High-moisture-retention antibacterial silicone hydrogel contact lens material and preparation method thereof

Abstract

The invention relates to the technical field of preparation of contact lens materials, and particularly discloses a high-moisture-retention and antibacterial silicone hydrogel contact lens material and a preparation method thereof.The high-moisture-retention and antibacterial silicone hydrogel contact lens material is prepared through the following steps that S1, a silicon-containing component is prepared; s2, preparing a hydrogel contact lens material; the antibacterial dispersion liquid is added, the antibacterial dispersion liquid contains a sodium alginate structure, a chlorogenic acid structure, zinc glycinate and an aloe extract, on one hand, active hydroxyl contained in the molecular structure of the sodium alginate can be combined with water molecules through hydrogen bonds, and on the other hand, the active hydroxyl serves as an anchoring point to be subjected to esterification reaction with carboxyl of chlorogenic acid, so that the antibacterial effect is achieved. The zinc glycinate is used as a source of organic zinc, and the aloe extract is rich in aloe polysaccharide and anthraquinone compounds, so that the moisture retention, oxygen permeability and antibacterial property of the hydrogel contact lens material can be improved by introducing the aloe extract into the hydrogel contact lens material.

Description

Technical Field

[0001] The present application relates to the technical field of contact lens material preparation, and more specifically, to a highly moisturizing and antibacterial silicone hydrogel contact lens material and a preparation method thereof. Background Art

[0002] Contact lenses are an important medical device for vision correction and beauty. Among them, silicone hydrogel has become the mainstream material for modern contact lenses due to its ultra-high oxygen permeability, long-lasting moisture and comfort.

[0003] However, although the siloxane component in traditional silicone hydrogel materials can significantly improve oxygen permeability, its hydrophobicity will reduce the hydrophilicity of the material, resulting in insufficient wettability of the lens surface, which can easily cause dry eye discomfort. To balance this contradiction, conventional solutions require the introduction of a high proportion of hydrophilic monomers, but this will lead to a decrease in cross-linking density and a loose network structure. Rapid evaporation of water will cause the gel to shrink and deform, and lipids and proteins in tears will easily adsorb to the lens surface to form a biofilm. Traditional silicone hydrogels are enriched in silicone microdomains on the surface, which easily adsorb lipids and protein precipitation, which not only affects the oxygen permeability and comfort of the lens, but may also irritate the eyes and cause symptoms such as inflammation. Based on the above defects, the present application provides a highly moisturizing and antibacterial silicone hydrogel contact lens material and a preparation method thereof. Summary of the Invention

[0004] In order to solve the problems mentioned in the above background technology, the present application provides a highly moisturizing and antibacterial silicone hydrogel contact lens material and a preparation method thereof.

[0005] A method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material comprises the following steps: Step S1, preparing a silicon-containing component: uniformly mixing N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and deionized water, heating to 145-155° C. under nitrogen protection, continuing to stir and react for 1.8-2.2 hours, and cooling under reduced pressure to obtain a silicon-containing component, wherein the mass ratio of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane to deionized water is 4.6-5:1. During the above reaction process, -Si-O-CH3 of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane is first decomposed into Si-OH, and Si-OH is dehydrated and condensed to form a short-chain Si-O-Si polymer. Under high temperature and low pressure conditions, the Si-OH groups at the ends of the oligomer chains further undergo a condensation reaction to form a silicon-containing component with a polymer chain having a larger molecular weight; Step S2, preparing a hydrogel contact lens material: mixing polyvinyl alcohol and an antibacterial dispersion evenly, heating to 86-92° C., adding a functional monomer and citric acid, continuing stirring for 8-10 hours, cooling to 56-64° C., adding a photoinitiator, stirring evenly, irradiating with ultraviolet light, washing with deionized water, and balancing with a boric acid buffer to obtain a highly moisturizing and antibacterial silicone hydrogel contact lens material, wherein the mass ratio of polyvinyl alcohol, antibacterial dispersion, functional monomer, citric acid, and photoinitiator is 6-8:26-32:2.2-2.8:0.4-0.5:0.01-0.03.

[0006] Preferably, in step S2, the photoinitiator is photoinitiator 8700 or benzophenone ammonium chloride.

