Preparation method of washable antibacterial polyurethane material

Abstract

The invention belongs to the technical field of polyurethane, and is particularly a method for preparing a water-resistant antibacterial polyurethane material. The polyurethane resin and a quaternary ammonium salt phthalazinone hyperbranched polymer are mixed, left to stand for degassing, cast, and thermally cured to obtain the water-resistant antibacterial polyurethane material. The hyperbranched polymer contains a three-dimensional branched molecular chain, which forms a physical chain entanglement effect with the polyurethane molecular chain, has a good toughening effect on the polyurethane material, and is beneficial to improving the tensile strength and elongation at break of the material. The hyperbranched polymer contains a carbamate group, which can form a hydrogen bond force with the carbamate group of the polyurethane, thereby improving the interfacial bonding force between the two. After washing, the hyperbranched polymer is difficult to migrate out of the polyurethane material matrix, does not affect the fracture performance of the polyurethane material, and gives the polyurethane material excellent antibacterial performance and heat resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and in particular to a method for preparing a water-washable antibacterial polyurethane material. Background Art

[0002] Polyurethane has good elasticity, shock resistance, and hydrophilicity. It can be made into foam, elastomer, fiber and other materials, and is widely used in plastics, textiles, fiber membranes, etc. Improving the mechanical strength, heat resistance, antibacterial and other properties of polyurethane products is conducive to expanding its practical application in antibacterial textiles, medical and sanitary products, etc. Patent CN109881292B discloses a method for preparing polyurethane elastic fibers with excellent antibacterial properties. A branched quaternary ammonium salt with a special structure is reacted with polyurethane to obtain a polyurethane material with good lasting antibacterial ability. However, the patent does not improve the mechanical strength, heat resistance and other properties of the polyurethane material.

[0003] Phthalocyanine compounds have high thermal decomposition temperature and heat resistance. When introduced into materials such as polyurethane and epoxy resin, the heat resistance and other properties of the materials can be improved. Hyperbranched polymers are three-dimensional macromolecules with highly branched molecular chains. The ends and molecular chains contain a large number of active functional groups, which can be made into functional materials and widely used in materials such as fibers and plastics. The present invention utilizes quaternary ammonium salt phthalazinone hyperbranched polymers to improve the strength, antibacterial and heat resistance of polyurethane materials. Summary of the invention

[0004] The technical problem solved by the invention is to provide a preparation method of a quaternary ammonium phthalazinone hyperbranched polymer and a water-washable antibacterial polyurethane material, which solves the problem that the polyurethane material has low strength and no antibacterial property, and after being washed and soaked in water, the polyurethane material still maintains good strength and antibacterial property.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0006] A method for preparing a washable antibacterial polyurethane material comprises the following steps:

[0007] Step (1): adding phthalazinone acrylate monomer and trimethylolpropane tris(thioglycolic acid) to N,N-dimethylformamide, stirring to dissolve, adding benzoin dimethyl ether, irradiating under ultraviolet light to carry out polymerization reaction, adding ethanol to dilute the solution, filtering, then adding the precipitate to N,N-dimethylformamide, adding alkyl chloride to carry out quaternization reaction, adding ethanol to dilute the solution, filtering, washing the precipitate with ethanol, and drying to obtain a quaternary ammonium phthalazinone hyperbranched polymer.

[0008] The phthalazinone acrylate monomer has the structural formula shown in the following formula (I):

[0009] Formula (I).

[0010] Step (2): adding polyurethane resin and quaternary ammonium diazinone hyperbranched polymer to N,N-dimethylformamide, stirring and mixing, injecting into a casting mold, standing for degassing, thermal curing, demolding, and obtaining a washable antibacterial polyurethane material.

[0011] Furthermore, in step (1), the molar amounts of trimethylolpropane tris(thioglycolic acid) and alkyl chloride are 65-70% and 80-200% of the molar amount of the phthalazinone acrylate monomer, respectively.

[0012] Furthermore, the molecular formula of the alkyl chloride in step (1) is ClC n H 2n+1 , n is any integer between 8 and 12.

