CN114479623B - Coating material capable of resisting escherichia coli and staphylococcus aureus and preparation method thereof - Google Patents
Coating material capable of resisting escherichia coli and staphylococcus aureus and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2401/02—Cellulose; Modified cellulose
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a coating material capable of resisting escherichia coli and staphylococcus aureus and a preparation method thereof, wherein the coating material comprises a polylactic acid base film, and a barrier layer, a self-cleaning coating and an antibacterial layer which are arranged on the surface of the polylactic acid base film; the barrier layer is a nano silicon oxide/graphene composite modified polylactic acid layer; the self-cleaning coating is a nitrogen functionalized carbon dot modified cellulose nanofiber layer; the antibacterial layer is a polyvinylidene fluoride layer modified by nano silicon oxide/silver oxide. The coating material provided by the invention has good barrier and antibacterial properties, excellent mechanical properties and a simple preparation method.
Description
The technical field is as follows:
the invention relates to the technical field of coating, in particular to a coating material capable of resisting escherichia coli and staphylococcus aureus and a preparation method thereof.
Background art:
the polymer coating is a coating material prepared by using one or more polymers or high molecular materials as basic raw materials and adopting a special process. The high molecular material used for preparing the polymer coating film is cellulose ester material at first, and then the polymers such as polypropylene, polyethylene, polyvinyl alcohol, aromatic polyamide, polylactic acid and the like with various properties are gradually adopted, so that a plurality of different types of polymer coating films are developed. Polymer coatings have received increasing attention due to their wide application in the fields of chemical, physical and biological sensors, microelectronic devices, nonlinear optics and molecular devices. And the coating material with special function is internationally regarded as an important material for scientific and technical innovation in the 21 st century. At present, various functional coating materials are widely applied in the fields of industry, medical use and other science and technology, and play more and more important roles.
Polylactic acid is a colorless and transparent high molecular polymer, and has a plurality of excellent properties such as nonirritant, nontoxicity, good mechanical property and the like. Polylactic acid is a biological base material and a completely biodegradable material, can be biologically decomposed under certain conditions, greatly reduces the environmental load, is an effective way for solving white pollution, and is widely applied to a plurality of fields. With the development of industry, the functional requirements of coating materials are higher and higher, and the coating with single performance can not meet the requirements. Therefore, how to improve the versatility of the coating material is a major research point.
The invention content is as follows:
the invention aims to solve the technical problem of providing a coating material capable of resisting escherichia coli and staphylococcus aureus and a preparation method thereof aiming at the defects of the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a coating material capable of resisting escherichia coli and staphylococcus aureus comprises a polylactic acid base film, and a barrier layer, a self-cleaning coating and an antibacterial layer which are arranged on the surface of the polylactic acid base film; the barrier layer is a nano silicon oxide/graphene composite modified polylactic acid layer; the self-cleaning coating is a nitrogen functionalized carbon dot modified cellulose nanofiber layer; the antibacterial layer is a polyvinylidene fluoride layer modified by nano silicon oxide/silver oxide.
Preferably, the thicknesses of the polylactic acid-based film, the barrier layer, the self-cleaning coating layer and the antibacterial layer are respectively 50mm and 200 nm: 100-200 nm: 100 nm.
In order to better solve the technical problems, the invention also provides the following technical scheme:
a preparation method of a coating material capable of resisting escherichia coli and staphylococcus aureus comprises the following steps:
(1) preparing a polylactic acid base film by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid, dissolving polylactic acid in tetrahydrofuran, adding gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring ethyl orthosilicate, deionized water and absolute ethyl alcohol, adding a hydrochloric acid solution as a catalyst, performing hydrolysis treatment at normal temperature to obtain a silica-containing sol, adding the prepared graphene dispersion solution and the modified polylactic acid solution, performing vigorous stirring at room temperature to obtain a composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying and aging to obtain the polylactic acid base film containing the barrier layer;
(4) dissolving glucose and urea in deionized water to prepare a solution, then transferring the solution into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, centrifuging a reaction product, filtering supernatant collected by centrifugation, and freeze-drying to prepare a nitrogen-doped carbon dot;
(5) mixing cellulose nano-fiber, glycerol and deionized water, heating and stirring vigorously, then adding the prepared nitrogen-doped carbon dots while stirring, stirring to prepare a coating liquid, uniformly coating the coating liquid on the surface of a polylactic acid base film containing a barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer and a self-cleaning coating;
(6) fully and uniformly mixing polyvinylidene fluoride, silver oxide and nano silicon oxide, and then processing the mixture by adopting a tablet press to prepare flaky mixed particles; the prepared flaky mixed particles are used as a target material, and an antibacterial layer is deposited on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating by adopting a vacuum low-power electron beam evaporation method, so that the coating material capable of resisting escherichia coli and staphylococcus aureus is prepared.