[0007] Preferably, in step S2, the peak wavelength of the irradiation is 365 nm and the intensity is 80 mw / cm 2 , irradiation time is 36-44min.

[0008] Preferably, the functional monomer in step S2 is composed of a silicon-containing component, N-vinyl pyrrolidone and polyethylene glycol acrylate in a mass ratio of 18-26:12-18:24-30.

[0009] Preferably, the antibacterial dispersion is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring evenly at room temperature, adjusting the pH value to 8.2-8.4, then adding a mixture of tris(hydroxymethylaminomethane), phosphate buffer and immobilized lipase dropwise, controlling the addition to be completed within 10 minutes, heating to 42-46°C, continuing stirring for 4-6 hours, then adjusting the pH value to 6.4-6.8, washing with deionized water until neutral, and drying to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 6-8:100-120:15, and the mass ratio of tris(hydroxymethylaminomethane), phosphate buffer and immobilized lipase in mixture a is 2-4:400:0.06-1. During the above reaction process, under the catalysis of the immobilized lipase, the carboxyl group on the sodium alginate and the amino group on the tris(hydroxymethylaminomethane) undergo an amidation reaction to obtain amidated sodium alginate; Step A2, adding amidated sodium alginate and p-toluenesulfonic acid to deionized water, and adding a mixture of chlorogenic acid and deionized water b dropwise while stirring, and controlling the dripping to be completed within 10 minutes. After the dripping is completed, the temperature is raised to 64-72°C, and the reaction is stirred for 4.2-4.6 hours. After the reaction is completed, the mixture is filtered, washed, and dried to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 3-5:0.02-0.04:55-65:20-26, and the mass ratio of chlorogenic acid to deionized water in the mixture b is 0.4-0.6:20. In the above reaction process, p-toluenesulfonic acid is used as a catalyst, and amidated sodium alginate and chlorogenic acid undergo an esterification reaction to obtain esterified sodium alginate; Step A3, mix zinc glycine and deionized water evenly, adjust the pH to 8.4-8.8, heat to 45-55 ° C, stir and dropwise add a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water c, control the dripping within 15 minutes, continue stirring for 2.2-2.6 hours, then dropwise add glacial acetic acid, stir and react for 0.6-1 hour, wash to obtain an antibacterial dispersion, wherein zinc glycine, deionized water, mixture c and glacial acetic acid The mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water is 1.2-1.6:40-50:20-28:0.06-0.08 in the mixed solution c. The mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water is 2.6-3.2:0.6-0.8:0.2-0.4:25. During the above reaction process, glacial acetic acid is used as a catalyst, and the calcium ions in the saturated calcium chloride aqueous solution can chemically cross-link with the sodium alginate, thereby obtaining an antibacterial dispersion.

[0010] Preferably, in step A1, the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:1.6-2.2:26-30.

[0011] A highly weather-resistant silicone hydrogel contact lens material is prepared by the method.

[0012] Compared with the prior art, the present invention has the following beneficial effects: The present application incorporates an antibacterial dispersion containing a sodium alginate structure, a chlorogenic acid structure, zinc glycine, and an aloe vera extract. The active hydroxyl groups in the sodium alginate molecular structure can, on the one hand, hydrogen bond with water molecules, significantly enhancing its moisture retention and oxygen permeability. On the other hand, they act as anchor points, undergoing an esterification reaction with the carboxyl groups of chlorogenic acid, thereby introducing the antibacterial active units in chlorogenic acid and improving the antibacterial and moisture retention properties of the hydrogel contact lens material. Zinc glycine serves as a source of organic zinc, which can further enhance the antibacterial properties of the hydrogel contact lens material. The aloe vera extract is rich in aloe polysaccharides and anthraquinone compounds. Aloe polysaccharides enhance the moisture retention and oxygen permeability of the hydrogel contact lens material by forming a water-locking film and activating aquaporins. Anthraquinone compounds have excellent antibacterial properties. At the same time, the aloe vera extract can form hydrogen bonds with the active hydroxyl groups in the sodium alginate and chlorogenic acid structures, thereby improving the dispersibility and compatibility between the components. Its introduction into the hydrogel contact lens material can enhance the moisture retention, oxygen permeability, and antibacterial properties of the hydrogel contact lens material. DETAILED DESCRIPTION

[0013] In order to make the implementation methods of the present application easier to understand, the present application will be described in detail below with reference to specific examples. These examples are only for illustration and are not intended to limit the scope of application of the present application.