[0013] Furthermore, in step (1), the power of the UV lamp is 300-600W, and the polymerization reaction time is 1-3h.

[0014] Furthermore, in step (2), the quaternization reaction is carried out at a temperature of 100-140° C. and for a time of 24-72 hours.

[0015] Furthermore, in step (2), the mass of the quaternary ammonium salt of diazonium phthalazinone hyperbranched polymer is 2-12% of the mass of the polyurethane resin.

[0016] Further, the preparation method of the diazonium ketone acrylate monomer comprises the following steps:

[0017] Step (a): Add N,N'-dimethylethylenediamine and 2-(ethylene oxide-2-methyl)-4-phenylphthalazinone (190-220% of the molar amount of N,N'-dimethylethylenediamine) to tetrahydrofuran, heat to 50-60°C, react for 8-12 hours, rotary evaporate, separate by silica gel column chromatography, eluent is a mixed solution of petroleum ether and ethyl acetate, gradient elution, to obtain an intermediate.

[0018] Step (b): adding the intermediate, 220-260% of the molar amount of the intermediate 2-isocyanatoethyl methacrylate, and dibutyltin dilaurate to toluene, heating to 60-75° C., reacting for 2-4 hours, rotary evaporation, and separation by silica gel column chromatography, using a mixed solution of petroleum ether and ethyl acetate as the eluent, and gradient elution to obtain a diazonium ketone acrylate monomer.

[0019] The invention has the following technical effects: the invention uses N,N'-dimethylethylenediamine, 2-(ethylene oxide-2-methyl)-4-phenylphthalazinone, 2-isocyanatoethyl methacrylate and the like as materials to prepare a phthalazinone acrylate monomer containing a tertiary amine group, a carbamate group and two alkenyl groups, and then uses the two alkenyl groups to react with trimethylolpropane tris(thioglycolic acid) containing three mercapto groups to obtain a quaternary ammonium salt phthalazinone hyperbranched polymer.

[0020] The invention utilizes quaternary ammonium salt phthalazinone hyperbranched polymer and polyurethane for blending and casting. The hyperbranched polymer contains three-dimensional branched molecular chains, which form a physical chain entanglement with the polyurethane molecular chains. The hyperbranched polymer contains carbamate groups, so it has good compatibility with the polyurethane, has a good toughening effect on the polyurethane material, and is beneficial to improving the tensile strength and elongation at break of the material.

[0021] The quaternary ammonium salt phthalazinone hyperbranched polymer contains carbamate groups, which can form hydrogen bonding forces with carbamate groups of polyurethane, thereby improving the interface bonding force between the two. After being washed with water, the hyperbranched polymer is difficult to migrate out of the polyurethane material matrix, and the fracture performance of the polyurethane material is not affected. The tensile strength retention rate and the elongation at break decrease in a small range, and the retention rate is very high.

[0022] The main chain of the quaternary ammonium salt phthalazinone hyperbranched polymer of the invention contains a large number of quaternary ammonium salt antibacterial groups, has a strong killing effect on bacteria such as Escherichia coli, and enables the polyurethane material to exhibit excellent antibacterial performance. In addition, the hyperbranched polymer has high interface bonding force with the polyurethane material, and after water washing, the hyperbranched polymer is difficult to migrate out of the polyurethane material matrix, does not affect the antibacterial performance of the polyurethane material, and has a high antibacterial retention rate.

[0023] The quaternary ammonium salt phthalazinone hyperbranched polymer contains a high temperature resistant phthalazinone structure and can be added into a polyurethane material to increase its thermal decomposition temperature, thereby making the polyurethane material have better heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is the reaction formula for preparing diazonium ketone acrylate monomer.

[0025] Figure 2 It is a reaction formula for preparing quaternary ammonium phthalazinone hyperbranched polymer. DETAILED DESCRIPTION

[0026] The polyurethane resin of the present invention is Lubrizol 5717NT1.

