阅读说明：本技术 壳聚糖水凝胶及制备方法、抗病毒喷剂、抗病毒液体手套 (Chitosan hydrogel, preparation method thereof, antiviral spray and antiviral liquid glove ) 是由 尤庆亮 杨春林 王仁亮 肖本雄 蒋湛 徐亨 王金露 于 2020-06-12 设计创作，主要内容包括：本发明涉及壳聚糖水凝胶及制备方法、抗病毒喷剂、抗病毒液体手套,壳聚糖水凝胶的反应原料包括：以质量份数计,部分丙烯酸酯化的壳聚糖水溶液90～108份、聚乙烯吡咯烷酮水溶液42～60份、明胶水溶液40～60份、0.4～0.6份光引发剂1173、1.8～2.3份气相二氧化硅、4.8～5.2份羊油酯、4.8～5.5份椰子油二乙醇酰胺、1.9～2.1份脂肪醇聚氧乙烯醚硫酸钠；部分丙烯酸酯化的壳聚糖水溶液包括：以质量份数计,壳聚糖醋酸水溶液420～580份、丙烯酸酯缩水甘油醚的乙醇溶液42～60份。该壳聚糖水凝胶能制备具有显著抗菌抗病毒效果的液体手套及抗病毒喷剂。(The invention relates to chitosan hydrogel and a preparation method thereof, an antiviral spray and an antiviral liquid glove, wherein the chitosan hydrogel comprises the following reaction raw materials: 90-108 parts of partially acrylated chitosan aqueous solution, 42-60 parts of polyvinylpyrrolidone aqueous solution, 40-60 parts of gelatin aqueous solution, 0.4-0.6 part of photoinitiator 1173, 1.8-2.3 parts of fumed silica, 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of fatty alcohol-polyoxyethylene ether sodium sulfate; the partially acrylated aqueous chitosan solution comprises: 420-580 parts of chitosan acetic acid aqueous solution and 42-60 parts of acrylate glycidyl ether ethanol solution in parts by mass. The chitosan hydrogel can be used for preparing liquid gloves and antiviral spray with remarkable antibacterial and antiviral effects.)

1. The chitosan hydrogel is characterized in that reaction raw materials of the chitosan hydrogel comprise: by mass, 90-108 parts of a partially acrylated chitosan aqueous solution with the concentration of 30-35%, 42-60 parts of a polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 40-60 parts of a gelatin aqueous solution with the concentration of 20-35%, 0.4-0.6 part of a photoinitiator 1173, 1.8-2.3 parts of fumed silica, 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of fatty alcohol polyoxyethylene ether sodium sulfate;

the partially acrylated aqueous chitosan solution comprises: 420-580 parts of 25-35% chitosan acetic acid aqueous solution and 42-60 parts of 4.5-5.5% acrylate glycidyl ether ethanol solution.

2. The chitosan hydrogel of claim 1, wherein said acrylate glycidyl ether is replaced with methacrylate glycidyl ether or a similar acrylate monomer.

3. The chitosan hydrogel according to claim 1 or 2, wherein the reaction raw materials of the chitosan hydrogel further comprise: AgNO with concentration of 0.001mol/L in parts by mass₃3.5-4.3 parts of an aqueous solution.

4. The chitosan hydrogel according to claim 1 or 2, wherein the reaction raw materials of the chitosan hydrogel further comprise: 0.8-1.1 parts of nano silver solution with the concentration of 2000mg/L in parts by mass.

5. The chitosan hydrogel according to claim 1 or 2, wherein the reaction raw material of the chitosan hydrogel further comprises a bacteriostatic agent, and the bacteriostatic agent is any one or more of salicylic acid, trichlorohydroxydiphenyl ether, blumea oil, o-cymene-5-ol, parachlorometaxylenol, and zinc pyrithione.

6. An antiviral liquid glove, wherein the antiviral liquid glove is formed by applying the chitosan hydrogel according to any one of claims 1 to 5 to a human hand.

