CN110698942A - High-barrier Ag-TiO2Modified polyacrylic acid antibacterial paint and preparation method thereof - Google Patents
High-barrier Ag-TiO2Modified polyacrylic acid antibacterial paint and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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Abstract
The invention relates to the technical field of antibacterial materials, and discloses high-barrier Ag-TiO2The modified polyacrylic acid antibacterial coating comprises the following formula raw materials: modified nano TiO2-Ag composite material, carboxymethyl chitosan, poly hexamethylene guanidine hydrochloride, phthalic anhydride, methyl acrylate, 1H, 7H-dodecafluoroheptyl acrylate, perfluoro octyl ethyl methacrylate, cross-linking agent, initiator and emulsifier. The Ag-TiO with high barrier property2Modified polyacrylic acid antibacterial coating and preparation method thereof, and nano TiO2the-Ag composite material can perform oxidation reaction on protease in bacteria body to destroy normal metabolism and reproduction of bacteria and microorganisms, thereby playing a role in sterilization, and the nano TiO plays a role in sterilization2the-Ag composite material has good compatibility in polyacrylic resin, the hydrophobic property of the polyacrylic material reduces the air contentThe adhesion of water molecules on the surface of the material keeps the surface of the material dry, and inhibits the propagation of bacteria and microorganisms.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to Ag-TiO with high barrier property2Modified polyacrylic acid antibacterial paint and a preparation method thereof.
Background
The acrylate resin is formed by taking an acrylate monomer as a main raw material through free radical polymerization, and the functional monomer is introduced into the molecular chain of the acrylate resin, so that a plurality of new functions can be given to the acrylate resin, and the acrylate resin has wide application in the fields of industry and agriculture, machinery, aerospace, electronics and electricity, buildings, medicines and the like.
The antibacterial material is a novel functional material with the functions of killing or inhibiting microorganisms and bacteria, the antibacterial material mainly comprises antibacterial ceramic, antibacterial fiber fabric, antibacterial metal material and the like, a certain antibacterial agent is usually added into the existing antibacterial material, so that the material has the functions of inhibiting bacteria or sterilizing, and the antibacterial agent is mainly divided into organic antibacterial agents such as vanillin, acyl aniline, biguanidine and the like; inorganic antibacterial agents such as nano silver, zinc oxide, copper oxide and the like, nano silver and silver ions have excellent antibacterial performance, but the silver material has poor dispersibility in acrylic resin and is easy to aggregate and agglomerate, so that the antibacterial performance of the silver material is greatly reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Ag-TiO with high barrier property2The modified polyacrylic acid antibacterial coating and the preparation method thereof solve the problem of poor antibacterial performance of the polyacrylic acid material and simultaneously solve the problem of poor dispersibility of the silver antibacterial material in polyacrylic acid resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: high-barrier Ag-TiO2The modified polyacrylic acid antibacterial coating comprises the following formula raw materials in parts by weight: 8-19 parts of modified nano TiO2-Ag composite material, 2-5 parts of carboxymethyl chitosan, 2.5-4 parts of polyhexamethylene guanidine hydrochloride, 0.5-1 part of phthalic anhydride, 45-50 parts of methyl acrylate, 10-14 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 12-16 parts of perfluorooctyl ethyl methacrylate, 0.3-0.5 part of cross-linking agent, 0.2-0.5 part of initiator and 0.5-1 part of emulsifier.
Preferably, the crosslinking agent is divinylbenzene.
Preferably, the initiator is ammonium persulfate.
Preferably, the emulsifier is cetyltrimethylammonium bromide.
Preferably, the modified nano TiO2Preparation method of-Ag composite materialThe method comprises the following steps:
(1) adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding tetrabutyl titanate and AgNO3Placing a reaction bottle in an ultrasonic dispersion instrument, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 1-2 h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75-85 ℃, stirring at a constant speed for reaction for 6-10 h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with a proper amount of diethyl ether, fully drying, placing the solid product in a resistance furnace, heating at a rate of 10-15 ℃, carrying out heat preservation and calcination at a temperature of 850-880 ℃ for 2-3 h, and preparing to obtain the nano-Ag loaded TiO2。
(2) Adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2And silane coupling agent, heating the solution in a constant-temperature water bath kettle to 80-90 ℃, stirring at a constant speed and refluxing for reaction for 10-15 h, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with a proper amount of diethyl ether, and fully drying to prepare the modified nano TiO2-an Ag composite material.
