CN113913049B - Photocatalyst fluorescent ink and preparation method thereof - Google Patents
Photocatalyst fluorescent ink and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses photocatalyst fluorescent ink and a preparation method thereof, and relates to the technical field of ink. The self-made fluorescent agent is frozen into microspheres, and then the titanium dioxide is adsorbed on the surface of the self-made fluorescent agent by utilizing plasmas, electrostatic spraying and microwaves, so that the stability of the ink is improved; then, by using low-temperature plasma to assist radio frequency magnetron sputtering, cerium oxide is coordinated and chelated on the surface of the titanium dioxide microsphere, so that the visible light activity of the titanium dioxide is improved, and the ink can be catalytically degraded under visible light; the self-made fluorescent agent is prepared from veratone, pyrene formaldehyde and boron trifluoride, so that the ink can show patterns only under the irradiation of infrared wavelength, is not easy to decompose under the irradiation of infrared for a long time, and has good light stability. The photocatalyst fluorescent ink prepared by the invention has the effects of good confidentiality, light stability and degradability.
Description
Technical Field
The invention relates to the technical field of ink, in particular to photocatalyst fluorescent ink and a preparation method thereof.
Background
For a long time, the information security problem is very important for the country, the enterprise and the individual, and the combination of paper and ink is an important medium for transmitting information by the huge palace; although current network technology is rapidly developed, a lot of data and information are transmitted and stored through a network, in many occasions and some special units, the stored important even confidential documents still remain paper printed matters or handwritten matters.
How to protect the contents of these paper documents from theft becomes an important issue. At present, the protection measures mainly adopt two methods of invisible ink and file crushing; the file crushing treatment method is simple, but causes a great amount of waste, increases the cost of companies and causes a certain harm to the environment; the invisible ink on the market mainly develops color under the stimulation of heating, acid-base solution and the like, and can achieve the invisible confidentiality effect, but once stolen, the invisible ink cannot disappear before copying and transmission, so the invisible ink can be synthesized into the visible light decomposable and discolored ink by utilizing the photocatalyst technology, and is used when writing confidential documents, so that the possibility of information leakage is reduced to the greatest extent.
Disclosure of Invention
The invention aims to provide photocatalyst fluorescent ink and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the photocatalyst fluorescent ink is characterized by mainly comprising the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat for 30-40 min at-45 ℃, heating to-20 ℃ at a speed of 1-3 ℃/min, and preserving heat for 50-60 min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, pretreating for 120-130 s, placing the self-made fluorescent agent microspheres in a receiving device, placing a titanium dioxide solution in a syringe, placing the titanium dioxide solution in a mass ratio of titanium dioxide to 65% hydrochloric acid of 1:3-4, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, spraying for 100-120 s at an injection speed of 0.01-0.02 mm/s, washing with 10% sodium hydroxide to pH 6-7, washing with deionized water for 5-7 times, and placing the titanium dioxide solution in a microwave reactor for treatment for 4-6 min to obtain titanium dioxide porous microspheres;
(4) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 30-40 s, and then placing in a magnetron sputtering processor, and processing for 50-70 s to obtain composite microspheres;
(5) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 5-10 min at 50-100 rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. Dissolving veratone in absolute ethyl alcohol with the mass of 5.5-6 times of that of the veratone, adding pyrene formaldehyde with the mass of 0.6-1.2 times of that of the veratone while stirring at the speed of 50-60 rpm, regulating the stirring speed to 200-300 rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6-6.5 times of that of the veratone, stirring at 200-300 rpm for 4-5 h, filtering, washing with deionized water for 3-5 times, washing with an ethanol-water mixed solvent for 4-6 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6-7 h to obtain a chalcone compound;
b. adding the chalcone compound into methanol with the mass of 8.5-9 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1-1.5 times of that of the chalcone compound and diethylamine with the mass of 0.8-0.85 times of that of the chalcone compound, heating to 51-55 ℃, reacting for 7-8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6-7, adding dichloromethane with the mass of 4-6 times of that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4-5 times in sequence, adding anhydrous magnesium sulfate until no caking appears, drying for 4-6 h, concentrating under reduced pressure at 200rpm and 65 ℃ for 2-3 h to obtain nitrone compounds;
c. Adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:13.5-14:9-9.5, heating to 80-85 ℃ while stirring at the speed of 100-200 rpm, reacting for 10-12 h, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 3-5 h, and filtering to obtain a dipyrrole compound;
d. placing dipyrrole compound and dichloromethane with the mass of 80-85 times of that of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 0-5 ℃ in an ice water bath at the temperature of 0 ℃, adding triethylamine/dichloromethane mixed solution with the mass of 16-16.5 times of that of the dipyrrole compound into the three-neck flask under the nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass of 18-18.5 times of that of the dipyrrole compound into the three-neck flask at the speed of 10-15 drops/min, stirring the boron trifluoride diethyl ether/dichloromethane mixed solution at the speed of 100-200 rpm for 24-26 hours at room temperature, washing with deionized water and saturated sodium chloride for 4-6 times in sequence, and concentrating under the pressure of 300rpm and 40 ℃ for 3-4 hours to obtain the self-made fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 35 Pa to 40Pa, and the cold air quantity is 5.5 m to 6m 3 /min。
Further, in the step (3), the gas pressure of the cold plasma modification treatment equipment is 7-9 Pa, the discharge power is 100-120W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53.
Further, in the step (3), the nozzle of the injector is a 14-16G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 30-40 kV, and the temperature is 100-120 ℃.