[0014] The contents of the main raw materials and their components used in the examples and comparative examples are as follows: Immobilized lipase was produced by Shangke Biopharmaceuticals (Shanghai) Co., Ltd. with the product code SZ-PLE-100(CALB)-IMMO. Polyvinyl alcohol was sold by Shanxi Jinyang Pharmaceutical Excipients Co., Ltd. with the CAS number 9002-89-5. Sodium alginate was sold by Leshengyuan Biotechnology (Nanjing) Co., Ltd. with the CAS number 9005-38-3. Chlorogenic acid was sold by Shanghai Zhongfeng Biotechnology Co., Ltd. with the CAS number 327-97-9. Aloe vera extract was freeze-dried aloe vera gel powder produced by Xi'an Ruierli Bioengineering Co., Ltd., and purslane extract was purslane extract produced by Xi'an Ruierli Bioengineering Co., Ltd.

[0015] The present application is further described in detail below with reference to the following examples and comparative examples.

[0016] Preparation Examples 1-3 and Comparative Preparation Examples 1-3 provide methods for preparing antibacterial dispersions.

[0017] Preparation Example 1 This preparation example provides a method for preparing an antibacterial dispersion, which is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring at room temperature at a speed of 460 rpm for 12 minutes until uniform, adjusting the pH value to 8.2 with a 1% mass fraction sodium bicarbonate aqueous solution, and then adding a mixture of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase dropwise, controlling the dropwise addition to be completed within 10 minutes, heating to 42°C, and continuing stirring for 4 hours, and then adjusting the pH value to 6.4 with a 0.03% mass fraction citric acid aqueous solution, washing with deionized water until neutral, and drying at 52°C to constant weight to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 6:100:15, and the mass ratio of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in the mixture a is 2:400:0.06, and the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:1.6:26; Step A2, adding amidated sodium alginate and p-toluenesulfonic acid to deionized water, controlling the speed to 600 rpm, and adding a mixture b of chlorogenic acid and deionized water dropwise while stirring, and controlling the dripping to be completed within 10 minutes. After the dripping is completed, the temperature is raised to 64°C, the speed is maintained unchanged, and the reaction is stirred for 4.2 hours. After the reaction is completed, the mixture is filtered, washed with anhydrous ethanol and deionized water 3 times each, and dried at 60°C to constant weight to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 3:0.02:55:20, and the mass ratio of chlorogenic acid and deionized water in the mixture b is 0.4:20; Step A3, stirring zinc glycinate and deionized water at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH to 8.4 with a mass fraction of 0.02% sodium carbonate aqueous solution, heating to 45 ° C, maintaining the speed unchanged, stirring and adding dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water c, controlling the dripping within 15 minutes, continuing stirring for 2.2 hours, then adding glacial acetic acid dropwise, stirring the reaction for 0.6 hours, and washing with anhydrous ethanol and deionized water three times each to obtain an antibacterial dispersion, wherein the mass ratio of zinc glycinate, deionized water, mixed solution c and glacial acetic acid is 1.2:40:20:0.06, and the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water in the mixed solution c is 2.6:0.6:0.2:25.

[0018] Preparation Example 2 This preparation example provides a method for preparing an antibacterial dispersion, which is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring at room temperature at a speed of 500 rpm for 15 minutes until uniform, adjusting the pH value to 8.3 with a 2.4% mass fraction sodium bicarbonate aqueous solution, and then adding a mixture of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase dropwise, controlling the dropwise addition to be completed within 10 minutes, heating to 44°C, and continuing stirring for 5 hours, and then adjusting the pH value to 6.6 with a 0.02% mass fraction citric acid aqueous solution, washing with deionized water to neutrality, and drying at 54°C to constant weight to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 7:110:15, and the mass ratio of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in the mixture a is 3:400:0.08, and the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:1.9:28; Step A2, add amidated sodium alginate and p-toluenesulfonic acid to deionized water, control the speed to 620 rpm, and add the mixture b of chlorogenic acid and deionized water dropwise while stirring. The dripping is controlled within 10 minutes. After the dripping is completed, the temperature is raised to 68°C, the speed is maintained unchanged, and the reaction is stirred for 4.4 hours. After the reaction is completed, filter and wash with anhydrous ethanol and deionized water 4 times each, and dry at 64°C to constant weight to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 4:0.03:60:23, and the mass ratio of chlorogenic acid and deionized water in the mixture b is 0.5:20. Step A3, stirring zinc glycinate and deionized water at a speed of 530 rpm for 18 minutes until uniform, adjusting the pH to 8.6 with a mass fraction of 0.04% sodium carbonate aqueous solution, heating to 50 ° C, maintaining the speed unchanged, stirring and adding dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water c, controlling the dripping within 15 minutes, continuing stirring for 2.4 hours, then adding glacial acetic acid dropwise, stirring the reaction for 0.8 hours, and washing with anhydrous ethanol and deionized water four times each to obtain an antibacterial dispersion, wherein the mass ratio of zinc glycinate, deionized water, mixed solution c and glacial acetic acid is 1.4:45:24:0.07, and the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water in the mixed solution c is 2.9:0.7:0.3:25.

