Antibacterial hybrid waterborne polyurethane as well as preparation method and application thereof

Abstract

The invention relates to antibacterial hybrid waterborne polyurethane as well as a preparation method and application thereof, aiming at different hardness degrees of two sides of a base material, two polyols with different glass transition temperatures are used for synthesizing a polyurethane prepolymer, and nano silicon dioxide or coupling agent modified nano silicon dioxide is introduced to increase the bonding force of the waterborne polyurethane, so that the antibacterial hybrid waterborne polyurethane is prepared. And particularly, the bonding effect at high temperature is improved. Besides, zirconium phosphate loaded with silver ions is added into a waterborne polyurethane system, so that the waterborne polyurethane system is endowed with antibacterial property, and nano silicon dioxide or coupling agent modified nano silicon dioxide and the zirconium phosphate loaded with the silver ions are synergistically used, so that a stable hydrogen bond network is formed; the zirconium phosphate loaded with the silver ions is stably dispersed in a waterborne polyurethane system, and the antibacterial property is provided.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives and relates to an antibacterial hybrid waterborne polyurethane and a preparation method and application thereof. Background Art

[0002] In the automotive interiors sector, solvent-based polyurethanes have long dominated the market, owing to their strong initial tack and fast drying times. In recent years, with growing environmental awareness and increasingly stringent VOC requirements in the automotive industry, low-VOC water-based polyurethane automotive interior covering adhesives are gradually replacing traditional solvent-based polyurethane adhesives. However, water-based covering adhesives exhibit inferior bonding performance compared to similar solvent-based products, necessitating improvements to enhance their bonding properties.

[0003] Furthermore, waterborne polyurethane adhesives are prone to growing bacteria and mold over long periods of use, particularly in the relatively humid environment of a vehicle interior, potentially impacting user health. While most countries and industry standards currently don't mandate antimicrobial properties for vehicles other than ambulances and hospital vehicles, antimicrobial treatment of high-touch areas like car seats to enhance overall antimicrobial resistance is becoming a selling point for mid- to high-end vehicles. Consequently, there's a demand for inherent antimicrobial properties in waterborne polyurethane adhesives. Enhancing their antimicrobial properties can help them appeal to the high-end market or specialized vehicles, increasing their added value.

[0004] To improve the antibacterial properties of adhesive systems, the conventional method is to directly add inorganic antimicrobial agents to impart antimicrobial properties. However, in water-based adhesive systems, inorganic antimicrobial agents are prone to sedimentation, affecting product stability and potentially causing antimicrobial performance failure. The present invention introduces hydrophilic nano-silica and silver ion-loaded zirconium phosphate. Through their synergistic effect, the antimicrobial agent can be stably dispersed in the hydrocolloid for a long period of time, resulting in a more effective antimicrobial effect. Summary of the Invention

[0005] In view of the defects of the prior art, the technical problem to be solved by the present invention is that zirconium phosphate loaded with silver ions is incompatible with the waterborne polyurethane adhesive system and zirconium phosphate is prone to sedimentation.

[0006] In order to achieve the above technical objectives, the technical solutions adopted by the present invention are as follows: In a first aspect, an antibacterial hybrid waterborne polyurethane comprises: Any one of a polyurethane prepolymer, silver ion-loaded zirconium phosphate, and nano-silica or nano-silica modified with a coupling agent; The silver ion-loaded zirconium phosphate is selected from sheet-shaped zirconium phosphate loaded with silver or cubic zirconium phosphate loaded with silver, and its particle size ranges from 0.1 to 10 μm; Nano-silica is selected from silica particles or silica aqueous dispersion, and the average particle size of the silica does not exceed 100 nm; the polyurethane prepolymer contains a hydrophilic chain extender and at least two polyols with different glass transition temperatures. At the same time, the polyurethane prepolymer is terminated with a -NCO group, wherein the hydrophilic chain extender is a polyol or polyamine containing at least one -COOH or -SO3H group.