Preferably, the stearic acid, tetrabutyl titanate and AgNO3The molar ratio of the three substances is 1.5-2:4-5: 1.
Preferably, the silane coupling agent is tridecafluorooctyltriethoxysilane and nano Ag-supported TiO2The mass ratio is 1: 15-18.
Preferably, the high-barrier Ag-TiO2The preparation method of the modified polyacrylic acid antibacterial coating comprises the following steps:
(1) adding proper amount of the mixture into a reaction bottleN,NAnd (2) adding 2.5-4 parts of polyhexamethylene guanidine hydrochloride and 0.5-1 part of phthalic anhydride in a dimethylformamide solvent in sequence, placing a reaction bottle in a constant-temperature water bath kettle, heating to 70-80 ℃, stirring at a constant speed for reaction for 25-30 h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product by using a proper amount of anhydrous ether, and fully drying to prepare the phthaloyl imidization polyhexamethylene guanidine hydrochloride.
(2) Introducing N into the reaction bottle2Discharging air, adding ethanol solvent, 45-50 parts of methyl acrylate and 10-14 parts of 1H,1H, 7H-dodecafluoroheptyl propyleneAcid ester, 12-16 parts of perfluorooctyl ethyl methacrylate, 0.5-1 part of emulsifying agent cetyl trimethyl ammonium bromide, 0.3-0.5 part of cross-linking agent divinylbenzene and 8-19 parts of modified nano TiO2-Ag composite material, placing a reaction bottle in a constant temperature water bath kettle, heating to 50-60 ℃, stirring at constant speed for 1-2 h, adding 0.2-0.5 part of initiator ammonium persulfate, heating to 75-85 ℃, stirring at constant speed for reflux reaction for 1-2 h, adding the poly (guanidinium hexamethylene) phthalimide prepared in the step (1), stirring at constant speed for reflux reaction for 2-3 h, adding 2-5 parts of carboxymethyl chitosan, stirring at constant speed for reaction for 8-10 h at 80-90 ℃, placing the solution in an oven, heating to 60-70 ℃, slowly volatilizing ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 70-85%, and preparing the high-barrier-property Ag-TiO composite material2Modified polyacrylic acid antibacterial coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Ag-TiO with high barrier property2Modified polyacrylic acid antibacterial coating and preparation method thereof, Ag in-situ growth is adopted in nano TiO2Forming nano TiO on the surface of the substrate2-Ag composite, TiO2Under the action of illumination, photoproduction electrons and holes are generated, and the holes oxidize Ag into Ag+In the cavity and Ag+Can carry out oxidation reaction on protease in bacteria body to destroy normal metabolism and reproduction of bacteria and microorganisms, thereby playing the role of sterilization or disinfection, and modifying TiO by silane coupling agent tridecafluorooctyltriethoxysilane2Greatly improves the nano TiO2The compatibility of the-Ag composite material and the polyacrylic resin enables the-Ag composite material to be uniformly dispersed in the polyacrylic material, and avoids nanometer TiO2Aggregation of the-Ag composite material into large particles decreases the antibacterial activity.
The Ag-TiO with high barrier property2Modified polyacrylic acid antibacterial coating and preparation method thereof, 1H, 7H-dodecafluoroheptyl acrylate and perfluorooctyl ethyl methacrylate are used as grafting monomers, the prepared polyacrylic acid has excellent hydrophobicity, and a silane coupling agent tridecafluorooctyl tris (tert-butyl-octyl-tri-methyl-acrylate)The ethoxysilane also has good hydrophobicity, greatly enhances the hydrophobic property of the polyacrylic acid material, reduces the adhesion of water molecules in the air on the surface of the material, keeps the surface of the material dry, and inhibits the propagation of bacteria and microorganisms.
