A weather-resistant antibacterial adhesive and preparation method thereof

Abstract

The present invention relates to the field of adhesive technology and discloses a weather-resistant antibacterial adhesive and its preparation method. The preparation method comprises: reacting a zinc oxide / carbon nitride composite material with ethyl bromide, followed by further reaction with methyl iodide to obtain an antibacterial agent; mixing modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate to obtain a modified acrylate monomer; reacting a polyurethane prepolymer with the modified acrylate monomer to obtain a modified polyurethane acrylate; and mixing the modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, an antibacterial agent, and a photoinitiator to obtain a weather-resistant antibacterial adhesive.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and in particular to a weather-resistant antibacterial adhesive and a preparation method thereof. Background Art

[0002] Polyurethane adhesives are adhesives containing highly polar urethane and isocyanate groups in their molecular chains, offering advantages such as adjustable hardness, low-temperature resistance, and excellent flexibility. Adhesives prepared from polyurethane as a matrix exhibit excellent adhesion to a variety of materials, as the polar groups in the polyurethane molecular structure can react with substances containing active hydrogen to form hydrogen bonds, covalent bonds, and other chemical bonds with high bond energy. These adhesives also possess excellent low-temperature resistance and abrasion resistance. UV-curing adhesives offer advantages such as fast curing speeds and excellent overall performance. Due to its unique molecular structure, polyurethane acrylates, after curing, combine the excellent bonding and fatigue resistance of polyurethane with the weather resistance and good adhesion of acrylates. Furthermore, the process is simple and easy to produce, making them widely used in many fields.

[0003] Existing technology, such as Chinese patent application CN109401719A, discloses a dual-cure polyurethane hot melt adhesive, its preparation method, and its use. This adhesive is synthesized by adding additives such as 2-(4-benzoyl-3-hydroxyphenoxy)ethyl methacrylate, a silane coupling agent, fumed silica, and a tackifying resin to a polyurethane prepolymer. This is then blended with an acrylate diluent to improve the compatibility of the components. The resulting polyurethane hot melt adhesive exhibits high initial bond strength, good toughness, strong weather resistance, and ease of application. However, the polyurethane adhesive produced by this method suffers from poor antibacterial properties, limiting its application. Summary of the Invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a weather-resistant antibacterial adhesive and a preparation method thereof, wherein the adhesive has weather resistance and antibacterial properties and good mechanical properties.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a weather-resistant antibacterial adhesive comprises the following steps:

[0007] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0008] The antibacterial agent is prepared by the following steps:

[0009] Step (1), mixing graphite phase carbon nitride, zinc acetate, and water, adding a regulator to adjust the pH value, ultrasonically dispersing, dropwise adding a polyethyleneimine aqueous solution, reacting after the dropwise addition is complete, centrifuging, filtering, washing, and drying to obtain a zinc oxide / carbon nitride composite material;

[0010] Step (2), mixing the zinc oxide / carbon nitride composite material with ethanol with ultrasonication, adding ethyl bromide, reacting, adding methyl iodide after the reaction is completed, continuing the reaction, filtering, washing, and drying to obtain an antibacterial agent;

[0011] The modified acrylate monomer comprises the following steps of preparation:

[0012] 1-allylimidazole, 2-bromoethanol, and acetonitrile are mixed and reacted, and after the reaction is completed, the mixture is purified and dried to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate are mixed to obtain a modified acrylate monomer;

[0013] Step 2: Mix polytetramethylene ether glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate, and perform a first reaction. After the reaction is completed, 1,4-butanediol is added and a second reaction is performed. After the reaction is completed, a polyurethane prepolymer is obtained. Mix the polyurethane prepolymer, a modified acrylate monomer, and p-hydroxyanisole and perform a third reaction. After the reaction is completed, a modified polyurethane acrylate is obtained.

[0014] Step 3: Mix and stir the modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone. After stirring evenly, add the antibacterial agent and the photoinitiator, and continue stirring to obtain a weather-resistant antibacterial adhesive.

[0015] Preferably, when preparing the antibacterial agent, in step (1), the mass ratio of graphite phase carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 1-2:4.5-8:50-80:10-11, and the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.1-0.15:10; the dropwise addition conditions are: dropwise addition for 8-10 minutes under a pH value of 10-11; and the reaction conditions are: reaction at a temperature of 150-160°C for 10-12 hours.

[0016] Preferably, the conditioning agent comprises a 1 mol / L sodium hydroxide aqueous solution; and the washing liquid of the washing operation comprises water and ethanol.

[0017] Preferably, when preparing the antibacterial agent, in step (2): the mass ratio of the zinc oxide / carbon nitride composite material, ethanol, ethyl bromide, and methyl iodide is 10:20-30:4-5:4-5; the reaction conditions are: react at room temperature for 12-14 hours; and the continued reaction conditions are: continue the reaction at room temperature for 12-14 hours.