[0007] Furthermore, the coupling agent-modified nano-silica comprises the following raw materials in parts by weight: 15 to 30 parts of silane coupling agent, 5 to 15 parts of organic orthosilicate, 1 to 20 parts of water, 50 to 70 parts of alcohol solvent, and 0.001 to 0.01 parts of catalyst; The silane coupling agent is selected from any one of an amino-containing silane coupling agent, a urea-containing silane coupling agent, and an imidazole-containing silane coupling agent.

[0008] Preferably, the amino-containing silane coupling agent is selected from any one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0009] The urea-containing silane coupling agent is selected from any one or two of 3-ureapropyltrimethoxysilane and 3-ureapropyltriethoxysilane.

[0010] The imidazole-containing silane coupling agent is selected from any one or two of N-(trimethoxysilylpropyl)imidazole and N-(triethoxysilylpropyl)imidazole.

[0011] Preferably, the organic orthosilicate is selected from one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.

[0012] Preferably, the alcohol solvent is selected from any one or more of methanol, ethanol and isopropanol.

[0013] Preferably, the catalyst is selected from any one or more of tetrabutyl titanate and dibutyltin dilaurate.

[0014] Preferably, the coupling agent-modified nano-silica is synthesized using a sol-gel method.

[0015] Furthermore, the polyurethane prepolymer comprises the following raw materials in parts by weight: 68-72 parts of polyol, 23-24 parts of diisocyanate, 4-7 parts of hydrophilic chain extender, 2-4 parts of polyol chain extender, 1-2 parts of neutralizer, and 0.001-0.01 parts of catalyst.

[0016] The number average molecular weight of the polyol is in the range of 200 to 4000; preferably, the number average molecular weight of the polyol is in the range of 600 to 4000.

[0017] The polyol is selected from one or both of polyester polyol and polyether polyol.

[0018] The polyester polyol is selected from one or more of adipic acid polyester polyol, phthalic acid polyester polyol, aliphatic polyester polyol or polycaprolactone polyol.

[0019] The polyether polyol is selected from one or more of polytetramethylene glycol and polypropylene glycol.

[0020] Preferably, the polyol is selected from at least two of polybutylene adipate diol, polyisopropylene adipate diol, polyneopentyl adipate diol, polytetramethylene ether diol, and polypropylene glycol.

[0021] The diisocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,6-hexamethylene diisocyanate.

[0022] The diisocyanate is preferably isophorone diisocyanate or diphenylmethane diisocyanate.

[0023] The hydrophilic chain extender is selected from at least one of dimethylolbutyric acid (DMBA), dimethylolpropionic acid (DMPA), and sodium ethylenediaminesulfonate (A95). Preferably, the hydrophilic chain extender is selected from dimethylolpropionic acid.

[0024] The polyol chain extender is selected from: one or more of 1,4-butanediol, 1,6-hexanediol, and 1,3-butanediol; the neutralizer is selected from: one or more of triethylamine, triethanolamine, and N,N-dimethylethanolamine.

[0025] The catalyst is selected from any one or more of an organic bismuth catalyst and an organic tin catalyst; Preferably, the catalyst is selected from dibutyltin dilaurate (DBTDL).

[0026] Furthermore, the preparation method of the polyurethane prepolymer includes: S1, mixing a polyol, a diisocyanate, and a hydrophilic chain extender together for reaction, then adding the polyol chain extender for reaction, and then adding a catalyst for reaction until the -NCO content of the reaction mixture is ≤10 wt%; S2. Neutralization reaction: Cool the polyurethane prepolymer to 30-60° C. and add a neutralizing agent under the shearing action of a high-speed disperser to react for 5-60 minutes.

[0027] Preferably, in step S1, acetone in an amount of 1 to 2 times the total weight of the hydrophilic chain extender is added during the mixing of the polyol, diisocyanate and hydrophilic chain extender; Preferably, after cooling in step S2, 40-60 wt% of acetone of the polyurethane prepolymer is first added to reduce the viscosity of the polyurethane prepolymer, and then a neutralizing agent is added under the shearing action of a high-speed disperser to carry out a neutralization reaction.

