CN113372766A - Water-based high-molecular antibacterial material with good water resistance and preparation method thereof - Google Patents
Water-based high-molecular antibacterial material with good water resistance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based high-molecular antibacterial material with good water resistance and a preparation method thereof, wherein the water-based high-molecular antibacterial material is prepared from the following components in parts by weight: 50-70 parts of modified starch, 20-30 parts of modified waterborne polyurethane, 40-50 parts of reactive emulsifier, 10-15 parts of nano-silver dispersant, 5-10 parts of negative ion crystal and 10-20 parts of phenol antioxidant. The invention solves the problems of low initial viscosity and poor water resistance of a coating film formed by the waterborne polyurethane, the water resistance, the salt water resistance, the corrosion resistance and other physical and mechanical properties of the coating can be effectively improved by adding the reactive emulsifier, and the anionic crystal is matched, so that the waterborne high polymer coating can release a large amount of anions, the formaldehyde, the voc and the dust content of indoor air are effectively reduced, and the effects of killing bacteria and removing peculiar smell are achieved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based high-molecular antibacterial material with good water resistance and a preparation method thereof.
Background
Along with the enhancement of the environmental awareness of people and the increasing standardization of the indexes of the environment-friendly materials by the country, the water-based high polymer materials are effectively developed and utilized, wherein the most common coating is used in the aspect of environment-friendly coatings: the general name of a liquid or solid material which can form a layer of solid coating film with protection, decoration or special properties (such as insulation, corrosion resistance, marks and the like) when being coated on the surface of an object is widely applied to the fields of furniture, clothing, chemical industry, metallurgy, shipbuilding, fire fighting, national defense and the like, and the content of voc in the coating can be reduced to a higher degree by taking a water-based high polymer material as an injection material in the coating.
The water-soluble polymer is also called water-soluble resin or water-soluble polymer, so that the water-soluble polymer substance is one of the most important polymers in the present society, and is in a rapid development stage in both production and application, for example, modern food industry has relied on water-soluble polymers matched with cellulose products, hydrophilic gum, modified edible starch, pectin and the like, and a great deal of development and research is devoted to fat substitutes.
In the existing research on water-based polymer coatings, such as "an art coating and a preparation method thereof" (patent No. CN 104592825B) disclosed by Chinese patent network, the Chinese patent discloses a preparation method of the art coating, which comprises the steps of firstly adding 28-34 parts of water into a dispersion cylinder, sequentially adding 0.2-0.3 part of hydroxyethyl cellulose, 0.15-0.2 part of bentonite and 0.15-0.2 part of water-based multifunctional auxiliary agent under the stirring state of 350-550r/min, stirring for 1min-3min, then increasing the rotating speed to 800-1000r/min, sequentially adding 0.6-0.7 part of water-based dispersing agent, 0.1-0.2 part of water-based wetting agent, 0.4-0.5 part of water-based defoaming agent, 3-7 parts of titanium dioxide, 18-22 parts of kaolin, 9-15 parts of calcium carbonate and 2-4 parts of diatomite, increasing the rotation speed to 1800-plus 2000r/min again, dispersing for 15-20min at the rotation speed, detecting until the system fineness is less than or equal to 60, then reducing the rotation speed to 1000-plus 1200r/min, stirring, sequentially adding 20-25 parts of emulsion, 1.3-1.6 parts of film-forming assistant, 1.0-1.2 parts of antifreeze, 0.3-0.4 part of sterilization preservative and 1.2-1.8 parts of thickener, and fully stirring for 15-20min to obtain the artistic paint, wherein the prepared paint has low processability and poor water resistance; for another example, publication No. CN102838912B discloses a preparation method of an aqueous rust-bearing coating, the prepared polymeric rust-converting agent has a pure plant source as a raw material, is low in cost, meets the national policy of sustainable development and comprehensive utilization of resources, has a good rust-converting function, can be directly mixed into a coating to serve as an additive of the aqueous rust-bearing coating, and can also serve as a monomer to participate in acrylate emulsion polymerization, the rust-bearing emulsion has high rust-converting capability, good stability and extremely low VOC content, belongs to an environment-friendly aqueous polymeric coating, but does not have good bactericidal capability, and has insufficient processing adaptability in the preparation process, and the technical realization elements are: the invention aims to overcome the defects of the prior art and provide a novel antibacterial waterproof coating which is simple in preparation process, has good water resistance and antibacterial performance, and simultaneously has the properties of salt water resistance, corrosion resistance and other physical and mechanical properties.