The Ag-TiO with high barrier property2The modified polyacrylic acid antibacterial coating and the preparation method thereof are characterized in that phthalimide poly-guanidine hexamethylene hydrochloride is used as a functional monomer to modify polyacrylic resin, simultaneously carboxymethyl chitosan is added to highly crosslink with the polyacrylic resin to form a compact crosslinking structure, so that the barrier property of the material is greatly increased, water molecules and oxygen can be prevented from passing through the material, the material can be used as a high-barrier coating to inhibit the growth and reproduction of bacteria in the coating, and the antibacterial property of the material is enhanced by a guanidino antibacterial group contained in the poly-guanidine hydrochloride.
The Ag-TiO with high barrier property2The modified polyacrylic acid antibacterial coating and the preparation method thereof are characterized in that chitosan and polyacrylic acid resin are used for forming cross-linking, and a large number of hydroxyl and amino structures of the chitosan can generate complexation with silver, so that aggregation and agglomeration between the silver are avoided.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: high-barrier Ag-TiO2The modified polyacrylic acid antibacterial coating comprises the following formula raw materials in parts by weight: 8-19 parts of modified nano TiO2-Ag composite material, 2-5 parts of carboxymethyl chitosan, 2.5-4 parts of polyhexamethylene guanidine hydrochloride, 0.5-1 part of phthalic anhydride, 45-50 parts of methyl acrylate, 10-14 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 12-16 parts of perfluorooctyl ethyl methacrylate, 0.3-0.5 part of cross-linking agent, 0.2-0.5 part of initiator and 0.5-1 part of emulsifier, wherein the cross-linking agent is divinylbenzene, the initiator is ammonium persulfate, and the emulsifier is hexadecyl trimethyl ammonium bromide.
Modified nano TiO2The preparation method of the-Ag composite material comprises the following steps:
(1) adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding titanic acid tetraButyl ester and AgNO3The molar ratio of the three substances is 1.5-2:4-5:1, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 1-2 h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75-85 ℃, stirring at constant speed for reaction for 6-10 h, decompressing and concentrating the solution to remove the solvent, washing the solid product with a proper amount of diethyl ether, fully drying, placing the solid product in a resistance furnace, heating at the rate of 10-15 ℃, and carrying out heat preservation calcination at the temperature of 850-2。
(2) Adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2And silane coupling agent tridecafluorooctyltriethoxysilane with the mass ratio of 15-18:1, placing the solution in a constant temperature water bath kettle, heating to 80-90 ℃, stirring at a constant speed and refluxing for 10-15 h, decompressing and concentrating the solution to remove the solvent, washing the solid product with a proper amount of diethyl ether, and fully drying to prepare the modified nano TiO2-an Ag composite material.
High-barrier Ag-TiO2The preparation method of the modified polyacrylic acid antibacterial coating comprises the following steps:
(1) adding proper amount of the mixture into a reaction bottleN,NAnd (2) adding 2.5-4 parts of polyhexamethylene guanidine hydrochloride and 0.5-1 part of phthalic anhydride in a dimethylformamide solvent in sequence, placing a reaction bottle in a constant-temperature water bath kettle, heating to 70-80 ℃, stirring at a constant speed for reaction for 25-30 h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product by using a proper amount of anhydrous ether, and fully drying to prepare the phthaloyl imidization polyhexamethylene guanidine hydrochloride.
(2) Introducing N into the reaction bottle2Discharging air, adding ethanol solvent, 45-50 parts of methyl acrylate, 10-14 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 12-16 parts of perfluorooctyl ethyl methacrylate, 0.5-1 part of emulsifier hexadecyl trimethyl ammonium bromide, 0.3-0.5 part of cross-linking agent divinylbenzene and 8-19 parts of modified nano TiO2-Ag composite material, placing the reaction bottle in a constant temperature water bath kettle, heating to 50-60 ℃, stirring at constant speed for 1-2 h, adding 0.2-0.5 part of initiator ammonium persulfate, heating to 75-85 ℃, stirring at constant speed, refluxing and reacting for 1-2h, adding the phthalimide polyhexamethylene guanidine hydrochloride prepared in the step (1), stirring at a constant speed and refluxing for reaction for 2-3 h, adding 2-5 parts of carboxymethyl chitosan, stirring at a constant speed and reacting for 8-10 h at 80-90 ℃, placing the solution in a drying oven, heating to 60-70 ℃, slowly volatilizing an ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 70-85%, and preparing the high-barrier-property Ag-TiO2Modified polyacrylic acid antibacterial coating.