[0028] Preferably, the method for preparing the polyurethane prepolymer further comprises: S3, acetone removal process, set the temperature at 40-60 ° C, the pressure in the container does not exceed 0.1 Pa, and remove acetone by vacuum.

[0029] In a second aspect, the preparation method of the antibacterial hybrid waterborne polyurethane described above comprises: mixing a polyurethane prepolymer, an organic orthosilicate, nano-silica or nano-silica modified with a coupling agent, and then uniformly dispersing the mixture by a mechanical method.

[0030] Preferably, the mechanical method is specifically: using a high-speed disperser to disperse at a rotation speed of 500-5000 rpm; preferably, the dispersion time is 5-60 minutes; more preferably, the dispersion time is 30 minutes.

[0031] In a third aspect, the antibacterial hybrid waterborne polyurethane described above is used for bonding between a polyurethane substrate and a plastic substrate.

[0032] Wherein, the plastic substrate includes any one of polybutylene terephthalate (PBT), polycarbonate (PC), polyamide (PA), acrylonitrile-butadiene-styrene copolymer (ABS) or polyphenylene sulfide (PPS).

[0033] In a fourth aspect, the antibacterial hybrid waterborne polyurethane described above is used as a coating adhesive for automobile interior decoration.

[0034] The beneficial effects of the present invention are as follows: first, in view of the different hardness and softness of the two sides of the substrates to be bonded, two polyols with different glass transition temperatures are designed to synthesize polyurethane prepolymers. Secondly, the introduction of nano-silica or coupling agent-modified nano-silica can increase the adhesion to different substrates, especially improve the bonding effect at high temperatures, and avoid adhesive failure or cohesive failure. Finally, zirconium phosphate loaded with silver ions is added to the waterborne polyurethane system to impart antibacterial properties to the waterborne polyurethane adhesive. The nano-silica or coupling agent-modified nano-silica is used in conjunction with the silver ion-loaded zirconium phosphate to form a stable hydrogen bond network, so that the silver ion-loaded zirconium phosphate is stably dispersed in the waterborne polyurethane system and provides antibacterial properties. DETAILED DESCRIPTION

[0035] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0036] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0037] If the specific experimental conditions are not specified in the examples, they are usually based on conventional conditions in the field or conditions recommended by the reagent company; the materials, reagents, etc. used in the examples can be purchased through commercial channels unless otherwise specified.

[0038] Example 1 Synthesis of nano-silica modified with an amino coupling agent by the sol-gel method: 22.5 parts of 3-aminopropyltrimethoxysilane and 7.5 parts of ethyl orthosilicate are added to a mixed solvent of 70 parts of water / ethanol, wherein the weight ratio of water / ethanol is 1:6, and then 0.005 parts of dibutyltin dilaurate (DBTDL) catalyst is added. The temperature is raised to 50°C and the reaction is stirred for 2 hours until the solution becomes clear and transparent. The solution is then allowed to stand for 1 hour to obtain a nano-silica solution modified with an amino coupling agent.

[0039] Example 2 Sol-gel method for synthesizing nano-silica modified with a urea-containing coupling agent: 21 parts of 3-ureapropyltrimethoxysilane and 9 parts of ethyl orthosilicate are added to a mixed solvent of 70 parts of water / ethanol, wherein the weight ratio of water / ethanol is 1:6, and then 0.005 parts of dibutyltin dilaurate (DBTDL) catalyst is added. The temperature is raised to 60°C and the reaction is stirred for 2 hours until the solution becomes clear and transparent. The solution is then allowed to stand for 1 hour to obtain a nano-silica solution modified with a urea-containing coupling agent.

[0040] Example 3 Synthesis of nano-silica modified with an imidazole coupling agent by the sol-gel method: 22 parts of N-(triethoxysilylpropyl)imidazole and 8 parts of ethyl orthosilicate are added to a mixed solvent of 70 parts of water / ethanol, wherein the weight ratio of water / ethanol is 1:6, and then 0.005 parts of dibutyltin dilaurate (DBTDL) catalyst is added. The temperature is raised to 50°C and the reaction is stirred for 2 hours until the solution becomes clear and transparent. The solution is then allowed to stand for 1 hour to obtain a nano-silica solution modified with an imidazole coupling agent.