Preferably, in the step (2), the concentration of the graphene dispersion liquid is 10mg/ml, and the mass ratio of polylactic acid, gamma-isocyanatopropyltriethoxysilane, and tetrahydrofuran in the modified polylactic acid solution is 1: (0.2-0.3): 20.
preferably, in step (3), the concentration of the hydrochloric acid solution is 1mol/L, and the volume ratio of the tetraethoxysilane, the deionized water, the absolute ethyl alcohol, the hydrochloric acid solution, the graphene dispersion liquid and the modified polylactic acid solution is (2-2.3): 0.35:10:1:60:20.
Preferably, in the step (3), the time of the normal-temperature hydrolysis treatment is 3-4h, the time of vigorous stirring at room temperature is 2h, the time of drying is 20-30h, and the time of aging is 20-30 d.
Preferably, in the step (4), the mass ratio of the glucose, the urea and the deionized water is 1: 0.5: 60-70.
Preferably, in the step (4), the reaction temperature is 200 ℃, and the reaction time is 5-7 h; the rotation speed of the centrifugation is 3000rpm, and the centrifugation time is 30 min.
Preferably, in the step (5), the mass ratio of the cellulose nanofibers, the glycerol, the deionized water and the nitrogen-doped carbon dots is 4: (1-1.5): (100-200): (0.03-0.05); the temperature for heating and violent stirring is 75-85 ℃, the time is 20-40min, and the stirring time is 1-2 h.
Preferably, in the step (6), the mass ratio of the polyvinylidene fluoride to the silver oxide to the nano silicon oxide is 1: (0.2-0.5): (0.2-0.5); electricity at the time of the depositionThe high voltage of the sub-beam is 2kV, the beam current is 4.5A, and the pressure of the vacuum chamber is 10 -2 Pa。
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the coating material provided by the invention comprises a polylactic acid base film, and a barrier layer, a self-cleaning coating and an antibacterial layer which are arranged on the surface of the polylactic acid base film; the barrier layer is a nano silicon oxide/graphene composite modified polylactic acid layer; the self-cleaning coating is a nitrogen functionalized carbon dot modified cellulose nanofiber layer; the antibacterial layer is a polyvinylidene fluoride layer modified by nano silicon oxide/silver oxide. The nano silicon oxide and graphene composite modified polylactic acid material is deposited on the surface of the polylactic acid base film to form a compact coating, so that the barrier property of the material is effectively improved. The cellulose nano-fiber can improve the barrier property of the coating film, and the antibacterial property and the self-cleaning property are improved to a certain extent after the nitrogen-doped carbon dot modification. The invention also adopts nano silicon oxide and silver oxide to modify polyvinylidene fluoride to prepare the material with excellent antibacterial property. The coating material provided by the invention comprises multiple functional layers and has excellent performance.
According to the invention, gamma-isocyanate propyl triethoxysilane is adopted to modify polylactic acid, and when the silica sol, the graphene solution and the modified polylactic acid solution are mixed, the addition of gamma-isocyanate propyl triethoxysilane can effectively improve the interface bonding force between an inorganic network and an organic phase, so that the density of the inorganic network structure is improved, and the barrier property of the material is improved. The method comprises the steps of preparing nitrogen-doped carbon dots under a certain condition by using glucose as a carbon source and urea as a nitrogen source, mixing the nitrogen-doped carbon dots with cellulose nanofibers to prepare the self-cleaning coating, performing composite modification by using polyvinylidene fluoride as a matrix and adopting silver oxide and nano silicon oxide, and then depositing an antibacterial layer on the surface of the self-cleaning coating by adopting a vacuum low-power electron beam evaporation method; the coating material provided by the invention has excellent antibacterial property, good barrier property and good mechanical property.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples further illustrate the invention, the examples are only used for explaining the invention, not to constitute any limitation of the invention.