[0018] Preferably, the washing liquid of the washing operation comprises water and ethanol.

[0019] Preferably, in the preparation of the modified acrylate monomer, the mass ratio of 1-allylimidazole, 2-bromoethanol, and acetonitrile is 1-1.1:1.25-1.3:20-25; the reaction conditions are: reaction in a nitrogen atmosphere at a temperature of 70-80°C for 45-48 hours; and the mass ratio of modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate is 1:1:1-2.

[0020] Preferably, the purification operation comprises: removing the solvent acetonitrile by rotary evaporation at a temperature of 70-80° C. to obtain a reaction product, and washing the reaction product three times by adding ether in an amount 3-5 times the mass of the reaction product.

[0021] Preferably, in the step 2, the molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.8-1:0.4-0.5:2.5-3:0.3-0.5, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol; the mass ratio of polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole is 10-12:1:0.04-0.05; the first reaction conditions are: a first reaction in a nitrogen atmosphere at a temperature of 50-65°C for 2-3h; the second reaction conditions are: a second reaction in a nitrogen atmosphere at a temperature of 65-75°C for 2-3h; and the third reaction conditions are: a third reaction in a nitrogen atmosphere at a temperature of 70-85°C for 1-2h.

[0022] Preferably, in step three, the mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent, and photoinitiator is 100-120:6-8:5-6:30-40:6-8:2-3.

[0023] Preferably, a weather-resistant antibacterial adhesive is prepared by the preparation method of the weather-resistant antibacterial adhesive as described above.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] Graphitic carbon nitride is a lamellar two-dimensional material with layers connected by van der Waals forces. It has a regular six-membered ring and π electron conjugation system, forming a unique electronic structure. This structure enables graphitic carbon nitride to have a certain absorption effect on ultraviolet light. Adding it to polyurethane acrylate-based adhesives can improve the aging resistance and mechanical properties of the adhesive.

[0026] The present invention synthesizes zinc oxide particles in situ on the surface of the graphite-phase carbon nitride through the chelation of zinc ions by amino groups of graphite-phase carbon nitride and polyethyleneimine, so that the surface of the zinc oxide / carbon nitride composite material has amino groups. Then, the amino groups are alkylated to convert some of the amino groups into quaternary ammonium salts, thereby obtaining an antibacterial agent having an amino group and a quaternary ammonium salt structure on the surface. The quaternary ammonium salt and zinc oxide can form a dual antibacterial activity mechanism, and the graphite-phase carbon nitride and the zinc oxide particles have a synergistic anti-ultraviolet aging effect, so that the weather resistance and antibacterial properties of the antibacterial agent are improved. Simultaneously, the antibacterial agent surface has an active group amino group, which can interact with the matrix to improve the dispersibility and compatibility of the antibacterial agent in the matrix.

[0027] The present invention utilizes a quaternization reaction between allyl imidazole and 2-bromoethanol to form a complex between the imidazole ring and the quaternary ammonium salt structure, thereby enhancing antibacterial properties. Furthermore, the imidazole ring, which contains hydroxyl groups, can react with the terminal isocyanate groups of the polyurethane prepolymer, resulting in a modified polyurethane acrylate with enhanced antibacterial properties. Furthermore, the imidazole ring, as a polar group, can increase the intermolecular forces of the polyurethane acrylate, thereby improving the mechanical properties of the matrix.

[0028] In the present invention, bishydroxy polydimethylsiloxane is introduced into the polymerization reaction of polyurethane acrylate, copolymerizing the bishydroxy polydimethylsiloxane within the molecular chain, thereby improving the water resistance and adhesion of the substrate. The modified polyurethane acrylate is mixed with trimethylolpropane triacrylate, acetone, glycidyl methacrylate, an antimicrobial agent, and a photoinitiator. The glycidyl methacrylate provides carbon-carbon double bonds and epoxy-active groups in the curing system, which not only participate in the photocuring reaction but also react with amino groups on the surface of the antimicrobial agent to form a ring-opening group, thereby improving the compatibility between the antimicrobial agent and the substrate. The resulting adhesive exhibits weather resistance, antimicrobial properties, and excellent mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a process flow chart for preparing the weather-resistant antibacterial adhesive of the present invention;

[0030] Figure 2 It is a line graph of the antibacterial rates of Examples 1-5 and Comparative Examples 1-3 in the performance test of the present invention. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] This embodiment discloses a method for preparing a weather-resistant antibacterial adhesive, comprising the following steps:

[0034] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0035] The antibacterial agent is prepared by the following steps:

