Hydrophilic antibacterial medical non-woven fabric and preparation process thereof

Abstract

The invention relates to the technical field of medical non-woven fabrics, and particularly discloses a hydrophilic and bacteriostatic medical non-woven fabric and a preparation process thereof.The hydrophilic and bacteriostatic medical non-woven fabric is prepared by taking a polyester non-woven fabric as a base material, dipping in a composite antibacterial dipping solution containing zinc oxide-tin dioxide and a benzophenone derivative and a dipping solution containing catechol and 3-aminopropyltriethoxysilane, and preparing the hydrophilic and bacteriostatic medical non-woven fabric. According to the medical non-woven fabric, the base material is coated with the coating with the antibacterial function and good hydrophilicity, hydrophilization and antibacterial functionalization of the medical non-woven fabric product are achieved, the prepared medical non-woven fabric is good in antibacterial effect and good in hydrophilicity, and the requirements of the medical non-woven fabric product are met.

Description

Technical Field

[0001] The invention relates to the technical field of medical nonwoven fabrics, in particular to a hydrophilic and antibacterial medical nonwoven fabric and a preparation process thereof. Background Art

[0002] Non-woven fabric is a fabric formed by directional or random arrangement of textile long fibers or short fibers and reinforcement by physical or chemical means. It has the characteristics of short process flow, fast production rate, high output and low cost, and is suitable for the production of various disposable products in the medical, sanitary and health care industries. Compared with traditional pure cotton medical products, medical non-woven fabric products have the characteristics of high dust filtration, easy disinfection and sterilization, and easy to be compounded with other materials. As disposable products that can be discarded after use, they also have the advantages of safety, hygiene and prevention of cross contamination. However, non-woven fabric products are generally made of chemical synthetic fibers at present, and the fibers themselves do not have hydrophilicity and antibacterial properties. This shortcoming limits their development in the medical field. Therefore, the present invention develops a medical non-woven fabric with both hydrophilicity and antibacterial properties to solve the problem of poor hydrophilicity and antibacterial properties of medical non-woven fabric products. Summary of the invention

[0003] The purpose of the present invention is to provide a hydrophilic and antibacterial medical non-woven fabric and a preparation process thereof, so as to solve the problem that the medical non-woven fabric products have poor hydrophilicity and poor antibacterial properties.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, the preparation method comprising:

[0006] The polyester non-woven fabric is washed with ethanol and deionized water, and dried at 50-70°C for 0.5-1.5h to obtain a pretreated polyester non-woven fabric, and the pretreated polyester non-woven fabric is immersed in a composite antibacterial impregnation solution for 8-12min, taken out after the impregnation, and cross-linked and cured for 1-3h under an ultraviolet light source with a wavelength of 360-370nm, and washed with ethanol after curing, and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric, and the composite antibacterial polyester non-woven fabric is immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 2-4h, taken out after the impregnation, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0007] As a limitation of the present invention, the amounts of the components of the composite antibacterial impregnation solution are as follows, by weight: 4.5 to 5.5 parts of benzophenone derivatives, 28 to 32 parts of zinc oxide-tin dioxide, 75 to 85 parts of ethanol, and 45 to 55 parts of deionized water.

[0008] As a limitation of the present invention, the preparation method of the benzophenone derivative is:

[0009] Mix 6-bromo-1-hexanol and methylimidazole, stir evenly, react at 40-50°C for 22-26h with nitrogen as protective gas, wash with ether after the reaction to obtain hexanol quaternary ammonium salt, mix benzoylbenzoic acid, N,N-dimethylformamide and dichloromethane, stir evenly to obtain benzoylbenzoic acid organic solution, slowly add oxalyl chloride dropwise to the benzoylbenzoic acid organic solution at -5-5°C, stir evenly, react at 25-30°C, 100-300rpm for 7-9h, and the reaction is completed. The mixture is then washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. The quaternary ammonium salt of hexanol, triethylamine, and dichloromethane are mixed to obtain an organic solution of the quaternary ammonium salt of hexanol. The benzoylbenzoyl chloride and dichloromethane are mixed, stirred evenly, and added dropwise to the organic solution of the quaternary ammonium salt of hexanol. The mixture is reacted at 25 to 30° C. and 100 to 300 rpm for 7 to 9 hours. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

[0010] As a limitation of the present invention, when preparing the quaternary ammonium salt of hexanol, the mass ratio of 6-bromo-1-hexanol to methylimidazole used is (2.4-2.6):(1.0-1.2).

