CN111493092A - Silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, protective film and preparation method - Google Patents
Silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, protective film and preparation method Download PDFInfo
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- CN111493092A CN111493092A CN202010301510.8A CN202010301510A CN111493092A CN 111493092 A CN111493092 A CN 111493092A CN 202010301510 A CN202010301510 A CN 202010301510A CN 111493092 A CN111493092 A CN 111493092A
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- A—HUMAN NECESSITIES
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, a protective film and a preparation method, wherein the antibacterial agent comprises the following preparation steps: 1) preparing polyurethane aerogel; 2) preparing a nano zirconium phosphate polyurethane aerogel composite carrier; 3) preparing the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent. According to the antibacterial agent provided by the invention, the silver-loaded nano zirconium phosphate is adsorbed on the polyurethane aerogel, and the characteristics of high specific surface area and high porosity of the polyurethane aerogel are utilized, so that the silver-loaded nano zirconium phosphate can be prevented from being agglomerated or lost, and the antibacterial effect can be effectively improved; the antibacterial protective film disclosed by the invention has a good antibacterial effect on escherichia coli and staphylococcus aureus, can be used for protecting screens or shells of electronic products and the like, and has a good market application prospect.
Description
Technical Field
The invention relates to the field, and in particular relates to a silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, a protective film and a preparation method.
Background
Many electronic products such as mobile phones, flat panels, and cases have protective films attached to their screens or housings to prevent them from being physically scratched, and some film products have been provided with an antimicrobial agent for the purpose of achieving antimicrobial properties.
The antibacterial agent is a substance or a product with bacteriostatic and bactericidal properties, and has various categories, wherein the silver ion antibacterial agent is widely used due to the advantages of safety, broad spectrum, anergic bacteria, remarkable bacteriostatic effect and the like. The contact reaction antibacterial mechanism of the silver ion antibacterial agent is as follows: silver ion contact reaction, which causes the destruction or dysfunction of common components of microorganisms; when a trace amount of silver ions reach the microbial cell membrane, the silver ions are firmly adsorbed by virtue of coulomb attraction because the silver ions carry negative charges, penetrate through the cell wall to enter the cell and react with SH groups to solidify proteins, destroy the activity of cell synthetases, and lose division and proliferation capacity to die.
However, silver ion antibacterial agents also have the following disadvantages: the stability and durability of silver ions are poor, so that the antibacterial aging of the conventional silver ion antibacterial agent is shortened. In order to improve the defects of the silver-loaded antibacterial agent, the nano particles are usually used as a carrier, for example, the nano zirconium phosphate silver-loaded antibacterial agent can improve the stability of silver ions, but the nano particles have the defect of easy agglomeration, so that the antibacterial activity is reduced, and the antibacterial effect is influenced.
A more reliable solution is now needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent comprises the following preparation steps:
1) preparing polyurethane aerogel;
2) preparing a nano zirconium phosphate polyurethane aerogel composite carrier: the material is prepared from polyurethane aerogel and a nano zirconium phosphate carrier;
3) adding the nano zirconium phosphate polyurethane aerogel composite carrier into water containing a dispersing agent to obtain nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid; adding a silver nitrate solution into the nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid under a dark condition, reacting for 12-48 hours, filtering and drying to obtain a silver-loaded nano zirconium phosphate polyurethane aerogel composite, namely the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent.
Preferably, the preparation method of the polyurethane aerogel comprises the following steps:
1) adding diphenylmethane diisocyanate into acetone, and stirring to dissolve to obtain a first solution;
2) adding propylene glycol polyether into acetone, and stirring for dissolving to obtain a second solution;
3) mixing the first solution and the second solution, and stirring for dissolving; adding dibutyltin dilaurate into the mixture;
4) standing to obtain gel, soaking and washing the gel with acetone, and then drying the gel under the condition of supercritical carbon dioxide to obtain the polyurethane aerogel.