[0036] Step (1), mixing graphite phase carbon nitride, zinc acetate, and water, adding 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, ultrasonically dispersing at 40°C for 30 minutes, adding polyethyleneimine aqueous solution dropwise for 8 minutes, reacting at 150°C for 12 hours after the addition is complete, centrifuging, filtering, taking the filter cake, adding water 5 times the mass of the filter cake and ethanol, washing three times in sequence, and drying at 50°C for 28 hours to obtain a zinc oxide / carbon nitride composite material;

[0037] The mass ratio of graphite carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 1:4.5:50:10; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.1:10;

[0038] Step (2), mixing the zinc oxide / carbon nitride composite material with ethanol in a mass ratio of 1:20 by ultrasonication, adding ethyl bromide, reacting at room temperature for 12 hours, adding iodomethane, and continuing to react at room temperature for 12 hours, filtering, taking the filter cake, adding water and ethanol 5 times the mass of the filter cake, washing three times in sequence, and drying at 50°C for 28 hours to obtain an antibacterial agent;

[0039] The mass ratio of zinc oxide / carbon nitride composite material, ethyl bromide and methyl iodide is 10:4:4;

[0040] The modified acrylate monomer comprises the following steps of preparation:

[0041] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1:1.25:20, reacted at 70°C in a nitrogen atmosphere for 48 hours, and after completion of the reaction, the acetonitrile solvent was removed by rotary evaporation at 70°C to obtain a reaction product, which was washed three times with ether in an amount three times the mass of the reaction product, and dried at 40°C for 24 hours to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:2 to obtain a modified acrylate monomer;

[0042] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 50°C in a nitrogen atmosphere for 3 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 65°C for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 10:1:0.04, and the mixture is reacted for a third time at 70°C for 2 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0043] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.8:0.4:2.5:0.3, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0044] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 150 r / min and room temperature for 0.5 h, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 20 min to obtain a weather-resistant antibacterial adhesive;

[0045] The mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 120:6:6:40:6:3.

[0046] Example 2

[0047] This embodiment discloses a method for preparing a weather-resistant antibacterial adhesive, comprising the following steps:

[0048] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0049] The antibacterial agent is prepared by the following steps:

[0050] Step (1), mixing graphite phase carbon nitride, zinc acetate, and water, adding 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, ultrasonically dispersing at 45°C for 25 minutes, adding polyethyleneimine aqueous solution dropwise for 8 minutes, reacting at 155°C for 11 hours after the addition is complete, centrifuging, filtering, taking the filter cake, adding water and ethanol 6 times the mass of the filter cake, washing three times in sequence, and drying at 55°C for 24 hours to obtain a zinc oxide / carbon nitride composite material;

[0051] The mass ratio of graphite carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 1.3:5.5:60:10.3; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.11:10;

[0052] Step (2), mixing the zinc oxide / carbon nitride composite material with ethanol in a mass ratio of 1:22 by ultrasonication, adding ethyl bromide, reacting at room temperature for 13 hours, adding iodomethane, and continuing to react at room temperature for 13 hours, filtering, taking the filter cake, adding water and ethanol 6 times the mass of the filter cake, washing three times in sequence, and drying at 55°C for 24 hours to obtain an antibacterial agent;

[0053] The mass ratio of zinc oxide / carbon nitride composite material, ethyl bromide, and methyl iodide is 10:4.2:4.2;

[0054] The modified acrylate monomer comprises the following steps of preparation:

[0055] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1:1.26:20, reacted at 75°C in a nitrogen atmosphere for 46 hours, and after completion of the reaction, the acetonitrile solvent was removed by rotary evaporation at 75°C to obtain a reaction product, which was washed three times with ether in an amount three times the mass of the reaction product, and dried at 45°C for 21 hours to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:1.8 to obtain a modified acrylate monomer;

[0056] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 55°C in a nitrogen atmosphere for 2.8 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 70°C for 2.5 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 10.5:1:0.04, and the mixture is reacted for a third time at 75°C for 1.5 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0057] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.85:0.45:2.8:0.35, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0058] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 155 r / min and room temperature for 0.8 h, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 25 min to obtain a weather-resistant antibacterial adhesive;

[0059] Among them, the mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 115:6.5:5.8:38:6.5:2.8.

