CN111849328A - Preparation method and application of antiviral moisture-permeable coating - Google Patents
Preparation method and application of antiviral moisture-permeable coating Download PDFInfo
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- CN111849328A CN111849328A CN202010657689.0A CN202010657689A CN111849328A CN 111849328 A CN111849328 A CN 111849328A CN 202010657689 A CN202010657689 A CN 202010657689A CN 111849328 A CN111849328 A CN 111849328A
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Abstract
The invention discloses a preparation method of an antiviral moisture-permeable coating and application of the coating in preparation of an antiviral moisture-permeable film, which comprises the following steps: 1) reacting polyethyleneimine with halogenated hydrocarbon to obtain polyethyleneimine quaternary ammonium salt; 2) the antiviral moisture-permeable coating is obtained by matching polyethyleneimine quaternary ammonium salt and oxalic acid in the water-based polymer. After the antiviral moisture-permeable coating is attached to the porous base film, heat treatment is performed. The porous base film is used as a base material of the moisture permeable film to obtain the antiviral moisture permeable film. The moisture-permeable film has antiviral capacity, and the influence of the added quaternary ammonium salt polymer on the water vapor transmission rate is not obvious, so that the antiviral moisture-permeable film has the characteristics of high moisture transmission rate, excellent antiviral performance, aerosol barrier, virus inhibition and high water vapor transmission rate, and can be used for preparing medical protective clothing.
Description
Technical Field
The invention relates to the field of antiviral moisture permeable materials, in particular to a preparation method of an antiviral moisture permeable coating and application of the antiviral moisture permeable coating in preparation of an antiviral moisture permeable film.
Background
With the increase of environmental pollution and the increasing influence of human beings on the natural environment, the spread and transmission of bacteria and viruses are more and more obvious. The number of people dying from viruses every year around the world is over 400 million, and the health of human beings is seriously threatened. Recently, viral infections such as SARS virus, Ebola virus, H1N1 virus, NCP virus, etc. have had serious social effects.
The medical protective clothing is used as basic material for resisting virus, and the health of medical care personnel is guaranteed. The protective clothing fabric takes the breathable film as an isolation layer and is compounded with the non-woven fabric to form the fabric. The ventilated membrane of the existing protective clothing is mainly a polyethylene film, so that the cost is low, but the moisture permeability is poor, the moisture condensation can be caused after the protective clothing is worn for a period of time, and the comfort level is poor. Meanwhile, the film has lower strength, is easy to tear and has potential safety hazards. The thermoplastic polyurethane film has higher moisture permeability, and the comfort of the fabric can be obviously improved.
However, high performance protective clothing materials such as polyethylene films and thermoplastic polyurethane films do not have an antiviral effect, and viruses can be deposited on the surface of the protective clothing, so that there is a possibility of indirect infection when the protective clothing is replaced. Therefore, the invention relates to an antiviral and high moisture permeable isolation material which has great significance.
Disclosure of Invention
The invention aims to provide a preparation method of an antiviral moisture-permeable coating and application of the coating in preparation of an antiviral moisture-permeable film, wherein the coating can form the antiviral moisture-permeable film with excellent water resistance.
The gist of the present invention is explained below.
A preparation method of an antiviral moisture-permeable coating comprises the following steps:
1) reacting polyethyleneimine with halogenated hydrocarbon to obtain polyethyleneimine quaternary ammonium salt;
2) the antiviral moisture-permeable coating is obtained by matching polyethyleneimine quaternary ammonium salt and oxalic acid in the water-based polymer.
The invention is formed by compounding polyethyleneimine quaternary ammonium salt and oxalic acid in a water-based polymer, wherein the weight ratio of the solid components of the water-based polymer and the polyethyleneimine quaternary ammonium salt is 1: 0.01 to 0.2. The water-based polymer has high hydrophilicity and can provide good moisture permeability. The polyethyleneimine quaternary ammonium salt is multi-chain quaternary ammonium salt, has extremely high antiviral property, and can kill viruses in a short time. The oxalic acid can form a macromolecular compound with the polyethyleneimine quaternary ammonium salt, so that the dissolution of the polyethyleneimine quaternary ammonium salt in water can be remarkably reduced, and the long-term antiviral effect is realized.