Further, the power of the microwave reactor in the step (3) is 160-200W, and the frequency is 2450MHz.
In the step (4), oxygen is used as a treatment atmosphere, the gas flow is 0.8-1L/min, and the treatment power is 4-6 kW.
Further, in the step (4), the sputtering power in the magnetron sputtering processor is 100-120W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 80-100 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 6-10 cm.
Further, the photocatalyst fluorescent ink prepared by the preparation method of the photocatalyst fluorescent ink mainly comprises, by weight, 30-40 parts of self-made fluorescent agent, 20-30 parts of titanium dioxide, 10-15 parts of cerium oxide, 5-8 parts of ethylene glycol, 1-3 parts of glycerol and 55-65 parts of softened water.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the ink by the steps of self-made fluorescent agent preparation, electrostatic assembly, cerium oxide plating and the like in sequence, so as to realize the effects of good confidentiality, light stability and degradability.
Firstly, preparing a self-made fluorescent agent from veratone, pyrene formaldehyde and boron trifluoride; condensing methyl of veratone and aldehyde group of pyrene formaldehyde to form carbon-carbon double bond, performing addition reaction on the carbon-carbon double bond, and introducing nitro to form nitrone compound; then the nitro and ketone groups of the veratone are utilized to form a ring, and the nitroketone compounds are condensed to form a dipyrrole group; the imino on the dipyrrole group is coordinated with boron trifluoride to form an aza-fluorine boron dipyrrole compound, so that the ink has a fluorescence effect; the pyrene formaldehyde can expand the conjugated system of the aza-fluoro-boron dipyrrole compound, and meanwhile, the smaller steric hindrance of the pyrene formaldehyde enables the aza-fluoro-boron dipyrrole compound to tend to be planarized, so that the energy gap is reduced, and the wavelength is red shifted; in addition, the veratone is utilized to introduce electron donating groups at the two ends of the aza-fluoroborodipyrrole compound, so that the wavelength is further red shifted, the ink can rapidly generate photosensitive reaction only under the irradiation of infrared wavelength, the pattern is displayed, and the ink is not easy to be decomposed by irradiation under the long-time infrared irradiation, so that the ink has better light stability.
Secondly, preparing the self-made fluorescent agent into microspheres by spray freeze drying, so as to improve the dispersibility of the self-made fluorescent agent; preparing titanium dioxide porous microspheres by plasma, electrostatic spraying and microwave-assisted electrostatic self-assembly; in the plasma treatment process, the surface of the self-made fluorescent agent microsphere is modified by using electronegative gas, so that the surface is negatively charged; the titanium dioxide is atomized by utilizing electrostatic spraying to form positively charged liquid drops, the positively charged liquid drops can be electrostatically adsorbed with self-made fluorescent agent microspheres and uniformly deposited on the surface, the titanium dioxide deposition is accelerated by utilizing microwave irradiation, and the collision between the self-made fluorescent agent microspheres and titanium dioxide atoms is promoted to generate interatomic reaction, so that the self-made fluorescent agent microspheres and the titanium dioxide atoms are tightly crosslinked, the stability of the ink is improved, and the long-term storage of the ink is facilitated; then, by using low-temperature plasma to assist radio frequency magnetron sputtering, cerium oxide is coordinated and chelated with active groups on the surfaces of titanium dioxide microspheres, so that the visible light activity of the titanium dioxide is improved, free radicals and active oxygen with extremely strong oxidizing ability are produced by excitation catalysis under the irradiation of visible light, the free radicals and the active oxygen react with self-made fluorescent agents, molecular chains are broken, the ink is automatically degraded and discolored, and water generated by the reaction of the active oxygen and the self-made fluorescent agents can further dilute the ink, so that text blurring disappears and cannot be recovered.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the photocatalyst fluorescent ink prepared in the following examples is as follows:
confidentiality: and (3) taking the embodiment and the comparative example with the same volume to perform confidentiality effect test, writing on white paper, and selecting different light sources to irradiate.
Light stability: the light stabilization effect test is carried out by taking the examples with the same volume and the comparative examples, and after the examples are placed for 20d at room temperature under natural light, writing is carried out on white paper, and fluorescent intensity is observed by utilizing infrared lamp light or visible light irradiation.
Degradability: the degradability effect test is carried out by taking the examples with the same volume and the comparative examples, writing on white paper, and checking whether the characters disappear or not after irradiating for 2min by using visible light.