[0011] As a limitation of the present invention, when preparing benzoylbenzoyl chloride, the amount of each component used is: 1.9-2.1 parts of benzoylbenzoic acid, 0.009-0.011 parts of N,N-dimethylformamide, 1.1-1.3 parts of oxalyl chloride, and 39.5-40.0 parts of dichloromethane, calculated by mass.

[0012] As a limitation of the present invention, when preparing the benzophenone derivative, the amounts of the components used are: 1.9 to 2.1 parts of quaternary ammonium salt of hexanol, 1.4 to 1.6 parts of triethylamine, and 1.9 to 2.1 parts of benzoylbenzoyl chloride, calculated by weight.

[0013] As a limitation of the present invention, the preparation method of the zinc oxide-tin dioxide is:

[0014] Tin dioxide and deionized water are mixed, and ultrasonic dispersion is performed for 8 to 12 minutes to obtain a tin dioxide dispersion. Zinc chloride and deionized water are mixed to obtain a zinc chloride solution. The zinc chloride solution is slowly dripped into the tin dioxide dispersion, and the pH is adjusted with a sodium hydroxide solution. The mixture is reacted at 50 to 70° C. and 300 to 500 rpm for 2 to 4 hours. The mixture is heated to 95 to 105° C., high pressure crystallized for 10 to 14 hours, cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 380 to 420° C. for 4 to 6 hours to obtain zinc oxide-tin dioxide.

[0015] As a limitation of the present invention, when preparing zinc oxide-tin dioxide, the mass ratio of tin dioxide to zinc chloride used is (0.4-0.6):(3.9-4.1).

[0016] As a limitation of the present invention, the preparation method of the catechol / 3-aminopropyltriethoxysilane impregnation solution is:

[0017] The catechol and tris(hydroxymethyl)aminomethane) buffer solution are mixed and stirred to obtain a catechol solution. 3-aminopropyltriethoxysilane and ethanol are mixed to obtain a 3-aminopropyltriethoxysilane solution. The catechol solution and the 3-aminopropyltriethoxysilane solution are mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] A zinc oxide-tin dioxide composite material was synthesized with zinc oxide and tin dioxide. A heterojunction structure was formed between zinc oxide and tin dioxide, thereby enhancing the photocatalytic activity of tin dioxide, enabling the composite material to produce zinc ions and more ROS, which interact with the bacterial surface through electrostatics, changing the membrane potential and surface tension of the bacterial cell membrane, causing bacterial metabolic disorders, thereby killing the bacteria and decomposing bacterial debris.

[0020] A benzophenone derivative was synthesized from 6-bromo-1-hexanol, methylimidazole, benzoyl benzoate and oxalyl chloride. One end of the derivative contains a benzophenone group, which can be triggered by ultraviolet light to produce ROS that kill bacteria. The other end is an imidazolium cation with antibacterial effect, which can release the killed bacteria on the surface through anion exchange, thereby achieving a long-term bactericidal effect. In addition, the derivative is cross-linked on the surface of the substrate by ultraviolet irradiation, and provides adsorption sites for zinc oxide-tin dioxide composite particles, so that the antibacterial group is more tightly combined with the polymer substrate.

[0021] The adhesion of catechol and the hydrophilicity of 3-aminopropyltriethoxysilane are used to form a cross-linked network through Schiff base reaction and Michael addition reaction, forming a hydrophilic coating with good adhesion on the surface of the material, thereby improving the hydrophilicity of the composite material. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Polyester nonwoven fabric (40g / cm 2) was provided by Changshu Juntong, methylimidazole (R000400), benzoylbenzoic acid (R033743), catechol (R019722), and 3-aminopropyltriethoxysilane (R003067) were provided by Shanghai Yien, and tris(hydroxymethyl)aminomethane buffer (pH=8.5) was provided by Tianjin Aoran.

[0024] Embodiment 1: A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, specifically:

[0025] Step 1: Preparation of zinc oxide-tin dioxide

[0026] By mass, 0.5 parts of tin dioxide and 20 parts of deionized water were mixed, and ultrasonic dispersion was performed for 10 minutes to obtain a tin dioxide dispersion. 4 parts of zinc chloride and 6 parts of deionized water were mixed to obtain a zinc chloride solution. 10 parts of the zinc chloride solution were slowly dripped into 20.5 parts of the tin dioxide dispersion, and the pH was adjusted to 9 with a sodium hydroxide solution. The reaction was carried out at 60° C. and 400 rpm for 3 hours, and the temperature was raised to 100° C., and high-pressure crystallization was performed for 12 hours. The mixture was cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 400° C. for 5 hours to obtain zinc oxide-tin dioxide.