Disclosure of Invention
The invention aims to: in order to solve the problems of insufficient processing adaptability and poor functionality, the water-based polymer antibacterial material with good water resistance and the preparation method are provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-based high-molecular antibacterial material with good water resistance is prepared from the following components in parts by weight: 50-70 parts of modified starch, 20-30 parts of modified waterborne polyurethane, 40-50 parts of reactive emulsifier, 10-15 parts of nano-silver dispersant, 5-10 parts of negative ion crystal and 10-20 parts of phenol antioxidant.
As a further description of the above technical solution:
the modified starch is prepared by the following steps:
step S1: the modified starch takes corn starch as a raw material, sodium periodate as an oxidant and hydrochloric acid as an acidolysis agent, the acidolysis agent and the oxidant are added into deionized water to be mixed, and then the corn starch is added and stirred to prepare starch milk;
step S2: then transferring the prepared starch milk to a chemical reaction kettle for carrying out one-step acidolysis oxidation reaction;
step S3: after the acidolysis oxidation reaction is finished, washing the obtained material until the material is neutral, then sequentially drying and grinding, and finally filtering the powdery material to obtain powdery dialdehyde starch;
step S4: and detecting the prepared powdery dialdehyde starch by using a Fourier transform infrared spectrometer, and verifying whether the powdery dialdehyde starch is qualified or not according to the characterization.
As a further description of the above technical solution:
in the step S1, the hydrochloric acid concentration is preferably 0.6mol/l, and the starch milk concentration is most preferably 8 mol/l.
As a further description of the above technical solution:
in the step S2, the acidolysis oxidation reaction needs to be controlled at the reaction temperature of 35-55 ℃ for 2-4 hours.
As a further description of the above technical solution:
the modified waterborne polyurethane is prepared by the following steps:
step S5: injecting deionized water into a reaction kettle with a stirring mechanism, adding a stabilizer, a dispersant and a modifier into the reaction kettle in a stirring state in a dropwise injection mode, then dropwise adding hydrochloric acid to adjust the pH value, and finally adding zinc chloride to prepare a zinc chloride solution;
step S6: after the zinc chloride solution is clarified, dropwise adding sodium hydroxide to adjust the pH value of the solution, reacting for 4.5-6 hours under the conditions of vacuum and 120-140 ℃, then sequentially carrying out centrifugal treatment, washing obtained precipitates with water and alcohol, and finally carrying out vacuum drying for 12 hours at the temperature of 50 ℃ to obtain nano zinc oxide;
step S7: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a small molecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at the temperature of 80-85 ℃ to prepare a prepolymerization solution;
step S8: adding the zinc oxide solution into the pre-polymerization solution under high-speed shearing force, dispersing for 40 minutes, adding the nano zinc oxide, stirring for 50 minutes, and removing the organic solvent by reduced pressure distillation to obtain the high-solid-content waterborne polyurethane solution.
As a further description of the above technical solution:
in step S1, the adjusted pH value is 2.5, and in step S6, the adjusted pH value is 10.
The water-based high-molecular antibacterial material with good water resistance is prepared by the following steps:
and step 9: weighing cardanol, triethylamine and maleic anhydride according to the formula amount, and then simultaneously putting maleic anhydride and cardanol into a reaction kettle with a stirring mechanism;
step 10: starting a stirring mechanism arranged in the reaction kettle, heating the reaction kettle in a water bath, and carrying out heat preservation reaction for 1.5 hours when the internal temperature of the reaction kettle is raised to 170 ℃;
step 11: after 1.5 hours of constant temperature reaction at 170 ℃, the temperature is raised to 190 ℃ within 2.1-3.3 hours, and constant temperature reaction is carried out for 1.1 hours, thus finishing the esterification reaction;
step 12: after the constant temperature reaction at 190 ℃ for 1.1 hour is finished, sampling and detecting the viscosity and the acid value of the mixture, and when the viscosity is less than 3s (Grignard) and the acid value is not more than 145mgKOH/g, cooling to 50 ℃;
step 13: and introducing ultrasonic oscillation equipment while slowly stirring, and slowly adding triethylamine to complete filtration to obtain the reactive emulsifier.