[0041] Example 4 Waterborne polyurethane was synthesized according to the following steps (wherein each raw material is calculated by weight): S1. Preparation of a polyurethane prepolymer containing a hydrophilic monomer: two polyols were added to a three-necked flask: 15 parts of polyneopentyl adipate diol and 125 parts of polybutylene adipate diol. The polyols were vacuum dehydrated at 120°C for 2 hours, cooled to 80-85°C, 4 parts of dimethylol propionic acid and 6 parts of acetone were added, and stirred for 20 minutes. 45 parts of isophorone diisocyanate were added and reacted at 80-85°C for 2 hours. Then 6 parts of 1,4-butanediol were added and reacted at 80-85°C for 1 hour. 0.001 parts of catalyst DBTDL were added and reacted at 70-80°C until the -NCO content was reduced to 5wt%, thereby obtaining a polyurethane prepolymer containing a hydrophilic monomer.

[0042] S2. Neutralization reaction: cool the polyurethane prepolymer to 40-45° C., add 82 parts of acetone to reduce the viscosity of the polyurethane prepolymer, and then add 3 parts of triethylamine under the shearing action of a high-speed disperser and react for 15-20 minutes.

[0043] S3, deacetone process: set the temperature to 55 ° C, the pressure in the container to 0.098 Pa, and remove acetone by vacuum for 1 to 3 hours. The acetone content is <200ppm, thereby obtaining a water-based polyurethane automotive interior coating adhesive with a solid content of 50%.

[0044] S4. Take 92.5 parts of the hydrocolloid prepared above, add 5 parts of 30% nano-silica hydrosol (average particle size 15 nm) and 2.5 parts of silver ion-loaded flaky zirconium phosphate (RS-CZY, Fujian Ruisen New Materials) in sequence, and disperse at a high-speed disperser speed of 1000 rpm for 30 minutes to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0045] Example 5 The synthesis steps of the waterborne polyurethane were the same as those in Example 4, except that 93 parts of the hydrogel prepared above were taken in S4, 4 parts of the amino-containing coupling agent-modified nano-silica solution prepared in Example 1, and 3 parts of cubic zirconium phosphate loaded with silver ions (RS-LZY, Fujian Ruisen New Materials) were added in sequence, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0046] Example 6 The synthesis steps of the waterborne polyurethane were the same as those in Example 4, except that 93 parts of the hydrogel prepared above were taken in S4, 4 parts of the urea-containing coupling agent-modified nano-silica solution prepared in Example 2, and 3 parts of silver ion-loaded flaky zirconium phosphate (RS-CZY, Fujian Ruisen New Materials) were added in sequence, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0047] Example 7 The synthesis steps of the waterborne polyurethane were the same as those in Example 4, except that 93 parts of the hydrogel prepared above were taken in S4, 4 parts of the nano-silica solution modified with an imidazole coupling agent prepared in Example 3, and 3 parts of cubic zirconium phosphate loaded with silver ions (RS-LZY, Fujian Ruisen New Materials) were added in sequence, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0048] Example 8 The waterborne polyurethane is synthesized according to the following steps (wherein each raw material is calculated by weight); S1. Preparation of a polyurethane prepolymer containing a hydrophilic monomer: two polyols were added to a three-necked flask: 130 parts of polybutylene adipate diol and 10 parts of polytetramethylene ether diol. The polyols were vacuum dehydrated at 120°C for 2 hours, cooled to 80-85°C, 5 parts of dimethylolpropionic acid and 4 parts of acetone were added, stirred for 20 minutes, 24 parts of diphenylmethane diisocyanate were added, and the mixture was reacted at 80-85°C for 2 hours. Then 4 parts of 1,4-butanediol were added and the mixture was reacted at 80-85°C for 1 hour. 0.002 parts of a catalyst were added and the mixture was reacted at 70-80°C until the -NCO content was reduced to 10 wt%, thereby obtaining a polyurethane prepolymer containing a hydrophilic monomer.

