CN111529762B

CN111529762B - Chitosan hydrogel, preparation method thereof, antiviral spray and antiviral liquid glove

Info

Publication number: CN111529762B
Application number: CN202010533737.5A
Authority: CN
Inventors: 尤庆亮; 杨春林; 王仁亮; 肖本雄; 蒋湛; 徐亨; 王金露
Original assignee: Jianghan University
Current assignee: Jianghan University
Priority date: 2020-06-12
Filing date: 2020-06-12
Publication date: 2022-07-08
Anticipated expiration: 2040-06-12
Also published as: CN111529762A

Abstract

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.

Description

Chitosan hydrogel, preparation method thereof, antiviral spray and antiviral liquid glove

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 infectious diseases like Xinguan pneumonia is caused by strong infectivity, and the virus is mainly spread through aerial droplets and enters a human body through a respiratory tract, so that the speed is high, the invasiveness is strong, a carrier is not easy to find in the early period, and an exposer is 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 aqueous partially acrylated 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 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% 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:

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, 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 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 ethanol solution of 4.5-5.5% acrylate glycidyl ether or methacrylate glycidyl ether or similar acrylate monomers into the chitosan componentIn the dispersion, continuously reacting for 1.5-2.5 h at 50-65 ℃ after the dripping is finished, adding acetic acid to adjust the pH to 4-5, and clarifying the chitosan dispersion 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:

example 1

The reaction raw materials of the chitosan hydrogel provided in this example include:

95g of a 32% aqueous solution of partially acrylated chitosan, 48g of a 20% aqueous solution of polyvinylpyrrolidone, 45g of a 30% aqueous solution of gelatin, 0.45g of a photoinitiator 1173, 1.9g of fumed silica, 4.9g of lanolin, 4.9g of coconut oil diethanolamide and 1.9g of sodium fatty alcohol polyoxyethylene ether sulfate.

The partially acrylated aqueous chitosan solution comprises: 450g of chitosan acetic acid aqueous solution with the concentration of 30 percent and 45g of acrylate glycidyl ether ethanol solution with the concentration of 5 percent.

Example 2

The reaction raw materials of the chitosan hydrogel provided in this example include: 100g of a 32% aqueous solution of partially acrylated chitosan, 50g of a 20% aqueous solution of polyvinylpyrrolidone, 50g of a 30% aqueous solution of gelatin, 0.5g of a photoinitiator 1173, 2g of fumed silica, 5g of lanolin, 5g of coconut oil diethanolamide and 2g of sodium fatty alcohol polyoxyethylene ether sulfate.

The partially acrylated aqueous chitosan solution comprises: 500g of a 30% chitosan acetic acid aqueous solution, and 50g of a 5% acrylate glycidyl ether ethanol solution.

Example 3

105g of a 32% aqueous solution of partially acrylated chitosan, 55g of a 20% aqueous solution of polyvinylpyrrolidone, 55g of a 30% aqueous solution of gelatin, 0.6g of a photoinitiator 1173, 2.2g of fumed silica, 5.1g of lanolin, 5.2g of coconut oil diethanolamide and 2.05g of sodium fatty alcohol polyoxyethylene ether sulfate.

The partially acrylated aqueous chitosan solution comprises: 530g of a 30% chitosan acetic acid aqueous solution and 54g of a 5% acrylate glycidyl ether ethanol solution.

Example 4

in examples 1 to 3, the acrylate glycidyl ether (ethanol solution of acrylate glycidyl ether) in the components of the partially acrylated chitosan aqueous solution was replaced with methacrylate glycidyl ether or similar acrylate monomers.

Example 5

In examples 1 to 3, AgNO was added to the reaction material of the chitosan hydrogel at a concentration of 0.001mol/L₃4g of aqueous solution.

Example 6

In examples 1 to 3, 1g of nano-silver solution with a concentration of 2000mg/L was added to the reaction material of the chitosan hydrogel.

Example 7

In examples 1 to 3, the reaction raw material of the chitosan hydrogel further contains a bacteriostatic agent, which is any one or a combination of more of salicylic acid, trichlorohydroxydiphenyl ether, blumea oil, o-cymene-5-ol, parachlorometaxylenol, and zinc pyrithione.