[0027] Step 2: Preparation of benzophenone derivatives

[0028] By mass, 2.5 parts of 6-bromo-1-hexanol and 1.1 parts of methylimidazole were mixed, stirred evenly, reacted at 45°C for 24 hours with nitrogen as protective gas, and washed with ether after the reaction to obtain a quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoic acid, 0.01 parts of N,N-dimethylformamide and 39.75 parts of dichloromethane were mixed and stirred evenly to obtain a benzoylbenzoic acid organic solution. At 0°C, 1.2 parts of oxalyl chloride were slowly added dropwise to 41.76 parts of the benzoylbenzoic acid organic solution, stirred evenly, and reacted at 27°C and 200rpm for 8 hours. After the reaction is completed, the mixture is washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. 2 parts of quaternary ammonium salt of hexanol, 1.5 parts of triethylamine and 26.5 parts of dichloromethane are mixed to obtain an organic solution of quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoyl chloride and 13.25 parts of dichloromethane are mixed, stirred evenly, and added dropwise to 30 parts of the organic solution of quaternary ammonium salt of hexanol. The mixture is reacted at 27°C and 200rpm for 8h. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

[0029] Step 3: Preparation of composite antibacterial impregnation solution

[0030] 5.0 parts of benzophenone derivative, 30.0 parts of zinc oxide-tin dioxide, 80.0 parts of ethanol and 50.0 parts of deionized water were mixed by mass, stirred evenly, and ultrasonically dispersed for 20 minutes to obtain a composite antibacterial impregnation solution.

[0031] Step 4: Prepare the catechol / 3-aminopropyltriethoxysilane impregnation solution

[0032] By mass, 0.2 parts of catechol and 104.8 parts of tris(hydroxymethyl)aminomethane) buffer solution were mixed and stirred to obtain a catechol solution, 0.6 parts of 3-aminopropyltriethoxysilane and 7.9 parts of ethanol were mixed to obtain a 3-aminopropyltriethoxysilane solution, and 105 parts of the catechol solution and 8.5 parts of the 3-aminopropyltriethoxysilane solution were mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

[0033] Step 5: Preparation of hydrophilic and antibacterial medical nonwoven fabric

[0034] The polyester non-woven fabric was washed with ethanol and deionized water, and dried at 60°C for 1 hour to obtain a pretreated polyester non-woven fabric. The pretreated polyester non-woven fabric was immersed in a composite antibacterial impregnation solution for 10 minutes, taken out after the impregnation, and photo-crosslinked and cured for 2 hours under an ultraviolet light source with a wavelength of 365 nm. After curing, it was washed with ethanol and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric. The composite antibacterial polyester non-woven fabric was immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 3 hours. After the impregnation, it was taken out, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0035] Embodiment 2: A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, specifically:

[0036] Step 1: Preparation of zinc oxide-tin dioxide

[0037] By mass, 0.5 parts of tin dioxide and 20 parts of deionized water were mixed, and ultrasonic dispersion was performed for 10 minutes to obtain a tin dioxide dispersion. 4 parts of zinc chloride and 6 parts of deionized water were mixed to obtain a zinc chloride solution. 10 parts of the zinc chloride solution were slowly dripped into 20.5 parts of the tin dioxide dispersion, and the pH was adjusted to 9 with a sodium hydroxide solution. The reaction was carried out at 60° C. and 400 rpm for 3 hours, and the temperature was raised to 100° C., and high-pressure crystallization was performed for 12 hours. The mixture was cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 400° C. for 5 hours to obtain zinc oxide-tin dioxide.