[0049] S2, neutralization reaction: cool the polyurethane prepolymer to 40-45° C., add 76 parts of acetone to reduce the viscosity of the polyurethane prepolymer, and then add 4 parts of triethylamine under the shearing action of a high-speed disperser and react for 15-20 minutes.

[0050] S3, deketone process: set the temperature to 55 ° C, the pressure to 0.098 Pa, deketone for 1 to 3 hours, the acetone content is <200 ppm, thereby obtaining a water-based polyurethane adhesive with a solid content of 50%.

[0051] S4. Take 92.5 parts of the hydrocolloid prepared above, add 5 parts of 30% nano-silica hydrosol (average particle size 15 nm) and 2.5 parts of silver ion-loaded flaky zirconium phosphate (RS-CZY, Fujian Ruisen New Materials) in sequence, and disperse at a high-speed disperser speed of 1000 rpm for 30 minutes to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0052] Example 9 The synthesis steps of the waterborne polyurethane were the same as those in Example 8, except that 93 parts of the hydrogel prepared above were taken in S4, 4 parts of the amino-containing coupling agent-modified nano-silica solution prepared in Example 1, and 3 parts of cubic zirconium phosphate loaded with silver ions (RS-LZY, Fujian Ruisen New Materials) were added in sequence, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0053] Example 10 The synthesis steps of the waterborne polyurethane were the same as those in Example 8, except that 93 parts of the hydrogel prepared above were taken in S4, 4 parts of the urea-containing coupling agent-modified nano-silica solution prepared in Example 2, and 3 parts of silver ion-loaded flaky zirconium phosphate (RS-CZY, Fujian Ruisen New Materials) were added in sequence, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0054] Example 11 The synthesis steps of the waterborne polyurethane were the same as those in Example 8, except that 93 parts of the hydrogel prepared above were taken in S4, 4 parts of the nano-silica solution modified with an imidazole coupling agent prepared in Example 3, and 3 parts of cubic zirconium phosphate loaded with silver ions (RS-LZY, Fujian Ruisen New Materials) were added in sequence, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0055] Comparative Example 1 The steps for synthesizing waterborne polyurethane are the same as those in Example 4, except that 100 parts of the above-prepared hydrogel are directly dispersed in a high-speed disperser at a speed of 1000 rpm for 30 minutes in S4 to obtain hybrid waterborne polyurethane.

[0056] Comparative Example 2 The synthesis steps of waterborne polyurethane were the same as those in Example 4, except that 97.5 parts of the hydrogel prepared above were taken in S4, 2.5 parts of silver ion-loaded flaky zirconium phosphate (RS-CZY, Fujian Ruisen New Materials) were added, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 min to obtain a hybrid antibacterial hybrid waterborne polyurethane.

[0057] Comparative Example 3 The synthesis steps of waterborne polyurethane were the same as those in Example 4, except that 96 parts of the hydrogel prepared above were added to 4 parts of the amino-containing coupling agent-modified nano-silica solution prepared in Example 1 in S4, and the mixture was dispersed at a high-speed disperser speed of 1000 rpm for 30 minutes to obtain a hybrid waterborne polyurethane.

[0058] Test section: The properties of the waterborne polyurethane adhesive samples prepared in Examples 4-11 and Comparative Examples 1-3 were tested, and the test results are listed in Table 1.

[0059] Sample Preparation: Apply the prepared waterborne polyurethane adhesive sample evenly to a 10cm x 10cm polyurethane (PU) leather surface to a wet film thickness of 15-20μm. Bake at 80°C for 30 minutes to obtain a PU leather sample with a dry film thickness of 5-10μm. A film thickness less than 5μm will result in insufficient adhesion, while a film too thick can lead to defects such as bubbles, which also affect adhesion.

[0060] Bond strength: Referring to ISO 29863:2018, the PU rubber sample was laminated to an acrylonitrile-butadiene-styrene copolymer (ABS) test piece. After maintaining the lamination pressure for 20 minutes, a static shear test was performed at room temperature and 80°C. The shear test time was recorded. The longer the test time, the better the bond strength of the adhesive.