Example 1
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 30 parts of self-made fluorescent agent, 20 parts of titanium dioxide, 10 parts of cerium oxide, 5 parts of ethylene glycol, 1 part of glycerol and 55 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 30min, heating to-20 ℃ at a speed of 1 ℃/min, and preserving heat for 50min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, pretreating for 120 seconds, placing the self-made fluorescent agent microspheres in a receiving device, placing a titanium dioxide solution in a syringe, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:3, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, spraying for 120 seconds, washing with 10% sodium hydroxide with the mass fraction of 10% until the pH value is 6, washing with deionized water for 5 times, placing in a microwave reactor, and treating for 4 minutes to obtain titanium dioxide porous microspheres;
(4) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 30s, and then placing in a magnetron sputtering processor, and processing for 50s to obtain composite microspheres;
(5) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 10min at 50rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. dissolving veratone in absolute ethyl alcohol with the mass of 5.5 times of that of the veratone, adding pyrene formaldehyde with the mass of 0.6 times of that of the veratone while stirring at the speed of 50rpm, regulating the stirring speed to 200rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6 times of that of the veratone, stirring at 200rpm for 5 hours, filtering, washing with deionized water for 3 times, washing with an ethanol-water mixed solvent for 4 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6 hours to obtain a chalcone compound;
b. adding the chalcone compound into methanol with the mass of 8.5 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1 time of that of the chalcone compound and diethylamine with the mass of 0.8 time of that of the chalcone compound, heating to 51 ℃, reacting for 8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass of 4 times of that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no caking appears, drying for 4 hours, concentrating under reduced pressure at 200rpm and 65 ℃ for 2 hours to obtain nitrone compounds;
c. Adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:13.5:9, heating to 80 ℃ while stirring at a speed of 100rpm, reacting for 10 hours, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 3 hours, and filtering to obtain a dipyrrole compound;
d. placing a dipyrrole compound and dichloromethane with the mass 80 times of that of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 0 ℃ in an ice water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution with the mass 16 times of that of the dipyrrole compound into the three-neck flask under a nitrogen atmosphere, wherein the mass ratio of the triethylamine to the dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass 18 times of that of the dipyrrole compound into the three-neck flask at the speed of 10 drops/min, stirring the boron trifluoride diethyl ether/dichloromethane mixed solution at the speed of 100rpm for 26 hours at room temperature, washing with deionized water and saturated sodium chloride for 4 times in sequence, and concentrating under reduced pressure for 3 hours at the temperature of 300rpm and 40 ℃ to obtain the self-made fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 35Pa, and the cold air quantity is 5.5m 3 /min。
Further, in the step (3), the gas pressure of the cold plasma modification treatment device is 7Pa, the discharge power is 100W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53.
Further, in the step (3), the nozzle of the injector is a 14G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 30kV, and the temperature is 100 ℃.
Further, the microwave reactor in the step (3) has a power of 160W and a frequency of 2450MHz.
Further, in the step (4), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.8L/min, and the treatment power is 4kW.
Further, in the step (4), the sputtering power in the magnetron sputtering processor is 100W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 80 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 6cm.
Example 2
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 40 parts of self-made fluorescent agent, 30 parts of titanium dioxide, 15 parts of cerium oxide, 8 parts of ethylene glycol, 3 parts of glycerol and 65 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 40min, heating to-20 ℃ at the speed of 3 ℃/min, and preserving heat for 60min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, pretreating for 130s, placing the self-made fluorescent agent microspheres in a receiving device, placing a titanium dioxide solution in a syringe, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:4, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, spraying for 100s at the injection speed of 0.02mm/s, washing with 10% sodium hydroxide with the mass fraction of 10% until the pH value is 7, washing with deionized water for 7 times, placing the titanium dioxide solution in a microwave reactor, and treating for 6min to obtain titanium dioxide porous microspheres;
(4) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 40s, and then placing in a magnetron sputtering processor, and processing for 70s to obtain composite microspheres;
(5) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 5min at 100rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. dissolving veratone in absolute ethyl alcohol with the mass of 6 times of that of the veratone, adding pyrene formaldehyde with the mass of 1.2 times of that of the veratone while stirring at the speed of 60rpm, regulating the stirring speed to 300rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass of 6.5 times of that of the veratone, stirring at 300rpm for 4 hours, filtering, washing with deionized water for 5 times, washing with an ethanol-water mixed solvent for 6 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 7 hours to obtain a chalcone compound;
b. Adding the chalcone compound into methanol with the mass of 9 times of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1.5 times of the chalcone compound and diethylamine with the mass of 0.85 times of the chalcone compound, heating to 55 ℃, reacting for 8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 7, adding dichloromethane with the mass of 6 times of the chalcone compound, extracting, and obtaining an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 5 times, adding anhydrous magnesium sulfate until no caking appears, drying for 6h, concentrating under reduced pressure at 200rpm and 65 ℃ for 3h to obtain nitrone compound;
c. adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:14:9.5, heating to 85 ℃ while stirring at a speed of 200rpm, reacting for 12 hours, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 5 hours, and filtering to obtain a dipyrrole compound;
d. placing a dipyrrole compound and methylene dichloride with 85 times of the mass of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 5 ℃ in an ice water bath at 0 ℃, adding a triethylamine/methylene dichloride mixed solution with 16.5 times of the mass of the dipyrrole compound into the three-neck flask under a nitrogen atmosphere, wherein the mass ratio of the triethylamine to the methylene dichloride in the three-ethylamine/methylene dichloride mixed solution is 1:6, adding boron trifluoride diethyl ether/methylene dichloride mixed solution with 18.5 times of the mass of the dipyrrole compound into the three-neck flask at a speed of 15 drops/min, stirring the boron trifluoride diethyl ether/methylene dichloride mixed solution at a speed of 200rpm for 24 hours at room temperature, washing with deionized water and saturated sodium chloride for 6 times in sequence, and concentrating under reduced pressure for 4 hours at 300rpm and 40 ℃ to obtain the self-made fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 40Pa, and the cold air quantity is 6m 3 /min。
Further, in the step (3), the gas pressure of the cold plasma modification treatment device is 9Pa, the discharge power is 120W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53.
Further, in the step (3), the nozzle of the injector is a 16G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 40kV, and the temperature is 120 ℃.
Further, the power of the microwave reactor in the step (3) is 200W, and the frequency is 2450MHz.
Further, in the step (4), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 1L/min, and the treatment power is 6kW.