A preparation method of a water-based high-molecular antibacterial material formula with good water resistance is characterized by comprising the following specific operation steps:
step A1, firstly, preparing various ingredients of the water-based polymer antibacterial coating, including modified starch, modified water-based polyurethane, a reactive emulsifier, a nano-silver dispersant, an anion crystal and a phenol antioxidant;
step A2: taking modified starch and modified waterborne polyurethane, adding deionized water into a reaction kettle with a stirring mechanism, and controlling the reaction kettle to operate to stir the added ingredients until the ingredients are uniformly mixed to obtain a mixture A;
step A3: sequentially adding reactive emulsifiers into the mixture A in the stirring kettle, continuously stirring, and uniformly mixing to obtain a mixture B;
and A4, continuously adding the nano-silver dispersing agent, the negative ion crystal and the classified antibacterial agent into the reaction kettle, and stirring to obtain the water-based polymer antibacterial coating, wherein the stirring time is 7-9min, and the stirring speed is 800 r/min.
As a further description of the above technical solution:
the water-based polymer antibacterial material also comprises one or a mixture of at least two of a flatting agent, a delustering agent, a coupling agent, a defoaming agent and a brightener.
As a further description of the above technical solution:
the stabilizer is polyvinylpyrrolidone (PVP) or trisnonylphenyl phosphite (TNP).
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, the waterborne polyurethane is modified, so that the prepared waterborne polymer antibacterial coating has antibacterial activity on escherichia coli and staphylococcus aureus, the problems of low initial viscosity and poor water resistance of a formed coating film caused by a large amount of hydrophilic groups in the side chain of the waterborne polyurethane are solved, the water resistance, salt water resistance, corrosion resistance and other physical and mechanical properties of the coating can be effectively improved by adding the reactive emulsifier, and the waterborne polymer coating can release a large amount of negative ions by matching with the negative ion crystal, so that the formaldehyde, voc and dust content of indoor air are effectively reduced, and the effects of killing bacteria and removing peculiar smell are achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that:
example one
Firstly, preparing modified starch, modified waterborne polyurethane and a reactive emulsifier in sequence:
step S1: the modified starch takes corn starch as a raw material, sodium periodate as an oxidant and hydrochloric acid as an acidolysis agent, the acidolysis agent and the oxidant are added into deionized water to be mixed, and then the corn starch is added and stirred to prepare starch milk;
step S2: then transferring the prepared starch milk to a chemical reaction kettle for carrying out one-step acidolysis oxidation reaction;
step S3: after the acidolysis oxidation reaction is finished, washing the obtained material until the material is neutral, then sequentially drying and grinding, and finally filtering the powdery material to obtain powdery dialdehyde starch;
step S4: detecting the prepared powdery dialdehyde starch by using a Fourier transform infrared spectrometer, and verifying whether the powdery dialdehyde starch is qualified or not according to the characterization;
step S5: injecting deionized water into a reaction kettle with a stirring mechanism, adding a stabilizer, a dispersant and a modifier into the reaction kettle in a stirring state in a dropwise injection mode, then dropwise adding hydrochloric acid to adjust the pH value, and finally adding zinc chloride to prepare a zinc chloride solution;
step S6: after the zinc chloride solution is clarified, dropwise adding sodium hydroxide to adjust the pH value of the solution, reacting for 4.5 hours at the temperature of 120-140 ℃ in vacuum, then sequentially carrying out centrifugal treatment, washing obtained precipitates with water and alcohol, and finally carrying out vacuum drying for 12 hours at the temperature of 50 ℃ to obtain nano zinc oxide;
step S7: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a small molecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at 80 ℃ to obtain a prepolymerization solution;
step S8: adding the zinc oxide solution into the prepolymerization solution under high-speed shearing force, dispersing for 40 minutes, adding the nano zinc oxide, stirring for 50 minutes, and removing the organic solvent by reduced pressure distillation to prepare a high-solid-content waterborne polyurethane solution;
and step 9: weighing cardanol, triethylamine and maleic anhydride according to the formula amount, and then simultaneously putting maleic anhydride and cardanol into a reaction kettle with a stirring mechanism;