[0027] 2-(2-Methyl-2-oxirane)-4-phenylphthalazinone was prepared according to the method of the literature "Synthesis, Antiviral, and Antimicrobial Activity of N-and S-Alkylated Phthalazine Derivatives" (DOI No. 10.1002 / jhet.2316).

[0028] 10 mmol of 4-phenyl-1(2H)-phthalazinone ( ), 11mmol epichlorohydrin, 11mmol potassium carbonate were added to 15mL N,N-dimethylformamide, reacted for 12h, filtered and the filtrate was distilled under reduced pressure, and the product was recrystallized from ethanol to obtain 2-(ethylene oxide-2-methyl)-4-phenylphthalazinone. The structural formula is .

[0029] The implementation method is as follows:

[0030] Preparation method of phthalazinone acrylate monomer:

[0031] Step (a): Add N,N'-dimethylethylenediamine and 2-(ethylene oxide-2-methyl)-4-phenylphthalazinone (190-220% of the molar amount of N,N'-dimethylethylenediamine) to tetrahydrofuran, heat to 50-60°C, react for 8-12 hours, rotary evaporate, separate by silica gel column chromatography, eluent is a mixed solution of petroleum ether and ethyl acetate, gradient elution, to obtain an intermediate.

[0032] Step (b): adding the intermediate, 220-260% of the molar amount of the intermediate 2-isocyanatoethyl methacrylate, and dibutyltin dilaurate to toluene, heating to 60-75° C., reacting for 2-4 hours, rotary evaporation, and separation by silica gel column chromatography, using a mixed solution of petroleum ether and ethyl acetate as the eluent, and gradient elution to obtain a diazonium ketone acrylate monomer.

[0033] The preparation method of quaternary ammonium salt phthalazinone hyperbranched polymer is as follows: phthalazinone acrylate monomer and trimethylolpropane tris(thioglycolic acid) are added to N,N-dimethylformamide, stirred and dissolved, benzoin dimethyl ether is added, irradiated under a 300-600W ultraviolet lamp, and polymerization reaction is carried out for 1-3 hours, ethanol is added to the solution for dilution, and after suction filtration, the precipitate is added to N,N-dimethylformamide, and alkyl chloride is added, wherein the molar amount of trimethylolpropane tris(thioglycolic acid) and the molar amount of alkyl chloride are 65-70% and 80-200% of the molar amount of phthalazinone acrylate monomer respectively; the molecular formula of alkyl chloride is ClC n H 2n+1, n is any integer between 8 and 12; the temperature is raised to 100-140° C., and the quaternization reaction is carried out for 24-72 hours. Ethanol is added to the solution for dilution, the solution is filtered, the precipitate is washed with ethanol, and the solution is dried to obtain a quaternary ammonium salt of diazonium phthalazinone hyperbranched polymer.

[0034] The preparation method of the water-resistant antibacterial polyurethane material is as follows: polyurethane resin and quaternary ammonium diazinone hyperbranched polymer of 2-12% of the mass of the polyurethane resin are added to N,N-dimethylformamide, stirred and mixed, injected into a casting mold, allowed to stand for degassing, thermally cured, and demolded to obtain the water-resistant antibacterial polyurethane material. Embodiment 1:

[0035] (1): Add 40mmol N,N'-dimethylethylenediamine and 82mmol 2-(2-methyl-2-oxirane)-4-phenylphthalazinone to 250mL tetrahydrofuran, heat to 50℃, react for 12h, rotary evaporate, separate by silica gel column chromatography, eluent is a mixed solution of petroleum ether and ethyl acetate, gradient elution, to obtain the intermediate. Light yellow solid, actual yield 18.26g, yield 70.80%.

[0036] (2): 30 mmol of the intermediate, 78 mmol of 2-isocyanatoethyl methacrylate, and 0.42 mmol of dibutyltin dilaurate were added to 300 mL of toluene, heated to 70°C, reacted for 2 h, rotary evaporated, and separated by silica gel column chromatography. The eluent was a mixed solution of petroleum ether and ethyl acetate, and gradient eluted to obtain diazonium ketone acrylate monomer. The actual yield was 25.39 g, and the yield was 88.62%.

