylate is 1:1, and the mass of the 4-phenyl benzophenone is 3 wt% of the total mass of the primer; adding a polyurethane acrylate prepolymer, poly (N-2-hydroxypropyl) methacrylamide, dipropylene glycol diacrylate and 4-phenyl benzophenone into a container, and stirring at room temperature for 50min to obtain the surface coating, wherein the mass ratio of the polyurethane acrylate prepolymer, the poly (N-2-hydroxypropyl) methacrylamide and the dipropylene glycol diacrylate is 1:1:2, and the mass of the 4-phenyl benzophenone is 3 wt% of the total mass of the surface 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. Then coating the bottom coating on the surface of the instrument, and carrying out ultraviolet curing for 2min to obtain a bottom coating; coating the surface layer coating on the surface of the obtained bottom coating, and curing for 3min by using ultraviolet light to obtain a face coating; and (3) placing the instrument in water, soaking for 30min at room temperature, taking out and drying 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.