step 10: starting a stirring mechanism arranged in the reaction kettle, heating the reaction kettle in a water bath, and carrying out heat preservation reaction for 1.5 hours when the internal temperature of the reaction kettle is raised to 170 ℃;
step 11: after 1.5 hours of constant temperature reaction at 170 ℃, the temperature is raised to 190 ℃ within 2.1 hours, and constant temperature reaction is carried out for 1.1 hours to complete esterification reaction;
step 12: after the constant temperature reaction at 190 ℃ for 1.1 hour is finished, sampling and detecting the viscosity and the acid value of the mixture, and when the viscosity is less than 3s (Grignard) and the acid value is not more than 145mgKOH/g, cooling to 50 ℃;
step 13: and introducing ultrasonic oscillation equipment while slowly stirring, and slowly adding triethylamine to complete filtration to obtain the reactive emulsifier.
And finally, preparing the water-based polymer antibacterial coating:
step A1, firstly, preparing various ingredients of the water-based polymer antibacterial coating, including modified starch, modified water-based polyurethane, a reactive emulsifier, a nano-silver dispersant, an anion crystal and a phenol antioxidant;
step A2: taking modified starch and modified waterborne polyurethane, adding deionized water into a reaction kettle with a stirring mechanism, and controlling the reaction kettle to operate to stir the added ingredients until the ingredients are uniformly mixed to obtain a mixture A;
step A3: sequentially adding reactive emulsifiers into the mixture A in the stirring kettle, continuously stirring, and uniformly mixing to obtain a mixture B;
and A4, continuously adding the nano-silver dispersing agent, the negative ion crystals and the classified antibacterial agent into the reaction kettle, and stirring to obtain the water-based polymer antibacterial coating, wherein the stirring time is 7-9min, and the stirring speed is 800 r/min.
Example two
Firstly, preparing modified starch, modified waterborne polyurethane and a reactive emulsifier in sequence:
step S1: the modified starch takes corn starch as a raw material, sodium periodate as an oxidant and hydrochloric acid as an acidolysis agent, the acidolysis agent and the oxidant are added into deionized water to be mixed, and then the corn starch is added and stirred to prepare starch milk;
step S2: then transferring the prepared starch milk to a chemical reaction kettle for carrying out one-step acidolysis oxidation reaction;
step S3: after the acidolysis oxidation reaction is finished, washing the obtained material until the material is neutral, then sequentially drying and grinding, and finally filtering the powdery material to obtain powdery dialdehyde starch;
step S4: detecting the prepared powdery dialdehyde starch by using a Fourier transform infrared spectrometer, and verifying whether the powdery dialdehyde starch is qualified or not according to the characterization;
step S5: injecting deionized water into a reaction kettle with a stirring mechanism, adding a stabilizer, a dispersant and a modifier into the reaction kettle in a stirring state in a dropwise injection mode, then dropwise adding hydrochloric acid to adjust the pH value, and finally adding zinc chloride to prepare a zinc chloride solution;
step S6: after the zinc chloride solution is clarified, dropwise adding sodium hydroxide to adjust the pH value of the solution, reacting for 6 hours at the temperature of 120-140 ℃ in vacuum, then sequentially carrying out centrifugal treatment, washing obtained precipitates with water and alcohol, and finally carrying out vacuum drying for 12 hours at the temperature of 50 ℃ to obtain nano zinc oxide;
step S7: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a small molecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at the temperature of 80-85 ℃ to prepare a prepolymerization solution;
step S8: adding the zinc oxide solution into the prepolymerization solution under high-speed shearing force, dispersing for 40 minutes, adding the nano zinc oxide, stirring for 50 minutes, and removing the organic solvent by reduced pressure distillation to prepare a high-solid-content waterborne polyurethane solution;
and step 9: weighing cardanol, triethylamine and maleic anhydride according to the formula amount, and then simultaneously putting maleic anhydride and cardanol into a reaction kettle with a stirring mechanism;
step 10: starting a stirring mechanism arranged in the reaction kettle, heating the reaction kettle in a water bath, and carrying out heat preservation reaction for 1.5 hours when the internal temperature of the reaction kettle is raised to 170 ℃;
step 11: after 1.5 hours of constant temperature reaction at 170 ℃, the temperature is raised to 190 ℃ within 3.3 hours, and constant temperature reaction is carried out for 1.1 hours to complete esterification reaction;