[0037] (3): Add 20mmol of phthalazinone acrylate monomer and 13mmol of trimethylolpropane tris(thioglycolic acid) to 180mL of N,N-dimethylformamide, stir to dissolve, add 0.08mmol of benzoin dimethyl ether, irradiate under 300W ultraviolet light, and perform polymerization reaction for 3h. Add ethanol to dilute the solution, filter and add the precipitate to 300mL of N,N-dimethylformamide, add 16mmol of 1-chlorododecane (ClC 12 H 25 ), the temperature was raised to 120°C, and the quaternization reaction was carried out for 48 hours. Ethanol was added to the solution for dilution, and the solution was filtered, and the precipitate was washed with ethanol and dried to obtain a quaternary ammonium phthalazinone hyperbranched polymer.

[0038] (4): Add 100 g of polyurethane resin and 2 g of quaternary ammonium diazinone hyperbranched polymer into 50 mL of N,N-dimethylformamide, stir to mix, inject into a casting mold, let stand to degas, heat cure at 140°C for 6 h, and demold to obtain a water-resistant antibacterial polyurethane material. Embodiment 2:

[0039] (1): Prepare diazonium ketone acrylate monomer according to the method of Example 1.

[0040] (2): Add 20 mmol of phthalazinone acrylate monomer and 13.33 mmol of trimethylolpropane tris(thioglycolic acid) to 180 mL of N,N-dimethylformamide, stir to dissolve, add 0.09 mmol of benzoin dimethyl ether, irradiate under 400 W ultraviolet light, and perform polymerization reaction for 3 h. Add ethanol to dilute the solution, filter, and then add the precipitate to 350 mL of N,N-dimethylformamide, add 23 mmol of 1-chlorodecane (ClC 10 H 21 ), the temperature was raised to 100°C, and the quaternization reaction was carried out for 72 hours. Ethanol was added to dilute the solution, and the solution was filtered, and the precipitate was washed with ethanol and dried to obtain a quaternary ammonium salt of diazonium phthalide hyperbranched polymer.

[0041] (3): Add 100 g of polyurethane resin and 5 g of quaternary ammonium diazinone hyperbranched polymer into 50 mL of N,N-dimethylformamide, stir to mix, inject into the casting mold, stand to degas, heat cure at 140°C for 6 h, and demold to obtain a water-resistant antibacterial polyurethane material. Embodiment 3:

[0042] (1): Prepare diazonium ketone acrylate monomer according to the method of Example 1.

[0043] (2): Add 20 mmol of phthalazinone acrylate monomer and 14 mmol of trimethylolpropane tris(thioglycolic acid) to 200 mL of N,N-dimethylformamide, stir to dissolve, add 0.09 mmol of benzoin dimethyl ether, irradiate under 600 W ultraviolet light, and perform polymerization reaction for 1 hour. Add ethanol to dilute the solution, filter, and then add the precipitate to 350 mL of N,N-dimethylformamide, add 32 mmol of 1-chlorodecane (ClC 10 H 21 ), the temperature was raised to 140°C, and the quaternization reaction was carried out for 24 hours. Ethanol was added to the solution for dilution, and the solution was filtered, and the precipitate was washed with ethanol and dried to obtain a quaternary ammonium salt of diazonium phthalide hyperbranched polymer.

[0044] (3): Add 100 g of polyurethane resin and 8 g of quaternary ammonium diazinone hyperbranched polymer into 50 mL of N,N-dimethylformamide, stir to mix, inject into the casting mold, stand to degas, heat cure at 140°C for 6 h, and demold to obtain a water-resistant antibacterial polyurethane material. Embodiment 4:

[0045] (1): Prepare diazonium ketone acrylate monomer according to the method of Example 1.