7. An antiviral spray, characterized in that the chitosan hydrogel of any one of claims 1 to 5 is diluted with purified water to prepare the antiviral spray; the mass ratio of the chitosan hydrogel to the purified water is 1: 3 to 20.

8. A method for preparing the chitosan hydrogel of claim 1 or 2, comprising the steps of:

preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylation>Dissolving 75% chitosan serving as a raw material in an acetic acid aqueous solution with the pH value of 3-5 to prepare a chitosan acetic acid aqueous solution with the concentration of 25-35%, taking 420-580 parts of the chitosan acetic acid aqueous solution by mass, heating to 56-62 ℃, and adding NaHCO (NaHCO) under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 42-60 parts of ethyl alcohol solution of acrylic ester glycidyl ether or methacrylic ester glycidyl ether or similar acrylic ester monomers with the concentration of 4.5-5.5% into the chitosan dispersion liquid, and continuing to drip after drippingReacting for 1.5-2.5 h at 50-65 ℃, adding acetic acid to adjust the pH to 4-5, and clarifying the chitosan dispersion liquid to obtain the partially acrylated chitosan aqueous solution;

taking 90-108 parts by mass of the partially acrylated chitosan aqueous solution with the concentration of 30-35%, adding 42-60 parts by mass of polyvinylpyrrolidone aqueous solution with the concentration of 15-25% and 40-60 parts by mass of gelatin aqueous solution with the concentration of 20-35%; adding 0.4-0.6 part of photoinitiator 1173, adding 1.8-2.3 parts of fumed silica, adding 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 4-8 min, standing and defoaming to obtain the chitosan hydrogel.

9. A method for preparing the silver ion chitosan hydrogel of claim 3, which comprises the following steps:

preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylation>Dissolving 75% chitosan serving as a raw material in an acetic acid aqueous solution with the pH value of 3-5 to prepare a chitosan acetic acid aqueous solution with the concentration of 25-35%, taking 420-580 parts of the chitosan acetic acid aqueous solution by mass, heating to 56-62 ℃, and adding NaHCO (NaHCO) under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 42-60 parts of an ethanol solution of 4.5-5.5% acrylate glycidyl ether or methacrylate glycidyl ether or similar acrylate monomers into the chitosan dispersion liquid, continuously reacting at 50-65 ℃ for 1.5-2.5 h after dripping, adding acetic acid to adjust the pH value to 4-5, and clarifying the chitosan dispersion liquid to obtain the partially acrylated chitosan aqueous solution;

taking 90-108 parts by mass of the partially acrylated chitosan aqueous solution with the concentration of 30-35%, adding 42-60 parts by mass of polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 40-60 parts by mass of gelatin aqueous solution with the concentration of 20-35%, and AgNO with the concentration of 0.001mol/L₃3.5-4.3 parts of an aqueous solution; adding 0.4-0.6 part of photoinitiator 1173, and adding 1.8-2.3 parts of gasAdding 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut diethanolamide and 1.9-2.1 parts of sodium fatty alcohol-polyoxyethylene ether sulfate into the phase silicon dioxide; dispersing for 4-8 min, standing and defoaming to obtain the silver ion chitosan hydrogel.

10. A preparation method of the nano-silver chitosan hydrogel as claimed in claim 4, which is characterized by comprising the following steps:

preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylation>Dissolving 75% chitosan serving as a raw material in an acetic acid aqueous solution with the pH value of 3-5 to prepare a chitosan acetic acid aqueous solution with the concentration of 25-35%, taking 420-580 parts of the chitosan acetic acid aqueous solution by mass, heating to 56-62 ℃, and adding NaHCO (NaHCO) under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 42-60 parts of an ethanol solution of 4.5-5.5% acrylate glycidyl ether or methacrylate glycidyl ether or similar acrylate monomers into the chitosan dispersion liquid, continuously reacting at 50-65 ℃ for 1.5-2.5 h after dripping, adding acetic acid to adjust the pH value to 4-5, and clarifying the chitosan dispersion liquid to obtain the partially acrylated chitosan aqueous solution;

taking 90-108 parts by mass of the partially acrylated chitosan aqueous solution with the concentration of 30-35%, adding 42-60 parts by mass of polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 40-60 parts by mass of gelatin aqueous solution with the concentration of 20-35% and 0.8-1.1 part by mass of nano-silver solution with the concentration of 2000 mg/L; adding 0.4-0.6 part of photoinitiator 1173, adding 1.8-2.3 parts of fumed silica, adding 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 4-8 min, standing and defoaming to obtain the nano-silver chitosan hydrogel.