The diameter of the cellulose nano-fiber adopted in the following examples is 10 +/-2 nm, and the length is 200 +/-5 nm; the particle size of the nano silicon oxide is 20 +/-2 nm; the grain size of the silver oxide is 2-3 mu m; the sheet diameter of the graphene is 0.5-1 μm.
Example 1
(1) Preparing a polylactic acid base film with the thickness of 50mm by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid with the concentration of 10mg/ml, dissolving 1g of polylactic acid in 20g of tetrahydrofuran, then adding 0.2g of gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring 2.3ml of ethyl orthosilicate, 0.35ml of deionized water and 10ml of absolute ethyl alcohol, adding 1ml of hydrochloric acid solution with the concentration of 1mol/L as a catalyst, carrying out hydrolysis treatment for 3 hours at normal temperature to obtain silicasol, adding 60ml of the prepared graphene dispersion liquid and 20ml of modified polylactic acid solution, carrying out vigorous stirring for 2 hours at room temperature to obtain composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying for 24 hours at 60 ℃, and then aging for 28 days at room temperature to obtain the polylactic acid base film containing a barrier layer with the thickness of 200 nm;
(4) dissolving 1g of glucose and 0.5g of urea in 60g of deionized water to prepare a solution, then transferring the solution into a reaction kettle, reacting for 5 hours at 200 ℃, cooling to room temperature after the reaction is finished, centrifuging the reaction product for 30 minutes at the rotating speed of 3000rpm, filtering the supernatant collected by centrifugation, and freeze-drying for 24 hours at-10 ℃ to prepare a nitrogen-doped carbon dot;
(5) mixing 4g of cellulose nanofiber, 1.2g of glycerol and 150g of deionized water, heating to 80 ℃, vigorously stirring for 30min, adding 0.035g of the prepared nitrogen-doped carbon dots while stirring, stirring for 1h to prepare a coating liquid, uniformly coating the coating liquid on the surface of the polylactic acid base film containing the barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer with the thickness of 200nm and the self-cleaning coating with the thickness of 200 nm;
(6)fully and uniformly mixing 10g of polyvinylidene fluoride, 3g of silver oxide and 3g of nano silicon oxide, and then processing by adopting a tablet press to prepare flaky mixed particles; using the prepared flaky mixed particles as a target material, and adopting a vacuum low-power electron beam evaporation method to control the high voltage of an electron beam to be 2kV, the beam current to be 4.5A and the pressure of a vacuum chamber to be 10 -2 And Pa, depositing an antibacterial layer with the thickness of 100nm on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating to prepare the coating material capable of resisting escherichia coli and staphylococcus aureus.
Example 2
(1) Preparing a polylactic acid base film with the thickness of 50mm by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid with the concentration of 10mg/ml, dissolving 1g of polylactic acid in 20g of tetrahydrofuran, adding 0.3g of gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring 2.3ml of ethyl orthosilicate, 0.35ml of deionized water and 10ml of absolute ethyl alcohol, adding 1ml of hydrochloric acid solution with the concentration of 1mol/L as a catalyst, carrying out hydrolysis treatment for 4 hours at normal temperature to obtain silicasol, adding 60ml of the prepared graphene dispersion liquid and 20ml of modified polylactic acid solution, carrying out vigorous stirring for 2 hours at room temperature to obtain composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying for 24 hours at 60 ℃, and then aging for 28 days at room temperature to obtain the polylactic acid base film containing a barrier layer with the thickness of 200 nm;
(4) dissolving 1g of glucose and 0.5g of urea in 70g of deionized water to prepare a solution, then transferring the solution into a reaction kettle, reacting for 7 hours at 200 ℃, cooling to room temperature after the reaction is finished, centrifuging the reaction product for 30 minutes at the rotating speed of 3000rpm, filtering the supernatant collected by centrifugation, and freeze-drying for 24 hours at-10 ℃ to prepare the nitrogen-doped carbon dots;
(5) mixing 4g of cellulose nanofiber, 1.2g of glycerol and 150g of deionized water, heating to 80 ℃, vigorously stirring for 30min, adding 0.04g of the prepared nitrogen-doped carbon dots while stirring, stirring for 2h to prepare a coating solution, uniformly coating the coating solution on the surface of a polylactic acid base film containing a barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer with the thickness of 200nm and a self-cleaning coating with the thickness of 200 nm;
(6) fully and uniformly mixing 10g of polyvinylidene fluoride, 3g of silver oxide and 3g of nano silicon oxide, and then processing by adopting a tablet press to prepare flaky mixed particles; using the prepared flaky mixed particles as a target material, and adopting a vacuum low-power electron beam evaporation method to control the high voltage of an electron beam to be 2kV, the beam current to be 4.5A and the pressure of a vacuum chamber to be 10 -2 And Pa, depositing an antibacterial layer with the thickness of 100nm on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating to prepare the coating material capable of resisting escherichia coli and staphylococcus aureus.