[0046] (2): Add 20 mmol of phthalazinone acrylate monomer and 13.3 mmol of trimethylolpropane tris(thioglycolic acid) to 180 mL of N,N-dimethylformamide, stir to dissolve, add 0.08 mmol of benzoin dimethyl ether, irradiate under 600 W ultraviolet light, and perform polymerization reaction for 1 hour. Add ethanol to dilute the solution, filter, and then add the precipitate to 400 mL of N,N-dimethylformamide, add 40 mmol of 1-chlorooctane (ClC 8 H 17 ), the temperature was raised to 140°C, and the quaternization reaction was carried out for 24 hours. Ethanol was added to the solution for dilution, and the solution was filtered, and the precipitate was washed with ethanol and dried to obtain a quaternary ammonium salt of diazonium phthalide hyperbranched polymer.

[0047] (3): Add 100 g of polyurethane resin and 12 g of quaternary ammonium diazinone hyperbranched polymer into 50 mL of N,N-dimethylformamide, stir to mix, inject into a casting mold, let stand to degas, heat cure at 140°C for 6 h, and demold to obtain a water-resistant antibacterial polyurethane material.

[0048] Comparative Example 1:

[0049] (1): Add 100 g of polyurethane resin to 50 mL of N,N-dimethylformamide, stir to mix, inject into a casting mold, let stand to degas, heat cure at 140°C for 6 h, and demold to obtain a polyurethane material.

[0050] Comparative Example 2:

[0051] (1): Prepare diazonium ketone acrylate monomer according to the method of Example 1.

[0052] (2): Add 20 mmol of diazinone acrylate monomer and 13 mmol of trimethylolpropane tri(thioglycolic acid) into 180 mL of N,N-dimethylformamide, stir to dissolve, add 0.08 mmol of benzoin dimethyl ether, irradiate under 300 W ultraviolet lamp, and carry out polymerization reaction for 3 hours. Add ethanol to dilute the solution, filter it, wash it with ethanol, and dry it to obtain diazinone hyperbranched polymer.

[0053] (3): Add 100 g of polyurethane resin and 2 g of diazonium phthalide hyperbranched polymer into 50 mL of N,N-dimethylformamide, stir to mix, inject into a casting mold, let stand to degas, heat cure at 140°C for 6 h, and demold to obtain a polyurethane material.

[0054] Comparative Example 3:

[0055] (1): Prepare diazonium ketone acrylate monomer according to the method of Example 1.

[0056] (2): 20mmol ethylene glycol dimethacrylate ( ), 13mmol trimethylolpropane tris(thioglycolic acid) was added to 180mL N,N-dimethylformamide, stirred to dissolve, 0.08mmol benzoin dimethyl ether was added, irradiated under a 300W ultraviolet lamp, and polymerization reaction was carried out for 3h, ethanol was added to dilute the solution, filtered, washed with ethanol, and dried to obtain a hyperbranched polymer.

[0057] (3): Add 100 g of polyurethane resin and 2 g of hyperbranched polymer to 50 mL of N,N-dimethylformamide, stir to mix, inject into a casting mold, let stand to degas, heat cure at 140°C for 6 h, and demold to obtain a polyurethane material.

[0058] The tensile properties of polyurethane materials were tested using a universal material testing machine according to GB / T 2567-2021. The polyurethane material was placed in 30°C water, soaked and stirred for 30 minutes, taken out and dried, and the soaking, stirring, washing and drying process was repeated 50 times in total; then the tensile properties were measured. The test results are shown in the table below.

[0059] Table 1 Polyurethane material performance test

[0060]

[0061] It can be seen from the above table that Comparative Example 1 is a common polyurethane material with a tensile strength of 35.6 MPa and an elongation at break of 461.4%.

[0062] The polyurethane materials of Examples 1-4 are added with a phthalazinone hyperbranched polymer, the hyperbranched polymer contains a three-dimensional branched molecular chain, which forms a physical chain entanglement with the polyurethane molecular chain, and the hyperbranched polymer contains a carbamate group ( ), so it has good compatibility with polyurethane and has a good toughening effect on polyurethane materials, with a tensile strength of 42.7-60.6 MPa and an elongation at break of 574.9-704.3%.