Preferably, the preparation method of the nano zirconium phosphate polyurethane aerogel composite carrier comprises the following steps:
1) preparing a nano zirconium phosphate carrier: adding sufficient sodium dihydrogen phosphate aqueous solution into zirconium oxychloride aqueous solution to react to obtain a nano zirconium phosphate carrier;
2) adding a nano zirconium phosphate carrier and a dispersing agent into water to form nano zirconium phosphate carrier dispersion liquid;
3) adding polyurethane aerogel into water to form polyurethane aerogel dispersion liquid, mixing the nano zirconium phosphate carrier dispersion liquid with the polyurethane aerogel dispersion liquid, adding a coupling agent, carrying out blending reaction, and drying under the supercritical carbon dioxide condition to obtain the nano zirconium phosphate polyurethane aerogel composite carrier.
Preferably, the supercritical carbon dioxide drying temperature is 50-115 deg.C, time is 5-24 hr, and pressure is 5-25 MPa.
Preferably, the dispersant is one or more of polyethylene wax, glyceryl tristearate and vinyl bis stearamide.
The invention also provides an antibacterial protective film which comprises the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent.
Preferably, the raw materials for preparing the antibacterial protective film comprise the following components in parts by weight:
preferably, the raw materials for preparing the antibacterial protective film comprise the following components in parts by weight:
preferably, the raw materials for preparing the antibacterial protective film comprise the following components in parts by weight:
preferably, the preparation method of the antibacterial protective film comprises the following steps:
1) preparing the polyurethane aerogel;
2) a nano zirconium phosphate polyurethane aerogel composite carrier;
3) preparing the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent;
4) adding propylene glycol methyl ether, polyester acrylic monomer and polyurethane modified acrylic resin prepolymer into a reaction vessel, stirring for 1-4h at 60-105 ℃, cooling to 40-60 ℃, then adding silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, aminosiloxane, α -hydroxyalkyl benzophenone and curing agent into the reaction vessel, stirring for 1.5-5h, and cooling to below 35 ℃ to obtain a coating;
5) and coating the paint on the surface of the base material, and drying to obtain the antibacterial protective film.
The invention has the beneficial effects that: according to the antibacterial agent provided by the invention, the silver-loaded nano zirconium phosphate is adsorbed on the polyurethane aerogel, and the characteristics of high specific surface area and high porosity of the polyurethane aerogel are utilized, so that the silver-loaded nano zirconium phosphate can be prevented from being agglomerated or lost, and the antibacterial effect can be effectively improved; the antibacterial protective film disclosed by the invention has a good antibacterial effect on escherichia coli and staphylococcus aureus, can be used for protecting screens or shells of electronic products and the like, and has a good market application prospect.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The embodiment provides a silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, which comprises the following preparation steps:
1. preparing a polyurethane aerogel:
1-1, adding diphenylmethane diisocyanate into acetone, and stirring to dissolve to obtain a first solution;
1-2, adding propylene glycol polyether into acetone, and stirring for dissolving to obtain a second solution;
1-3, mixing the first solution and the second solution, and stirring for dissolving; adding dibutyltin dilaurate into the mixture;
1-4, standing to obtain gel, soaking and washing with acetone, and then drying under the condition of supercritical carbon dioxide to obtain the polyurethane aerogel. The specific surface area of the polyurethane aerogel is 300-800m2/g。
2. Preparing a nano zirconium phosphate polyurethane aerogel composite carrier by using polyurethane aerogel and a nano zirconium phosphate carrier:
2-1, preparing a nano zirconium phosphate carrier: adding sufficient sodium dihydrogen phosphate aqueous solution into zirconium oxychloride aqueous solution to react to obtain a nano zirconium phosphate carrier;
2-2, adding the nano zirconium phosphate carrier and a dispersing agent into water to form nano zirconium phosphate carrier dispersion liquid;
and 2-3, adding polyurethane aerogel into water to form polyurethane aerogel dispersion liquid, mixing the nano zirconium phosphate carrier dispersion liquid with the polyurethane aerogel dispersion liquid, adding a coupling agent, carrying out blending reaction, and drying under the supercritical carbon dioxide condition to obtain the nano zirconium phosphate polyurethane aerogel composite carrier.
3. Adding the nano zirconium phosphate polyurethane aerogel composite carrier into water containing a dispersing agent to obtain nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid; adding a silver nitrate solution into the nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid under a dark condition, reacting for 12-48 hours, filtering and drying to obtain a silver-loaded nano zirconium phosphate polyurethane aerogel composite, namely the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent.