In the step 1), the number average molecular weight of the polyethyleneimine is 3000-100000.
The halogenation is brominated hydrocarbon or iodohydrocarbon with 4-12 carbon atoms. The halogenated hydrocarbon is one or more than two (including two) of bromobutane, bromohexane, bromooctane and iodobutane;
in the step 1), polyethyleneimine and halogenated hydrocarbon are reacted to obtain polyethyleneimine quaternary ammonium salt, and the method specifically comprises the following steps:
under protective gas, adding polyethyleneimine, halogenated hydrocarbon and potassium carbonate into ethanol, stirring, heating, refluxing, cooling, filtering to remove solids, and removing volatiles from the filtrate to obtain polyethyleneimine quaternary ammonium salt.
The protective gas is protected by nitrogen
The weight ratio of the polyethyleneimine to the halogenated hydrocarbon to the potassium carbonate is 5-15: 5-40: 5-15, most preferably 10: 10-20: 10.
stirring, heating and refluxing for 6-10 h at 70-90 ℃, and most preferably stirring, heating and refluxing for 8h at 80 ℃.
The filtrate is devolatilized at 100 deg.C to 120 deg.C, and most preferably, the filtrate is devolatilized at 110 deg.C.
In the step 2), the waterborne polymer is formed by crosslinking waterborne isocyanate, and the weight ratio of the waterborne polymer to the solid content of the waterborne isocyanate is 1: 0.05 to 0.2. The uncrosslinked aqueous polymer is easily dissolved in water when used, and isocyanate crosslinking improves the stability of the material and maintains high moisture permeability for a long period of time. The water-based polymer is preferably one or more (including two) of polyvinyl alcohol, polyurethane emulsion, hydroxyethyl cellulose and hydroxypropyl cellulose. The water-based polymer is preferably polyvinyl alcohol, and more preferably polyvinyl alcohol with the polymerization degree of 1700-2500 and the hydrolysis degree of 88-99%.
The polyethyleneimine quaternary ammonium salt is synthesized from polyethyleneimine and halogenated hydrocarbon, wherein the weight ratio of the polyethyleneimine to the halogenated hydrocarbon is 1: 0.05 to 0.2.
Dissolving the water-based polymer in water, cooling, adding isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid, uniformly stirring and defoaming in vacuum to obtain the antiviral moisture-permeable coating
The antiviral moisture-permeable coating is prepared by compounding polyethyleneimine quaternary ammonium salt and oxalic acid in a water-based polymer, and specifically comprises the following components:
dissolving the water-based polymer in water, cooling, then adding isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid, uniformly stirring and defoaming in vacuum to obtain the antiviral moisture-permeable coating.
The ratio of the water-based polymer, water, isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid is 2-15 g: 70-120 mL: 5-20 g: 0.3-3 g: 0.3 to 3g, most preferably 5 to 10 g: 90-95 ml: 10 g: 1 g: 1g of the total weight of the composition.
The application of the antiviral moisture-permeable coating in preparing the antiviral moisture-permeable film and the forming method of the antiviral moisture-permeable film are characterized in that the antiviral moisture-permeable coating is attached to a porous base film and then is subjected to heating treatment. The porous base film serves as a base material of the moisture permeable film, and not only provides a porous base material, but also provides corresponding mechanical properties. High strength wet-laid polyethylene films are preferred.
An antiviral moisture-permeable film formed by the method for forming an antiviral moisture-permeable film.