[0063] In addition, the carbamate groups of the hyperbranched polymer can form hydrogen bonding forces with the carbamate groups of the polyurethane, thereby improving the interfacial bonding strength between the two. After washing with water, the hyperbranched polymer is difficult to migrate out of the polyurethane material matrix and will not affect the fracture performance of the polyurethane material. The decrease in the tensile strength retention rate and the elongation at break is very small, and the retention rate is very high.

[0064] The diazonium ketone hyperbranched polymer added in Comparative Example 2 contains a three-dimensional branched molecular chain and a carbamate group, and has a good toughening effect on the polyurethane material, and has a strong interfacial bonding force with the polyurethane. After washing with water, the hyperbranched polymer will not migrate out of the polyurethane material matrix, and will not affect the fracture performance of the polyurethane material. The decrease in the tensile strength retention rate and the elongation at break is very small, and the retention rate is very high.

[0065] Comparative Example 3 uses ethylene glycol dimethacrylate and trimethylolpropane tris(thioglycolic acid) to carry out polymerization reaction, and the obtained hyperbranched polymer also has an improvement effect on the fracture performance of polyurethane materials, and the tensile strength and elongation at break are higher than those in Comparative Example 1. However, the hyperbranched polymer does not contain carbamate groups, and has poor compatibility with polyurethane materials, and the improvement of tensile strength and elongation at break is lower than that of each embodiment. In addition, the interfacial bonding force with polyurethane is low. After multiple washings, the hyperbranched polymer will migrate out of the material matrix, resulting in a large decrease in the tensile strength and elongation at break of the material, and the retention rate is lower than that of each embodiment.

[0066] The antibacterial properties of polyurethane materials were tested by the oscillating bottle method. Escherichia coli was used as the test strain. 5 mL of activated Escherichia coli solution (10 8 CFU / mL) was placed in a flask, and then the polyurethane material was added, with the polyurethane material of Comparative Example 1 as the control group, and the polyurethane materials of Examples 1-4 and Comparative Examples 2-3 as the experimental group; the culture was shaken on a shaker at 24°C for 12 hours. 0.5mL of the cultured bacterial solution was transferred and diluted by a ten-fold dilution method, and 0.1mL of the diluted bacterial solution was transferred and placed in a culture dish containing agar culture medium, and cultured at 37°C for 24 hours. After the culture, the colonies were counted. The antibacterial rate was calculated.

[0067] The inhibition rate W = (AB) / A, A is the number of colonies in the control group after cultivation; B is the number of colonies in the experimental group after cultivation.

[0068] The polyurethane material was placed in 30°C water, soaked and stirred for 30 minutes, taken out and dried, and the soaking, stirring, washing and drying process was repeated 50 times in total; then the antibacterial properties were measured.

[0069] Table 2 Antibacterial performance test of polyurethane materials

[0070]

[0071] The main chain of the quaternary ammonium phthalazinone hyperbranched polymer added in Example 1-4 contains a large number of quaternary ammonium antibacterial groups ( ), has a strong killing effect on bacteria such as Escherichia coli, making the polyurethane material exhibit excellent antibacterial properties, and the interfacial bonding force between the hyperbranched polymer and the polyurethane material is high. After washing, the hyperbranched polymer is difficult to migrate out of the polyurethane material matrix, and will not affect the antibacterial properties of the polyurethane material, and the antibacterial retention rate is high.

[0072] The phthalazinone hyperbranched polymer added in Comparative Example 2 and the hyperbranched polymer added in Comparative Example 3 do not contain quaternary ammonium salt antibacterial groups, and cannot impart antibacterial properties to the polyurethane material, and do not show an antibacterial rate against Escherichia coli.

[0073] The thermal properties of polyurethane materials were tested using a thermogravimetric analyzer in a nitrogen atmosphere, with the temperature rising from 25°C to 700°C at a heating rate of 10°C / min.