[0019] Preparation Example 3 This preparation example provides a method for preparing an antibacterial dispersion, which is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring at room temperature at a speed of 540 rpm for 18 minutes until uniform, adjusting the pH value to 8.4 with a 5.2% mass fraction sodium bicarbonate aqueous solution, and then adding a mixture of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase dropwise, controlling the dropwise addition to be completed within 10 minutes, heating to 46°C, and continuing stirring for 6 hours, and then adjusting the pH value to 6.8 with a 0.01% mass fraction citric acid aqueous solution, washing with deionized water to neutrality, and drying at 56°C to constant weight to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 8:120:15, the mass ratio of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in the mixture a is 4:400:1, and the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:2.2:30; Step A2, add amidated sodium alginate and p-toluenesulfonic acid to deionized water, control the speed to 640 rpm, and add the mixture b of chlorogenic acid and deionized water dropwise while stirring. The dripping is controlled within 10 minutes. After the dripping is completed, the temperature is raised to 72°C, the speed is maintained unchanged, and the stirring reaction is carried out for 4.6 hours. After the reaction is completed, filter and wash with anhydrous ethanol and deionized water 5 times each, and dry at 68°C to constant weight to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 5:0.04:65:26, and the mass ratio of chlorogenic acid and deionized water in the mixture b is 0.6:20. Step A3, stirring zinc glycinate and deionized water at a speed of 560 rpm for 20 minutes until uniform, adjusting the pH to 8.8 with a mass fraction of 0.02% sodium carbonate aqueous solution, heating to 55 ° C, maintaining the speed unchanged, stirring and adding dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water c, controlling the dripping within 15 minutes, continuing stirring for 2.6 hours, then adding glacial acetic acid dropwise, stirring and reacting for 1 hour, and washing with anhydrous ethanol and deionized water 5 times each to obtain an antibacterial dispersion, wherein the mass ratio of zinc glycinate, deionized water, mixed solution c and glacial acetic acid is 1.6:50:28:0.08, and the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water in the mixed solution c is 3.2:0.8:0.4:25.

[0020] Comparative Preparation Example 1 This comparative preparation example provides a method for preparing an antibacterial dispersion, which is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring at room temperature at a speed of 460 rpm for 12 minutes until uniform, adjusting the pH value to 8.2 with a 1% mass fraction sodium bicarbonate aqueous solution, and then adding a mixture of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase dropwise, controlling the dropwise addition to be completed within 10 minutes, heating to 42°C, and continuing stirring for 4 hours, and then adjusting the pH value to 6.4 with a 0.03% mass fraction citric acid aqueous solution, washing with deionized water until neutral, and drying at 52°C to constant weight to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 6:100:15, and the mass ratio of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in the mixture a is 2:400:0.06, and the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:1.6:26; Step A2, adding amidated sodium alginate and p-toluenesulfonic acid to deionized water, controlling the rotation speed to 600 rpm, and adding a mixture of trans-cinnamic acid and deionized water b dropwise while stirring, and controlling the dripping to be completed within 10 minutes. After the dripping is completed, the temperature is raised to 64°C, the rotation speed is maintained unchanged, and the stirring reaction is carried out for 4.2 hours. After the reaction is completed, the mixture is filtered, washed with anhydrous ethanol and deionized water three times each, and dried at 60°C to constant weight to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 3:0.02:55:20, and the mass ratio of trans-cinnamic acid and deionized water in the mixture b is 0.4:20; Step A3, stirring zinc glycinate and deionized water at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH to 8.4 with a mass fraction of 0.02% sodium carbonate aqueous solution, heating to 45 ° C, maintaining the speed unchanged, stirring and adding dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water c, controlling the dripping within 15 minutes, continuing stirring for 2.2 hours, then adding glacial acetic acid dropwise, stirring the reaction for 0.6 hours, and washing with anhydrous ethanol and deionized water three times each to obtain an antibacterial dispersion, wherein the mass ratio of zinc glycinate, deionized water, mixed solution c and glacial acetic acid is 1.2:40:20:0.06, and the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water in the mixed solution c is 2.6:0.6:0.2:25.