[0060] Example 3

[0061] This embodiment discloses a method for preparing a weather-resistant antibacterial adhesive, comprising the following steps:

[0062] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0063] The antibacterial agent is prepared by the following steps:

[0064] Step (1), mixing graphite phase carbon nitride, zinc acetate and water, adding 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10.5, ultrasonically dispersing at 45°C for 25 minutes, adding polyethyleneimine aqueous solution dropwise for 9 minutes, reacting at 155°C for 11 hours after the addition is complete, centrifuging and filtering, taking the filter cake, adding water and ethanol 6 times the mass of the filter cake, washing three times in sequence, and drying at 55°C for 24 hours to obtain a zinc oxide / carbon nitride composite material;

[0065] The mass ratio of graphite carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 1.5:6.5:65:10.5; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.12:10;

[0066] Step (2), mixing the zinc oxide / carbon nitride composite material with ethanol in a mass ratio of 1:25 by ultrasonication, adding ethyl bromide, reacting at room temperature for 13 hours, adding iodomethane, and continuing to react at room temperature for 13 hours. After the reaction is completed, filtering, taking the filter cake, adding water and ethanol 6 times the mass of the filter cake, washing three times in sequence, and drying at 55°C for 24 hours to obtain an antibacterial agent;

[0067] The mass ratio of zinc oxide / carbon nitride composite material, ethyl bromide and methyl iodide is 10:4.5:4.5;

[0068] The modified acrylate monomer comprises the following steps of preparation:

[0069] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1.05:1.27:22, and reacted at 75°C in a nitrogen atmosphere for 46 hours. After the reaction, the acetonitrile solvent was removed by rotary evaporation at 75°C to obtain a reaction product, which was washed three times with ether in an amount 4 times the mass of the reaction product, and dried at 45°C for 21 hours to obtain a modified imidazole. The modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:1.5 to obtain a modified acrylate monomer.

[0070] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 58°C in a nitrogen atmosphere for 2.5 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 70°C for 2.5 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 11:1:0.045, and the mixture is reacted for a third time at 78°C for 1.5 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0071] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.9:0.45:2.8:0.4, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0072] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 165 r / min and room temperature for 0.8 h, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 25 min to obtain a weather-resistant antibacterial adhesive;

[0073] The mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 110:7:5.5:35:7:2.5.

[0074] Example 4

[0075] This embodiment discloses a method for preparing a weather-resistant antibacterial adhesive, comprising the following steps:

[0076] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0077] The antibacterial agent is prepared by the following steps:

[0078] Step (1), mixing graphite phase carbon nitride, zinc acetate, and water, adding 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 11, ultrasonically dispersing at 45°C for 25 minutes, adding polyethyleneimine aqueous solution dropwise for 10 minutes, reacting at 155°C for 11 hours after the addition is complete, centrifuging, filtering, taking the filter cake, adding 8 times the mass of the filter cake and ethanol, washing three times in sequence, and drying at 55°C for 24 hours to obtain a zinc oxide / carbon nitride composite material;

[0079] The mass ratio of graphite carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 1.8:7.5:75:10.8; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.14:10;

[0080] Step (2), mixing the zinc oxide / carbon nitride composite material with ethanol in a mass ratio of 1:28 by ultrasonication, adding ethyl bromide, reacting at room temperature for 13 hours, adding methyl iodide, and continuing to react at room temperature for 13 hours. After the reaction is completed, filtering, taking the filter cake, adding water and ethanol 8 times the mass of the filter cake, washing three times in sequence, and drying at 55°C for 24 hours to obtain an antibacterial agent;

[0081] The mass ratio of zinc oxide / carbon nitride composite material, ethyl bromide, and methyl iodide is 10:4.8:4.8;

[0082] The modified acrylate monomer comprises the following steps of preparation:

[0083] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1.1:1.28:24, reacted at 75°C in a nitrogen atmosphere for 46 hours, and after completion of the reaction, the acetonitrile solvent was removed by rotary evaporation at 80°C to obtain a reaction product, which was washed three times with ether in an amount 4 times the mass of the reaction product, and dried at 45°C for 21 hours to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:1.2 to obtain a modified acrylate monomer;

[0084] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 62°C in a nitrogen atmosphere for 2.2 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 70°C for 2.5 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 11.5:1:0.05, and the mixture is reacted for a third time at 80°C for 1.2 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0085] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.9:0.5:3:0.4, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0086] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 175 r / min and room temperature for 1 hour, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 25 minutes to obtain a weather-resistant antibacterial adhesive;

[0087] Among them, the mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 105:7.5:5.2:32:7.5:2.2.

[0088] Example 5

[0089] This embodiment discloses a method for preparing a weather-resistant antibacterial adhesive, comprising the following steps:

[0090] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0091] The antibacterial agent is prepared by the following steps:

[0092] Step (1), mixing graphite phase carbon nitride, zinc acetate and water, adding 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 11, ultrasonically dispersing at 50°C for 20 minutes, adding polyethyleneimine aqueous solution dropwise for 10 minutes, reacting at 160°C for 10 hours after the addition is completed, centrifuging and filtering, taking the filter cake, adding water and ethanol 8 times the mass of the filter cake, washing three times in sequence, and drying at 60°C for 20 hours to obtain a zinc oxide / carbon nitride composite material;