Example 8

Referring to fig. 1, this embodiment provides a method for preparing chitosan hydrogel, which includes the following steps:

s1: preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylated 80% chitosan as raw material, dissolving in acetic acid water solution with pH of 3-5 to obtain 30% chitosan acetic acid water solution, collecting chitosan acetic acid water solution 450g (can be contained in three-neck flask), heating to 60 deg.C, adding NaHCO under high speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 45g of 5% ethanol solution of acrylate glycidyl ether into the chitosan dispersion liquid, continuing to react for 2h at 60 ℃, adding acetic acid to adjust the pH value to be 4-5, and clarifying the chitosan dispersion liquid to obtain a partially acrylated chitosan aqueous solution.

S2: preparing the chitosan hydrogel, which specifically comprises the following steps: taking 95g of 32% partially acrylated chitosan aqueous solution, adding 48g of 20% polyvinylpyrrolidone aqueous solution and 45g of 30% gelatin aqueous solution; adding 0.45g of photoinitiator 1173, adding 1.9g of fumed silica, adding 4.9g of lanolin fatty ester, 4.9g of coconut oil diethanolamide and 1.9g of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 5min by using a high-speed dispersion machine, standing and defoaming to obtain the rapid UV photocuring chitosan hydrogel.

Example 9

The embodiment provides a preparation method of chitosan hydrogel, which comprises the following steps:

s1: preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylated 80% chitosan as raw material, dissolving in acetic acid water solution with pH of 3-5 to obtain 30% chitosan acetic acid water solution, collecting chitosan acetic acid water solution 500g (can be contained in three-neck flask), heating to 60 deg.C, adding NaHCO under high speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 50g of ethanol solution of 5% acrylate glycidyl ether into the chitosan dispersion liquid, continuing to react for 2h at 60 ℃ after dripping, adding acetic acid to adjust the pH value to be 4-5, and clarifying the chitosan dispersion liquid to obtain a partially acrylated chitosan aqueous solution.

S2: preparing the chitosan hydrogel, which specifically comprises the following steps: taking 100g of a 32% partially acrylated chitosan aqueous solution, adding 50g of a 20% polyvinylpyrrolidone aqueous solution and 50g of a 30% gelatin aqueous solution; adding 0.5g of photoinitiator 1173, adding 2g of fumed silica, adding 5g of lanolin fatty acid ester, 5g of coconut diethanolamide and 2g of sodium fatty alcohol-polyoxyethylene ether sulfate; dispersing for 5min by using a high-speed dispersion machine, standing and defoaming to obtain the rapid UV photocuring chitosan hydrogel.

Example 10

s1: preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylated 80% chitosan as raw material, dissolving in acetic acid water solution with pH of 3-5 to obtain 30% chitosan acetic acid water solution, collecting 530g of chitosan acetic acid water solution (which can be contained in three-neck flask)) Heating to 60 deg.C, adding NaHCO while stirring at high speed₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; and slowly dripping 54g of an ethanol solution of 5% acrylate glycidyl ether into the chitosan dispersion liquid, continuing to react for 2 hours at 60 ℃ after dripping is finished, adding acetic acid to adjust the pH value to be 4-5, and clarifying the chitosan dispersion liquid to obtain a partially acrylated chitosan aqueous solution.

S2: preparing the chitosan hydrogel, which specifically comprises the following steps: taking 105g of a 32% partially acrylated chitosan aqueous solution, adding 55g of a 20% polyvinylpyrrolidone aqueous solution, 55g of a 30% gelatin aqueous solution, adding 0.6g of a photoinitiator 1173, adding 2.2g of fumed silica, adding 5.1g of lanolin, 5.2g of coconut oil diethanolamide and 2.05g of sodium fatty alcohol polyoxyethylene ether sulfate; dispersing for 5min by using a high-speed dispersion machine, standing and defoaming to obtain the rapid UV photocuring chitosan hydrogel.

In the embodiments 8-10, the chemical reaction formula for preparing the chitosan hydrogel is as follows:

example 11

In embodiments 8 to 10, the ethanol solution of the acrylate glycidyl ether may be replaced with an ethanol solution of methacrylate glycidyl ether or a similar acrylate monomer, and the chemical reaction formula is:

example 12

The embodiment provides a preparation method of a rapid UV (ultraviolet) photocuring nano-silver chitosan hydrogel, which comprises the following steps:

s1: preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylated 80% chitosan as raw material, dissolving in acetic acid water solution with pH of 3-5 to obtain 30% chitosan acetic acid water solutionTaking 500g of chitosan acetic acid aqueous solution, heating to 60 ℃, and adding NaHCO under high-speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 50g of ethanol solution of 5% acrylate glycidyl ether into the chitosan dispersion liquid, continuing to react for 2h at 60 ℃ after dripping, adding acetic acid to adjust the pH value to be 4-5, and clarifying the chitosan dispersion liquid to obtain a partially acrylated chitosan aqueous solution.