[0038] Step 2: Preparation of benzophenone derivatives

[0039] By mass, 2.5 parts of 6-bromo-1-hexanol and 1.1 parts of methylimidazole were mixed, stirred evenly, reacted at 45°C for 24 hours with nitrogen as protective gas, and washed with ether after the reaction to obtain a quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoic acid, 0.01 parts of N,N-dimethylformamide and 39.75 parts of dichloromethane were mixed and stirred evenly to obtain a benzoylbenzoic acid organic solution. At 0°C, 1.2 parts of oxalyl chloride were slowly added dropwise to 41.76 parts of the benzoylbenzoic acid organic solution, stirred evenly, and reacted at 27°C and 200rpm for 8 hours. After the reaction is completed, the mixture is washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. 2 parts of quaternary ammonium salt of hexanol, 1.5 parts of triethylamine and 26.5 parts of dichloromethane are mixed to obtain an organic solution of quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoyl chloride and 13.25 parts of dichloromethane are mixed, stirred evenly, and added dropwise to 30 parts of the organic solution of quaternary ammonium salt of hexanol. The mixture is reacted at 27°C and 200rpm for 8h. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

[0040] Step 3: Preparation of composite antibacterial impregnation solution

[0041] 4.5 parts of benzophenone derivative, 28.0 parts of zinc oxide-tin dioxide, 75.0 parts of ethanol and 45.0 parts of deionized water were mixed by weight, stirred evenly, and ultrasonically dispersed for 20 minutes to obtain a composite antibacterial impregnation solution.

[0042] Step 4: Prepare the catechol / 3-aminopropyltriethoxysilane impregnation solution

[0043] By mass, 0.15 parts of catechol and 104.8 parts of tris(hydroxymethyl)aminomethane) buffer solution were mixed and stirred to obtain a catechol solution, 0.5 parts of 3-aminopropyltriethoxysilane and 7.9 parts of ethanol were mixed to obtain a 3-aminopropyltriethoxysilane solution, and 104.95 parts of the catechol solution and 8.4 parts of the 3-aminopropyltriethoxysilane solution were mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

[0044] Step 5: Preparation of hydrophilic and antibacterial medical nonwoven fabric

[0045] The polyester non-woven fabric was washed with ethanol and deionized water, and dried at 60°C for 1 hour to obtain a pretreated polyester non-woven fabric. The pretreated polyester non-woven fabric was immersed in a composite antibacterial impregnation solution for 10 minutes, taken out after the impregnation, and photo-crosslinked and cured for 2 hours under an ultraviolet light source with a wavelength of 365 nm. After curing, it was washed with ethanol and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric. The composite antibacterial polyester non-woven fabric was immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 3 hours. After the impregnation, it was taken out, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0046] Embodiment 3: A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, specifically:

[0047] Step 1: Preparation of zinc oxide-tin dioxide

[0048] By mass, 0.5 parts of tin dioxide and 20 parts of deionized water were mixed, and ultrasonic dispersion was performed for 10 minutes to obtain a tin dioxide dispersion. 4 parts of zinc chloride and 6 parts of deionized water were mixed to obtain a zinc chloride solution. 10 parts of the zinc chloride solution were slowly dripped into 20.5 parts of the tin dioxide dispersion, and the pH was adjusted to 9 with a sodium hydroxide solution. The reaction was carried out at 60° C. and 400 rpm for 3 hours, and the temperature was raised to 100° C., and high-pressure crystallization was performed for 12 hours. The mixture was cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 400° C. for 5 hours to obtain zinc oxide-tin dioxide.

[0049] Step 2: Preparation of benzophenone derivatives

[0050] By mass, 2.5 parts of 6-bromo-1-hexanol and 1.1 parts of methylimidazole were mixed, stirred evenly, reacted at 45°C for 24 hours with nitrogen as protective gas, and washed with ether after the reaction to obtain a quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoic acid, 0.01 parts of N,N-dimethylformamide and 39.75 parts of dichloromethane were mixed and stirred evenly to obtain a benzoylbenzoic acid organic solution. At 0°C, 1.2 parts of oxalyl chloride were slowly added dropwise to 41.76 parts of the benzoylbenzoic acid organic solution, stirred evenly, and reacted at 27°C and 200rpm for 8 hours. After the reaction is completed, the mixture is washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. 2 parts of quaternary ammonium salt of hexanol, 1.5 parts of triethylamine and 26.5 parts of dichloromethane are mixed to obtain an organic solution of quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoyl chloride and 13.25 parts of dichloromethane are mixed, stirred evenly, and added dropwise to 30 parts of the organic solution of quaternary ammonium salt of hexanol. The mixture is reacted at 27°C and 200rpm for 8h. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

[0051] Step 3: Preparation of composite antibacterial impregnation solution

[0052] By weight, 5.5 parts of benzophenone derivative, 32.0 parts of zinc oxide-tin dioxide, 85.0 parts of ethanol and 55.0 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 20 minutes to obtain a composite antibacterial impregnation solution.