[0074] Table 3 Thermal performance test of polyurethane materials

[0075]

[0076] The initial thermal decomposition temperature (5% mass loss) of the polyurethane material of Comparative Example 1 is 294.6° C. The quaternary ammonium salt phthalazinone hyperbranched polymers of Examples 1-4 contain a high temperature resistant phthalazinone structure, which can be added to the polyurethane material to increase its thermal decomposition temperature to 297.6-302.6° C., making the polyurethane material have better heat resistance.

[0077] The phthalazinone hyperbranched polymer added in Comparative Example 2 also contains a phthalazinone structure, and also improves the thermal decomposition temperature and heat resistance of the polyurethane.

[0078] The hyperbranched polymer of Comparative Example 3 does not contain a phthalazinone structure and does not improve the thermal decomposition temperature and heat resistance of the polyurethane.

Claims

1. A method for preparing a washable antibacterial polyurethane material, characterized in that: The preparation method comprises the following steps: Step (1): adding phthalazinone acrylate monomer and trimethylolpropane tris(thioglycolic acid) to N,N-dimethylformamide, stirring and dissolving, adding benzoin dimethyl ether, irradiating under ultraviolet light, carrying out polymerization reaction, adding ethanol to dilute the solution, filtering, then adding the precipitate to N,N-dimethylformamide, adding alkyl chloride, carrying out quaternization reaction, adding ethanol to dilute the solution, filtering, washing the precipitate with ethanol, and drying to obtain a quaternary ammonium phthalazinone hyperbranched polymer; The phthalazinone acrylate monomer has a structural formula as shown in the following formula (I): Formula (I); Step (2): adding polyurethane resin and quaternary ammonium diazinone hyperbranched polymer to N,N-dimethylformamide, stirring and mixing, injecting into a casting mold, standing for degassing, thermal curing, demolding, and obtaining a washable antibacterial polyurethane material.

2. The method for preparing the washable antibacterial polyurethane material according to claim 1, characterized in that: In the step (1), the molar amounts of trimethylolpropane tris(thioglycolic acid) and alkyl chloride are 65-70% and 80-200% of the molar amount of the phthalazinone acrylate monomer, respectively.

3. The method for preparing the washable antibacterial polyurethane material according to claim 1, characterized in that: The molecular formula of the alkyl chloride in step (1) is ClC n H 2n+1 , n is any integer between 8 and 12.

4. The method for preparing the washable antibacterial polyurethane material according to claim 1, characterized in that: In the step (1), the power of the ultraviolet lamp is 300-600W, and the polymerization reaction time is 1-3h.

5. The method for preparing the washable antibacterial polyurethane material according to claim 1, characterized in that: The temperature of the quaternization reaction in step (2) is 100-140° C. and the time is 24-72 hours.

6. The method for preparing the washable antibacterial polyurethane material according to claim 1, characterized in that: In the step (2), the mass of the quaternary ammonium salt phthalazinone hyperbranched polymer is 2-12% of the mass of the polyurethane resin.

7. The method for preparing the washable antibacterial polyurethane material according to claim 2, characterized in that: The preparation method of the diazonium ketone acrylate monomer comprises the following steps: Step (a): Add N,N'-dimethylethylenediamine and 2-(ethylene oxide-2-methyl)-4-phenylphthalazinone (190-220% of the molar amount of N,N'-dimethylethylenediamine) to tetrahydrofuran, raise the temperature to 50-60°C, react for 8-12 hours, rotary evaporate, and separate by silica gel column chromatography to obtain an intermediate; Step (b): adding the intermediate, 2-isocyanatoethyl methacrylate and dibutyltin dilaurate to toluene, performing rotary evaporation after the reaction, and performing silica gel column chromatography separation to obtain a phthalazinone acrylate monomer.

8. The method for preparing the washable antibacterial polyurethane material according to claim 7, characterized in that: In the step (b), the molar amount of 2-isocyanatoethyl methacrylate is 220-260% of the molar amount of the intermediate.

9. The method for preparing the washable antibacterial polyurethane material according to claim 7, characterized in that: In the step (b), the reaction temperature is 60-75° C. and the reaction time is 2-4 hours.

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