Further, in the step (4), the sputtering power in the magnetron sputtering processor is 120W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 100 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 10cm.
Comparative example 1
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 32 parts of boron dipyrromethene, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Placing the fluoboric dipyrrole into a spray freeze dryer, spraying, preserving heat for 35min at-45 ℃, heating to-20 ℃ at the speed of 2 ℃/min, and preserving heat for 54min to obtain fluoboric dipyrrole microspheres;
(2) Placing the fluoboric dipyrrole microspheres in cold plasma modification treatment equipment, pretreating for 126 seconds, placing the microspheres in a receiving device, placing a titanium dioxide solution in a syringe, setting a mass ratio of titanium dioxide in the titanium dioxide solution to 65% hydrochloric acid to be 1:3.12, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, injecting at a speed of 0.02mm/s, spraying for 117 seconds, washing with 10% sodium hydroxide to pH 7, washing with deionized water for 6 times, placing in a microwave reactor, and treating for 5 minutes to obtain titanium dioxide porous microspheres;
(3) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, and then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(4) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 8min at 70rpm to obtain the photocatalyst fluorescent ink.
Further, the spray freeze dryer of step (1) vacuum pressureThe force is 38Pa, and the cold air quantity is 5.7m 3 /min。
Further, in the step (2), the gas pressure of the cold plasma modification treatment equipment is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53; the power of the microwave reactor was 180W and the frequency was 2450MHz.
Further, the preparation step of the titanium dioxide precursor liquid in the step (2) comprises the following steps: adding anhydrous ethanol with the mass of 1.72 times of that of tetra-n-butyl titanate and tetra-n-butyl titanate into an ice water bath at the temperature of 0 ℃ at the speed of 140rpm while stirring at the speed of 2.5mL/min, wherein the mass ratio of the anhydrous ethanol, distilled water and glacial acetic acid in the anhydrous ethanol mixed solution is 1:0.32:0.33, and aging for 25 hours at room temperature to obtain the titanium dioxide precursor solution.
Further, in the step (2), the nozzle of the injector is a 15G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, in the step (3), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.9L/min, and the treatment power is 5kW.
Further, in the step (3), the sputtering power in the magnetron sputtering processor is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 91 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 7cm.
Comparative example 2
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and preserving heat for 54min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in a receiving device, placing a titanium dioxide solution in a syringe, wherein the mass ratio of titanium dioxide to 65% hydrochloric acid in the titanium dioxide solution is 1:3.12, establishing a high-voltage electrostatic field in a nozzle of the syringe and the receiving device, spraying for 117 seconds, washing with 10% sodium hydroxide until the pH value is 7, washing with deionized water for 6 times, and placing in a microwave reactor for 5 minutes to obtain titanium dioxide porous microspheres;
(4) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, and then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(5) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 8min at 70rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. dissolving veratone in absolute ethyl alcohol with the mass of 5.77 times of that of the veratone, adding pyrene formaldehyde with the mass of 1.09 times of that of the veratone while stirring at the speed of 56rpm, regulating the stirring speed to 220rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6.35 times of that of the veratone, stirring at 260rpm for 4.5 hours, filtering, washing with deionized water for 4 times, washing with an ethanol-water mixed solvent for 5 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6.5 hours to obtain a chalcone compound;
b. adding the chalcone compound into methanol with the mass of 8.71 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1.29 times of that of the chalcone compound and diethylamine with the mass of 0.83 times of that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass of 5.13 times of that of the chalcone compound, extracting, and obtaining an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no caking appears, drying for 5.5h, concentrating under reduced pressure at 200rpm and 65 ℃ for 2.5h to obtain nitrone compound;
c. Adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:13.59:9.32, heating to 83 ℃ while stirring at a speed of 150rpm, reacting for 11.5h, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 4h, and filtering to obtain a dipyrrole compound;
d. placing a dipyrrole compound and dichloromethane with the mass 83.21 times of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice water bath at 0 ℃, adding triethylamine/dichloromethane mixed solution with the mass 16.31 times of the dipyrrole compound into the three-neck flask under nitrogen atmosphere, wherein the mass ratio of the triethylamine to the dichloromethane in the three-neck flask mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass 18.31 times of the dipyrrole compound into the three-neck flask at the speed of 13 drops/min, stirring the boron trifluoride diethyl ether and the dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution at the speed of 110rpm for 25.5 hours at room temperature, washing with deionized water and saturated sodium chloride for 5 times, and concentrating under reduced pressure for 3.5 hours at 300rpm and 40 ℃.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air quantity is 5.7m 3 /min。
Further, in the step (3), the nozzle of the injector is a 15G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, the power of the microwave reactor in the step (3) is 180W, and the frequency is 2450MHz.
Further, in the step (4), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.9L/min, and the treatment power is 5kW.
Further, in the step (4), the sputtering power in the magnetron sputtering processor is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 91 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 7cm.