[0093] The mass ratio of graphite carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 2:8:80:11; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.15:10;

[0094] Step (2), mixing the zinc oxide / carbon nitride composite material with ethanol in a mass ratio of 1:30 by ultrasonication, adding ethyl bromide, reacting at room temperature for 14 hours, adding iodomethane, and continuing to react at room temperature for 14 hours. After the reaction is completed, filtering, taking the filter cake, adding water and ethanol 8 times the mass of the filter cake, washing three times in sequence, and drying at 60°C for 20 hours to obtain an antibacterial agent;

[0095] The mass ratio of zinc oxide / carbon nitride composite material, ethyl bromide and methyl iodide is 10:5:5;

[0096] The modified acrylate monomer comprises the following steps of preparation:

[0097] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1.1:1.3:25, reacted at 80°C in a nitrogen atmosphere for 45 hours, and after completion of the reaction, the acetonitrile solvent was removed by rotary evaporation at 80°C to obtain a reaction product, which was washed three times with ether in an amount 5 times the mass of the reaction product, and dried at 50°C for 18 hours to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:1 to obtain a modified acrylate monomer;

[0098] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 65°C for 2 hours in a nitrogen atmosphere. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 75°C for 2 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 12:1:0.05, and the mixture is reacted for a third time at 85°C for 1 hour. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0099] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 1:0.5:3:0.5, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0100] Step 3: Mix modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone, stir at a speed of 180 r / min and room temperature for 1 hour, stir evenly, add an antibacterial agent and a photoinitiator in a dark environment, and continue stirring for 30 minutes to obtain a weather-resistant antibacterial adhesive;

[0101] The mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 100:8:5:30:8:2.

[0102] Comparative Example 1

[0103] This comparative example discloses a method for preparing an adhesive, comprising the following steps:

[0104] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0105] The antibacterial agent is prepared by the following steps:

[0106] Step (1), zinc acetate and water are mixed, 1 mol / L sodium hydroxide aqueous solution is added to adjust the pH value to 10, ultrasonic dispersion is carried out at 40°C for 30 minutes, polyethyleneimine aqueous solution is added dropwise for 8 minutes, and after the dropwise addition is completed, the mixture is reacted at 150°C for 12 hours. After the reaction is completed, the mixture is centrifuged and filtered to obtain a filter cake, and water and ethanol 5 times the mass of the filter cake are added and washed three times in sequence, and the mixture is dried at 50°C for 28 hours to obtain a zinc oxide composite material;

[0107] The mass ratio of zinc acetate, water and polyethyleneimine aqueous solution is 4.5:50:10; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.1:10;

[0108] Step (2), mixing the zinc oxide composite material and ethanol in a mass ratio of 1:20 with ultrasound, adding bromoethane, reacting at room temperature for 12 hours, adding iodomethane, and continuing to react at room temperature for 12 hours, filtering, taking the filter cake, adding water and ethanol 5 times the mass of the filter cake, washing three times in sequence, and drying at 50°C for 28 hours to obtain an antibacterial agent;

[0109] The mass ratio of zinc oxide composite material, ethyl bromide and methyl iodide is 10:4:4;

[0110] The modified acrylate monomer comprises the following steps of preparation:

[0111] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1:1.25:20, reacted at 70°C in a nitrogen atmosphere for 48 hours, and after completion of the reaction, the acetonitrile solvent was removed by rotary evaporation at 70°C to obtain a reaction product, which was washed three times with ether in an amount three times the mass of the reaction product, and dried at 40°C for 24 hours to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:2 to obtain a modified acrylate monomer;

[0112] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 50°C in a nitrogen atmosphere for 3 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 65°C for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 10:1:0.04, and the mixture is reacted for a third time at 70°C for 2 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0113] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.8:0.4:2.5:0.3, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0114] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 150 r / min and room temperature for 0.5 h, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 20 min to obtain a weather-resistant antibacterial adhesive;

[0115] The mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 120:6:6:40:6:3.

[0116] Comparative Example 2

[0117] This comparative example discloses a method for preparing an adhesive, comprising the following steps:

[0118] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0119] The antibacterial agent is prepared by the following steps:

[0120] The graphite phase carbon nitride, zinc acetate and water were mixed, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10, ultrasonic dispersion was carried out at 40°C for 30 minutes, polyethyleneimine aqueous solution was added dropwise for 8 minutes, and after the addition was completed, the mixture was reacted at 150°C for 12 hours. After the reaction was completed, the mixture was centrifuged and filtered to obtain a filter cake, which was washed three times with water and ethanol 5 times the mass of the filter cake in sequence, and dried at 50°C for 28 hours to obtain an antibacterial agent.