S2: preparing silver ion chitosan hydrogel, taking 100g of 32% partially acrylated chitosan aqueous solution, adding 50g of 20% polyvinylpyrrolidone aqueous solution, 50g of 30% gelatin aqueous solution, 1g of 2000mg/L nano-silver solution, adding 0.5g of photoinitiator 1173, adding 2g of fumed silica, adding 5g of lanolin, 4.8-5.5 parts of coconut oil diethanolamide and 2g of sodium fatty alcohol polyoxyethylene ether sulfate; dispersing for 5min, standing and defoaming to obtain the rapid UV photocuring nano silver chitosan hydrogel.

Example 13

The embodiment provides a preparation method of a rapid UV (ultraviolet) photocuring silver ion chitosan hydrogel, which comprises the following steps:

s1: preparing a partially acrylated chitosan aqueous solution, specifically: selecting deacetylated 80% chitosan as raw material, dissolving in acetic acid water solution with pH of 3-5 to obtain 30% chitosan acetic acid water solution, collecting chitosan acetic acid water solution 500g, heating to 60 deg.C, adding NaHCO under high speed stirring₃Adjusting the pH value to 7-8 to obtain turbid chitosan dispersion liquid; slowly dripping 50g of ethanol solution of 5% acrylate glycidyl ether into the chitosan dispersion liquid, continuing to react for 2h at 60 ℃ after dripping, adding acetic acid to adjust the pH value to be 4-5, and clarifying the chitosan dispersion liquid to obtain a partially acrylated chitosan aqueous solution.

S2: preparing silver ion chitosan hydrogel, taking 100g of partially acrylated chitosan aqueous solution with the concentration of 32%, adding 50g of polyvinylpyrrolidone aqueous solution with the concentration of 20%, 50g of gelatin aqueous solution with the concentration of 30%, and AgNO with the concentration of 0.001mol/L₃4g of aqueous solution, adding 0.5g of photoinitiator 1173, adding 2g of fumed silica, adding 5g of lanolin fatty ester, 4.8-5.5 parts of coconut diethanolamide and 2g of sodium fatty alcohol polyoxyethylene ether sulfate; dispersing for 5min, standing and defoaming to obtain the rapid UV photocuring silver ion chitosan hydrogel.

In addition, the chitosan hydrogels obtained in examples 10, 12, and 13 were subjected to a film formation test and an antibacterial test:

taking about 10mL of chitosan hydrogel by a scraper, placing the chitosan hydrogel on a glass plate of a BGD 218 automatic film coating instrument with a film coating thickness of 50um, carrying out blade coating at a speed of 20-50mm/min to form a film, wherein the film surface drying is about 20-30s under the condition of heating and drying the plate at 35 ℃, the UV-LED lamp curing surface drying time is 15-20s, and the UV-LED photocuring surface drying time is 10-15s under the condition of heating and drying the plate at 35 ℃.

The results of the chitosan hydrogel-related property tests are shown in tables 1 and 2.

TABLE 1

TABLE 2

Wherein, the UV light curing mode: LED UV lamp 50W (365 nm); drying at 35 ℃: heating and drying the plate at 35 ℃; the coating film thickness is 30 um.

Through the coating experiments and the antibacterial experiments of the examples 10, 12 and 13, the chitosan film with good mechanical property and antibacterial property can be obtained from the tables 1 and 2; example 10 to avoid aversion to silver ions by some users, the chitosan gel without silver ions and silver nanoparticles was tested for antibacterial performance, and also exhibited good antibacterial performance (e.coli inhibition > 90%; staphylococcus aureus > 95%; candida albicans > 81%), and both example 13 with silver ions (Ag +) and example 12 with silver nanoparticles showed excellent antibacterial performance (e.coli inhibition > 99%; staphylococcus aureus > 99%; candida albicans > 99%).

From table 1, it can be seen that the gel films of photo-curing, thermal drying and photo-curing and thermal drying all have good mechanical properties and drying characteristics within 30 seconds, and the advantage of UV photo-curing is that the mechanical properties of the gel are greatly improved, and the durability is greatly improved.