step 12: after the constant temperature reaction at 190 ℃ for 1.1 hour is finished, sampling and detecting the viscosity and the acid value of the mixture, and when the viscosity is less than 3s (Grignard) and the acid value is not more than 145mgKOH/g, cooling to 50 ℃;
step 13: and introducing ultrasonic oscillation equipment while slowly stirring, and slowly adding triethylamine to complete filtration to obtain the reactive emulsifier.
And finally, preparing the water-based polymer antibacterial coating:
step A1, firstly, preparing various ingredients of the water-based polymer antibacterial coating, including modified starch, modified water-based polyurethane, a reactive emulsifier, a nano-silver dispersant, an anion crystal and a phenol antioxidant;
step A2: taking modified starch and modified waterborne polyurethane, adding deionized water into a reaction kettle with a stirring mechanism, and controlling the reaction kettle to operate to stir the added ingredients until the ingredients are uniformly mixed to obtain a mixture A;
step A3: sequentially adding reactive emulsifiers into the mixture A in the stirring kettle, continuously stirring, and uniformly mixing to obtain a mixture B;
and A4, continuously adding the nano-silver dispersing agent, the negative ion crystals and the classified antibacterial agent into the reaction kettle, and stirring to obtain the water-based polymer antibacterial coating, wherein the stirring time is 9min, and the stirring speed is 800 r/min.
EXAMPLE III
Firstly, preparing modified starch, modified waterborne polyurethane and a reactive emulsifier in sequence:
step S1: the modified starch takes corn starch as a raw material, sodium periodate as an oxidant and hydrochloric acid as an acidolysis agent, the acidolysis agent and the oxidant are added into deionized water to be mixed, and then the corn starch is added and stirred to prepare starch milk;
step S2: then transferring the prepared starch milk to a chemical reaction kettle for carrying out one-step acidolysis oxidation reaction;
step S3: after the acidolysis oxidation reaction is finished, washing the obtained material until the material is neutral, then sequentially drying and grinding, and finally filtering the powdery material to obtain powdery dialdehyde starch;
step S4: detecting the prepared powdery dialdehyde starch by using a Fourier transform infrared spectrometer, and verifying whether the powdery dialdehyde starch is qualified or not according to the characterization;
step S5: injecting deionized water into a reaction kettle with a stirring mechanism, adding a stabilizer, a dispersant and a modifier into the reaction kettle in a stirring state in a dropwise injection mode, then dropwise adding hydrochloric acid to adjust the pH value, and finally adding zinc chloride to prepare a zinc chloride solution;
step S6: after the zinc chloride solution is clarified, dropwise adding sodium hydroxide to adjust the pH value of the solution, reacting for 5 hours under the conditions of vacuum and 130 ℃, then sequentially carrying out centrifugal treatment, washing obtained precipitates with water and alcohol, and finally carrying out vacuum drying for 12 hours under the environment of 50 ℃ to obtain nano zinc oxide;
step S7: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a small molecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at 83 ℃ to obtain a prepolymerization solution;
step S8: adding the zinc oxide solution into the prepolymerization solution under high-speed shearing force, dispersing for 40 minutes, adding the nano zinc oxide, stirring for 50 minutes, and removing the organic solvent by reduced pressure distillation to prepare a high-solid-content waterborne polyurethane solution;
and step 9: weighing cardanol, triethylamine and maleic anhydride according to the formula amount, and then simultaneously putting maleic anhydride and cardanol into a reaction kettle with a stirring mechanism;
step 10: starting a stirring mechanism arranged in the reaction kettle, heating the reaction kettle in a water bath, and carrying out heat preservation reaction for 1.5 hours when the internal temperature of the reaction kettle is raised to 170 ℃;
step 11: after 1.5 hours of constant temperature reaction at 170 ℃, the temperature is raised to 190 ℃ within 2.8 hours, and constant temperature reaction is carried out for 1.1 hours, thus finishing the esterification reaction;
step 12: after the constant temperature reaction at 190 ℃ for 1.1 hour is finished, sampling and detecting the viscosity and the acid value of the mixture, and when the viscosity is less than 3s (Grignard) and the acid value is not more than 145mgKOH/g, cooling to 50 ℃;
step 13: and introducing ultrasonic oscillation equipment while slowly stirring, and slowly adding triethylamine to complete filtration to obtain the reactive emulsifier.