Comparative example 3
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and preserving heat for 54min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, adding titanium dioxide after pretreatment for 126s, placing the microspheres in a microwave reactor, and treating for 5min to obtain titanium dioxide porous microspheres;
(4) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, and then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(5) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 8min at 70rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. dissolving veratone in absolute ethyl alcohol with the mass of 5.77 times of that of the veratone, adding pyrene formaldehyde with the mass of 1.09 times of that of the veratone while stirring at the speed of 56rpm, regulating the stirring speed to 220rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6.35 times of that of the veratone, stirring at 260rpm for 4.5 hours, filtering, washing with deionized water for 4 times, washing with an ethanol-water mixed solvent for 5 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6.5 hours to obtain a chalcone compound;
b. adding the chalcone compound into methanol with the mass of 8.71 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1.29 times of that of the chalcone compound and diethylamine with the mass of 0.83 times of that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass of 5.13 times of that of the chalcone compound, extracting, and obtaining an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no caking appears, drying for 5.5h, concentrating under reduced pressure at 200rpm and 65 ℃ for 2.5h to obtain nitrone compound;
c. Adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:13.59:9.32, heating to 83 ℃ while stirring at a speed of 150rpm, reacting for 11.5h, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 4h, and filtering to obtain a dipyrrole compound;
d. placing a dipyrrole compound and dichloromethane with the mass 83.21 times of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice water bath at 0 ℃, adding triethylamine/dichloromethane mixed solution with the mass 16.31 times of the dipyrrole compound into the three-neck flask under nitrogen atmosphere, wherein the mass ratio of the triethylamine to the dichloromethane in the three-neck flask mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass 18.31 times of the dipyrrole compound into the three-neck flask at the speed of 13 drops/min, stirring the boron trifluoride diethyl ether and the dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution at the speed of 110rpm for 25.5 hours at room temperature, washing with deionized water and saturated sodium chloride for 5 times, and concentrating under reduced pressure for 3.5 hours at 300rpm and 40 ℃.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air quantity is 5.7m 3 /min。
Further, in the step (3), the gas pressure of the cold plasma modification treatment device is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53.
Further, the power of the microwave reactor in the step (3) is 180W, and the frequency is 2450MHz.
Further, in the step (4), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.9L/min, and the treatment power is 5kW.
Further, in the step (4), the sputtering power in the magnetron sputtering processor is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 91 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 7cm.
Comparative example 4
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and preserving heat for 54min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, pretreating for 126 seconds, placing the self-made fluorescent agent microspheres in a receiving device, placing a titanium dioxide solution in a syringe, wherein the mass ratio of titanium dioxide to 65% hydrochloric acid in the titanium dioxide solution is 1:3.12, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, spraying for 117 seconds, washing with 10% sodium hydroxide until the pH value is 7, and washing with deionized water for 6 times to obtain titanium dioxide porous microspheres;
(4) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, and then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(5) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 8min at 70rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. dissolving veratone in absolute ethyl alcohol with the mass of 5.77 times of that of the veratone, adding pyrene formaldehyde with the mass of 1.09 times of that of the veratone while stirring at the speed of 56rpm, regulating the stirring speed to 220rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6.35 times of that of the veratone, stirring at 260rpm for 4.5 hours, filtering, washing with deionized water for 4 times, washing with an ethanol-water mixed solvent for 5 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6.5 hours to obtain a chalcone compound;
b. Adding the chalcone compound into methanol with the mass of 8.71 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1.29 times of that of the chalcone compound and diethylamine with the mass of 0.83 times of that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass of 5.13 times of that of the chalcone compound, extracting, and obtaining an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no caking appears, drying for 5.5h, concentrating under reduced pressure at 200rpm and 65 ℃ for 2.5h to obtain nitrone compound;
c. adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:13.59:9.32, heating to 83 ℃ while stirring at a speed of 150rpm, reacting for 11.5h, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 4h, and filtering to obtain a dipyrrole compound;
d. placing a dipyrrole compound and dichloromethane with the mass 83.21 times of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice water bath at 0 ℃, adding triethylamine/dichloromethane mixed solution with the mass 16.31 times of the dipyrrole compound into the three-neck flask under nitrogen atmosphere, wherein the mass ratio of the triethylamine to the dichloromethane in the three-neck flask mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass 18.31 times of the dipyrrole compound into the three-neck flask at the speed of 13 drops/min, stirring the boron trifluoride diethyl ether and the dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution at the speed of 110rpm for 25.5 hours at room temperature, washing with deionized water and saturated sodium chloride for 5 times, and concentrating under reduced pressure for 3.5 hours at 300rpm and 40 ℃.
Further, the spraying in the step (2)The vacuum pressure of the fog freeze dryer is 38Pa, and the cold air quantity is 5.7m 3 /min。
Further, in the step (3), the gas pressure of the cold plasma modification treatment device is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53.
Further, in the step (3), the nozzle of the injector is a 15G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, in the step (4), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.9L/min, and the treatment power is 5kW.
Further, in the step (4), the sputtering power in the magnetron sputtering processor is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the substrate temperature is 91 ℃, the target is cerium oxide, and the distance from the target to the glass substrate is 7cm.