[0021] Comparative Preparation Example 2 This comparative preparation example provides a method for preparing an antibacterial dispersion, which is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring at room temperature at a speed of 460 rpm for 12 minutes until uniform, adjusting the pH value to 8.2 with a 1% mass fraction sodium bicarbonate aqueous solution, and then adding a mixture of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase dropwise, controlling the dropwise addition to be completed within 10 minutes, heating to 42°C, and continuing stirring for 4 hours, and then adjusting the pH value to 6.4 with a 0.03% mass fraction citric acid aqueous solution, washing with deionized water until neutral, and drying at 52°C to constant weight to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 6:100:15, and the mass ratio of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in the mixture a is 2:400:0.06, and the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:1.6:26; Step A2, adding amidated sodium alginate and p-toluenesulfonic acid to deionized water, controlling the speed to 600 rpm, and adding a mixture b of chlorogenic acid and deionized water dropwise while stirring, and controlling the dripping to be completed within 10 minutes. After the dripping is completed, the temperature is raised to 64°C, the speed is maintained unchanged, and the reaction is stirred for 4.2 hours. After the reaction is completed, the mixture is filtered, washed with anhydrous ethanol and deionized water 3 times each, and dried at 60°C to constant weight to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 3:0.02:55:20, and the mass ratio of chlorogenic acid and deionized water in the mixture b is 0.4:20; Step A3, stirring sodium selenite and deionized water at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH to 8.4 with a mass fraction of 0.02% sodium carbonate aqueous solution, heating to 45 ° C, maintaining the speed unchanged, stirring and adding dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water c, controlling the dripping within 15 minutes, continuing stirring for 2.2 hours, then adding glacial acetic acid dropwise, stirring the reaction for 0.6 hours, and washing with anhydrous ethanol and deionized water three times each to obtain an antibacterial dispersion, wherein the mass ratio of sodium selenite, deionized water, mixed solution c and glacial acetic acid is 1.2:40:20:0.06, and the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water in the mixed solution c is 2.6:0.6:0.2:25.

[0022] Comparative Preparation Example 3 This comparative preparation example provides a method for preparing an antibacterial dispersion, which is prepared by the following steps: Step A1, mixing sodium alginate and deionized water, stirring at room temperature at a speed of 460 rpm for 12 minutes until uniform, adjusting the pH value to 8.2 with a 1% mass fraction sodium bicarbonate aqueous solution, and then adding a mixture of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase dropwise, controlling the dropwise addition to be completed within 10 minutes, heating to 42°C, and continuing stirring for 4 hours, and then adjusting the pH value to 6.4 with a 0.03% mass fraction citric acid aqueous solution, washing with deionized water until neutral, and drying at 52°C to constant weight to obtain amidated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and mixture a is 6:100:15, and the mass ratio of tris (hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in the mixture a is 2:400:0.06, and the phosphate buffer is prepared by mixing sodium dihydrogen phosphate, disodium hydrogen phosphate and deionized water in a mass ratio of 1:1.6:26; Step A2, adding amidated sodium alginate and p-toluenesulfonic acid to deionized water, controlling the speed to 600 rpm, and adding a mixture b of chlorogenic acid and deionized water dropwise while stirring, and controlling the dripping to be completed within 10 minutes. After the dripping is completed, the temperature is raised to 64°C, the speed is maintained unchanged, and the reaction is stirred for 4.2 hours. After the reaction is completed, the mixture is filtered, washed with anhydrous ethanol and deionized water 3 times each, and dried at 60°C to constant weight to obtain esterified sodium alginate, wherein the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixture b is 3:0.02:55:20, and the mass ratio of chlorogenic acid and deionized water in the mixture b is 0.4:20; Step A3, stirring zinc glycinate and deionized water at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH to 8.4 with a mass fraction of 0.02% sodium carbonate aqueous solution, heating to 45 ° C, maintaining the speed unchanged, stirring and adding dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, purslane extract and deionized water c, controlling the dripping within 15 minutes, continuing stirring for 2.2 hours, then adding glacial acetic acid dropwise, stirring the reaction for 0.6 hours, and washing with anhydrous ethanol and deionized water three times each to obtain an antibacterial dispersion, wherein the mass ratio of zinc glycinate, deionized water, mixed solution c and glacial acetic acid is 1.2:40:20:0.06, and the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, purslane extract and deionized water in the mixed solution c is 2.6:0.6:0.2:25.