Example 1
(1) Preparation of nano Ag loaded TiO2Component 1: adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding tetrabutyl titanate and AgNO3And the molar ratio of the three substances is 1.5:4:1, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 40 ℃, performing ultrasonic dispersion treatment for 1h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75 ℃, stirring at a constant speed for reaction for 6h, performing reduced pressure concentration on the solution to remove the solvent, washing a solid product by using a proper amount of diethyl ether, fully drying, placing the solid product in a resistance furnace, heating at the rate of 10 ℃, and performing heat preservation and calcination at the temperature of 850 ℃ for 2 h to prepare the nano-Ag-loaded TiO2And (3) component 1.
(2) Preparation of modified nano TiO2-Ag composite 1: adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2The component 1 and the silane coupling agent tridecafluorooctyltriethoxysilane are mixed according to the mass ratio of 15:1, the solution is placed in a constant temperature water bath kettle and heated to 80 ℃, the mixture is stirred at a constant speed and refluxed for reaction for 10 hours, the solution is decompressed and concentrated to remove the solvent, a proper amount of ether is used for washing a solid product, and the solid product is fully dried to prepare the modified nano TiO2-Ag composite material 1.
(3) Preparation of phthalimided polyhexamethylene guanidine hydrochloride component 1: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, sequentially adding 2.5 parts of poly-hexamethylene guanidine hydrochloride and 0.5 part of phthalic anhydride, placing a reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for reaction for 25 hours, decompressing and concentrating the solution to remove the solvent, washing the solid product by using a proper amount of anhydrous ether, and fully drying to prepare the phthalimide poly-hexamethylene saltAcid guanidine component 1.
(4) Preparing high-barrier Ag-TiO2Modified polyacrylic acid antibacterial coating 1: introducing N into the reaction bottle2Discharging air, adding ethanol solvent, 45 parts of methyl acrylate, 10 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 12 parts of perfluorooctyl ethyl methacrylate, 0.5 part of emulsifying agent hexadecyl trimethyl ammonium bromide, 0.3 part of crosslinking agent divinylbenzene and 19 parts of modified nano TiO2-Ag composite material 1, placing a reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, stirring at a constant speed for 1h, adding 0.2 part of initiator ammonium persulfate, heating to 75 ℃, stirring at a constant speed for reflux reaction for 1h, adding the phthaloyl imidization poly (hexamethylene guanidine hydrochloride) component 1 prepared in the step (1), stirring at a constant speed for reflux reaction for 2 h, adding 2 parts of carboxymethyl chitosan, stirring at a constant speed for reaction for 8 h at a temperature of 80 ℃, placing the solution in an oven, heating to 60 ℃, slowly volatilizing an ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 70%, and preparing the high-barrier Ag-TiO composite material with high barrier property2Modified polyacrylic acid antibacterial coating 1.
Example 2
(1) Preparation of nano Ag loaded TiO2And (2) component: adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding tetrabutyl titanate and AgNO3The molar ratio of the three substances is 2:4:1, placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion treatment for 1h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed for reaction for 10h, performing reduced pressure concentration on the solution to remove the solvent, washing a solid product by using a proper amount of diethyl ether, fully drying, placing the solid product in a resistance furnace, heating at a rate of 15 ℃, and performing heat preservation and calcination at 850 ℃ for 3 h to prepare the nano Ag-loaded TiO2And (3) component 2.
(2) Preparation of modified nano TiO2-Ag composite 2: adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2The component 2 and the silane coupling agent tridecafluorooctyltriethoxysilane with the mass ratio of 15:1 are put into a constant temperature water bath kettle, heated to 90 ℃, stirred at a constant speed and refluxed for reaction for 10 hours, the solution is decompressed and concentrated to remove the solvent, and a proper amount of the solvent is usedWashing the solid product with ethyl ether, and fully drying to prepare the modified nano TiO2-Ag composite 2.