Example 3
(1) Preparing a polylactic acid base film with the thickness of 50mm by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid with the concentration of 10mg/ml, dissolving 1g of polylactic acid in 20g of tetrahydrofuran, then adding 0.25g of gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring 2.3ml of ethyl orthosilicate, 0.35ml of deionized water and 10ml of absolute ethyl alcohol, adding 1ml of hydrochloric acid solution with the concentration of 1mol/L as a catalyst, carrying out hydrolysis treatment for 4 hours at normal temperature to obtain silicasol, adding 60ml of the prepared graphene dispersion liquid and 20ml of modified polylactic acid solution, carrying out vigorous stirring for 2 hours at room temperature to obtain composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying for 24 hours at 60 ℃, and then aging for 28 days at room temperature to obtain the polylactic acid base film containing a barrier layer with the thickness of 200 nm;
(4) dissolving 1g of glucose and 0.5g of urea in 70g of deionized water to prepare a solution, then transferring the solution into a reaction kettle, reacting for 7 hours at 200 ℃, cooling to room temperature after the reaction is finished, centrifuging the reaction product for 30 minutes at the rotating speed of 3000rpm, filtering the supernatant collected by centrifugation, and freeze-drying for 24 hours at-10 ℃ to prepare the nitrogen-doped carbon dots;
(5) mixing 4g of cellulose nanofiber, 1.2g of glycerol and 150g of deionized water, heating to 80 ℃, vigorously stirring for 30min, adding 0.035g of the prepared nitrogen-doped carbon dots while stirring, stirring for 2h to prepare a coating liquid, uniformly coating the coating liquid on the surface of the polylactic acid base film containing the barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer with the thickness of 200nm and the self-cleaning coating with the thickness of 200 nm;
(6) fully and uniformly mixing 10g of polyvinylidene fluoride, 3g of silver oxide and 3g of nano silicon oxide, and then processing by adopting a tablet press to prepare flaky mixed particles; using the prepared flaky mixed particles as a target material, and adopting a vacuum low-power electron beam evaporation method to control the high voltage of an electron beam to be 2kV, the beam current to be 4.5A and the pressure of a vacuum chamber to be 10 -2 And Pa, depositing an antibacterial layer with the thickness of 100nm on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating to prepare the coating material capable of resisting escherichia coli and staphylococcus aureus.