[0023] Examples 1-3 and Comparative Examples 1-3 provide a highly moisturizing and antibacterial silicone hydrogel contact lens material and a preparation method thereof.

[0024] Example 1 This embodiment provides a method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material, comprising the following steps: Step S1, preparing a silicon-containing component: N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and deionized water were stirred at a speed of 620 rpm for 18 minutes until uniform, and the temperature was raised to 145° C. under nitrogen protection, the speed was maintained constant, and the stirring reaction was continued for 1.8 hours. The silicon-containing component was obtained by cooling under reduced pressure, wherein the mass ratio of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane to deionized water was 4.6:1; Step S2, preparing hydrogel contact lens material: polyvinyl alcohol and the antibacterial dispersion prepared in Preparation Example 1 were stirred at a speed of 500 rpm for 24 minutes until uniform, and then heated to 86 ° C., functional monomers and citric acid were added, and the speed was maintained constant and stirred for 8 hours. The temperature was lowered to 56 ° C., and photoinitiator 8700 was added and stirred for 14 minutes until uniform. The mixture was then placed in a 365 nm peak wavelength and an intensity of 80 mW / cm 2 The obtained materials were irradiated under ultraviolet light for 36 minutes, washed with deionized water three times, and then adjusted to pH 7.0 with 3% by mass boric acid buffer to obtain a highly moisturizing and antibacterial silicone hydrogel contact lens material, wherein the mass ratio of polyvinyl alcohol, antibacterial dispersion, functional monomer, citric acid and photoinitiator 8700 was 6:26:2.2:0.4:0.01, and the functional monomer consisted of a silicon-containing component, N-vinyl pyrrolidone and polyethylene glycol acrylate in a mass ratio of 18:12:24.

[0025] Example 2 This embodiment provides a method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material, comprising the following steps: Step S1, preparing a silicon-containing component: N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and deionized water were stirred at a speed of 640 rpm for 20 minutes until uniform, and the temperature was raised to 150° C. under nitrogen protection, the speed was maintained constant, and the stirring reaction was continued for 2 hours. The silicon-containing component was obtained by cooling under reduced pressure, wherein the mass ratio of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane to deionized water was 4.8:1; Step S2, preparing hydrogel contact lens material: polyvinyl alcohol and the antibacterial dispersion prepared in Preparation Example 2 were stirred at a speed of 520 rpm for 28 minutes until uniform, heated to 89°C, and then functional monomers and citric acid were added, and stirring was continued for 9 hours. The temperature was lowered to 60°C, and then benzophenone ammonium chloride was added, and stirring was continued for 18 minutes until uniform. The material was then placed in a 365 nm peak wavelength and an intensity of 80 mW / cm 2The obtained materials were irradiated under ultraviolet light for 40 minutes, washed with deionized water three times, and then adjusted to pH 7.1 with 3.5% boric acid buffer to obtain a highly moisturizing and antibacterial silicone hydrogel contact lens material, wherein the mass ratio of polyvinyl alcohol, antibacterial dispersion, functional monomer, citric acid and benzophenone ammonium chloride was 7:29:2.5:0.45:0.02, and the functional monomer was composed of a silicon-containing component, N-vinyl pyrrolidone and polyethylene glycol acrylate in a mass ratio of 22:15:27.