And finally, preparing the water-based polymer antibacterial coating:
step A1, firstly, preparing various ingredients of the water-based polymer antibacterial coating, including modified starch, modified water-based polyurethane, a reactive emulsifier, a nano-silver dispersant, an anion crystal and a phenol antioxidant;
step A2: taking modified starch and modified waterborne polyurethane, adding deionized water into a reaction kettle with a stirring mechanism, and controlling the reaction kettle to operate to stir the added ingredients until the ingredients are uniformly mixed to obtain a mixture A;
step A3: sequentially adding reactive emulsifiers into the mixture A in the stirring kettle, continuously stirring, and uniformly mixing to obtain a mixture B;
and A4, continuously adding the nano-silver dispersing agent, the negative ion crystals and the classified antibacterial agent into the reaction kettle, and stirring to obtain the water-based polymer antibacterial coating, wherein the stirring time is 8min, and the stirring speed is 750 r/min.
The physical property test of the water-based polymer antibacterial coating prepared by the sample of the above example is carried out, and the comparative example of the water-based polymer antibacterial coating prepared by the sample of the above example and the water-based polymer antibacterial coating purchased from the market is made, and the numerical values are shown in table 1:
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. The water-based polymer antibacterial material with good water resistance is characterized by being prepared from the following components in parts by weight: 50-70 parts of modified starch, 20-30 parts of modified waterborne polyurethane, 40-50 parts of reactive emulsifier, 10-15 parts of nano-silver dispersant, 5-10 parts of negative ion crystal and 10-20 parts of phenol antioxidant.
2. The aqueous polymeric antibacterial material with good water resistance of claim 1, wherein the modified starch is prepared by the following steps:
step S1: the modified starch takes corn starch as a raw material, sodium periodate as an oxidant and hydrochloric acid as an acidolysis agent, the acidolysis agent and the oxidant are added into deionized water to be mixed, and then the corn starch is added and stirred to prepare starch milk;
step S2: then transferring the prepared starch milk to a chemical reaction kettle for carrying out one-step acidolysis oxidation reaction;
step S3: after the acidolysis oxidation reaction is finished, washing the obtained material until the material is neutral, then sequentially drying and grinding, and finally filtering the powdery material to obtain powdery dialdehyde starch;
step S4: and detecting the prepared powdery dialdehyde starch by using a Fourier transform infrared spectrometer, and verifying whether the powdery dialdehyde starch is qualified or not according to the characterization.
3. The aqueous polymeric antibacterial material with good water resistance according to claim 2, wherein in step S1, the concentration of hydrochloric acid is preferably 0.6mol/l, and the concentration of starch milk is most preferably 8 mol/l.
4. The aqueous polymeric antibacterial material with good water resistance according to claim 2, wherein in step S2, the acidolysis oxidation reaction is performed at a temperature of 35 ℃ to 55 ℃ for 2 to 4 hours.