Technical Field

The invention relates to the technical field of biomedical materials, in particular to chitosan hydrogel, a preparation method thereof, an antiviral spray and an antiviral liquid glove.

Background

The outbreak of new coronary pneumonia epidemic situation in 2020 greatly harms people's health, affects national social order and stability, and has a series of serious effects on economy, culture, exchange, outcrossing and the like. The serious harm of respiratory tract infectious diseases like new coronary pneumonia is caused by strong infectivity, mainly viruses are spread through air droplets and enter human bodies through respiratory tracts, the speed is high, the invasiveness is strong, carriers are not easy to find in the early stage, and exponents are prevented from being infected in a large area.

Cutting off the infection source and making personnel self-protection are very important, aiming at droplet transmission and contact transmission, the main measures adopted at present are six characters: wear gauze mask, the duty is washed hand. However, in practice, not all people can wash their hands under multiple conditions, but many people wear masks and gloves in a break to avoid virus infection, which is very necessary in the current situation of such serious epidemic situations, but wearing gloves can generate a large amount of white plastic pollution and garbage polluted by viruses, and meanwhile, wearing gloves can generate various problems of suffocation, sweating on hands, influence on operation, eczema and allergy.

At present, high-barrier gloves are necessary for medical staff at the front, and for more common workers, how to provide a general hand protection scheme which can protect hands and simultaneously cannot generate white pollution and secondary virus pollution is extremely important.

Disclosure of Invention

The application provides a chitosan hydrogel and a preparation method thereof, solves or partially solves the technical problem that the prior art lacks of a universal antibacterial glove which is convenient to use and can not generate white pollution and secondary virus pollution, realizes the provision of a chitosan acrylate hydrogel capable of being UV cured, and prepares a liquid glove and an antiviral spray with remarkable antibacterial and antiviral effects on the basis of the chitosan acrylate hydrogel.

The application provides a chitosan hydrogel, and the reaction raw materials include: by mass, 90-108 parts of a partially acrylated chitosan aqueous solution with the concentration of 30-35%, 42-60 parts of a polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 40-60 parts of a gelatin aqueous solution with the concentration of 20-35%, 0.4-0.6 part of a photoinitiator 1173, 1.8-2.3 parts of fumed silica, 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of fatty alcohol polyoxyethylene ether sodium sulfate;

the partially acrylated aqueous chitosan solution comprises: 420-580 parts of 25-35% chitosan acetic acid aqueous solution and 42-60 parts of 4.5-5.5% acrylate glycidyl ether ethanol solution.

Preferably, the method comprises the following steps: 95-105 parts by mass of a partially acrylated chitosan aqueous solution with the concentration of 30-35%, 45-55 parts by mass of a polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 45-55 parts by mass of a gelatin aqueous solution with the concentration of 20-35%, 0.45-0.55 part by mass of a photoinitiator 1173, 1.9-2.2 parts by mass of fumed silica, 4.85-5.1 parts by mass of lanolin, 4.85-5.3 parts by mass of coconut oil diethanolamide and 1.95-2.05 parts by mass of fatty alcohol polyoxyethylene ether sodium sulfate;

the partially acrylated aqueous chitosan solution comprises: 450-520 parts of 25-35% chitosan acetic acid aqueous solution and 45-55 parts of 4.5-5.5% acrylate glycidyl ether ethanol solution.