Most preferably, the preparation method of the antiviral moisture permeable film comprises the following steps:
1) under the protection of nitrogen, polyethyleneimine, iodobutane, octyl bromide and potassium carbonate are added into ethanol, stirred at 80 ℃ and heated for reflux for 8 hours. Cooling, filtering to remove solids, and removing volatile matters from the filtrate at a negative pressure of 110 ℃ under the protection of nitrogen to obtain polyethyleneimine quaternary ammonium salt;
the number average molecular weight of the polyethyleneimine is 25000;
the weight ratio of the polyethyleneimine to the iodobutane to the bromooctane to the potassium carbonate is 10: 10: 10: 10;
2) adding the polyurethane emulsion into water, cooling, adding isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid, uniformly stirring and defoaming in vacuum to obtain the antiviral moisture-permeable coating; coating the antiviral moisture-permeable coating on a polypropylene microporous membrane with the thickness of 40um, and drying for 1min by an oven at 60 ℃ to obtain an antiviral moisture-permeable membrane;
the ratio of the dosage of the polyurethane emulsion, water, isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid is 10 g: 90 ml: 10 g: 1 g: 1g of the total weight of the composition.
The water vapor transmission rate of the antiviral moisture-permeable film obtained by the optimal scheme is g/(24 h.m) 2) 18654.1, the average virus inactivation log value is 4.17, and the product not only has the characteristic of high moisture permeability, but also has excellent antiviral performance.
Compared with the prior art, the invention has the following advantages:
according to the present invention, hydrogen bonds are provided between the quaternary ammonium salt and the aqueous crosslinked polymer in the antiviral moisture-permeable coating material, thereby preventing the quaternary ammonium salt from dissolving out in water. Therefore, the elution of the quaternary ammonium salt can be prevented from lowering the antiviral property.
The moisture-permeable film has antiviral capacity, and the influence of the added quaternary ammonium salt polymer on the water vapor transmission rate is not obvious, so that the antiviral moisture-permeable film has the characteristic of high moisture transmission rate and excellent antiviral performance.
The antiviral moisture-permeable coating is coated on the porous base membrane, so that a compact antiviral moisture-permeable membrane can be obtained, has the functions of blocking aerosol, inhibiting viruses and having high water vapor transmission rate, and can be used for preparing medical protective clothing.
Detailed Description
The embodiments of the present invention are described in detail below.
The antiviral moisture-permeable coating is designed by combining a high moisture-permeable polymer with an antiviral component. Since the moisture permeable film is in direct contact with moisture, it is necessary to avoid dissolution of the moisture permeable polymer and the antiviral component. The invention adopts the water-based polymer crosslinked by water-based isocyanate as a film forming substance and the polyethyleneimine quaternary ammonium salt as an antiviral component, thereby taking the balance of compactness, moisture permeability and antiviral property into consideration.
In the method for forming an antiviral coating film of the present invention, the antiviral moisture-permeable coating material of the present invention is attached to a porous base film, and then heat treatment is performed to form an antiviral coating film.
The present invention will be described more specifically with reference to examples.
Example 1
10g of polyethyleneimine (BASF lupasol WF, Germany, with a number average molecular weight of 25000), 10g of bromobutane and 10g of potassium carbonate were added to ethanol under nitrogen protection, stirred at 80 ℃ and heated under reflux for 8 h. After cooling, the solid is removed by filtration, and the volatile matter is removed from the filtrate at 110 ℃ under the protection of nitrogen, thus obtaining the polyethyleneimine quaternary ammonium salt A.
Dissolving 5g of polyvinyl alcohol 1799 in 95ml of hot water, cooling to room temperature of 25 ℃, adding 10g of isocyanate, 1g of polyethyleneimine quaternary ammonium salt A and 1g of oxalic acid, uniformly stirring and defoaming in vacuum to obtain the antiviral moisture permeable coating. The antiviral moisture permeable coating is coated on PET non-woven fabric with the thickness of 30um, and is dried for 1min by an oven at the temperature of 60 ℃ to obtain the antiviral moisture permeable film.
Example 2
10g of polyethyleneimine (BASF lupasol WF, Germany, with a number average molecular weight of 25000), 10g of bromobutane, 10g of bromohexane and 10g of potassium carbonate were added to ethanol under nitrogen, and the mixture was stirred at 80 ℃ and heated under reflux for 8 hours. And cooling, filtering to remove solids, and removing volatile matters from the filtrate at 110 ℃ under negative pressure under the protection of nitrogen to obtain the polyethyleneimine quaternary ammonium salt B.