In the steps 1-4, the temperature of the supercritical carbon dioxide drying is 50-115 ℃, the time is 5-24 hours, and the pressure is 5-25 MPa.
Wherein, the dispersant in the steps 2 and 3 is one or more of polyethylene wax, glyceryl tristearate and vinyl bis stearamide.
The traditional nano zirconium phosphate silver-carrying antibacterial agent takes layered zirconium phosphate as a carrier, and can improve the stability of silver ions, so that the antibacterial agent has the advantages of high safety, good heat resistance, good chemical stability and the like. However, it has the following disadvantages: the nano zirconium phosphate silver-carrying antibacterial agent is easy to agglomerate due to the characteristics of nano particles, so that the antibacterial activity is reduced. In the invention, the polyurethane aerogel is used as the second carrier (the nano zirconium phosphate is used as the first carrier to directly carry silver), so that the silver-carrying nano zirconium phosphate is adsorbed in micropores on the surface of the silver-carrying nano zirconium phosphate, and the defects can be overcome. The polyurethane aerogel has the characteristics of high specific surface area, high porosity, low density, high transmittance and the like, and can effectively and quickly adsorb the silver-loaded nano zirconium phosphate in the solution through rich micropores, so that the silver-loaded nano zirconium phosphate is prevented from being agglomerated or lost; the adsorption is stable, the silver-loaded nano zirconium phosphate can be firmly adsorbed in micropores on the surface of the polyurethane aerogel, and the polyurethane aerogel can be firmly combined with other components in the material at the same time so as to be firmly attached to the protective film, so that the silver-loaded nano zirconium phosphate can be prevented from losing to cause the reduction of active ingredients; the polyurethane aerogel is used as a carrier, and the release amount of silver ions can be increased by increasing the surface area, so that the sterilizing capability of the polyurethane aerogel is greatly improved; that is, a very small amount of silver-loaded nano zirconium phosphate can generate a strong bactericidal effect; not only can improve the antibacterial effect, but also can reduce the loss of silver.
The embodiment also provides an antibacterial protective film, which comprises the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent;
the antibacterial protective film is prepared from the following raw materials in parts by weight:
wherein, the curing agent is one or more of diaminocyclohexane, vinyl triamine and dimethylamino propylamine.
The preparation method of the antibacterial protective film comprises the following steps:
1) preparing the polyurethane aerogel;
2) a nano zirconium phosphate polyurethane aerogel composite carrier;
3) preparing the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent;
4) adding propylene glycol methyl ether, polyester acrylic monomer and polyurethane modified acrylic resin prepolymer into a reaction vessel, stirring for 1-4h at 60-105 ℃, cooling to 40-60 ℃, then adding silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, aminosiloxane, α -hydroxyalkyl benzophenone and curing agent into the reaction vessel, stirring for 1.5-5h, and cooling to below 35 ℃ to obtain a coating;
5) and coating the paint on the surface of the base material, and drying to obtain the antibacterial protective film. The thickness of the antibacterial protective film is controlled to be 2um-5 um.
More specific examples and comparative examples are provided below to further illustrate the invention.
Example 1
An antibacterial protective film is prepared from the following raw materials in parts by weight:
the preparation method of the antibacterial protective film comprises the following steps:
1) preparing the polyurethane aerogel (prepared as described above);
2) a nano zirconium phosphate polyurethane aerogel composite carrier (prepared by the method);
3) preparing the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent:
adding the nano zirconium phosphate polyurethane aerogel composite carrier into water containing a dispersing agent (specifically, glyceryl tristearate) to obtain nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid; adding a silver nitrate solution into the nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid under a dark condition, reacting for 36 hours, filtering and drying to obtain a silver-loaded nano zirconium phosphate polyurethane aerogel composite, namely the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent.
4) Adding propylene glycol methyl ether, a polyester acrylic monomer and a polyurethane modified acrylic resin prepolymer into a reaction vessel, stirring for 2h at 90 ℃, cooling to 45 ℃, then adding a silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, aminosiloxane, α -hydroxyalkyl benzophenone and a curing agent into the reaction vessel, stirring for 3.5h, and cooling to below 35 ℃ to obtain a coating;
5) and coating the paint on the surface of the base material, and drying to obtain the antibacterial protective film. The thickness of the antibacterial protective film is controlled to be 5 um.