Preferably, the method comprises the following steps: 100 parts of a 32% partially acrylated chitosan aqueous solution, 50 parts of a 20% polyvinylpyrrolidone aqueous solution, 50 parts of a 30% gelatin aqueous solution, 0.5 part of a photoinitiator 1173, 2 parts of fumed silica, 5 parts of lanolin, 5 parts of coconut oil diethanolamide and 2 parts of sodium fatty alcohol polyoxyethylene ether sulfate;

the partially acrylated aqueous chitosan solution comprises: the weight portion of the chitosan-acetic acid aqueous solution is 500 portions of chitosan-acetic acid aqueous solution with the concentration of 30 percent, and 50 portions of acrylic ester glycidyl ether ethanol solution with the concentration of 5 percent.

Preferably, the acrylate glycidyl ether is replaced with methacrylate glycidyl ether or a similar acrylate monomer.

Preferably, the reaction raw materials of the chitosan hydrogel further comprise: AgNO with concentration of 0.001mol/L in parts by mass₃3.5-4.3 parts of an aqueous solution.

Preferably, the reaction raw materials of the chitosan hydrogel further comprise: 0.8-1.1 parts of nano silver solution with the concentration of 2000mg/L in parts by mass.

Preferably, the reaction raw material of the chitosan hydrogel further comprises a bacteriostatic agent, wherein the bacteriostatic agent is any one or combination of more of salicylic acid, trichloro-hydroxy-diphenyl ether, blumea oil, o-cymene-5-alcohol, parachlorometaxylenol and zinc pyrithione.

Based on the same inventive concept, the application also provides a preparation method of the chitosan hydrogel, which comprises the following steps:

preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylation>Dissolving 75% chitosan serving as a raw material in an acetic acid aqueous solution with the pH value of 3-5 to prepare a chitosan acetic acid aqueous solution with the concentration of 25-35%, taking 420-580 parts of the chitosan acetic acid aqueous solution by mass, heating to 56-62 ℃, and adding NaHCO (NaHCO) under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 42-60 parts of ethyl alcohol solution of acrylic ester glycidyl ether or methacrylic ester glycidyl ether or similar acrylic ester monomers with the concentration of 4.5-5.5% into the chitosan dispersion liquid, and continuously reacting at 50-65 DEG CAdding acetic acid for 1.5-2.5 h to adjust the pH value to 4-5, and clarifying the chitosan dispersion liquid to obtain the partially acrylated chitosan aqueous solution;

taking 90-108 parts by mass of the partially acrylated chitosan aqueous solution with the concentration of 30-35%, adding 42-60 parts by mass of polyvinylpyrrolidone aqueous solution with the concentration of 15-25% and 40-60 parts by mass of gelatin aqueous solution with the concentration of 20-35%; adding 0.4-0.6 part of photoinitiator 1173, adding 1.8-2.3 parts of fumed silica, adding 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 4-8 min, standing and defoaming to obtain the rapid UV photocuring hydrogel.

Based on the same inventive concept, the application also provides a preparation method of the silver ion chitosan hydrogel, which comprises the following steps:

preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylation>Dissolving 75% chitosan serving as a raw material in an acetic acid aqueous solution with the pH value of 3-5 to prepare a chitosan acetic acid aqueous solution with the concentration of 25-35%, taking 420-580 parts of the chitosan acetic acid aqueous solution by mass, heating to 56-62 ℃, and adding NaHCO (NaHCO) under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 42-60 parts of an ethanol solution of 4.5-5.5% acrylate glycidyl ether or methacrylate glycidyl ether or similar acrylate monomers into the chitosan dispersion liquid, continuously reacting at 50-65 ℃ for 1.5-2.5 h after dripping, adding acetic acid to adjust the pH value to 4-5, and clarifying the chitosan dispersion liquid to obtain the partially acrylated chitosan aqueous solution;

taking 90-108 parts by mass of the partially acrylated chitosan aqueous solution with the concentration of 30-35%, adding 42-60 parts by mass of polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 40-60 parts by mass of gelatin aqueous solution with the concentration of 20-35%, and AgNO with the concentration of 0.001mol/L₃3.5-4.3 parts of an aqueous solution; adding 0.4-0.6 part of photoinitiator 1173, adding 1.8-2.3 parts of fumed silica, and adding 4.8-5.2 parts of mutton fatEster, 4.8-5.5 parts of coconut diethanolamide and 1.9-2.1 parts of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 4-8 min, standing and defoaming to obtain the silver ion chitosan hydrogel.