[0026] Example 3 This embodiment provides a method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material, comprising the following steps: Step S1, preparing a silicon-containing component: N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and deionized water were mixed uniformly, heated to 155° C. under nitrogen protection, stirred and reacted for 2.2 hours, and cooled under reduced pressure to obtain a silicon-containing component, wherein the mass ratio of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane to deionized water was 5:1; Step S2, preparing hydrogel contact lens material: polyvinyl alcohol and the antibacterial dispersion prepared in Preparation Example 3 were stirred at a speed of 540 rpm for 32 minutes until uniform, heated to 92°C, and then functional monomers and citric acid were added, and stirring was continued for 10 hours. The temperature was lowered to 64°C, and then photoinitiator 8700 was added, and stirring was continued for 22 minutes until uniform. The material was then placed in a 365 nm peak wavelength and an intensity of 80 mW / cm 2 The obtained materials were irradiated under ultraviolet light for 44 minutes, washed with deionized water three times, and then adjusted to pH 7.2 with 4.0% boric acid buffer to obtain a highly moisturizing and antibacterial silicone hydrogel contact lens material, wherein the mass ratio of polyvinyl alcohol, antibacterial dispersion, functional monomer, citric acid and photoinitiator 8700 was 8:32:2.8:0.5:0.03, and the functional monomer consisted of a silicon-containing component, N-vinyl pyrrolidone and polyethylene glycol acrylate in a mass ratio of 26:18:30.

[0027] Comparative Example 1 Comparative Example 1 is the same as Example 1, except that the antibacterial dispersion in Example 1 is replaced by the antibacterial dispersion prepared in Comparative Preparation Example 1.

[0028] Comparative Example 2 Comparative Example 2 is the same as Example 1, except that the antibacterial dispersion in Example 1 is replaced by the antibacterial dispersion prepared in Comparative Preparation Example 2.

[0029] Comparative Example 3 Comparative Example 3 is the same as Example 1, except that the antibacterial dispersion in Example 1 is replaced by the antibacterial dispersion prepared in Comparative Preparation Example 3.

[0030] Performance testing Moisturizing performance test: The contact angles of the 10 mm diameter silicone hydrogel contact lens materials prepared in Examples 1-3 and Comparative Examples 1-3 were measured using a JCD-1000 contactometer using the sessile drop method with distilled water. Each sample was measured three times, and the average value was used to evaluate the moisturizing performance of the material. The specific test data are shown in Table 1. Oxygen permeability test: A 201T oxygen permeability meter (Creathch / Rehder-Dev Co., USA) was used to test the silicone hydrogel contact lens materials with a diameter of 10 mm prepared in Examples 1-3 and Comparative Examples 1-3 using polarography in accordance with the national standard GBT 11417.7-2012. The unit of Dk is 10-11 cm 2 / s·Pa, the test results are shown in Table 1; Antibacterial performance test: Escherichia coli and Staphylococcus aureus were cultured to the logarithmic phase and diluted with culture medium to 10 5 CFU / mL, and evenly spread it on the MH agar medium using a spreader. After the bacterial solution was completely absorbed by the agar, contact lens materials with a diameter of 10 mm were attached to the agar medium and cultured at 37 ° C for 24 h. A cotton swab was dipped in a 10 5 Escherichia coli and Staphylococcus aureus solutions with a CFU / mL concentration were evenly spread on NZYM broth. After the bacterial solutions were completely absorbed by the agar, silicone hydrogel contact lens materials prepared in Examples 1-3 and Comparative Examples 1-3, each with a diameter of 10 mm, were attached to the agar medium and incubated at 37°C for 24 hours. The antibacterial ring diameters of the two test schemes were measured (antibacterial ring diameter = antibacterial ring outer diameter - tested sample diameter). The test results are shown in Table 1. Table 1 Performance test of contact lens materials prepared in Examples 1-3 and Comparative Examples 1-3

[0031] As shown in Table 1, compared with Comparative Examples 1-3, the silicone hydrogel contact lens material prepared in the present application has high oxygen permeability, moisture retention and antibacterial properties.