[0121] The mass ratio of graphite carbon nitride, zinc acetate, water, and polyethyleneimine aqueous solution is 1:4.5:50:10; the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.1:10;

[0122] Acrylate monomers are prepared by the following steps:

[0123] Pentaerythritol triacrylate and hydroxyethyl methacrylate were mixed in a mass ratio of 1:3 to obtain an acrylate monomer;

[0124] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 50°C in a nitrogen atmosphere for 3 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 65°C for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 10:1:0.04, and the mixture is reacted for a third time at 70°C for 2 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0125] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.8:0.4:2.5:0.3, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0126] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 150 r / min and room temperature for 0.5 h, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 20 min to obtain a weather-resistant antibacterial adhesive;

[0127] The mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 120:6:6:40:6:3.

[0128] Comparative Example 3

[0129] This comparative example discloses a method for preparing an adhesive, comprising the following steps:

[0130] Step 1, preparing an antibacterial agent and a modified acrylate monomer;

[0131] The antibacterial agent is prepared by the following steps:

[0132] Step (1), mixing graphite carbon nitride, zinc acetate, and water, adding 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, ultrasonically dispersing at 40°C for 30 minutes, reacting at 150°C for 12 hours, centrifuging, filtering, taking the filter cake, adding water 5 times the mass of the filter cake and ethanol, washing three times in sequence, and drying at 50°C for 28 hours to obtain an antibacterial agent;

[0133] Among them, the mass ratio of graphite phase carbon nitride, zinc acetate and water is 1:4.5:60;

[0134] The modified acrylate monomer comprises the following steps of preparation:

[0135] 1-allylimidazole, 2-bromoethanol, and acetonitrile were mixed in a mass ratio of 1:1.25:20, reacted at 70°C in a nitrogen atmosphere for 48 hours, and after completion of the reaction, the acetonitrile solvent was removed by rotary evaporation at 70°C to obtain a reaction product, which was washed three times with ether in an amount three times the mass of the reaction product, and dried at 40°C for 24 hours to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate were mixed in a mass ratio of 1:1:2 to obtain a modified acrylate monomer;

[0136] Step 2: polytetramethylene glycol, bishydroxy polydimethylsiloxane, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted for a first time at 50°C in a nitrogen atmosphere for 3 hours. After the reaction is completed, 1,4-butanediol is added, and the mixture is reacted for a second time at 65°C for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained; the polyurethane prepolymer, modified acrylate monomer, and p-hydroxyanisole are mixed in a mass ratio of 10:1:0.04, and the mixture is reacted for a third time at 70°C for 2 hours. After the reaction is completed, a modified polyurethane acrylate is obtained;

[0137] The molar ratio of polytetramethylene ether glycol, bishydroxypropyl polydimethylsiloxane, isophorone diisocyanate, and 1,4-butanediol is 0.8:0.4:2.5:0.3, and the amount of dibutyltin dilaurate added is 0.05wt% of the mass of polytetramethylene ether glycol;

[0138] Step 3: Modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone were mixed, stirred at a speed of 150 r / min and room temperature for 0.5 h, and after stirring evenly, an antibacterial agent and a photoinitiator were added in a light-proof environment, and stirring was continued for 20 min to obtain a weather-resistant antibacterial adhesive;

[0139] The mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent and photoinitiator is 120:6:6:40:6:3.

[0140] In the above embodiments and comparative examples: graphite phase carbon nitride is from Suzhou Kaifa New Material Technology Co., Ltd., model few-layer graphite phase carbon nitride nanosheets, with an average number of layers less than 10, a thickness of 1-3 nm, and a particle size of 10-15 μm; zinc acetate is from Wuxi Jingke Chemical Co., Ltd., CAS No.: 557-34-6; sodium hydroxide is from Hubei Shenglun Chemical Technology Co., Ltd., CAS No.: 1310-73-2; polyethyleneimine is from Shanghai Aladdin Biochemical Technology Co., Ltd., Mw = 10000, CAS No.: 9002-98-6; ethanol is from Haiyishi Chemical Co., Ltd., CAS No.: 64-17-5; bromoethane from Guangdong Xiaoda Chemical Co., Ltd., CAS No.: 74-96-4; iodomethane from Anhui Jinyueguan New Material Technology Co., Ltd., CAS No.: 74-88-4; 1-allylimidazole from Hubei Xinghengye Technology Co., Ltd., CAS No.: 31410-01-2; 2-bromoethanol from Hubei Kewode Chemical Co., Ltd., CAS No.: 540-51-2; acetonitrile from Anhui Jinyueguan New Material Technology Co., Ltd., CAS No.: 75-05-8; ether from Alfa Aesar, CAS No.: 60-29-7; Pentaerythritol triacrylate from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 3524-68-3; Hydroxyethyl methacrylate from Qianyan Chemical Technology (Wuhan) Co., Ltd., CAS No.: 868-77-9; Polytetramethylenetetrahydrofuran ether glycol from Shanghai Kaikuo Chemical Materials Co., Ltd., average molecular weight 1000, CAS No.: 25190-06-1; Bishydroxy polydimethylsiloxane from Hubei Langbowan Biopharmaceutical Co., Ltd., product No. LBW-0077, CAS No.: 70131-67-8; Isophorone diisocyanate from Shandong New Dynamic Energy Chemical Co., Ltd., CAS No.: 4098-71-9; Dibutyltin dilaurate from Maoming Xiongda Chemical Co., Ltd., CAS No.: 77-58-7; 1,4-Butanediol was from Maoming Xiongda Chemical Co., Ltd., CAS No.: 110-63-4; p-Hydroxyanisole was from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 150-76-5; Glycidyl methacrylate was from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 106-91-2; Trimethylolpropane triacrylate was from Pandex (Shanghai) International Trading Co., Ltd., CAS No.: 15625-89-5; Acetone was from Shandong Wenshao Chemical Co., Ltd., CAS No.: 67-64-1; Photoinitiator was from Nanjing Milan Chemical Co., Ltd., Model Photoinitiator 1173, CAS No.: 7374-98-5.