In addition, on the basis of the embodiment 10, the chitosan antibacterial and bacteriostatic gel prepared by salicylic acid, trichloro-hydroxy diphenyl ether, blumea oil, o-cymene-5-ol, Parachlorometaxylenol (PCMX) and Zinc Pyrithione (ZPT) according to effective addition concentration shows excellent antibacterial effect through tests, and is very suitable for application of hand antibacterial and nursing in epidemic situation periods and special places. The results are shown in the following table 3 (chitosan hydrogel bacteriostatic performance test results):

TABLE 3

Wherein the blumea oil and the o-cymene-5-ol are natural extracts, and the safety and the effectiveness are fully determined, so that the blumea oil and the o-cymene-5-ol have more excellent safety and wide application.

Example 14

This example provides an application of the chitosan hydrogel of any of examples 1 to 7, that is, the chitosan hydrogel cured by the fast UV light is applied to the hands of the human body to form liquid gloves, and for some specific fields, if there is no LED-UV light source, the antibacterial chitosan gel is directly coated on the hands and dried in the air, which also has good antibacterial and bacteriostatic properties (35 ℃ drying is a temperature close to the hands), so that the liquid gloves prepared from the chitosan hydrogel can well realize the comfort and continuous antibacterial and antiviral effects of the hands of the ordinary people

Example 15

The embodiment provides an application of the chitosan hydrogel of any one of embodiments 1 to 7, namely diluting the chitosan hydrogel with purified water to prepare an antiviral spray; wherein the mass ratio of the chitosan hydrogel to the purified water is 1: 3-20, preferably 1: 8. After the viscosity of the chitosan hydrogel is reduced, the chitosan hydrogel can be prepared into a spray, and can also be used for long-acting (5-10 days) antibacterial and antiviral applications of surfaces (computer keyboards, elevator keys and door handles) of certain specific parts, such as disinfection and sterilization of articles in classrooms, tables of libraries, books and the like, so that long-term effective antibacterial protection of the specific parts is realized.

The application provides a chitosan acrylate hydrogel capable of being cured by UV, and based on the chitosan acrylate hydrogel, a liquid glove and an antiviral spray with remarkable antibacterial and antiviral effects are prepared. The hydrogel can be completely cured within 10-15 seconds under the irradiation of sunlight or LED type UV light; the hydrogel can also form a surface with lasting antibacterial and antiviral properties by the adsorption of nano silver or silver ions and the like with chitosan, thereby achieving the effect of continuously protecting users of the gel gloves within 4-6h and preventing the infection of viruses or bacteria to human bodies; after the liquid glove is used, the gel layer can be washed off only by a common washing process of washing hands, chitosan is a bio-based natural polymer, is very easy to degrade, cannot cause plastic pollution, and cannot cause secondary pollution due to viruses and germs on the surface, so that the liquid glove is convenient for ordinary people to keep the comfort and the continuous antibacterial and antiviral effects of hands.

The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

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 or methacrylate glycidyl ether ethanol solution;

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

2. The chitosan hydrogel of claim 1, 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.

3. The chitosan hydrogel of claim 1, 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.

4. An antiviral liquid glove, wherein the antiviral liquid glove is formed by applying the chitosan hydrogel according to any one of claims 1 to 3 to a human hand.

5. An antiviral spray, characterized in that the chitosan hydrogel of any one of claims 1 to 3 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.

6. A method for preparing the chitosan hydrogel of claim 1, 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; taking 42-60 parts of an ethanol solution of acrylate glycidyl ether or methacrylate glycidyl ether with the concentration of 4.5-5.5%, slowly dripping the ethanol solution into the chitosan dispersion liquid, continuing to react at 50-65 ℃ for 1.5-2.5 h after dripping is finished, 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% 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.

7. A method for preparing the chitosan hydrogel of claim 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 25-35% chitosan acetic acid aqueous solution, taking 420-580 parts by mass of the chitosan acetic acid aqueous solution, and heating to 56-6 parts by massNaHCO was added at 2 ℃ with 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 acrylate glycidyl ether or methacrylate glycidyl ether with the concentration of 4.5-5.5% into the chitosan dispersion liquid, continuing to react at 50-65 ℃ for 1.5-2.5 h after dripping is finished, 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, 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 silver ion chitosan hydrogel.

8. A method for preparing the chitosan hydrogel of claim 3, 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 an ethanol solution of acrylate glycidyl ether or methacrylate glycidyl ether with the concentration of 4.5-5.5% into the chitosan dispersion liquid, continuing to react at 50-65 ℃ for 1.5-2.5 h after dripping is finished, 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.