(3) Preparation of phthalimided polyhexamethylene guanidine hydrochloride component 2: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, sequentially adding 3 parts of poly-hexamethylene guanidine hydrochloride and 0.6 part of phthalic anhydride, placing a reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 30 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product by using a proper amount of anhydrous ether, and fully drying to prepare the phthalimide poly-hexamethylene guanidine hydrochloride component 2.
(4) Preparing high-barrier Ag-TiO2Modified polyacrylic acid antibacterial coating 2: introducing N into the reaction bottle2Discharging air, adding ethanol solvent, 46 parts of methyl acrylate, 11 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 13 parts of perfluorooctyl ethyl methacrylate, 0.6 part of emulsifying agent hexadecyl trimethyl ammonium bromide, 0.4 part of crosslinking agent divinylbenzene and 16 parts of modified nano TiO2-Ag composite material 2, placing a reaction bottle in a constant temperature water bath kettle, heating to 50 ℃, stirring at a constant speed for 1h, adding 0.4 part of initiator ammonium persulfate, heating to 75 ℃, stirring at a constant speed for reflux reaction for 2 h, adding the phthaloyl imidization poly (hexamethylene guanidine hydrochloride) component 2 prepared in the step (1), stirring at a constant speed for reflux reaction for 3 h, adding 3 parts of carboxymethyl chitosan, stirring at a constant speed for reaction for 10h at a temperature of 90 ℃, placing the solution in an oven, heating to 60 ℃, slowly volatilizing an ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 74%, and preparing the high-barrier Ag-TiO composite material2Modified polyacrylic acid antibacterial coating 2.
Example 3
(1) Preparation of nano Ag loaded TiO2And (3) component: adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding tetrabutyl titanate and AgNO3The molar ratio of the three substances is 1.8:4.5:1, placing the reaction bottle in an ultrasonic disperser, heating to 45 ℃, performing ultrasonic dispersion treatment for 1.5 h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at constant speed for reaction for 8 h, decompressing and concentrating the solution to remove the solventWashing the solid product with proper amount of ether, drying, calcining in a resistance furnace at 125 deg.c for 2.5 hr at 870 deg.c to obtain nanometer Ag supported TiO2And (3) component.
(2) Preparation of modified nano TiO2-Ag composite 3: adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2The component 3 and the silane coupling agent tridecafluorooctyltriethoxysilane with the mass ratio of 17:1 are put into a constant temperature water bath kettle, heated to 85 ℃, stirred at a constant speed and refluxed for 125 hours, the solution is decompressed and concentrated to remove the solvent, a proper amount of ether is used for washing a solid product, and the solid product is fully dried to prepare the modified nano TiO2-Ag composite 3.
(3) Preparation of phthalimide polyhexamethylene guanidine hydrochloride component 3: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, 3.2 parts of poly-guanidine hexamethylene hydrochloride and 0.7 part of phthalic anhydride are sequentially added, the reaction bottle is placed in a constant-temperature water bath kettle and heated to 75 ℃, the reaction is carried out for 28 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, a proper amount of anhydrous ether is used for washing the solid product, and the solid product is fully dried to prepare the phthalimide poly-guanidine hexamethylene hydrochloride component 3.
(4) Preparing high-barrier Ag-TiO2Modified polyacrylic acid antibacterial coating 3: introducing N into the reaction bottle2Discharging air, adding an ethanol solvent, 47 parts of methyl acrylate, 12 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 14 parts of perfluorooctyl ethyl methacrylate, 0.8 part of emulsifier hexadecyl trimethyl ammonium bromide, 0.4 part of cross-linking agent divinylbenzene and 13 parts of modified nano TiO2-Ag composite material 3, placing a reaction bottle in a constant temperature water bath kettle, heating to 55 ℃, stirring at a constant speed for 1.5 h, adding 0.4 part of initiator ammonium persulfate, heating to 80 ℃, stirring at a constant speed for reflux reaction for 1.5 h, adding the phthalimide polyhexamethylene guanidine hydrochloride component 3 prepared in the step (1), stirring at a constant speed for reflux reaction for 2.5 h, adding 3.5 parts of carboxymethyl chitosan, stirring at a constant speed for reaction for 9 h at 85 ℃, placing the solution in an oven, heating to 65 ℃, and slowly heatingVolatilizing the ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 78 percent, and preparing the high-barrier Ag-TiO2Modified polyacrylic acid antibacterial coating 3.