Example 2
The difference between the embodiment 2 and the embodiment 1 is only that the content of each component in the antibacterial protective film is different, specifically:
the antibacterial protective film is prepared from the following raw materials in parts by weight:
example 3
The difference between the embodiment 3 and the embodiment 1 is only that the content of each component in the antibacterial protective film is different, specifically:
comparative example 1
The only difference from example 1 is that: the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent in example 1 was replaced with the same weight parts of silver powder.
The preparation method of the antibacterial protective film comprises the following steps:
1) adding propylene glycol methyl ether, polyester acrylic monomer and polyurethane modified acrylic resin prepolymer into a reaction vessel, stirring for 2h at 90 ℃, cooling to 45 ℃, adding silver powder, aminosiloxane, α -hydroxyalkyl benzophenone and curing agent into the reaction vessel, stirring for 3.5h, and cooling to below 35 ℃ to obtain a coating;
2) and coating the paint on the surface of the base material, and drying to obtain the antibacterial protective film. The thickness of the antibacterial protective film is controlled to be 5 um.
Comparative example 2
The only difference from example 1 is that: the same weight parts of a commercially available nano-zirconium phosphate silver-loaded antimicrobial were used in place of the silver-loaded nano-zirconium phosphate polyurethane aerogel antimicrobial of example 1.
The preparation method of the antibacterial protective film comprises the following steps:
1) adding propylene glycol methyl ether, a polyester acrylic monomer and a polyurethane modified acrylic resin prepolymer into a reaction vessel, stirring for 2h at 90 ℃, cooling to 45 ℃, adding a nano zirconium phosphate silver-loaded antibacterial agent, aminosiloxane, α -hydroxyalkyl benzophenone and a curing agent into the reaction vessel, stirring for 3.5h, and cooling to below 35 ℃ to obtain a coating;
2) and coating the paint on the surface of the base material, and drying to obtain the antibacterial protective film. The thickness of the antibacterial protective film is controlled to be 5 um.
Comparative example 3
The only difference from example 1 is that: the antibacterial protective film does not contain polyurethane modified acrylic resin prepolymer, and the weight portion of the polyester acrylic monomer is 80.
Performance testing
The coatings prepared in examples 1-3 and comparative examples 1-3 were coated on the surface of a substrate, cured and dried to obtain an antibacterial protective film, the thickness of the film layer was controlled to 5um, and then the following performance tests were performed on the protective film:
the test items included the following:
1. contact angle test: JYSP-360 type contact angle measuring instrument;
2. adhesion force: lattice method
3. Pencil hardness:
the test was carried out according to ASTM D3363-2005 "Standard test method for measuring coating hardness by Pencil test method", with a YASUDA pencil hardness tester, a load of 750g, and a pencil hardness test;
4. antibacterial property:
anti-escherichia coli, anti-staphylococcus aureus, using the standard: ISO 22196: 2011;
the test results are shown in table 1 below:
table 1: performance test result recording table
From the test results of examples 1 to 3 of the table above, the following conclusions can be drawn: the antibacterial protective film obtained by the invention has good antibacterial effect on escherichia coli and staphylococcus aureus, and has good strength.
From the comparison of comparative example 1 and example 1, it can be seen that: compared with silver powder, the antibacterial property of the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent can be remarkably improved, and the advantages of the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent can be fully embodied.
From the results of comparison of comparative example 2, comparative example 1 and example 1, it can be seen that: the antibacterial effect of the silver-loaded nano zirconium phosphate antibacterial agent is obviously better than that of silver powder, mainly because the release amount of silver ions can be improved by loading silver with the nano zirconium phosphate with large surface area, so that the bactericidal capability of the silver-loaded nano zirconium phosphate antibacterial agent is obviously improved.
The effect of the nano silver-loaded zirconium phosphate antibacterial agent is obviously weaker than that of the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, mainly because the nano silver-loaded zirconium phosphate antibacterial agent is easy to agglomerate, so that the antibacterial activity is reduced, and in addition, the nano silver-loaded zirconium phosphate antibacterial agent is easy to lose in a membrane material (in the processing process and the using process), so that the antibacterial performance is reduced.