[0053] Step 4: Prepare the catechol / 3-aminopropyltriethoxysilane impregnation solution

[0054] By mass, 0.25 parts of catechol and 104.8 parts of tris(hydroxymethyl)aminomethane) buffer solution were mixed and stirred to obtain a catechol solution, 0.7 parts of 3-aminopropyltriethoxysilane and 7.9 parts of ethanol were mixed to obtain a 3-aminopropyltriethoxysilane solution, and 105.05 parts of the catechol solution and 8.6 parts of the 3-aminopropyltriethoxysilane solution were mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

[0055] Step 5: Preparation of hydrophilic and antibacterial medical nonwoven fabric

[0056] The polyester non-woven fabric was washed with ethanol and deionized water, and dried at 60°C for 1 hour to obtain a pretreated polyester non-woven fabric. The pretreated polyester non-woven fabric was immersed in a composite antibacterial impregnation solution for 10 minutes, taken out after the impregnation, and photo-crosslinked and cured for 2 hours under an ultraviolet light source with a wavelength of 365 nm. After curing, it was washed with ethanol and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric. The composite antibacterial polyester non-woven fabric was immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 3 hours. After the impregnation, it was taken out, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0057] Based on Example 1, control experiments were carried out, specifically Comparative Example 1, Comparative Example 2 and Comparative Example 3, as described below:

[0058] Comparative Example 1: No zinc oxide was used to modify tin dioxide, and the other conditions were the same as those in Example 1.

[0059] A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, specifically comprising:

[0060] Step 1: Preparation of benzophenone derivatives

[0061] By mass, 2.5 parts of 6-bromo-1-hexanol and 1.1 parts of methylimidazole were mixed, stirred evenly, reacted at 45°C for 24 hours with nitrogen as protective gas, and washed with ether after the reaction to obtain a quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoic acid, 0.01 parts of N,N-dimethylformamide and 39.75 parts of dichloromethane were mixed and stirred evenly to obtain a benzoylbenzoic acid organic solution. At 0°C, 1.2 parts of oxalyl chloride were slowly added dropwise to 41.76 parts of the benzoylbenzoic acid organic solution, stirred evenly, and reacted at 27°C and 200rpm for 8 hours. After the reaction is completed, the mixture is washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. 2 parts of quaternary ammonium salt of hexanol, 1.5 parts of triethylamine and 26.5 parts of dichloromethane are mixed to obtain an organic solution of quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoyl chloride and 13.25 parts of dichloromethane are mixed, stirred evenly, and added dropwise to 30 parts of the organic solution of quaternary ammonium salt of hexanol. The mixture is reacted at 27°C and 200rpm for 8h. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

[0062] Step 2: Preparation of composite antibacterial impregnation solution

[0063] 5.0 parts of benzophenone derivative, 30.0 parts of tin dioxide, 80.0 parts of ethanol and 50.0 parts of deionized water were mixed by weight, stirred evenly, and ultrasonically dispersed for 20 minutes to obtain a composite antibacterial impregnation solution.

[0064] Step 3: Prepare the catechol / 3-aminopropyltriethoxysilane impregnation solution

[0065] By mass, 0.2 parts of catechol and 104.8 parts of tris(hydroxymethyl)aminomethane) buffer solution were mixed and stirred to obtain a catechol solution, 0.6 parts of 3-aminopropyltriethoxysilane and 7.9 parts of ethanol were mixed to obtain a 3-aminopropyltriethoxysilane solution, and 105 parts of the catechol solution and 8.5 parts of the 3-aminopropyltriethoxysilane solution were mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

[0066] Step 4: Preparation of hydrophilic and antibacterial medical nonwoven fabric

[0067] The polyester non-woven fabric was washed with ethanol and deionized water, and dried at 60°C for 1 hour to obtain a pretreated polyester non-woven fabric. The pretreated polyester non-woven fabric was immersed in a composite antibacterial impregnation solution for 10 minutes, taken out after the impregnation, and photo-crosslinked and cured for 2 hours under an ultraviolet light source with a wavelength of 365 nm. After curing, it was washed with ethanol and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric. The composite antibacterial polyester non-woven fabric was immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 3 hours. After the impregnation, it was taken out, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0068] Comparative Example 2: A composite antibacterial impregnation solution was prepared using quaternary ammonium salt of hexanol, and the other conditions were the same as those in Example 1.