5. The aqueous polymeric antibacterial material with good water resistance of claim 1, wherein the modified aqueous polyurethane is prepared by the following steps:
step S5: injecting deionized water into a reaction kettle with a stirring mechanism, adding a stabilizer, a dispersant and a modifier into the reaction kettle in a stirring state in a dropwise injection mode, then dropwise adding hydrochloric acid to adjust the pH value, and finally adding zinc chloride to prepare a zinc chloride solution;
step S6: after the zinc chloride solution is clarified, dropwise adding sodium hydroxide to adjust the pH value of the solution, reacting for 4.5-6 hours under the conditions of vacuum and 120-140 ℃, then sequentially carrying out centrifugal treatment, washing obtained precipitates with water and alcohol, and finally carrying out vacuum drying for 12 hours at the temperature of 50 ℃ to obtain nano zinc oxide;
step S7: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a small molecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at the temperature of 80-85 ℃ to prepare a prepolymerization solution;
step S8: adding the zinc oxide solution into the pre-polymerization solution under high-speed shearing force, dispersing for 40 minutes, adding the nano zinc oxide, stirring for 50 minutes, and removing the organic solvent by reduced pressure distillation to obtain the high-solid-content waterborne polyurethane solution.
6. The aqueous polymeric antibacterial material with excellent water resistance according to claim 5, wherein the adjusted pH value in step S1 is 2.5, and the adjusted pH value in step S6 is 10.
7. The aqueous polymeric antibacterial material with good water resistance according to claim 1, wherein the reactive emulsifier is prepared by the following steps:
and step 9: weighing cardanol, triethylamine and maleic anhydride according to the formula amount, and then simultaneously putting maleic anhydride and cardanol into a reaction kettle with a stirring mechanism;
step 10: starting a stirring mechanism arranged in the reaction kettle, heating the reaction kettle in a water bath, and carrying out heat preservation reaction for 1.5 hours when the internal temperature of the reaction kettle is raised to 170 ℃;
step 11: after 1.5 hours of constant temperature reaction at 170 ℃, the temperature is raised to 190 ℃ within 2.1-3.3 hours, and constant temperature reaction is carried out for 1.1 hours, thus finishing the esterification reaction;
step 12: after the constant temperature reaction at 190 ℃ for 1.1 hour is finished, sampling and detecting the viscosity and the acid value of the mixture, and when the viscosity is less than 3s (Grignard) and the acid value is not more than 145mgKOH/g, cooling to 50 ℃;
step 13: and introducing ultrasonic oscillation equipment while slowly stirring, and slowly adding triethylamine to complete filtration to obtain the reactive emulsifier.
8. The preparation method of the aqueous polymer antibacterial material formula with good water resistance according to any one of claims 1 to 7, characterized by comprising the following specific operation steps:
step A1, firstly, preparing various ingredients of the water-based polymer antibacterial coating, including modified starch, modified water-based polyurethane, a reactive emulsifier, a nano-silver dispersant, an anion crystal and a phenol antioxidant;
step A2: taking modified starch and modified waterborne polyurethane, adding deionized water into a reaction kettle with a stirring mechanism, and controlling the reaction kettle to operate to stir the added ingredients until the ingredients are uniformly mixed to obtain a mixture A;
step A3: sequentially adding reactive emulsifiers into the mixture A in the stirring kettle, continuously stirring, and uniformly mixing to obtain a mixture B;
and A4, continuously adding the nano-silver dispersing agent, the negative ion crystal and the classified antibacterial agent into the reaction kettle, and stirring to obtain the water-based polymer antibacterial coating, wherein the stirring time is 7-9min, and the stirring speed is 800 r/min.
9. The method for preparing an aqueous polymer antibacterial material with good water resistance according to claim 8, wherein the aqueous polymer antibacterial material further comprises one or a mixture of at least two of a leveling agent, a delustering agent, a coupling agent, a defoaming agent and a brightener.
10. The method for preparing an aqueous polymer antibacterial material with good water resistance according to claim 9, wherein the stabilizer is polyvinylpyrrolidone (PVP) or trisnonylphenyl phosphite (TNP).
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