[0061] Antibacterial properties: Referring to the antibacterial test method of AATCC-100, the antibacterial effect of the prepared antibacterial adhesive on Escherichia coli, Staphylococcus aureus, and Candida albicans was tested.

[0062] Stability test: The waterborne polyurethane adhesive samples prepared in Examples 4-11 and Comparative Examples 1-3 were placed in an oven at 60°C for 7 days. After the expiration of the oven, the samples were removed from the oven and allowed to stand at room temperature for 1 hour to observe whether the adhesive samples were delaminated.

[0063] Table 1

[0064] From the results in Table 1, it can be seen that the antibacterial hybrid waterborne polyurethane prepared in Examples 4-11 can improve the bonding performance of waterborne polyurethane adhesive at room temperature and at a high temperature of 80°C by adding nano-silica or coupling agent to modify nano-silica. Since the surface of nano-silica contains a large amount of Si-OH, the silanol group itself is a polar group that can increase the bonding strength between the adhesive and the adherend, and also reacts with -COO in the polyurethane to form a hydroxyl group. - Alternatively, the urethane bonds (NHCOO) form hydrogen bonds, thereby improving the adhesive's bonding and cohesive strength. Furthermore, this hydrogen bond network can enhance the stability of cubic or flake zirconium phosphate-loaded silver in waterborne polyurethane systems, making it less likely to settle. This allows the zirconium phosphate-loaded silver to be evenly dispersed and stably provide an antibacterial effect.

[0065] Comparative Example 1 does not use nano-silica or nano-silica modified with a coupling agent and cubic or flaky zirconium phosphate-loaded silver. The bonding strength of the corresponding water-based polyurethane adhesive at 80° C. is significantly reduced, and there is no antibacterial effect.

[0066] Comparative Example 2 did not use nano-silica or coupling agent-modified nano-silica, and only added flaky zirconium phosphate-supported silver. The bonding strength at 80°C was significantly reduced, and the flaky zirconium phosphate-supported silver had poor stability in the waterborne polyurethane system. After accelerated stability testing, it was found that the flaky zirconium phosphate-supported silver was prone to sedimentation and precipitation, resulting in poor and unstable antibacterial effect.

[0067] Comparative Example 3 uses the amino-containing coupling agent modified nano-silica of Example 1, but does not use cubic or flaky zirconium phosphate loaded silver. The bonding strength at 80°C is improved, but the waterborne polyurethane lacks the antibacterial component, resulting in a lack of antibacterial effect.

[0068] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for parts thereof. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention. Although the above describes the specific embodiments of the present invention, it is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that, based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. An antibacterial hybrid waterborne polyurethane, characterized in that: include: Any one of a polyurethane prepolymer, silver ion-loaded zirconium phosphate, and nano-silica or nano-silica modified with a coupling agent; The silver ion-loaded zirconium phosphate is selected from sheet-shaped zirconium phosphate loaded with silver or cubic zirconium phosphate loaded with silver, and its particle size ranges from 0.1 to 10 μm; Nano-silica is selected from silica particles or silica aqueous dispersion, and the average particle size of the silica does not exceed 100 nm; the polyurethane prepolymer contains a hydrophilic chain extender and at least two polyols with different glass transition temperatures, and the polyurethane prepolymer is terminated with a -NCO group, and the hydrophilic chain extender is a polyol or polyamine containing at least one -COOH or -SO3H group.

2. The antibacterial hybrid waterborne polyurethane according to claim 1, characterized in that 15-30 parts of silane coupling agent, 5-15 parts of organic orthosilicate, 1-20 parts of water, 50-70 parts of alcohol solvent, 0.001-0.01 parts of catalyst; The silane coupling agent is selected from any one of an amino-containing silane coupling agent, a urea-containing silane coupling agent, and an imidazole-containing silane coupling agent.