From the results of comparing comparative example 3 with example 1, it can be seen that: the polyurethane modified acrylic resin prepolymer can improve the strength of the protective film.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. The silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent is characterized by comprising the following preparation steps:
1) preparing polyurethane aerogel;
2) preparing a nano zirconium phosphate polyurethane aerogel composite carrier: the material is prepared from polyurethane aerogel and a nano zirconium phosphate carrier;
3) adding the nano zirconium phosphate polyurethane aerogel composite carrier into water containing a dispersing agent to obtain nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid; adding a silver nitrate solution into the nano zirconium phosphate polyurethane aerogel composite carrier dispersion liquid under a dark condition, reacting for 12-48 hours, filtering and drying to obtain a silver-loaded nano zirconium phosphate polyurethane aerogel composite, namely the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent.
2. The silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent according to claim 1, wherein the preparation method of the polyurethane aerogel comprises the following steps:
1) adding diphenylmethane diisocyanate into acetone, and stirring to dissolve to obtain a first solution;
2) adding propylene glycol polyether into acetone, and stirring for dissolving to obtain a second solution;
3) mixing the first solution and the second solution, and stirring for dissolving; adding dibutyltin dilaurate into the mixture;
4) standing to obtain gel, soaking and washing the gel with acetone, and then drying the gel under the condition of supercritical carbon dioxide to obtain the polyurethane aerogel.
3. The silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent according to claim 2, wherein the preparation method of the nano zirconium phosphate polyurethane aerogel composite carrier comprises the following steps:
1) preparing a nano zirconium phosphate carrier: adding sufficient sodium dihydrogen phosphate aqueous solution into zirconium oxychloride aqueous solution to react to obtain a nano zirconium phosphate carrier;
2) adding a nano zirconium phosphate carrier and a dispersing agent into water to form nano zirconium phosphate carrier dispersion liquid;
3) adding polyurethane aerogel into water to form polyurethane aerogel dispersion liquid, mixing the nano zirconium phosphate carrier dispersion liquid with the polyurethane aerogel dispersion liquid, adding a coupling agent, carrying out blending reaction, and drying under the supercritical carbon dioxide condition to obtain the nano zirconium phosphate polyurethane aerogel composite carrier.
4. The silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent according to claim 3, wherein the supercritical carbon dioxide drying temperature is 50-115 ℃, the time is 5-24 hours, and the pressure is 5-25 MPa.
5. The silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent according to claim 3, wherein the dispersing agent is one or more of polyethylene wax, glyceryl tristearate, and vinyl bis stearamide.
6. An antibacterial protective film, characterized in that it comprises the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent as claimed in any one of claims 1 to 5.
7. The antibacterial protective film according to claim 6, characterized in that raw materials for preparing the antibacterial protective film comprise, by weight:
8. the antibacterial protective film according to claim 7, characterized in that raw materials for preparing the antibacterial protective film comprise, by weight:
9. the antibacterial protective film according to claim 7, characterized in that raw materials for preparing the antibacterial protective film comprise, by weight:
10. the antibacterial protective film according to claim 7, wherein the preparation method of the antibacterial protective film comprises the following steps:
1) preparing the polyurethane aerogel;
2) a nano zirconium phosphate polyurethane aerogel composite carrier;
3) preparing the silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent;
4) adding propylene glycol methyl ether, polyester acrylic monomer and polyurethane modified acrylic resin prepolymer into a reaction vessel, stirring for 1-4h at 60-105 ℃, cooling to 40-60 ℃, then adding silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, aminosiloxane, α -hydroxyalkyl benzophenone and curing agent into the reaction vessel, stirring for 1.5-5h, and cooling to below 35 ℃ to obtain a coating;
5) and coating the paint on the surface of the base material, and drying to obtain the antibacterial protective film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010301510.8A CN111493092A (en) | 2020-04-16 | 2020-04-16 | Silver-loaded nano zirconium phosphate polyurethane aerogel antibacterial agent, protective film and preparation method |
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