Example 4
(1) Preparing a polylactic acid base film with the thickness of 50mm by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid with the concentration of 10mg/ml, dissolving 1g of polylactic acid in 20g of tetrahydrofuran, then adding 0.2g of gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring 2.3ml of tetraethoxysilane, 0.35ml of deionized water and 10ml of absolute ethyl alcohol, adding 1ml of hydrochloric acid solution with the concentration of 1mol/L serving as a catalyst, hydrolyzing at normal temperature for 3 hours to prepare silicasol, adding 60ml of the prepared graphene dispersion liquid and 20ml of modified polylactic acid solution, violently stirring at room temperature for 2 hours to prepare composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying at 60 ℃ for 30 hours, and aging at room temperature for 30 days to prepare the polylactic acid base film containing a barrier layer with the thickness of 200 nm;
(4) dissolving 1g of glucose and 0.5g of urea in 65g of deionized water to prepare a solution, transferring the solution into a reaction kettle, reacting for 6 hours at 200 ℃, cooling to room temperature after the reaction is finished, centrifuging the reaction product for 30 minutes at the rotating speed of 3000rpm, filtering the supernatant collected by centrifugation, and freeze-drying for 24 hours at-10 ℃ to prepare the nitrogen-doped carbon dots;
(5) mixing 4g of cellulose nanofiber, 1.2g of glycerol and 150g of deionized water, heating to 80 ℃, vigorously stirring for 30min, adding 0.035g of the prepared nitrogen-doped carbon dots while stirring, stirring for 2h to prepare a coating liquid, uniformly coating the coating liquid on the surface of the polylactic acid base film containing the barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer with the thickness of 200nm and the self-cleaning coating with the thickness of 200 nm;
(6) fully and uniformly mixing 10g of polyvinylidene fluoride, 3g of silver oxide and 3g of nano silicon oxide, and then processing by adopting a tablet press to prepare flaky mixed particles; using the prepared flaky mixed particles as a target material, and adopting a vacuum low-power electron beam evaporation method to control the high voltage of an electron beam to be 2kV, the beam current to be 4.5A and the pressure of a vacuum chamber to be 10 -2 And Pa, depositing an antibacterial layer with the thickness of 100nm on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating to prepare the coating material capable of resisting escherichia coli and staphylococcus aureus.
Example 5
(1) Preparing a polylactic acid base film with the thickness of 50mm by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid with the concentration of 10mg/ml, dissolving 1g of polylactic acid in 20g of tetrahydrofuran, then adding 0.25g of gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring 2.3ml of ethyl orthosilicate, 0.35ml of deionized water and 10ml of absolute ethyl alcohol, adding 1ml of hydrochloric acid solution with the concentration of 1mol/L as a catalyst, carrying out hydrolysis treatment for 3.5 hours at normal temperature to obtain silicasol, adding 60ml of the prepared graphene dispersion liquid and 20ml of modified polylactic acid solution, carrying out vigorous stirring for 2 hours at room temperature to obtain composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying for 30 hours at 60 ℃, and then aging for 30 days at room temperature to obtain the polylactic acid base film containing a barrier layer with the thickness of 200 nm;
(4) dissolving 1g of glucose and 0.5g of urea in 70g of deionized water to prepare a solution, then transferring the solution into a reaction kettle, reacting for 7 hours at 200 ℃, cooling to room temperature after the reaction is finished, centrifuging the reaction product for 30 minutes at the rotating speed of 3000rpm, filtering the supernatant collected by centrifugation, and freeze-drying for 24 hours at-10 ℃ to prepare the nitrogen-doped carbon dots;
(5) mixing 4g of cellulose nanofibers, 1.2g of glycerol and 150g of deionized water, heating to 80 ℃, stirring vigorously for 30min, adding 0.035g of the prepared nitrogen-doped carbon dots while stirring, stirring for 2h to prepare a coating solution, uniformly coating the coating solution on the surface of the polylactic acid base film containing the barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer with the thickness of 200nm and the self-cleaning coating with the thickness of 200 nm;
(6) fully and uniformly mixing 10g of polyvinylidene fluoride, 3g of silver oxide and 3g of nano silicon oxide, and then processing by adopting a tablet press to prepare flaky mixed particles; using the prepared flaky mixed particles as a target material, and adopting a vacuum low-power electron beam evaporation method to control the high voltage of an electron beam to be 2kV, the beam current to be 4.5A and the pressure of a vacuum chamber to be 10 -2 And Pa, depositing an antibacterial layer with the thickness of 100nm on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating to prepare the coating material capable of resisting escherichia coli and staphylococcus aureus.
The performance of the prepared coating material was tested, and the test results are shown in table 1.