Example 4
(1) Preparation of nano Ag loaded TiO2And (4) component: adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding tetrabutyl titanate and AgNO3And the molar ratio of the three substances is 1.5:5:1, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 40 ℃, performing ultrasonic dispersion treatment for 2 hours, placing the reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed for reaction for 10 hours, performing reduced pressure concentration on the solution to remove the solvent, washing a solid product by using a proper amount of diethyl ether, fully drying, placing the solid product in a resistance furnace, heating at the rate of 15 ℃, and performing heat preservation and calcination at the temperature of 850 ℃ for 3 hours to prepare the nano-Ag-loaded TiO2And (4) component.
(2) Preparation of modified nano TiO2-Ag composite 4: adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2The component 4 and the silane coupling agent tridecafluorooctyltriethoxysilane with the mass ratio of 18:1 are put into a constant temperature water bath kettle, heated to 90 ℃, stirred at a constant speed and refluxed for reaction for 10 hours, the solution is decompressed and concentrated to remove the solvent, a proper amount of ether is used for washing a solid product, and the solid product is fully dried to prepare the modified nano TiO2-Ag composite 4.
(3) Preparation of phthalimide polyhexamethylene guanidine hydrochloride component 4: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, 3.5 parts of poly-guanidine-hexamethylenehydrochloride and 0.8 part of phthalic anhydride are sequentially added, the reaction bottle is placed in a constant-temperature water bath kettle and heated to 70 ℃, the reaction is carried out for 30 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, a proper amount of anhydrous ether is used for washing the solid product, and the solid product is fully dried to prepare the poly-guanidine-hexamethylenehydrochloride component 4 for phthalimide.
(4) Preparing high-barrier Ag-TiO2Modified polyacrylic acid antibacterial coating 4: introducing N into the reaction bottle2Discharging air, adding ethanol solvent, 48 parts of methyl acrylate and 13 parts of 1H,1H, 7H-dodecafluoroheptyl propyleneAcid ester, 15 parts of perfluorooctyl ethyl methacrylate, 0.8 part of emulsifying agent cetyl trimethyl ammonium bromide, 0.4 part of cross-linking agent divinylbenzene and 11 parts of modified nano TiO2-Ag composite material 4, placing a reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, stirring at a constant speed for 2 h, adding 0.4 part of initiator ammonium persulfate, heating to 75 ℃, stirring at a constant speed for reflux reaction for 2 h, adding the phthaloyl imidization poly (hexamethylene guanidine hydrochloride) component 4 prepared in the step (1), stirring at a constant speed for reflux reaction for 3 h, adding 4.5 parts of carboxymethyl chitosan, stirring at a constant speed for reaction for 10h at 85 ℃, placing the solution in an oven, heating to 70 ℃, slowly volatilizing an ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 80%, and preparing the high-barrier Ag-TiO composite material with high barrier property2Modified polyacrylic acid antibacterial coating 4.
Example 5
(1) Preparation of nano Ag loaded TiO2And (5) component: adding ethanol solvent and stearic acid into a reaction bottle, stirring at a constant speed to dissolve, and then adding tetrabutyl titanate and AgNO3The molar ratio of the three substances is 2:5:1, placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed for reaction for 10h, performing reduced pressure concentration on the solution to remove the solvent, washing a solid product by using a proper amount of diethyl ether, fully drying, placing the solid product in a resistance furnace, heating at a rate of 15 ℃, and performing heat preservation and calcination at 880 ℃ for 3 h to obtain the nano Ag loaded TiO2And (5) component.