Based on the same inventive concept, the application also provides a preparation method of the nano-silver chitosan hydrogel, which comprises the following steps:

preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylation>Dissolving 75% chitosan serving as a raw material in an acetic acid aqueous solution with the pH value of 3-5 to prepare a chitosan acetic acid aqueous solution with the concentration of 25-35%, taking 420-580 parts of the chitosan acetic acid aqueous solution by mass, heating to 56-62 ℃, and adding NaHCO (NaHCO) under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 42-60 parts of an ethanol solution of 4.5-5.5% acrylate glycidyl ether or methacrylate glycidyl ether or similar acrylate monomers into the chitosan dispersion liquid, continuously reacting at 50-65 ℃ for 1.5-2.5 h after dripping, adding acetic acid to adjust the pH value to 4-5, and clarifying the chitosan dispersion liquid to obtain the partially acrylated chitosan aqueous solution;

taking 90-108 parts by mass of the partially acrylated chitosan aqueous solution with the concentration of 30-35%, adding 42-60 parts by mass of polyvinylpyrrolidone aqueous solution with the concentration of 15-25%, 40-60 parts by mass of gelatin aqueous solution with the concentration of 20-35% and 0.8-1.1 part by mass of nano-silver solution with the concentration of 2000 mg/L; adding 0.4-0.6 part of photoinitiator 1173, adding 1.8-2.3 parts of fumed silica, adding 4.8-5.2 parts of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 1.9-2.1 parts of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 4-8 min, standing and defoaming to obtain the nano-silver chitosan hydrogel.

Based on the same inventive concept, the application also provides an antiviral liquid glove which is formed by smearing the chitosan hydrogel on a hand of a human body.

Based on the same inventive concept, the application also provides an antiviral spray, wherein the chitosan hydrogel is diluted by purified water to prepare the antiviral spray; the mass ratio of the chitosan hydrogel to the purified water is 1: 3 to 20.

One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:

the application provides an acrylate chitosan hydrogel capable of being cured by UV, and liquid gloves and antiviral spray with remarkable antibacterial and antiviral effects are prepared on the basis of the acrylate chitosan hydrogel, and the hydrogel can be completely cured in 10-15 seconds under the irradiation of sunlight or LED type UV light; the hydrogel has a surface with lasting antibacterial and antiviral properties, and can be smeared on the hand of a user to continuously protect the user within 4-6h and avoid the infection of viruses or bacteria to the human body; the gel layer can be washed off only by a common washing process of washing hands after use, and the chitosan is a bio-based natural polymer, is very easy to degrade, can not cause plastic pollution, and can not cause secondary pollution caused by viruses and germs attached to the surface. Therefore, the technical problem that the prior art lacks of the universal antibacterial gloves which are convenient to use and cannot generate white pollution and secondary virus pollution is solved or partially solved, the acrylate chitosan hydrogel capable of being subjected to UV curing is provided, and the technical effects of the liquid gloves and the antiviral spray with the remarkable antibacterial and antiviral effects are prepared on the basis of the acrylate chitosan hydrogel.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

Fig. 1 is a schematic flow chart of a method for preparing a chitosan hydrogel provided in example 8 of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all 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 application.

In order to solve or partially solve the technical problems in the prior art, the technical scheme adopted by the application is as follows:

the liquid gloves and the antiviral spray with obvious antibacterial and antiviral effects are prepared on the basis of the acrylate chitosan hydrogel which can be subjected to UV curing, and the chitosan is a bio-based natural polymer and is very easy to degrade, so that plastic pollution is avoided, secondary pollution caused by viruses and germs on the surface is avoided, and the liquid gloves have the functions of continuous sterilization and virus killing.

The chitosan hydrogel of the present application, its preparation method and application are described in detail by the following specific examples: