A transition metal antibacterial fluorescent aqueous polyurethane material, preparation method thereof and application thereof

Abstract

The present invention relates to the technical field of luminescent materials, and specifically relates to a transition metal antibacterial fluorescent waterborne polyurethane material, a preparation method thereof, and an application thereof. First, salicylaldehyde and ethanolamine are used as reactants to obtain Schiff base salicylaldehyde ethanolamine by reflux heating; salicylaldehyde ethanolamine is used as a ligand to reflux with zinc acetate to prepare a blue fluorescent transition metal complex. The polymer polyol and isocyanate are reacted and condensed, and then a hydrophilic group is introduced through a chain extension reaction and then reacted with transition metal complex powders in different proportions, and they are incorporated into the polyurethane molecular chain segment, and then emulsified and the organic solvent is removed to obtain an antibacterial blue fluorescent waterborne polyurethane material. The fluorescent waterborne polyurethane prepared by the present invention has the characteristics of good storage stability, high fluorescence intensity, environmental friendliness, high antibacterial rate, etc., and has the advantages of convenient use, recyclability, wide application fields, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and particularly to a transition metal antibacterial fluorescent waterborne polyurethane material, a preparation method thereof, and an application thereof. Background Art

[0002] Waterborne polyurethane is a polymer material that is environmentally friendly and pollution-free during the production process. It has been widely used in fields such as leather, coatings, and films. According to different usage scenarios, different formulations can effectively adjust the performance of waterborne polyurethane materials. Through chemical structure adjustment, different functions can also be imparted to waterborne polyurethane materials. When it is applied in fields such as marking anti-counterfeiting, medical treatment, and food, waterborne polyurethane is required to have fluorescence and antibacterial properties. Therefore, developing a cheap and easily prepared fluorescent waterborne polyurethane material is an urgent issue to be solved.

[0003] Transition metals can coordinate with multiple ligands of the same or different types. Their coordination numbers are complex and variable, and the formed complexes have peculiar structures and unusual properties, which have attracted extensive attention and achieved excellent research results. Due to the excellent fluorescence, catalytic, and antibacterial properties of transition metal complexes, they are widely used in catalytic materials, magnetic materials, fluorescent materials, and other materials. Transition metal complexes have the advantages of rich variety, low cost, and easy preparation. A large number of experiments show that the coordination of transition metals with ligands can enhance the fluorescence performance and improve the quantum yield. And because the complexes have good liposolubility, they can better penetrate the microbial cell wall. Subsequently, under the combined action of transition metal ions and complexes, the activity of microbial bioenzymes is affected, and their normal life activities are affected, achieving an antibacterial effect. However, due to the fact that transition metal complexes are usually in the form of solid powders and are difficult to process and utilize, their application and development are limited.

[0004] In view of the above defects, the creator of the present invention finally obtained the present invention through long-term research and practice. Summary of the Invention

[0005] The purpose of the present invention is to solve the problem that the compatibility between transition metal complexes in the form of solid powders and polymer polymers is poor, and it is difficult to process and form, which limits the application of transition metal complexes. The present invention provides a transition metal antibacterial fluorescent waterborne polyurethane material, a preparation method thereof, and an application thereof.

[0006] In order to achieve the above purpose, the present invention discloses a preparation method of a transition metal antibacterial fluorescent waterborne polyurethane material, including the following steps:

[0007] S1, dissolve salicylaldehyde and ethanolamine in anhydrous methanol, stir and reflux at 60 °C under hydrothermal conditions for 4 h. After cooling to room temperature, remove the solvent to obtain Schiff base salicylaldehyde ethanolamine;

[0008] S2. Dissolve Schiff base salicylaldehyde ethanolamine and zinc acetate in methanol, stir and reflux at 60 °C under hydrothermal conditions for 6 h, cool to room temperature, dissolve the remaining liquid in methanol after removing the solvent, and obtain the precipitated zinc complex of salicylaldehyde ethanolamine after standing.

[0009] S3. Dehydrate isocyanate and polymer polyol respectively. Under nitrogen protection, heat up the dehydrated isocyanate and polymer polyol and stir to react, add a diol chain extender, continue to react, then add a catalyst and an organic solvent, stir and react at 70 - 80 °C for 2 - 3 h, add a hydrophilic chain extender, and stir and react at 60 - 80 °C for 2 - 3 h to generate a polyurethane prepolymer, and cool it for later use.

[0010] S4. Add the ground powder of the zinc complex of salicylaldehyde ethanolamine obtained in step S2 to the polyurethane prepolymer obtained in step S3, stir and react at 75 - 80 °C for 4 h, cool to 30 - 40 °C, add 1.05 - 1.04 parts of a neutralizing agent, continue to stir for 20 - 30 min, add 150 parts of ultrapure water and disperse at high speed for 20 - 30 min, and rotary evaporate the organic solvent at 45 - 60 °C to obtain a transition metal antibacterial fluorescent waterborne polyurethane material.

[0011] In step S1, the dosage ratio of salicylaldehyde, ethanolamine, and methanol is 0.01 mol:0.01 mol:100 mL.

[0012] In step S2, the dosage ratio of salicylaldehyde ethanolamine, zinc acetate, and methanol is 0.02 mol:0.01 mol:100 mL.

[0013] In step S3, the isocyanate is any one or a combination of several of isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, 1,6 - hexane diisocyanate, methylcyclohexyl diisocyanate, 4,4 - diphenylmethane diisocyanate, methylcyclohexyl diisocyanate, 1,5 - naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, methylcyclohexyl diisocyanate.

[0014] The polymer polyol is any one or a combination of several of polyethylene glycol - propylene glycol adipate diol, polytetrahydrofuran diol, polybutadiene diol, polypropylene glycol, polyethylene glycol adipate diol, tetrahydrofuran - propylene oxide copolymer diol, castor oil adipate diol, polybutadiene - acrylonitrile alcohol, polyethylene glycol adipate diol, polycarbonate 1,6 - hexanediol ester diol, polycaprolactone diol, and polyethylene adipate - 1,4 - butanediol ester diol.

[0015] The mass ratio of isocyanate, polymer polyol, diol chain extender, catalyst, organic solvent, and hydrophilic chain extender in step S3 is 10 - 5:10 - 20:1.5 - 2.5:0.01 - 0.02:50:1.5 - 2.0.

[0016] In step S4, the mass of the neutralizing agent is 1.4 - 1.05 parts, and the mass of ultrapure water is 150 parts.

[0017] In step S4, the organic solvent is any one or a combination of acetone, cyclohexanone, methyl ethyl ketone, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, toluene, ethyl acetate, dioxane;

[0018] The hydrophilic chain extender is any one or a combination of two of sodium 1,4-butylene glycol-2-sulfonate, sodium 1,2-propylene glycol-3-sulfonate, sodium ethylenediaminoethanesulfonate, and its homologues, derivatives, and isomers;

[0019] The diol chain extender is any one or a combination of polyethylene glycol 1,6-hexanediol, diethylene glycol, dipropylene glycol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,4-butanediol;

[0020] The catalyst is any one or a combination of organotin catalysts and tertiary amine catalysts.

[0021] The organotin catalysts are any one or a combination of dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, and the tertiary amine catalysts are any one or a combination of N,N-dimethylcyclohexylamine, triethylenediamine, tetramethyl-1,4-butanediamine, pentamethyldiethylenetriamine.

[0022] In step S4, the neutralizing agent is any one or a combination of potassium hydroxide, sodium hydroxide, ammonia water, triethylamine, sodium bicarbonate.

[0023] The present invention also discloses a transition metal antibacterial fluorescent waterborne polyurethane material prepared by the above preparation method.

[0024] The synthesis process of salicylaldehyde ethanolamine (HL) and transition metal salicylaldehyde ethanolamine (ZnL2) in the present invention is as follows:

[0025]

[0026] The synthesis process of transition metal antibacterial fluorescent waterborne polyurethane is as follows:

[0027]

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] 1. The present invention endows polyurethane with excellent fluorescence performance and antibacterial performance through transition metal complexes;

[0030] 2. In the present invention, salicylaldehyde and ethanolamine are used to generate Schiff base, and then complexed with zinc ions to prepare zinc salicylaldehyde ethanolamine complex. The complex is incorporated into the polyurethane polymer chain segment by reacting the remaining hydroxyl groups on the complex with isocyanate groups through chemical bonds, obtaining a fluorescent polyurethane material with stable fluorescence performance and antibacterial performance at the same time.

[0031] 3. When the zinc salicylaldehyde ethanolamine complex is incorporated into the polyurethane polymer chain segment, the fluorescence chromaticity is uniform, and the transition metal complex is stably compatible with the polyurethane emulsion. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a flow chart of the preparation method of the transition metal fluorescent antibacterial waterborne polyurethane material of the present invention;

[0033] Figure 2 is the fluorescence diagram of the transition metal fluorescent antibacterial waterborne polyurethane materials prepared in Examples 1-3 and Comparative Example 1;

[0034] Figure 3 is the fluorescence emission spectrum diagram and the corresponding CIE coordinate diagram of Examples 1-3;

[0035] Figure 4 is the antibacterial effect diagram of the transition metal fluorescent antibacterial waterborne polyurethane materials prepared in Examples 1-3 and Comparative Example 1 against Escherichia coli. DETAILED DESCRIPTION OF THE INVENTION

[0036] The above and other technical features and advantages of the present invention will be described in more detail below with reference to the accompanying drawings.

[0037] A preparation method of an antibacterial fluorescent tunable waterborne polyurethane material, as Figure 1 shown, includes the following operating steps:

[0038] S1: Dissolve salicylaldehyde and ethanolamine in anhydrous methanol, place it under hydrothermal conditions at 60 °C and stir and reflux for 4 hours, then cool to room temperature, remove the solvent at 45 °C through a rotary evaporation device, and the remaining yellow liquid is Schiff base salicylaldehyde ethanolamine; the dosage ratio of salicylaldehyde, ethanolamine, and methanol is 0.01 mol: 0.01 mol: 100 mL;

[0039] S2: Dissolve Schiff base salicylaldehyde ethanolamine and zinc acetate in methanol. Place it under hydrothermal conditions at 60 °C and stir and reflux for 6 hours. Then cool it to room temperature. After removing the solvent through a rotary evaporation device at 45 °C, dissolve the remaining liquid in a small amount of methanol. After standing for a period of time, the precipitate is the zinc complex of salicylaldehyde ethanolamine. The dosage ratio of salicylaldehyde ethanolamine, zinc acetate, and methanol is 0.02 mol: 0.01 mol: 100 mL;

[0040] S3: Dehydrate the polymer polyol and isocyanate under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 100 - 110 °C for 6 h; Grind the zinc complex of salicylaldehyde ethanolamine into powder and dehydrate it under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 60 °C for 12 h. The isocyanate is any one or a combination of isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, 1,6 - hexane diisocyanate, methylcyclohexyl diisocyanate, 4,4 - diphenylmethane diisocyanate, methylcyclohexyl diisocyanate, 1,5 - naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, methylcyclohexyl diisocyanate; The polymer polyol is any one or a combination of polyethylene glycol - propylene glycol adipate diol, polytetrahydrofuran diol, polybutadiene diol, polypropylene glycol, polyethylene glycol bis(2 - hydroxyethyl) adipate diol, tetrahydrofuran - propylene oxide copolymer diol, castor oil adipate diol, polybutadiene - acrylonitrile alcohol, polyethylene glycol adipate diol, poly(1,6 - hexanediol carbonate) diol, polycaprolactone diol, and its poly(1,4 - butanediol adipate) diol.

[0041] S4: Under nitrogen protection, heat 10 - 15 parts of isocyanate and 10 - 20 parts of polymeric polyol in S2 to 80 - 90 °C and stir for 2 - 3 h. Then add 1.5 - 2.5 parts of diol chain extender, 0.01 - 0.02 parts of catalyst, 50 parts of organic solvent, and stir at 75 - 80 °C for 2 - 3 h. After that, add 1.5 - 2.0 parts of hydrophilic chain extender and stir at 60 - 80 °C for 2 - 3 h to form a polyurethane prepolymer. Add the ground powder of 0.01 - 0.1 parts by total mass of zinc complex of salicylaldehyde - ethanolamine to the obtained polyurethane prepolymer, stir and react at 75 - 80 °C for 4 h, cool to 30 - 40 °C, add 1.04 - 1.05 parts of neutralizer, continue to stir for 20 - 30 min, add 150 parts of ultrapure water and disperse at high speed for 20 - 30 min, and rotary evaporate the organic solvent at 45 - 60 °C to obtain the transition metal antibacterial fluorescent water - borne polyurethane material. The organic solvent in the above step is any one or a combination of acetone, cyclohexanone, butanone, dimethyl sulfoxide, N,N - dimethylformamide, tetrahydrofuran, toluene, ethyl acetate, dioxane; the hydrophilic chain extender is any one or a combination of two of 1,4 - butanediol - 2 - sulfonate, 1,2 - propanediol - 3 - sulfonate, ethylenediaminoethanesulfonate and its homologues, derivatives and isomers; the diol chain extender is any one or a combination of more of 1,6 - hexanediol, diethylene glycol, dipropylene glycol, ethylene glycol, 1,2 - propanediol, neopentyl glycol, 1,4 - butanediol; the catalyst is any one or a combination of more of organotin catalysts and tertiary amine catalysts; the organotin catalysts are one or more of dibutyltin diacetate, dibutyltin dilaurate, stannous octoate; the tertiary amine catalysts are any one or a combination of more of N,N - dimethylcyclohexylamine, triethylenediamine, tetramethyl - 1,4 - butanediamine, pentamethyldiethylenetriamine.

[0042] Example 1

[0043] Dissolve 1.05 g of salicylaldehyde and 0.6 g of ethanolamine in 100 mL of anhydrous methanol, place it under hydrothermal conditions at 60 °C and stir and reflux for 4 hours, then cool to room temperature. Remove the solvent through a rotary evaporation device at 45 °C. The remaining yellow liquid is Schiff base salicylaldehyde - ethanolamine. Dissolve 3.3 g of salicylaldehyde - ethanolamine and 1.1 g of zinc acetate in 100 mL of methanol, place it under hydrothermal conditions at 60 °C and stir and reflux for 6 hours, then cool to room temperature. Dissolve the remaining liquid after removing the solvent through a rotary evaporation device at 45 °C in a small amount of methanol. After standing for a period of time, the precipitate is zinc complex of salicylaldehyde - ethanolamine;

[0044] Polybutylene glycol 1000 and isocyanate were dehydrated for 6 h respectively under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 100 - 110 °C; the zinc complex of salicylaldehyde ethanolamine was ground into powder and dehydrated for 12 h under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 60 °C.

[0045] Under the protection of a nitrogen atmosphere, 20 g of isophorone diisocyanate and 19 g of polybutylene glycol 1000 were added to a four-necked flask. The temperature was raised to 90 °C and maintained for 2 h, and after it was cooled to 80 °C, 3.2 g of 2,2-dimethylolbutanoic acid was added and maintained for 2 h. Then, 3 g of 1,4-butanediol was added. During the polymerization process, 0.135 g of dibutyltin dilaurate was added dropwise to the flask, and an appropriate amount of acetone was added to dilute the viscosity of the reaction system. Subsequently, 0.226 g of the zinc complex of salicylaldehyde ethanolamine dispersed in acetone was added to the reaction system for 4 h. The system was cooled to 40 °C, and 2 g of triethylamine was poured into the mixture as a neutralizing agent for 30 min. Finally, deionized water was poured into the mixture at a shear rate of 3000 rpm for 30 min. After removing acetone at 40 °C using a rotary evaporator under reduced pressure, a transition metal fluorescent antibacterial aqueous polyurethane emulsion was obtained. This aqueous polyurethane emulsion emits blue fluorescence under 365 nm ultraviolet light irradiation (as Figure 2 Figure 3 shown), and the antibacterial rate against Escherichia coli reaches 99.999% (as Figure 4 shown).

[0046] Example 2

[0047] 1.05 g of salicylaldehyde and 0.6 g of ethanolamine were dissolved in 100 mL of anhydrous methanol, and after being placed under hydrothermal conditions at 60 °C and stirred and refluxed for 4 h, it was cooled to room temperature. The solvent was removed at 45 °C through a rotary evaporation device. The remaining yellow liquid was the Schiff base salicylaldehyde ethanolamine. 3.3 g of salicylaldehyde ethanolamine and 1.1 g of zinc acetate were dissolved in 100 mL of methanol, and after being placed under hydrothermal conditions at 60 °C and stirred and refluxed for 6 h, it was cooled to room temperature. The liquid remaining after removing the solvent at 45 °C through a rotary evaporation device was dissolved in a small amount of methanol, and the precipitate obtained after standing for a period of time was the zinc complex of salicylaldehyde ethanolamine;

[0048] Polybutylene glycol 1000 and isocyanate were dehydrated for 6 h respectively under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 100 - 110 °C; the zinc complex of salicylaldehyde ethanolamine was ground into powder and dehydrated for 12 h under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 60 °C

[0049] Under the protection of a nitrogen atmosphere, 20 g of isophorone diisocyanate and 19 g of polybutylene glycol 1000 were added to a four-necked flask. The temperature was raised to 90 °C and maintained for 2 h, and after cooling to 80 °C, 3.2 g of 2,2-dimethylolbutanoic acid was added and maintained for 2 h. Then, 3 g of 1,4-butanediol was added. During the polymerization process, 0.135 g of dibutyltin dilaurate was added dropwise to the flask, and an appropriate amount of acetone was added to dilute the viscosity of the reaction system. Subsequently, 0.452 g of zinc salicylaldehyde ethanolamine complex dispersed in acetone was added to the reaction system for 4 h. The system was cooled to 40 °C, and 2 g of triethylamine was poured into the mixture as a neutralizing agent for 30 min. Finally, deionized water was poured into the mixture at a shear rate of 3000 rpm for 30 min. After removing acetone at 40 °C using a rotary evaporator under reduced pressure, a transition metal fluorescent antibacterial aqueous polyurethane emulsion was obtained. This aqueous polyurethane emulsion emits blue fluorescence under ultraviolet light irradiation at 365 nm (as Figure 2 , Figure 3 shown), and the antibacterial rate against Escherichia coli reaches 99.999%.

[0050] Comparative Example 1

[0051] Polybutylene glycol 1000 and isocyanate were dehydrated for 6 h under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 100 - 110 °C respectively; the zinc salicylaldehyde ethanolamine complex was ground into powder and dehydrated for 12 h under the conditions of a vacuum degree ≤ 0.1 MPa and a temperature of 60 °C;

[0052] Under the protection of a nitrogen atmosphere, 20 g of isophorone diisocyanate and 19 g of polybutylene glycol 1000 were added to a four-necked flask. The temperature was raised to 90 °C and maintained for 2 h, and after cooling to 80 °C, 3.2 g of 2,2-dimethylolbutanoic acid was added and maintained for 2 h. Then, 3 g of 1,4-butanediol was added. During the polymerization process, 0.135 g of dibutyltin dilaurate was added dropwise to the flask, and an appropriate amount of acetone was added to dilute the viscosity of the reaction system. The system was cooled to 40 °C, and 2 g of triethylamine was poured into the mixture as a neutralizing agent for 30 min. Finally, deionized water was poured into the mixture at a shear rate of 3000 rpm for 30 min. After removing acetone at 40 °C using a rotary evaporator under reduced pressure, an aqueous polyurethane emulsion was obtained. This aqueous polyurethane emulsion has no fluorescent effect and no antibacterial effect.

[0053] The above are only the preferred embodiments of the present invention, which are illustrative rather than restrictive to the present invention. Those skilled in the art understand that many changes, modifications, and even equivalents can be made within the spirit and scope defined by the claims of the present invention, but all will fall within the protection scope of the present invention.

Claims

1. A preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material, characterized in that, It includes the following steps: S1. Dissolve salicylaldehyde and ethanolamine in anhydrous methanol, stir and reflux at 60 °C under hydrothermal conditions for 4 h. After cooling to room temperature, remove the solvent to obtain Schiff base salicylaldehyde ethanolamine; S2. Dissolve Schiff base salicylaldehyde ethanolamine and zinc acetate in methanol, stir and reflux at 60 °C under hydrothermal conditions for 6 h. After cooling to room temperature, dissolve the remaining liquid in methanol after removing the solvent, and let it stand to obtain the precipitate zinc complex of salicylaldehyde ethanolamine; S3. Dehydrate isocyanate and polymer polyol respectively. Under nitrogen protection, heat up the dehydrated isocyanate and polymer polyol and stir to react, add a diol chain extender, continue to react, then add a catalyst and an organic solvent, stir and react at 70 - 80 °C for 2 - 3 h, then add a hydrophilic chain extender, stir and react at 60 - 80 °C for 2 - 3 h to generate a polyurethane prepolymer, and cool it down for standby; S4. Add the ground powder of the zinc complex of salicylaldehyde ethanolamine obtained in step S2 into the polyurethane prepolymer obtained in step S3, stir and react at 75 - 80 °C for 4 h, cool down to 30 - 40 °C, add a neutralizer, continue to stir for 20 - 30 min, add ultrapure water and disperse at high speed for 20 - 30 min, and rotary evaporate the organic solvent at 45 - 60 °C to obtain a transition metal antibacterial fluorescent waterborne polyurethane material.

2. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, In step S1, the dosage ratio of salicylaldehyde, ethanolamine, and methanol is 0.01 mol:0.01 mol:100 mL.

3. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, In step S2, the dosage ratio of salicylaldehyde ethanolamine, zinc acetate, and methanol is 0.02 mol:0.01 mol:100 mL.

4. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, The isocyanate in step S3 is any one or several combinations of isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, 1,6 - hexane diisocyanate, methylcyclohexyl diisocyanate, 4,4 - diphenylmethane diisocyanate, methylcyclohexyl diisocyanate, 1,5 - naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, methylcyclohexyl diisocyanate; The polymer polyol is any one or more combinations of polyethylene - propylene adipate diol, polytetrahydrofuran diol, polybutadiene diol, polypropylene glycol, polyethylene glycol adipate diol, tetrahydrofuran - propylene oxide copolymer diol, castor oil adipate diol, polybutadiene - acrylonitrile alcohol, polyethylene adipate diol, polycarbonate 1,6 - hexanediol ester diol, polycaprolactone diol, and polyethylene adipate - 1,4 - butanediol ester diol.

5. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, In step S3, the mass fraction ratio of the isocyanate, polymer polyol, diol chain extender, catalyst, organic solvent, and hydrophilic chain extender is 10 - 5:10 - 20:1.5 - 2.5:0.01 - 0.02:50:1.5 - 2.

0.

6. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, In step S4, the mass fraction of the neutralizer is 1.4 - 1.05 parts, and the mass fraction of ultrapure water is 150 parts.

7. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, In the step S4, the organic solvent is any one or a combination of acetone, cyclohexanone, methyl ethyl ketone, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, toluene, ethyl acetate, and dioxane; The hydrophilic chain extender is 2,2-dimethylolbutyric acid; The diol chain extender is any one or a combination of 1,6-hexanediol, diethylene glycol, dipropylene glycol, ethylene glycol, 1,2-propanediol, neopentyl glycol, and 1,4-butanediol; The catalyst is any one or a combination of organotin catalysts and tertiary amine catalysts.

8. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 7, characterized in that, The organotin catalyst is any one or a combination of dibutyltin diacetate, dibutyltin dilaurate, and stannous octoate, and the tertiary amine catalyst is any one or a combination of N,N-dimethylcyclohexylamine, triethylenediamine, tetramethyl-1,4-butanediamine, and pentamethyldiethylenetriamine.

9. The preparation method of a transition metal antibacterial fluorescent aqueous polyurethane material according to claim 1, characterized in that, In the step S4, the neutralizing agent is any one or a combination of potassium hydroxide, sodium hydroxide, ammonia water, triethylamine, and sodium bicarbonate.

10. A transition metal antibacterial fluorescent aqueous polyurethane material prepared by the preparation method according to any one of claims 1 to 9.

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