[0141] Test example

[0142] The adhesives prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to performance tests. The specific test results are shown in Table 1:

[0143] Table 1

[0144]

[0145] The tests of the various indicators in Table 1 are based on the following standards: tensile strength is determined by referring to ASTM D638-2003 "Standard Test Method for Tensile Properties of Plastics"; peel strength is determined by referring to GB / T2791-1995 "Test Method for Peel Strength of Adhesives"; antibacterial rate is determined by referring to QB / T2591 "Antibacterial Plastics-Test Method for Antibacterial Performance and Antibacterial Effect", and Escherichia coli is selected as the bacteria; mildew resistance is determined by referring to GB / T 1741-2020 "Determination of Mildew Resistance of Paint Films"; weather resistance is determined by referring to GB / T23987-2009 "Artificial Weathering of Paint and Varnish Coatings - Exposure to Fluorescent Ultraviolet Light and Water".

[0146] According to the test results in Table 1, it can be seen that the adhesive prepared by the present invention has weather resistance and antibacterial properties and good mechanical properties.

[0147] The present invention utilizes the chelation of zinc ions by graphite-phase carbon nitride and the amino group of polyethyleneimine to in situ synthesize zinc oxide particles on the surface of the graphite-phase carbon nitride. The graphite-phase carbon nitride and the zinc oxide particles exhibit a synergistic anti-UV aging effect, thereby enhancing the weather resistance of the antibacterial agent. Furthermore, the graphite-phase carbon nitride, as an inorganic particle, also improves the mechanical properties of the substrate. Comparative Example 1, which lacks the graphite-phase carbon nitride's enhanced mechanical and weather resistance properties, exhibits lower mechanical properties and weather resistance than the examples.

[0148] The present invention alkylates the amino groups on the surface of a zinc oxide / carbon nitride composite material, converting some of the amino groups into quaternary ammonium salts, thereby producing an antibacterial agent having both amino and quaternary ammonium salt structures on the surface. The quaternary ammonium salt and zinc oxide form a dual antibacterial activity mechanism, thereby enhancing the antibacterial activity of the antibacterial agent. The quaternary ammonium salt and zinc oxide react with 2-bromoethanol to form a complex imidazole ring and quaternary ammonium salt structure, thereby enhancing the antibacterial activity. Furthermore, the imidazole ring, which contains hydroxyl groups, can react with the terminal isocyanate groups of a polyurethane prepolymer, resulting in a modified polyurethane acrylate having improved antibacterial activity. Furthermore, the imidazole ring, as a polar group, can increase the intermolecular forces of the polyurethane acrylate, thereby improving the mechanical properties of the matrix. The zinc oxide / carbon nitride composite material in the antibacterial agent of Comparative Example 2 is not alkylated, thus failing to generate a quaternary ammonium salt antibacterial structure. Furthermore, the acrylate monomer lacks the antibacterial modified imidazole, resulting in reduced antibacterial activity. Furthermore, due to the lack of the reinforcing effect of the imidazole polar group on the mechanical properties of the matrix, the mechanical properties and antibacterial activity of Comparative Example 2 are inferior to those of the examples.

