CN115449090B - Fluorocarbon resin emulsion modified silicone-acrylic emulsion and production process thereof - Google Patents

Fluorocarbon resin emulsion modified silicone-acrylic emulsion and production process thereof Download PDF

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CN115449090B
CN115449090B CN202211222524.6A CN202211222524A CN115449090B CN 115449090 B CN115449090 B CN 115449090B CN 202211222524 A CN202211222524 A CN 202211222524A CN 115449090 B CN115449090 B CN 115449090B
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emulsion
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fluorocarbon resin
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CN115449090A (en
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葛长英
姚超
陈安顺
吴晓兵
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Zhejiang Jiangong Decoration Materials Co ltd
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Abstract

The invention relates to the technical field of silicone-acrylate emulsion production and provides a fluorocarbon resin emulsion modified silicone-acrylate emulsion and a production process thereof, wherein the acrylic ester emulsion is modified by graphene oxide to obtain an antibacterial acrylic ester emulsion, methyl methacrylate and butyl acrylate are used as monomers to be copolymerized under the action of an initiator, then the monomers react with gamma-methacryloxypropyl trimethoxy silane, the copolymerized acrylic ester emulsion can be modified, and then the antibacterial acrylic ester emulsion is blended with the acrylic ester emulsion modified by gamma-methacryloxypropyl trimethoxy silane, so that the prepared pre-modified silicone-acrylate emulsion has better antibacterial performance; the pre-modified fluorocarbon resin emulsion is prepared by copolymerizing the fluorinated graphene and other resin monomers, and the pre-modified fluorocarbon resin emulsion can be enabled to have wear resistance and corrosion resistance, so that the silicone-acrylic emulsion modified by the fluorocarbon resin emulsion also has stronger corrosion resistance.