(2) Preparation of modified nano TiO2-Ag composite 5: adding ethanol solvent into a reaction bottle, and then adding nano Ag loaded TiO2The component 5 and the silane coupling agent tridecafluorooctyltriethoxysilane with the mass ratio of 18:1 are put into a constant temperature water bath kettle, heated to 90 ℃, stirred at a constant speed for reflux reaction for 15 hours, the solution is decompressed and concentrated to remove the solvent, a proper amount of ether is used for washing the solid product, and the solid product is fully dried to prepare the modified nano TiO2-an Ag composite 5.
(3) Preparation of phthalimide polyhexamethylene guanidine hydrochloride component 5: adding proper amount of the mixture into a reaction bottleN,NAnd (3) adding 4 parts of poly-hexamethylene guanidine hydrochloride and 1 part of phthalic anhydride in sequence into a dimethylformamide solvent, placing a reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 30 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product by using a proper amount of anhydrous ether, and fully drying to prepare the phthaloyl imidization poly-hexamethylene guanidine hydrochloride component 5.
(4) Preparing high-barrier Ag-TiO2Modified polyacrylic acid antibacterial coating 5: introducing N into the reaction bottle2Discharging air, adding ethanol solvent, 50 parts of methyl acrylate, 14 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 16 parts of perfluorooctyl ethyl methacrylate, 1 part of emulsifying agent hexadecyl trimethyl ammonium bromide, 0.5 part of crosslinking agent divinylbenzene and 8 parts of modified nano TiO2-Ag composite material 5, placing a reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for 2 h, adding 0.5 part of initiator ammonium persulfate, heating to 85 ℃, stirring at a constant speed for reflux reaction for 2 h, adding the phthaloyl imidization poly (hexamethylene guanidine hydrochloride) component 5 prepared in the step (1), stirring at a constant speed for reflux reaction for 3 h, adding 5 parts of carboxymethyl chitosan, stirring at a constant speed for reaction for 10h at a temperature of 90 ℃, placing the solution in an oven, heating to 70 ℃, slowly volatilizing an ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 85%, and preparing the high-barrier Ag-TiO composite material with high barrier property2Modified polyacrylic acid antibacterial coating 5.
In summary, the Ag-TiO with high barrier property2Modified polyacrylic acid antibacterial coating and preparation method thereof, Ag in-situ growth is adopted in nano TiO2Forming nano TiO on the surface of the substrate2-Ag composite, TiO2Under the action of illumination, photoproduction electrons and holes are generated, and the holes oxidize Ag into Ag+In the cavity and Ag+Can carry out oxidation reaction on protease in bacteria body to destroy normal metabolism and reproduction of bacteria and microorganisms, thereby playing the role of sterilization or disinfection, and modifying TiO by silane coupling agent tridecafluorooctyltriethoxysilane2Greatly improves the nano TiO2Compatibility of the Ag composite with the polyacrylic resin, so that it can be uniformly dispersed in the polyacrylic material,avoid the nanometer TiO2Aggregation of the-Ag composite material into large particles decreases the antibacterial activity.
The 1H,1H, 7H-dodecafluoroheptyl acrylate and perfluorooctyl ethyl methacrylate are used as grafting monomers, the prepared polyacrylic acid has excellent hydrophobicity, and the silane coupling agent tridecafluorooctyltriethoxysilane also has good hydrophobicity, so that the hydrophobicity of the polyacrylic acid material is greatly enhanced, the adhesion of water molecules in the air on the surface of the material is reduced, the surface of the material is kept dry, and the propagation of bacteria and microorganisms is inhibited.
The phthalimide poly-guanidine hexamethylene hydrochloride is used as a functional monomer to modify polyacrylic resin, simultaneously, carboxymethyl chitosan is added to highly crosslink with the polyacrylic resin to form a compact crosslinking structure, so that the barrier property of the material is greatly improved, water molecules and oxygen can be prevented from passing through the material, the material can be used as a high-barrier coating to inhibit the growth and reproduction of bacteria in the coating, and the antibacterial property of the material is enhanced by a guanidine antibacterial group contained in the poly-guanidine hydrochloride.
When the chitosan and the polyacrylic resin form cross-linking, a large number of hydroxyl and amino structures of the chitosan can generate complexation with silver, so that aggregation and agglomeration of the silver are avoided.