Adding 10g of polyurethane emulsion (AH 1618, Anhui Dahuatai) into 90ml of water, cooling to room temperature, adding 10g of isocyanate, 1g of polyethyleneimine quaternary ammonium salt and 1g of oxalic acid, uniformly stirring, and performing vacuum defoaming to obtain the antiviral moisture-permeable coating. The antiviral moisture permeable coating is coated on PET non-woven fabric with the thickness of 30um, and is dried for 1min by an oven at the temperature of 60 ℃ to obtain the antiviral moisture permeable film.
Example 3
10g of polyethyleneimine (BASF lupasol WF, Germany, with a number average molecular weight of 25000), 10g of bromobutane, 10g of octyl bromide and 10g of potassium carbonate were added to ethanol under nitrogen protection, and stirred at 80 ℃ and heated under reflux for 8 hours. And cooling, filtering to remove solids, and removing volatile matters from the filtrate at 110 ℃ under negative pressure under the protection of nitrogen to obtain the polyethyleneimine quaternary ammonium salt C.
5g of hydroxyethyl cellulose (HEC-60000, Shandong Yao) is dispersed in 95ml of water, and is completely dissolved by a small amount of ammonia water, 10g of isocyanate, 1g of polyethyleneimine quaternary ammonium salt and 1g of oxalic acid are added, and the mixture is uniformly stirred and defoamed in vacuum to obtain the antiviral moisture permeable coating. The antiviral moisture permeable coating is coated on a PP non-woven fabric with the thickness of 20um, and is dried for 1min by an oven at the temperature of 60 ℃ to obtain the antiviral moisture permeable film.
Example 4
10g of polyethyleneimine (BASF lupasol WF, Germany, with a number average molecular weight of 25000), 10g of bromohexane, 10g of bromooctane and 10g of potassium carbonate were added to ethanol under nitrogen protection, and the mixture was stirred at 80 ℃ and heated under reflux for 8 hours. And cooling, filtering to remove solids, and removing volatile matters from the filtrate at 110 ℃ under negative pressure under the protection of nitrogen to obtain the polyethyleneimine quaternary ammonium salt D.
5g of hydroxypropyl cellulose (chemical engineering in the rain field of the Feicheng) is dissolved in 95ml of water, 10g of isocyanate, 1g of polyethyleneimine quaternary ammonium salt D and 1g of oxalic acid are added, and the antiviral moisture-permeable coating is obtained by uniformly stirring and vacuum defoaming. The antiviral moisture-permeable coating is coated on a PE microporous membrane in a thickness of 20um, and is dried for 1min by an oven at 60 ℃ to obtain the antiviral moisture-permeable membrane.
Example 5
10g of polyethyleneimine (BASF lupasol WF, Germany, with a number average molecular weight of 25000), 10g of iodobutane, 10g of bromooctane and 10g of potassium carbonate were added to ethanol under nitrogen protection, and the mixture was stirred at 80 ℃ and heated under reflux for 8 hours. And cooling, filtering to remove solids, and removing volatile matters from the filtrate at 110 ℃ under negative pressure under the protection of nitrogen to obtain the polyethyleneimine quaternary ammonium salt E.
Adding 10g of polyurethane emulsion (AH 1618, Anhui Dahuatai) into 90ml of water, cooling to room temperature, adding 10g of isocyanate, 1g of polyethyleneimine quaternary ammonium salt E and 1g of oxalic acid, uniformly stirring and defoaming in vacuum to obtain the antiviral moisture-permeable coating. The antiviral moisture permeable coating is coated on a PP microporous membrane in the thickness of 40um, and is dried for 1min by an oven at the temperature of 60 ℃ to obtain the antiviral moisture permeable membrane.
Comparative example 1
Adding 10g of polyurethane emulsion into 90ml of water, cooling to room temperature, adding 10g of isocyanate, uniformly stirring, and carrying out vacuum defoaming to obtain the moisture-permeable coating. The moisture permeable coating is coated on PET non-woven fabric with the thickness of 30um, and is dried for 1min by an oven at the temperature of 60 ℃ to obtain the antiviral moisture permeable film.