Description

Fluorocarbon resin emulsion modified silicone-acrylic emulsion and production process thereof
Technical Field
The invention relates to the technical field of silicone-acrylic emulsion production, in particular to fluorocarbon resin emulsion modified silicone-acrylic emulsion and a production process thereof.
Background
The silicone-acrylate emulsion is short for organosilicon modified acrylic ester emulsion, wherein the acrylic ester emulsion is used as the basic resin of the water-based acrylic paint, and is widely applied due to the excellent weather resistance, acid and alkali resistance and corrosion resistance. However, it has many disadvantages such as poor water resistance, poor adhesion, low temperature brittleness, high temperature viscosity, etc., which limit its application, while in the main chain structure of polysiloxane molecule, si—o bond energy is high, and there is large molecular volume and low cohesive energy density, so that it has good high and low temperature resistance, weather resistance, low surface tension, etc., and the advantage of using the organosiloxane modified acrylate can effectively combine the advantages of the organosiloxane and the acrylic resin.
However, the conventional silicone-acrylic emulsion has no antibacterial property and poor corrosion resistance, which limits the development in the fields of paint and many fields, and therefore, the antibacterial property and the corrosion resistance of the conventional silicone-acrylic emulsion need to be improved through modification design.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a fluorocarbon resin emulsion modified silicone-acrylate emulsion and a production process thereof, aiming at improving the antibacterial performance and the corrosion resistance of the silicone-acrylate emulsion through the modification of the fluorocarbon resin emulsion.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the fluorocarbon resin emulsion modified silicone-acrylic emulsion comprises the following components in parts by weight: 90-100 parts of pre-modified silicone-acrylic emulsion, 20-30 parts of pre-modified fluorocarbon resin emulsion, 5-8 parts of castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, 3-6 parts of silane coupling agent and 280-300 parts of deionized water;
the pre-modified silicone-acrylate emulsion is prepared from antibacterial acrylate emulsion, methyl methacrylate, butyl acrylate and gamma-methacryloxypropyl trimethoxysilane.
Further, the preparation method of the antibacterial acrylate emulsion comprises the following steps: adding graphene oxide into deionized water, stirring for 10min to prepare a suspension system, and then performing ultrasonic dispersion and filtration on the suspension system; and (3) drying the filter residues in a vacuum drying oven with the temperature of 60 ℃ and the vacuum degree of 0.08MPa for 24 hours to obtain filler powder, and finally adding 5-8% of filler powder into the acrylic ester emulsion for mixing, and performing ultrasonic dispersion for 30 minutes after mixing to obtain the antibacterial acrylic ester emulsion.
Still further, the power of the ultrasonic dispersion is 150W, and the frequency of the ultrasonic dispersion is 20-22kHz.
Further, the preparation method of the pre-modified silicone-acrylic emulsion comprises the following steps:
step1, placing the four-neck flask into a controllable water bath kettle, weighing 8-12 parts by weight of surfactant and 200 parts by weight of deionized water, adding the surfactant and the 200 parts by weight of deionized water into the four-neck flask, stirring for 20min, and raising the water bath temperature to 80 ℃;
step2, weighing 45-50 parts by weight of methyl methacrylate and 15-18 parts by weight of butyl acrylate, uniformly mixing, adding 2-3 parts by weight of ammonium persulfate solution, stirring for 30min, and pre-emulsifying to obtain a monomer component;
and 3, dropwise adding the monomer component in the step2 and 8-12 parts by weight of ammonium sulfate solution into the four-neck flask in the step1, controlling the dropwise adding time to be 2h, dropwise adding gamma-methacryloxypropyl trimethoxysilane with the weight of 6-8% of the monomer component into the system, controlling the dropwise adding time to be 30min, immediately pouring 22-25 parts by weight of antibacterial acrylate emulsion after the dropwise adding is finished, mixing and stirring, and preserving heat for 30-40min at 80-85 ℃ after stirring for 20min to obtain the pre-modified silicone-acrylate emulsion.
Still further, the surfactant in the step1 is glyceryl monostearate.
Further, the mass fraction of the ammonium persulfate solution in the step2 is 2%.
Further, the preparation method of the pre-modified fluorocarbon resin emulsion comprises the following steps:
step a, weighing graphite fluoride, dissolving the graphite fluoride in an ethanol solution containing polyvinylpyrrolidone, performing ultrasonic dispersion for 10min to obtain a preparation solution with graphite fluoride concentration of 8mg/ml, then performing high-speed mechanical shearing stirring on the preparation solution, continuously stirring for 10h at a rotating speed of 1200r/min, performing centrifugal treatment on the preparation solution for 10min after stirring, taking supernatant, performing suction filtration to absorb excessive polyvinylpyrrolidone, and finally drying in a vacuum drying oven at 60 ℃ for 12h to obtain the graphene fluoride powder;
step b, weighing 20-22 parts by weight of methyl methacrylate, 18-20 parts by weight of butyl acrylate, 1-2 parts by weight of acrylic acid, 5-6 parts by weight of chlorotrifluoroethylene, 6-7 parts by weight of fluorinated graphene powder and 1-2 parts by weight of acrylamide sodium isopropyl sulfonate, and stirring at a high speed at normal temperature for pre-emulsification;
and c, pouring the pre-emulsification system in the step b into a reaction kettle, adding 45-48 parts by weight of deionized water and 0.1-0.3 part by weight of ammonium persulfate solution, starting stirring, heating, controlling the temperature, and reacting for 2-3 hours under the conditions of the stirring speed of 200-300r/min and the temperature of 80 ℃, and adjusting the pH value to 7-8 after the reaction is finished, thus obtaining the pre-modified fluorocarbon resin emulsion.