[0032] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material, characterized in that: The following steps are involved: Preparation of hydrogel contact lens material: polyvinyl alcohol and antibacterial dispersion are mixed uniformly, heated to 86-92°C, functional monomers and citric acid are added, stirring is continued for 8-10 hours, cooled to 56-64°C, photoinitiator is added, stirred uniformly, irradiated with ultraviolet light, washed with deionized water, and balanced with boric acid buffer to obtain a highly moisturizing and antibacterial silicone hydrogel contact lens material; The antibacterial dispersion is firstly prepared by subjecting sodium alginate and tris(hydroxymethyl)aminomethane to an amidation reaction to obtain amidated sodium alginate, then subjecting it to an esterification reaction with chlorogenic acid to obtain esterified sodium alginate, and finally subjecting it to a chemical cross-linking reaction with zinc glycinate and aloe extract; The functional monomer is composed of a silicon-containing component, N-vinyl pyrrolidone and polyethylene glycol acrylate in a mass ratio of 18-26:12-18:24-30; The silicon-containing component is prepared by a hydrolysis polymerization reaction of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

2. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 1, characterized in that: In the step S1, the mass ratio of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane to deionized water is 4.6-5:

1.

3. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 1, characterized in that: In step S2, the mass ratio of polyvinyl alcohol, antibacterial dispersion, functional monomer, citric acid and photoinitiator is 6-8:26-32:2.2-2.8:0.4-0.5:0.01-0.

03.

4. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 1, wherein: In step S2, the photoinitiator is photoinitiator 8700 or benzophenone ammonium chloride.

5. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 1, characterized in that: The peak wavelength of the irradiation is 365nm and the intensity is 80mw / cm 2 , the irradiation time is 36-44min.

6. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 1, characterized in that: The antibacterial dispersion is prepared by the following steps: Step A1: Sodium alginate and deionized water were mixed and stirred at room temperature. The pH value was adjusted to 8.2-8.

4. Then, a mixture of tris(hydroxymethyl)aminomethane, phosphate buffer, and immobilized lipase (a) was added dropwise. The addition was completed within 10 minutes. The mixture was heated to 42-46° C. and stirred for 4-6 hours. The pH value was then adjusted to 6.4-6.

8. The mixture was washed with deionized water until neutral and dried to obtain amidated sodium alginate. Step A2, adding amidated sodium alginate and p-toluenesulfonic acid to deionized water, and adding a mixture of chlorogenic acid and deionized water (b) dropwise while stirring. The addition is controlled to be completed within 10 minutes. After the addition is completed, the temperature is raised to 64-72° C. and stirred for reaction for 4.2-4.6 hours. After the reaction is completed, the mixture is filtered, washed, and dried to obtain esterified sodium alginate; Step A3: Mix zinc glycinate and deionized water evenly, adjust the pH to 8.4-8.8, raise the temperature to 45-55°C, stir and add dropwise a mixture of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract and deionized water (C), control the addition to be completed within 15 minutes, continue stirring for 2.2-2.6 hours, then add dropwise glacial acetic acid, stir the reaction for 0.6-1 hour, and wash to obtain an antibacterial dispersion.

7. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 6, characterized in that: In step A1, the mass ratio of sodium alginate, deionized water and mixed solution a is 6-8:100-120:15, and the mass ratio of tris(hydroxymethyl)aminomethane, phosphate buffer and immobilized lipase in mixed solution a is 2-4:400:0.06-1.

8. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 6, characterized in that: In step A2, the mass ratio of amidated sodium alginate, p-toluenesulfonic acid, deionized water and mixed solution b is 3-5:0.02-0.04:55-65:20-26. In the mixed solution b, the mass ratio of chlorogenic acid to deionized water is 0.4-0.6:

20.

9. The method for preparing a highly moisturizing and antibacterial silicone hydrogel contact lens material according to claim 6, characterized in that: In step A3, the mass ratio of zinc glycinate, deionized water, mixed solution c, and glacial acetic acid is 1.2-1.6:40-50:20-28:0.06-0.

08. In the mixed solution c, the mass ratio of esterified sodium alginate, saturated calcium chloride aqueous solution, aloe extract, and deionized water is 2.6-3.2:0.6-0.8:0.2-0.4:

25.

10. A highly moisturizing and antibacterial silicone hydrogel contact lens material, characterized in that: The highly moisturizing and antibacterial silicone hydrogel contact lens material is obtained by the preparation method of any one of claims 1 to 9.

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