[0069] A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, specifically comprising:

[0070] Step 1: Preparation of zinc oxide-tin dioxide

[0071] By mass, 0.5 parts of tin dioxide and 20 parts of deionized water were mixed, and ultrasonic dispersion was performed for 10 minutes to obtain a tin dioxide dispersion. 4 parts of zinc chloride and 6 parts of deionized water were mixed to obtain a zinc chloride solution. 10 parts of the zinc chloride solution were slowly dripped into 20.5 parts of the tin dioxide dispersion, and the pH was adjusted to 9 with a sodium hydroxide solution. The reaction was carried out at 60° C. and 400 rpm for 3 hours, and the temperature was raised to 100° C., and high-pressure crystallization was performed for 12 hours. The mixture was cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 400° C. for 5 hours to obtain zinc oxide-tin dioxide.

[0072] Step 2: Preparation of quaternary ammonium salt of hexanol

[0073] By mass, 2.5 parts of 6-bromo-1-hexanol and 1.1 parts of methylimidazole were mixed, stirred evenly, reacted at 45° C. for 24 hours under nitrogen as a protective gas, and washed with ether after the reaction to obtain a hexanol quaternary ammonium salt.

[0074] Step 3: Preparation of composite antibacterial impregnation solution

[0075] By mass, 5.0 parts of quaternary ammonium hexanol salt, 30.0 parts of zinc oxide-tin dioxide, 80.0 parts of ethanol and 50.0 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 20 minutes to obtain a composite antibacterial impregnation solution.

[0076] Step 4: Prepare the catechol / 3-aminopropyltriethoxysilane impregnation solution

[0077] By mass, 0.2 parts of catechol and 104.8 parts of tris(hydroxymethyl)aminomethane) buffer solution were mixed and stirred to obtain a catechol solution, 0.6 parts of 3-aminopropyltriethoxysilane and 7.9 parts of ethanol were mixed to obtain a 3-aminopropyltriethoxysilane solution, and 105 parts of the catechol solution and 8.5 parts of the 3-aminopropyltriethoxysilane solution were mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

[0078] Step 5: Preparation of hydrophilic and antibacterial medical nonwoven fabric

[0079] The polyester non-woven fabric was washed with ethanol and deionized water, and dried at 60°C for 1 hour to obtain a pretreated polyester non-woven fabric. The pretreated polyester non-woven fabric was immersed in a composite antibacterial impregnation solution for 10 minutes, taken out after the impregnation, and photo-crosslinked and cured for 2 hours under an ultraviolet light source with a wavelength of 365 nm. After curing, it was washed with ethanol and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric. The composite antibacterial polyester non-woven fabric was immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 3 hours. After the impregnation, it was taken out, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0080] Comparative Example 3: No catechol was added, and the remaining conditions were the same as those in Example 1.

[0081] A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, specifically comprising:

[0082] Step 1: Preparation of zinc oxide-tin dioxide

[0083] By mass, 0.5 parts of tin dioxide and 20 parts of deionized water were mixed, and ultrasonic dispersion was performed for 10 minutes to obtain a tin dioxide dispersion. 4 parts of zinc chloride and 6 parts of deionized water were mixed to obtain a zinc chloride solution. 10 parts of the zinc chloride solution were slowly dripped into 20.5 parts of the tin dioxide dispersion, and the pH was adjusted to 9 with a sodium hydroxide solution. The reaction was carried out at 60° C. and 400 rpm for 3 hours, and the temperature was raised to 100° C., and high-pressure crystallization was performed for 12 hours. The mixture was cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 400° C. for 5 hours to obtain zinc oxide-tin dioxide.

[0084] Step 2: Preparation of benzophenone derivatives

[0085] By mass, 2.5 parts of 6-bromo-1-hexanol and 1.1 parts of methylimidazole were mixed, stirred evenly, reacted at 45°C for 24 hours with nitrogen as protective gas, and washed with ether after the reaction to obtain a quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoic acid, 0.01 parts of N,N-dimethylformamide and 39.75 parts of dichloromethane were mixed and stirred evenly to obtain a benzoylbenzoic acid organic solution. At 0°C, 1.2 parts of oxalyl chloride were slowly added dropwise to 41.76 parts of the benzoylbenzoic acid organic solution, stirred evenly, and reacted at 27°C and 200rpm for 8 hours. After the reaction is completed, the mixture is washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. 2 parts of quaternary ammonium salt of hexanol, 1.5 parts of triethylamine and 26.5 parts of dichloromethane are mixed to obtain an organic solution of quaternary ammonium salt of hexanol. 2 parts of benzoylbenzoyl chloride and 13.25 parts of dichloromethane are mixed, stirred evenly, and added dropwise to 30 parts of the organic solution of quaternary ammonium salt of hexanol. The mixture is reacted at 27°C and 200rpm for 8h. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