[0149] In the present invention, the antibacterial agent has an active amino group on its surface, and glycidyl methacrylate provides a carbon-carbon double bond and an epoxy active group in the curing system, which can not only participate in the photocuring reaction, but also its epoxy group can react with the amino group on the surface of the antibacterial agent to open the ring, thereby improving the compatibility of the antibacterial agent with the substrate. In Comparative Example 3, no polyethyleneimine is added to the antibacterial agent, and the antibacterial agent does not have a quaternary ammonium salt antibacterial group on its surface. The number of amino active groups is reduced, the compatibility between the antibacterial agent and the adhesive matrix is ​​reduced, and the mechanical properties are reduced. At the same time, due to the lack of quaternary ammonium salt antibacterial groups in the antibacterial agent to form a synergistic antibacterial system with zinc oxide, the mechanical properties and antibacterial properties of Comparative Example 3 are lower than those of the embodiment.

[0150] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a weather-resistant antibacterial adhesive, characterized in that: The following steps are involved: Step 1, preparing an antibacterial agent and a modified acrylate monomer; The antibacterial agent is prepared by the following steps: Step (1), by weight, 1-2 parts of graphite phase carbon nitride, 4.5-8 parts of zinc acetate, and 50-80 parts of water are mixed, a regulator is added to adjust the pH value, ultrasonic dispersion is performed, 10-11 parts of a polyethyleneimine aqueous solution is added dropwise at a pH value of 10-11 for 8-10 minutes, and after the addition is complete, the mixture is reacted at a temperature of 150-160° C. for 10-12 hours. After the reaction is completed, the mixture is centrifuged, filtered, washed, and dried to obtain a zinc oxide / carbon nitride composite material; The polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine and water in a mass ratio of 0.1-0.15:10; Step (2), by weight, 10 parts of the zinc oxide / carbon nitride composite material and 20-30 parts of ethanol were mixed by ultrasonication, 4-5 parts of bromoethane were added, and the mixture was reacted at room temperature for 12-14 hours. After the reaction was completed, 4-5 parts of iodomethane were added, and the mixture was reacted at room temperature for another 12-14 hours. After the reaction was completed, the mixture was filtered, washed, and dried to obtain an antibacterial agent; The modified acrylate monomer comprises the following steps of preparation: 1-allylimidazole, 2-bromoethanol, and acetonitrile are mixed and subjected to quaternization reaction. After the reaction is completed, the mixture is purified and dried to obtain a modified imidazole; the modified imidazole, pentaerythritol triacrylate, and hydroxyethyl methacrylate are mixed to obtain a modified acrylate monomer; Step 2: Mix 0.8-1 parts of polytetramethylene ether glycol, 0.4-0.5 parts of bishydroxy polydimethylsiloxane, 2.5-3 parts of isophorone diisocyanate, and dibutyltin dilaurate, by mole fraction, and perform a first reaction. After the reaction is completed, add 0.3-0.5 parts of 1,4-butanediol, and perform a second reaction. After the reaction is completed, a polyurethane prepolymer is obtained. Mixing 10-12 parts by mass of a polyurethane prepolymer, 1 part of a modified acrylate monomer, and 0.04-0.05 parts of p-hydroxyanisole, and reacting for a third time to obtain a modified polyurethane acrylate; Step 3: Mix and stir the modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and acetone. After stirring evenly, add the antibacterial agent and photoinitiator in a light-proof environment and continue stirring to obtain a weather-resistant antibacterial adhesive.

2. The method for preparing a weather-resistant antibacterial adhesive according to claim 1, characterized in that: In the preparation of the modified acrylate monomer, the mass ratio of 1-allylimidazole, 2-bromoethanol, and acetonitrile is 1-1.1:1.25-1.3:20-25; and the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 70-80° C. for 45-48 hours.

3. The method for preparing a weather-resistant antibacterial adhesive according to claim 1, characterized in that: In the preparation of the modified acrylate monomer, the mass ratio of modified imidazole, pentaerythritol triacrylate and hydroxyethyl methacrylate is 1:1:1-2.

4. The method for preparing a weather-resistant antibacterial adhesive according to claim 1, characterized in that: In the step 2, the amount of dibutyltin dilaurate added is 0.05 wt% of the mass of polytetramethylene ether glycol.

5. The method for preparing a weather-resistant antibacterial adhesive according to claim 1, characterized in that: In the step 2, the first reaction conditions are: in a nitrogen atmosphere, at a temperature of 50-65°C for the first reaction for 2-3 hours; the second reaction conditions are: in a nitrogen atmosphere, at a temperature of 65-75°C for the second reaction for 2-3 hours; the third reaction conditions are: in a nitrogen atmosphere, at a temperature of 70-85°C for the third reaction for 1-2 hours.

6. The method for preparing a weather-resistant antibacterial adhesive according to claim 1, characterized in that: In the step 3, the mass ratio of modified polyurethane acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, acetone, antibacterial agent, and photoinitiator is 100-120:6-8:5-6:30-40:6-8:2-3.

7. A weather-resistant antibacterial adhesive prepared by the method for preparing a weather-resistant antibacterial adhesive according to any one of claims 1 to 6.

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