Comparative example 5
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Mixing veratone and pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl ether to prepare a self-made fluorescent agent;
(2) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and preserving heat for 54min to obtain self-made fluorescent agent microspheres;
(3) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, pretreating for 126 seconds, placing the microspheres in a receiving device, placing a titanium dioxide solution in a syringe, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:3.12, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, injecting at the speed of 0.02mm/s, spraying for 117 seconds, washing with sodium hydroxide with the mass fraction of 10% until the pH value is 7, washing with deionized water for 6 times, placing in a microwave reactor, and treating for 5 minutes to obtain titanium dioxide porous microspheres;
(4) Mixing the titanium dioxide porous microspheres, glycol, glycerol and softened water according to the formula amount, and stirring for 8min at 70rpm to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) comprises the following steps:
a. dissolving veratone in absolute ethyl alcohol with the mass of 5.77 times of that of the veratone, adding pyrene formaldehyde with the mass of 1.09 times of that of the veratone while stirring at the speed of 56rpm, regulating the stirring speed to 220rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6.35 times of that of the veratone, stirring at 260rpm for 4.5 hours, filtering, washing with deionized water for 4 times, washing with an ethanol-water mixed solvent for 5 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6.5 hours to obtain a chalcone compound;
b. Adding the chalcone compound into methanol with the mass of 8.71 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1.29 times of that of the chalcone compound and diethylamine with the mass of 0.83 times of that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass of 5.13 times of that of the chalcone compound, extracting, and obtaining an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no caking appears, drying for 5.5h, concentrating under reduced pressure at 200rpm and 65 ℃ for 2.5h to obtain nitrone compound;
c. adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:13.59:9.32, heating to 83 ℃ while stirring at a speed of 150rpm, reacting for 11.5h, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 4h, and filtering to obtain a dipyrrole compound;
d. placing a dipyrrole compound and dichloromethane with the mass 83.21 times of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice water bath at 0 ℃, adding triethylamine/dichloromethane mixed solution with the mass 16.31 times of the dipyrrole compound into the three-neck flask under nitrogen atmosphere, wherein the mass ratio of the triethylamine to the dichloromethane in the three-neck flask mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass 18.31 times of the dipyrrole compound into the three-neck flask at the speed of 13 drops/min, stirring the boron trifluoride diethyl ether and the dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution at the speed of 110rpm for 25.5 hours at room temperature, washing with deionized water and saturated sodium chloride for 5 times, and concentrating under reduced pressure for 3.5 hours at 300rpm and 40 ℃.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air quantity is 5.7m 3 /min。
Further, in the step (3), the gas pressure of the cold plasma modification treatment device is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53.
Further, in the step (3), the nozzle of the injector is a 15G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, the power of the microwave reactor in the step (3) is 180W, and the frequency is 2450MHz.
Comparative example 6
A photocatalyst fluorescent ink and a preparation method thereof mainly comprise the following components in parts by weight: 32 parts of boron dipyrrole, 23 parts of titanium dioxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
The preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Placing the fluoboric dipyrrole into a spray freeze dryer, spraying, preserving heat at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and preserving heat for 54min to obtain microspheres;
(2) Mixing the microspheres, titanium dioxide, glycol, glycerol and softened water according to the formula amount, and stirring for 8min at 70rpm to obtain the photocatalyst fluorescent ink.
Further, the vacuum pressure of the spray freeze dryer in the step (1) is 38Pa, and the cold air quantity is 5.7m 3 /min。
Effect example
The following table 1 shows the results of performance analysis of the photocatalytic fluorescent inks according to the present invention using examples 1 to 2 and comparative examples 1 to 6.
TABLE 1
From comparison of the experimental data of examples 1, 2 and comparative example 6, it was found that the use of the self-made fluorescent agent in the product makes the ink develop only under infrared lamp light and has light stability; the titanium dioxide microspheres are prepared by using plasmas, electrostatic spraying and microwaves, so that the titanium dioxide and a self-made fluorescent agent are tightly crosslinked, the stability of the ink is improved, and cerium oxide is introduced to improve the visible light activity of the titanium dioxide, so that the ink can be degraded and vanished under visible light, and the confidentiality is good; from comparison of experimental data of examples 1 and 2 with comparative example 1, it is found that if a self-made fluorescent agent is prepared without using veratone, pyrene formaldehyde and boron trifluoride, a conjugated system of pyrene formaldehyde and smaller steric hindrance cannot be utilized, so that the energy gap of the self-made fluorescent agent is larger, and electron donating groups cannot be introduced, and the wavelength is in the visible light range, so that the ink can develop color under the visible light, and the confidentiality of the ink is poor; as can be seen from comparison of experimental data of examples 1 and 2 with comparative example 2, if a plasma source is not used in the process of preparing the titanium dioxide porous microspheres, the surface of the self-made fluorescent agent microspheres cannot be introduced with electronegative ions, so that electrostatic adsorption with titanium dioxide is weaker, the stability of ink is affected, the surface titanium dioxide is less, only a small amount of cerium oxide can be introduced, the molecular chain of the self-made fluorescent agent cannot be broken incompletely, and the degradability of the ink is affected; from comparison of experimental data of examples 1 and 2 and comparative example 3, it can be found that if electrostatic spraying is not used in the process of preparing titanium dioxide porous microspheres, titanium dioxide cannot be atomized and cannot be uniformly deposited on the surfaces of self-made fluorescent agent microspheres, agglomeration is easy to occur, the crosslinking degree of the titanium dioxide and the self-made fluorescent agent microspheres is affected, and the stability of ink is reduced; from comparison of experimental data of examples 1 and 2 with comparative example 4, it can be found that if microwave treatment is not used in the process of preparing the titanium dioxide porous microspheres, self-made fluorescent agent and titanium dioxide atoms cannot react, and the self-made fluorescent agent and the titanium dioxide atoms cannot be tightly crosslinked, so that the stability of the ink is affected; from comparison of experimental data of examples 1 and 2 with comparative example 5, it was found that if cerium oxide was not introduced, the wavelength range of titanium dioxide could not be widened, the visible light activity of titanium dioxide was reduced, and the titanium dioxide could not produce free radicals and active oxygen under the catalysis of visible light, so that the self-made fluorescent agent could not be destroyed, and the ink still remained on the paper and could not be degraded, so that the confidentiality of the ink was poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (6)
1. The preparation method of the photocatalyst fluorescent ink is characterized by mainly comprising, by weight, 30-40 parts of self-made fluorescent agent, 20-30 parts of titanium dioxide, 10-15 parts of cerium oxide, 5-8 parts of ethylene glycol, 1-3 parts of glycerol and 55-65 parts of softened water;
the preparation method of the photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) Dissolving veratone in absolute ethyl alcohol with the mass of 5.5-6 times of that of the veratone, adding pyrene formaldehyde with the mass of 0.6-1.2 times of that of the veratone while stirring at a speed of 50-60 rpm, regulating the stirring speed to 200-300 rpm, adding sodium hydroxide solution with the mass fraction of 10% and the mass fraction of 6-6.5 times of that of the veratone, stirring at 200-300 rpm for 4-5 h, filtering, washing with deionized water for 3-5 times, washing with an ethanol-water mixed solvent for 4-6 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6-7 h to obtain a chalcone compound;
(2) Adding the chalcone compound into methanol with the mass of 8.5-9 times of that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass of 1-1.5 times of that of the chalcone compound and diethylamine with the mass of 0.8-0.85 times of that of the chalcone compound, heating to 51-55 ℃, reacting for 7-8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6-7, adding dichloromethane with the mass of 4-6 times of that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4-5 times in sequence, adding anhydrous magnesium sulfate until no caking appears, drying for 4-6 hours, concentrating under reduced pressure at 200rpm and 65 ℃ for 2-3 hours to obtain nitrone compounds;
(3) Adding nitrone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to a mass ratio of 1:13.5-14:9-9.5, heating to 80-85 ℃ while stirring at a speed of 100-200 rpm, reacting for 10-12 h, cooling to room temperature, concentrating under reduced pressure at 300rpm and 90 ℃ for 3-5 h, and filtering to obtain a dipyrrole compound;
(4) Placing a dipyrrole compound and dichloromethane with the mass of 80-85 times of that of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 0-5 ℃ in an ice water bath at the temperature of 0 ℃, adding a triethylamine/dichloromethane mixed solution with the mass of 16-16.5 times of that of the dipyrrole compound into the three-neck flask under a nitrogen atmosphere, wherein the mass ratio of the triethylamine to the dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding boron trifluoride diethyl ether/dichloromethane mixed solution with the mass of 18-18.5 times of that of the dipyrrole compound at the speed of 10-15 drops/min, wherein the mass ratio of boron trifluoride diethyl ether to dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution is 1:3, stirring for 24-26 hours at the speed of 100-200 rpm at room temperature, washing 4-6 times with deionized water and saturated sodium chloride sequentially, and concentrating under reduced pressure for 3-4 hours at the temperature of 300rpm to obtain a self-made fluorescent agent;
(5) Placing the self-made fluorescent agent into a spray freeze dryer, spraying, preserving heat for 30-40 min at-45 ℃, heating to-20 ℃ at a speed of 1-3 ℃/min, and preserving heat for 50-60 min to obtain self-made fluorescent agent microspheres;
(6) Placing self-made fluorescent agent microspheres in cold plasma modification treatment equipment, pretreating for 120-130 s, placing the self-made fluorescent agent microspheres in a receiving device, placing a titanium dioxide solution in a syringe, placing the titanium dioxide solution in a mass ratio of titanium dioxide to 65% hydrochloric acid of 1:3-4, establishing a high-voltage electrostatic field in a syringe nozzle and the receiving device, spraying for 100-120 s at an injection speed of 0.01-0.02 mm/s, washing with 10% sodium hydroxide to pH 6-7 by mass fraction, washing with deionized water for 5-7 times, and placing the titanium dioxide solution in a microwave reactor for 4-6 min to obtain titanium dioxide porous microspheres;
(7) Placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 30-40 s, then placing the titanium dioxide porous microspheres in a magnetron sputtering processor with sputtering power of 100-120W and vacuum degree of 0.001Pa, placing the titanium dioxide porous microspheres on a glass substrate, wherein the temperature of the substrate is 80-100 ℃, the target is cerium oxide, the distance from the target to the glass substrate is 6-10 cm, and processing for 50-70 s to obtain composite microspheres;
(8) Mixing the composite microsphere, glycol, glycerol and softened water according to the formula amount, and stirring for 5-10 min at 50-100 rpm to obtain the photocatalyst fluorescent ink.
2. The method for preparing photocatalyst fluorescent ink according to claim 1, wherein the vacuum pressure of the spray freeze dryer in the step (5) is 35-40 Pa, and the cold air volume is 5.5-6 m 3 /min。
3. The method for preparing the photocatalyst fluorescent ink according to claim 1, wherein in the step (6), the gas pressure of the cold plasma modification treatment equipment is 7-9 Pa, the discharge power is 100-120W, sulfur hexafluoride is introduced into pure argon plasma, the flow rate is 60sccm, and the flow rate ratio is 0.53.
4. The method for preparing the photocatalyst fluorescent ink according to claim 1, wherein in the step (6), the injector nozzle is a 14-16G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 30-40 kV, and the temperature is 100-120 ℃.
5. The method for preparing photocatalyst fluorescent ink according to claim 1, wherein the power of the microwave reactor in the step (6) is 160-200 w, and the frequency is 2450MHz.
6. The method for preparing photocatalyst fluorescent ink according to claim 1, wherein in the step (7), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.8-1L/min, and the treatment power is 4-6 kW.