[0086] Step 3: Preparation of composite antibacterial impregnation solution

[0087] 5.0 parts of benzophenone derivative, 30.0 parts of zinc oxide-tin dioxide, 80.0 parts of ethanol and 50.0 parts of deionized water were mixed by mass, stirred evenly, and ultrasonically dispersed for 20 minutes to obtain a composite antibacterial impregnation solution.

[0088] Step 4: Prepare 3-aminopropyltriethoxysilane impregnation solution

[0089] 0.6 parts of 3-aminopropyltriethoxysilane and 7.9 parts of ethanol were mixed by mass to obtain a 3-aminopropyltriethoxysilane solution, and the mixture was stirred evenly to obtain a 3-aminopropyltriethoxysilane impregnation solution.

[0090] Step 5: Preparation of hydrophilic and antibacterial medical nonwoven fabric

[0091] The polyester non-woven fabric was washed with ethanol and deionized water, and dried at 60°C for 1 hour to obtain a pretreated polyester non-woven fabric. The pretreated polyester non-woven fabric was immersed in a composite antibacterial impregnation solution for 10 minutes, taken out after the impregnation, and photo-crosslinked and cured for 2 hours under an ultraviolet light source with a wavelength of 365 nm. After curing, it was washed with ethanol and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric. The composite antibacterial polyester non-woven fabric was immersed in a 3-aminopropyltriethoxysilane impregnation solution for 3 hours. After the impregnation was completed, it was taken out, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

[0092] Detection experiment:

[0093] The hydrophilic and antibacterial medical nonwoven fabrics required for the test were prepared according to the preparation methods in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively.

[0094] Hydrophilic performance test: According to "Determination of dynamic transfer properties of liquid water in porous materials Part 1: Textiles" (SN / T 1689.1-2005), use a liquid moisture management tester to cut samples from the prepared 6 kinds of hydrophilic and antibacterial medical non-woven fabrics. The sample size is 900mm×900mm. Place the sample flat on the sensor, place 0.15g of sodium chloride solution above the sample, and measure the sample's wetting time.

[0095] Antibacterial performance test: The antibacterial rate was tested using the fabric oscillation method. Samples were cut from the 6 prepared hydrophilic and antibacterial medical non-woven fabrics. Each sample was 5 mm × 5 mm in size and weighed 0.2 g. Each sample was placed in 25 ml of normal saline and 0.1 ml of 10% 6 CFU / mL of Staphylococcus aureus suspension / Escherichia coli suspension was shaken at 25℃, 150rpm for 1h. After shaking, normal saline was added to dilute it to 250mL. 0.1mL of the diluted solution was taken and cultured with 20mL of nutrient agar medium at 37℃ for 24h. The colonies were counted and the antibacterial rate of Staphylococcus aureus / Escherichia coli was calculated.

[0096]

[0097] Conclusion: It can be seen from the experiment that the wetting time, antibacterial rate of Staphylococcus aureus and antibacterial rate of Escherichia coli of the hydrophilic and antibacterial medical non-woven fabric prepared by the preparation method of Example 1 are better than those of the hydrophilic and antibacterial medical non-woven fabric prepared by the preparation methods of Comparative Examples 1, 2 and 3, which solves the problem of poor hydrophilicity and antibacterial property of medical non-woven fabric products.

[0098] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A method for preparing a hydrophilic and antibacterial medical nonwoven fabric, characterized in that: The preparation method is: The polyester non-woven fabric is washed with ethanol and deionized water, and dried at 50-70°C for 0.5-1.5h to obtain a pretreated polyester non-woven fabric, and the pretreated polyester non-woven fabric is immersed in a composite antibacterial impregnation solution for 8-12min, taken out after the impregnation, and cross-linked and cured for 1-3h under an ultraviolet light source with a wavelength of 360-370nm, and washed with ethanol after curing, and dried with nitrogen to obtain a composite antibacterial polyester non-woven fabric, and the composite antibacterial polyester non-woven fabric is immersed in a catechol / 3-aminopropyltriethoxysilane impregnation solution for 2-4h, taken out after the impregnation, washed with ethanol and deionized water, and dried to obtain a hydrophilic and antibacterial medical non-woven fabric.

2. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 1, characterized in that: The dosage of each component of the composite antibacterial impregnation solution is as follows: 4.5-5.5 parts of benzophenone derivative, 28-32 parts of zinc oxide-tin dioxide, 75-85 parts of ethanol, and 45-55 parts of deionized water.

3. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 2, characterized in that: The preparation method of benzophenone derivatives is: Mix 6-bromo-1-hexanol and methylimidazole, stir evenly, react at 40-50°C for 22-26h with nitrogen as protective gas, wash with ether after the reaction to obtain hexanol quaternary ammonium salt, mix benzoylbenzoic acid, N,N-dimethylformamide and dichloromethane, stir evenly to obtain benzoylbenzoic acid organic solution, slowly add oxalyl chloride dropwise to the benzoylbenzoic acid organic solution at -5-5°C, stir evenly, react at 25-30°C, 100-300rpm for 7-9h, and the reaction is completed. The mixture is then washed with dichloromethane, rotary evaporated, and dried to obtain benzoylbenzoyl chloride. The quaternary ammonium salt of hexanol, triethylamine, and dichloromethane are mixed to obtain an organic solution of the quaternary ammonium salt of hexanol. The benzoylbenzoyl chloride and dichloromethane are mixed, stirred evenly, and added dropwise to the organic solution of the quaternary ammonium salt of hexanol. The mixture is reacted at 25 to 30° C. and 100 to 300 rpm for 7 to 9 hours. After the reaction is completed, the mixture is washed with dichloromethane, allowed to stand for stratification, and the organic layer is washed with saturated brine and deionized water, dried over anhydrous magnesium sulfate, and washed with ether to obtain a benzophenone derivative.

4. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 3, characterized in that: When preparing the hexanol quaternary ammonium salt, the mass ratio of 6-bromo-1-hexanol to methylimidazole is (2.4-2.6):(1.0-1.2).

5. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 3, characterized in that: When preparing benzoylbenzoyl chloride, the amount of each component used is: 1.9-2.1 parts of benzoylbenzoic acid, 0.009-0.011 parts of N,N-dimethylformamide, 1.1-1.3 parts of oxalyl chloride, and 39.5-40.0 parts of dichloromethane.

6. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 3, characterized in that: When preparing benzophenone derivatives, the amount of each component used is as follows: 1.9-2.1 parts of quaternary ammonium salt of hexanol, 1.4-1.6 parts of triethylamine, 1.9-2.1 parts of benzoylbenzoyl chloride.

7. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 2, characterized in that: The preparation method of zinc oxide-tin dioxide is: Tin dioxide and deionized water are mixed, ultrasonically dispersed for 8 to 12 minutes to obtain a tin dioxide dispersion, zinc chloride and deionized water are mixed to obtain a zinc chloride solution, the zinc chloride solution is slowly dripped into the tin dioxide dispersion, the pH is adjusted with a sodium hydroxide solution, the reaction is carried out at 50 to 70° C. and 300 to 500 rpm for 2 to 4 hours, the temperature is raised to 95 to 105° C., high pressure crystallization is carried out for 10 to 14 hours, the mixture is cooled to room temperature, centrifuged, washed with ethanol and deionized water, dried, and calcined at 380 to 420° C. for 4 to 6 hours to obtain zinc oxide-tin dioxide.

8. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 7, characterized in that: When preparing zinc oxide-tin dioxide, the mass ratio of tin dioxide to zinc chloride is (0.4-0.6):(3.9-4.1).

9. The method for preparing a hydrophilic and antibacterial medical nonwoven fabric according to claim 1, characterized in that: The preparation method of catechol / 3-aminopropyltriethoxysilane impregnation solution is as follows: The catechol and tris(hydroxymethyl)aminomethane) buffer solution are mixed and stirred to obtain a catechol solution. 3-aminopropyltriethoxysilane and ethanol are mixed to obtain a 3-aminopropyltriethoxysilane solution. The catechol solution and the 3-aminopropyltriethoxysilane solution are mixed and stirred to obtain a catechol / 3-aminopropyltriethoxysilane impregnation solution.

Images