TABLE 1
The test results show that the coating material prepared by the invention has good functionality, good barrier property, good antibacterial property and excellent mechanical property.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (9)
1. A coating material capable of resisting escherichia coli and staphylococcus aureus is characterized by comprising a polylactic acid base film, and a barrier layer, a self-cleaning coating and an antibacterial layer which are arranged on the surface of the polylactic acid base film; the barrier layer is a nano silicon oxide/graphene composite modified polylactic acid layer; the self-cleaning coating is a nitrogen functionalized carbon dot modified cellulose nanofiber layer; the antibacterial layer is a polyvinylidene fluoride layer modified by nano silicon oxide/silver oxide;
the preparation method comprises the following steps:
(1) preparing a polylactic acid base film by adopting melt extrusion and tape casting processes;
(2) dispersing graphene in deionized water to prepare graphene dispersion liquid, dissolving polylactic acid in tetrahydrofuran, adding gamma-isocyanatopropyl triethoxysilane, and uniformly mixing to prepare modified polylactic acid solution;
(3) mixing and stirring ethyl orthosilicate, deionized water and absolute ethyl alcohol, adding a hydrochloric acid solution as a catalyst, performing hydrolysis treatment at normal temperature to obtain a silica-containing sol, adding the prepared graphene dispersion solution and the modified polylactic acid solution, performing vigorous stirring at room temperature to obtain a composite sol, uniformly coating the prepared composite sol on a polylactic acid base film, drying and aging to obtain the polylactic acid base film containing the barrier layer;
(4) dissolving glucose and urea in deionized water to prepare a solution, then transferring the solution into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, centrifuging a reaction product, filtering supernatant collected by centrifugation, and freeze-drying to prepare a nitrogen-doped carbon dot;
(5) mixing cellulose nano-fiber, glycerol and deionized water, heating and stirring vigorously, then adding the prepared nitrogen-doped carbon dots while stirring, stirring to prepare a coating liquid, uniformly coating the coating liquid on the surface of a polylactic acid base film containing a barrier layer, and drying to prepare the polylactic acid base film containing the barrier layer and a self-cleaning coating;
(6) fully and uniformly mixing polyvinylidene fluoride, silver oxide and nano silicon oxide, and then processing the mixture by adopting a tablet press to prepare flaky mixed particles; the prepared flaky mixed particles are used as a target material, and an antibacterial layer is deposited on the surface of the polylactic acid base film containing the barrier layer and the self-cleaning coating by adopting a vacuum low-power electron beam evaporation method, so that the coating material capable of resisting escherichia coli and staphylococcus aureus is prepared.
2. The coating material of claim 1, wherein the thicknesses of the polylactic acid-based film, the barrier layer, the self-cleaning coating layer and the antibacterial layer are 50mm, 200nm, 100-200nm and 100nm, respectively.
3. The coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (2), the concentration of the graphene dispersion liquid is 10mg/ml, and the mass ratio of polylactic acid, gamma-isocyanatopropyl triethoxysilane and tetrahydrofuran in the modified polylactic acid solution is 1: (0.2-0.3): 20.
4. the coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (3), the concentration of the hydrochloric acid solution is 1mol/L, and the volume ratio of the ethyl orthosilicate, the deionized water, the absolute ethyl alcohol, the hydrochloric acid solution, the graphene dispersion liquid and the modified polylactic acid solution is (2-2.3): 0.35:10:1:60:20.
5. The coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (3), the time of the normal-temperature hydrolysis treatment is 3-4 hours, the time of the vigorous stirring at the room temperature is 2 hours, the time of the drying is 20-30 hours, and the time of the aging is 20-30 days.
6. The coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (4), the mass ratio of the glucose to the urea to the deionized water is 1: 0.5: 60-70.
7. The coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (4), the reaction temperature is 200 ℃, and the reaction time is 5-7 h; the rotation speed of the centrifugation is 3000rpm, and the centrifugation time is 30 min.
8. The coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (5), the mass ratio of the cellulose nanofibers, glycerol, deionized water and nitrogen-doped carbon dots is 4: (1-1.5): (100-200): (0.03-0.05); the temperature for heating and violent stirring is 75-85 ℃, the time is 20-40min, and the stirring time is 1-2 h.
9. The coating material capable of resisting escherichia coli and staphylococcus aureus as claimed in claim 1, wherein in the step (6), the mass ratio of the polyvinylidene fluoride to the silver oxide to the nano silicon oxide is 1: (0.2-0.5): (0.2-0.5); the high voltage of the electron beam during deposition is 2kV, the beam current is 4.5A, and the pressure of the vacuum chamber is 10 -2 Pa。
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