Claims (8)
1. High-barrier Ag-TiO2The modified polyacrylic acid antibacterial coating comprises the following formula raw materials in parts by weight, and is characterized in that: 8-19 parts of modified nano TiO2-Ag composite material, 2-5 parts of carboxymethyl chitosan, 2.5-4 parts of polyhexamethylene guanidine hydrochloride, 0.5-1 part of phthalic anhydride, 45-50 parts of methyl acrylate, 10-14 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 12-16 parts of perfluorooctyl ethyl methacrylate, 0.3-0.5 part of cross-linking agent, 0.2-0.5 part of initiator and 0.5-1 part of emulsifier.
2. The Ag-TiO of claim 12The modified polyacrylic acid antibacterial coating is characterized in that: the crosslinking agent is divinylbenzene.
3. The Ag-TiO of claim 12The modified polyacrylic acid antibacterial coating is characterized in that: the initiator is ammonium persulfate.
4. The Ag-TiO of claim 12The modified polyacrylic acid antibacterial coating is characterized in that: the emulsifier is cetyl trimethyl ammonium bromide.
5. The Ag-TiO of claim 12The modified polyacrylic acid antibacterial coating is characterized in that: the modified nano TiO2The preparation method of the-Ag composite material comprises the following steps:
(1) adding stearic acid, tetrabutyl titanate and AgNO into an ethanol solvent3Performing ultrasonic dispersion treatment on the solution at 40-50 ℃ for 1-2 h, heating the solution to 75-85 ℃, reacting for 6-10 h, concentrating the solution under reduced pressure, washing a solid product, drying, placing the solid product in a resistance furnace, heating at the rate of 10-15 ℃, and performing heat preservation and calcination at the temperature of 850-880 ℃ for 2-3 h to prepare the nano Ag-loaded TiO2；
(2) Adding nano Ag loaded TiO into ethanol solvent2And silane coupling agent, heating the solution to 80-90 ℃, reacting for 10-15 h, decompressing the solution, washing a solid product, and drying to prepare the modified nano TiO2-an Ag composite material.
6. The modified nano TiO of claim 52-Ag composite material, characterized in that: the stearic acid, tetrabutyl titanate and AgNO3The molar ratio of the three substances is 1.5-2:4-5: 1.
7. The modified nano TiO of claim 52-Ag composite material, characterized in that: the silane coupling agent is tridecafluorooctyltriethoxysilane and nano Ag loaded TiO2The mass ratio is 1: 15-18.
8. The Ag-TiO of claim 12The modified polyacrylic acid antibacterial coating is characterized in that: the high-barrier Ag-TiO2The preparation method of the modified polyacrylic acid antibacterial coating comprises the following steps:
(1) to an appropriate amountN,NAdding 2.5-4 parts of poly-hexamethylene guanidine hydrochloride and 0.5-1 part of phthalic anhydride into a dimethylformamide solvent, heating the solution to 70-80 ℃, reacting for 25-30 h, concentrating the solution under reduced pressure, washing a solid product, and drying to prepare the poly-hexamethylene guanidine phthalimide;
(2) adding 45-50 parts of methyl acrylate, 10-14 parts of 1H,1H, 7H-dodecafluoroheptyl acrylate, 12-16 parts of perfluorooctyl ethyl methacrylate, 0.5-1 part of emulsifier hexadecyl trimethyl ammonium bromide, 0.3-0.5 part of cross-linking agent divinylbenzene and 8-19 parts of modified nano TiO into an ethanol solvent2-Ag composite material, the solution in N2Heating to 50-60 ℃ in atmosphere, stirring at constant speed for 1-2 h, adding 0.2-0.5 part of initiator ammonium persulfate, heating to 75-85 ℃, reacting for 1-2 h, adding the poly (guanidinium phthalimide) hydrochloride prepared in the step (1), reacting for 2-3 h, adding 2-5 parts of carboxymethyl chitosan, reacting for 8-10 h at 80-90 ℃, placing the solution in an oven, heating to 60-70 ℃, slowly volatilizing ethanol solvent, controlling the solid-to-liquid ratio of the solution to be 70-85%, and preparing the high-barrier-property Ag-TiO2Modified polyacrylic acid antibacterial coating.
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