It should be noted that, for the following examples and comparative examples, the antiviral property of the present invention against coronavirus HCoV-229E was evaluated by ISO 18184-2014 antiviral textile test, which was performed by GB/T12704.2-2009 textile Fabric moisture Permeability test method part 2: method B of Evaporation method "evaluates the moisture permeability of the present invention.
TABLE 1 Water vapor Transmission Rate test results of antiviral moisture permeable film
| Water vapor transmission rate g/(24h m) 2) | |
| Example 1 | 18651.3 |
| Example 2 | 17824.6 |
| Example 3 | 16918.3 |
| Example 4 | 18683.4 |
| Example 5 | 18654.1 |
| Comparative example 2 | 16607.7 |
TABLE 2 killing action and negative logarithm of coronavirus HCoV-229E of anti-virus moisture-permeable membrane
Note: the average inactivation log value of the three experiments is more than or equal to 4, and the virus can be judged to be inactivated.
And (4) conclusion: compared with the comparative example 1, the moisture-permeable films of the examples 1 to 5 have antiviral ability, and the influence of the addition of the quaternary ammonium salt polymer on the water vapor transmission rate is not obvious, so that the antiviral moisture-permeable film provided by the invention not only has the characteristic of high moisture-permeable rate, but also has excellent antiviral performance.
Claims (10)
1. A preparation method of an antiviral moisture-permeable coating is characterized by comprising the following steps:
1) reacting polyethyleneimine with halogenated hydrocarbon to obtain polyethyleneimine quaternary ammonium salt;
2) the antiviral moisture-permeable coating is obtained by matching polyethyleneimine quaternary ammonium salt and oxalic acid in the water-based polymer.
2. The preparation method of the antiviral moisture-permeable coating according to claim 1, wherein in the step 1), the polyethyleneimine has a number average molecular weight of 3000 to 100000.
3. The preparation method of the antiviral moisture-permeable coating according to claim 1, wherein in the step 1), the halide is a brominated hydrocarbon or an iodohydrocarbon having 4-12 carbon atoms.
4. The preparation method of the antiviral moisture-permeable coating according to claim 1, wherein in the step 1), polyethyleneimine and halogenated hydrocarbon are reacted to obtain polyethyleneimine quaternary ammonium salt, and the preparation method specifically comprises the following steps:
under protective gas, adding polyethyleneimine, halogenated hydrocarbon and potassium carbonate into ethanol, stirring, heating, refluxing, cooling, filtering to remove solids, and removing volatiles from the filtrate to obtain polyethyleneimine quaternary ammonium salt.
5. The preparation method of the antiviral moisture-permeable coating according to claim 4, wherein the weight ratio of the polyethyleneimine, the halogenated hydrocarbon and the potassium carbonate is 5-15: 5-40: 5 to 15.
6. The preparation method of the antiviral moisture-permeable coating according to claim 4, wherein the stirring and heating reflux is carried out at 70-90 ℃ for 6-10 h;
removing volatile matters from the filtrate at 100-120 ℃.
7. The method for preparing the antiviral moisture-permeable coating according to claim 1, wherein in the step 2), polyethyleneimine quaternary ammonium salt and oxalic acid are compounded in the aqueous polymer to obtain the antiviral moisture-permeable coating, which specifically comprises:
dissolving the water-based polymer in water, cooling, then adding isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid, uniformly stirring and defoaming in vacuum to obtain the antiviral moisture-permeable coating.
8. The preparation method of the antiviral moisture-permeable coating according to claim 7, wherein the ratio of the amounts of the water-based polymer, water, isocyanate, polyethyleneimine quaternary ammonium salt and oxalic acid is 2-15 g: 70-120 mL: 5-20 g: 0.3-3 g: 0.3 to 3 g.
9. Use of the antiviral moisture-permeable film according to any one of claims 1 to 8 in the preparation of an antiviral moisture-permeable film.
10. The application according to claim 9, comprising in particular: and attaching the antiviral moisture-permeable coating to a porous base film, and then heating to obtain the antiviral moisture-permeable film.
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