3. The antibacterial hybrid waterborne polyurethane according to claim 2, characterized in that: The alcohol solvent is selected from any one or more of methanol, ethanol and isopropanol; And / or, the amino-containing silane coupling agent is selected from any one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane; And / or, the urea-containing silane coupling agent is selected from: any one or two of 3-ureapropyltrimethoxysilane and 3-ureapropyltriethoxysilane; And / or, the imidazole-containing silane coupling agent is selected from: any one or two of N-(trimethoxysilylpropyl)imidazole and N-(triethoxysilylpropyl)imidazole; And / or, the organic orthosilicate is selected from: one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate; and / or, the catalyst is selected from: any one or more of tetrabutyl titanate and dibutyltin dilaurate; And / or, using a sol-gel method to synthesize nano-silica modified with an amino-containing coupling agent.

4. The antibacterial hybrid waterborne polyurethane according to claim 1, characterized in that The polyurethane prepolymer comprises the following raw materials in parts by weight: 68-72 parts of polyol, 23-24 parts of diisocyanate, 4-7 parts of hydrophilic chain extender, 2-4 parts of polyol chain extender, 1-2 parts of neutralizer, and 0.001-0.01 parts of catalyst; Wherein, the number average molecular weight of the polyol is in the range of 200 to 4000.

5. The antibacterial hybrid waterborne polyurethane according to claim 4, characterized in that The polyol is selected from: one or both of polyester polyol and polyether polyol; And / or, the diisocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate; And / or, the hydrophilic chain extender is selected from at least one of dimethylolbutyric acid, dimethylolpropionic acid, and sodium ethylenediaminesulfonate; and / or, the polyol chain extender is selected from: one or more of 1,4-butanediol, 1,6-hexanediol, and 1,3-butanediol; and / or, the neutralizing agent is selected from: one or more of triethylamine, triethanolamine, and N,N-dimethylethanolamine; And / or, the catalyst is selected from any one or more of an organic bismuth catalyst and an organic tin catalyst.

6. The antibacterial hybrid waterborne polyurethane according to claim 1, characterized in that The preparation method of the polyurethane prepolymer comprises: S1, mixing a polyol, a diisocyanate, and a hydrophilic chain extender together for reaction, then adding the polyol chain extender for reaction, and then adding a catalyst for reaction until the -NCO content of the reaction mixture is ≤10 wt%; S2. Neutralization reaction: Cool the polyurethane prepolymer to 30-60° C. and add a neutralizing agent under the shearing action of a high-speed disperser to react for 5-60 minutes.

7. The antibacterial hybrid waterborne polyurethane according to claim 6, characterized in that: In step S1, acetone in an amount of 1 to 2 times the total weight of the hydrophilic chain extender is added during the mixing of the polyol, diisocyanate and hydrophilic chain extender; and / or, after cooling in step S2, first adding 40-60 wt% acetone of the polyurethane prepolymer to reduce the viscosity of the polyurethane prepolymer, and then adding a neutralizing agent to carry out a neutralization reaction under the shearing action of a high-speed disperser; And / or, the preparation method of the polyurethane prepolymer further includes: S3, a deketone process, setting the temperature to 40-60° C., the pressure in the container not exceeding 0.1 Pa, and removing acetone by vacuum.

8. A method for preparing the antibacterial hybrid waterborne polyurethane according to any one of claims 1 to 7, characterized in that: The polyurethane prepolymer, silver ion-loaded zirconium phosphate, nano-silica or nano-silica modified by a coupling agent are mixed and then uniformly dispersed using a mechanical method.

9. Use of the antibacterial hybrid waterborne polyurethane according to any one of claims 1 to 7, characterized in that: Use of antimicrobial hybrid waterborne polyurethane for bonding between polyurethane substrates and plastic substrates; Wherein, the plastic substrate includes any one of polybutylene terephthalate, polycarbonate, polyamide, acrylonitrile-butadiene-styrene copolymer or polyphenylene sulfide.

10. Use of the antibacterial hybrid waterborne polyurethane according to any one of claims 1 to 7, characterized in that: Application of antibacterial hybrid waterborne polyurethane as automotive interior covering adhesive.

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