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|---|---|---|---|---|
| US6174938B1 (en) * | 1999-05-21 | 2001-01-16 | Binney & Smith Inc. | Water-based coloring compositions containing submicron polymeric particles |
| CN1471563A (en) * | 2000-08-24 | 2004-01-28 | �̿˹�˾ | Fluorescent inks for writing instruments using fluorescent dyes and white pigments |
| JP2004149601A (en) * | 2002-10-29 | 2004-05-27 | Mitsubishi Pencil Co Ltd | Decolorizing ink composition for writing tool |
| WO2005026276A1 (en) * | 2003-09-11 | 2005-03-24 | Kabushiki Kaisha Zac | Coating material |
| JP2005131640A (en) * | 1998-11-20 | 2005-05-26 | Asahi Kasei Chemicals Corp | Self-stratifying photocatalyst composition |
| CN101284965A (en) * | 2007-04-10 | 2008-10-15 | 樊官保 | Water-based intaglio ink equal to plate engraving ink and uses thereof |
| JP2008279407A (en) * | 2007-05-14 | 2008-11-20 | Kanac Corp | Visible light response type titanium dioxide photocatalyst powder and its manufacturing method and device |
| CN103849217A (en) * | 2012-12-07 | 2014-06-11 | 上海融京化工科技有限公司 | Novel high-performance water-based fluorescent ink |
| JP2015030831A (en) * | 2013-08-06 | 2015-02-16 | ゼブラ株式会社 | Photo-erasable aqueous ink composition and marking pen |
| WO2018099383A1 (en) * | 2016-11-30 | 2018-06-07 | 苏州百源基因技术有限公司 | Near-infrared light excited fluorescent dye, preparation method therefor, and applications thereof |
| CN109504177A (en) * | 2018-11-16 | 2019-03-22 | 合肥易美特建材有限公司 | A kind of lettering pen printing ink composition of lightfast antioxidant |
| CN110373048A (en) * | 2019-07-06 | 2019-10-25 | 王志胜 | A kind of polymolecularity light stablizes the preparation method of titanium dioxide |
| CN112300790A (en) * | 2020-11-18 | 2021-02-02 | 厦门宝太生物科技有限公司 | Graphene oxide polystyrene fluorescent microsphere and preparation method thereof |
| CN112795230A (en) * | 2021-01-13 | 2021-05-14 | 董凯辉 | Preparation method of quick-drying fluorescent ink |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7378371B2 (en) * | 2001-12-21 | 2008-05-27 | Show A Denko K.K. | Highly active photocatalyst particles, method of production therefor, and use thereof |
| US7455725B2 (en) * | 2004-09-20 | 2008-11-25 | Mattel, Inc. | Washable marker ink composition |
-
2021
- 2021-11-25 CN CN202111411665.8A patent/CN113913049B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005131640A (en) * | 1998-11-20 | 2005-05-26 | Asahi Kasei Chemicals Corp | Self-stratifying photocatalyst composition |
| US6174938B1 (en) * | 1999-05-21 | 2001-01-16 | Binney & Smith Inc. | Water-based coloring compositions containing submicron polymeric particles |
| CN1471563A (en) * | 2000-08-24 | 2004-01-28 | �̿˹�˾ | Fluorescent inks for writing instruments using fluorescent dyes and white pigments |
| JP2004149601A (en) * | 2002-10-29 | 2004-05-27 | Mitsubishi Pencil Co Ltd | Decolorizing ink composition for writing tool |
| WO2005026276A1 (en) * | 2003-09-11 | 2005-03-24 | Kabushiki Kaisha Zac | Coating material |
| CN101284965A (en) * | 2007-04-10 | 2008-10-15 | 樊官保 | Water-based intaglio ink equal to plate engraving ink and uses thereof |
| JP2008279407A (en) * | 2007-05-14 | 2008-11-20 | Kanac Corp | Visible light response type titanium dioxide photocatalyst powder and its manufacturing method and device |
| CN103849217A (en) * | 2012-12-07 | 2014-06-11 | 上海融京化工科技有限公司 | Novel high-performance water-based fluorescent ink |
| JP2015030831A (en) * | 2013-08-06 | 2015-02-16 | ゼブラ株式会社 | Photo-erasable aqueous ink composition and marking pen |
| WO2018099383A1 (en) * | 2016-11-30 | 2018-06-07 | 苏州百源基因技术有限公司 | Near-infrared light excited fluorescent dye, preparation method therefor, and applications thereof |
| CN109504177A (en) * | 2018-11-16 | 2019-03-22 | 合肥易美特建材有限公司 | A kind of lettering pen printing ink composition of lightfast antioxidant |
| CN110373048A (en) * | 2019-07-06 | 2019-10-25 | 王志胜 | A kind of polymolecularity light stablizes the preparation method of titanium dioxide |
| CN112300790A (en) * | 2020-11-18 | 2021-02-02 | 厦门宝太生物科技有限公司 | Graphene oxide polystyrene fluorescent microsphere and preparation method thereof |
| CN112795230A (en) * | 2021-01-13 | 2021-05-14 | 董凯辉 | Preparation method of quick-drying fluorescent ink |
Non-Patent Citations (1)
| Title |
|---|
| 大孔/介孔Ag/AgBr/TiO_2复合光催化剂的制备及其可见光光催化活性;胡自飞等;《化学与生物工程》;20200525(第05期);第14-20页 * |
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