Still further, the concentration of polyvinylpyrrolidone in the ethanol solution in the step a is 10mg/ml.
A production process of fluorocarbon resin emulsion modified silicone-acrylic emulsion comprises the following production steps:
step1, pouring the castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, the silane coupling agent and half of deionized water in a reaction kettle, and mixing and stirring;
step2, adding the pre-modified silicone-acrylate emulsion, the pre-modified fluorocarbon resin emulsion and the rest deionized water in the weight part into the system in Step1, and continuously stirring for 3-4 hours at the rotating speed of 500-600r/min and the temperature of 65-70 ℃ to obtain the fluorocarbon resin emulsion modified silicone-acrylate emulsion.
Further, the rotational speed of the mixing and stirring in Step1 is 300-400r/min, and the stirring time is 30-40min.
Advantageous effects
The invention provides fluorocarbon resin emulsion modified silicone-acrylic emulsion and a production process thereof, and compared with the prior art, the fluorocarbon resin emulsion modified silicone-acrylic emulsion has the following beneficial effects:
1. according to the invention, the antibacterial acrylate emulsion is obtained by modifying the acrylate emulsion through graphene oxide, methyl methacrylate and butyl acrylate are used as monomers to be copolymerized under the action of an initiator, then the monomers are reacted with gamma-methacryloxypropyl trimethoxy silane, the copolymerized acrylate emulsion can be modified, and then the antibacterial acrylate emulsion is blended with the acrylate emulsion modified by gamma-methacryloxypropyl trimethoxy silane, so that the prepared pre-modified silicone-acrylate emulsion has good antibacterial performance.
2. According to the preparation method, graphite fluoride is dissolved in ethanol solution containing polyvinylpyrrolidone, fluorine and hydroxyl are isoelectric and have similar polarity, so that graphite fluoride can be effectively dissolved in the ethanol solution, stable dispersion of the graphite fluoride is promoted while the polyvinylpyrrolidone is added, the graphite fluoride lamellar is peeled off based on the generated strong shearing force at high speed to obtain the graphene fluoride, and the graphene fluoride is copolymerized with other resin monomers to prepare the pre-modified fluorocarbon resin emulsion, so that the pre-modified fluorocarbon resin emulsion can obtain wear resistance and corrosion resistance, and the silicon-acrylic emulsion modified by the fluorocarbon resin emulsion also has stronger corrosion resistance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the fluorocarbon resin emulsion modified silicone-acrylate emulsion of the embodiment comprises the following components in parts by weight: 90 parts of pre-modified silicone-acrylic emulsion, 20 parts of pre-modified fluorocarbon resin emulsion, 5 parts of castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, 3 parts of silane coupling agent and 280 parts of deionized water;
the pre-modified silicone-acrylate emulsion is prepared from antibacterial acrylate emulsion, methyl methacrylate, butyl acrylate and gamma-methacryloxypropyl trimethoxy silane.
The preparation method of the antibacterial acrylate emulsion comprises the following steps: adding graphene oxide into deionized water, stirring for 10min to prepare a suspension system, and then performing ultrasonic dispersion and filtration on the suspension system; and (3) drying the filter residues in a vacuum drying oven with the temperature of 60 ℃ and the vacuum degree of 0.08MPa for 24 hours to obtain filler powder, and finally adding 5% of filler powder into the acrylate emulsion for mixing, and performing ultrasonic dispersion for 30 minutes after mixing to obtain the antibacterial acrylate emulsion.
The power of the ultrasonic dispersion was 150W, and the frequency of the ultrasonic dispersion was 20kHz.
The preparation method of the pre-modified silicone-acrylic emulsion comprises the following steps:
step1, placing the four-neck flask into a controllable water bath pot, weighing 8 parts by weight of surfactant and 200 parts by weight of deionized water, adding the surfactant and the deionized water into the four-neck flask, stirring for 20min, and raising the temperature of the water bath to 80 ℃;
step2, weighing 45 parts by weight of methyl methacrylate and 15 parts by weight of butyl acrylate, uniformly mixing, adding 2 parts by weight of ammonium persulfate solution, stirring for 30min, and pre-emulsifying to obtain a monomer component;
and 3, dropwise adding the monomer component in the step2 and 8 parts by weight of ammonium sulfate solution into the four-neck flask in the step1, controlling the dropwise adding time to be 2 hours, dropwise adding gamma-methacryloxypropyl trimethoxysilane with the weight being 6% of the monomer component into the system, controlling the dropwise adding time to be 30 minutes, immediately pouring 22 parts by weight of antibacterial acrylate emulsion after the dropwise adding is finished, mixing and stirring, and preserving the heat for 30 minutes at 80 ℃ after stirring for 20 minutes to obtain the pre-modified silicone-acrylate emulsion.
The surfactant in the step1 is glyceryl monostearate.
The mass fraction of the ammonium persulfate solution in the step2 is 2%.
The preparation method of the pre-modified fluorocarbon resin emulsion comprises the following steps:
step a, weighing graphite fluoride, dissolving the graphite fluoride in an ethanol solution containing polyvinylpyrrolidone, performing ultrasonic dispersion for 10min to obtain a preparation solution with graphite fluoride concentration of 8mg/ml, then performing high-speed mechanical shearing stirring on the preparation solution, continuously stirring for 10h at a rotating speed of 1200r/min, performing centrifugal treatment on the preparation solution for 10min after stirring, taking supernatant, performing suction filtration to absorb excessive polyvinylpyrrolidone, and finally drying in a vacuum drying oven at 60 ℃ for 12h to obtain the graphene fluoride powder;
step b, weighing 20 parts by weight of methyl methacrylate, 18 parts by weight of butyl acrylate, 1 part by weight of acrylic acid, 5 parts by weight of chlorotrifluoroethylene, 6 parts by weight of fluorinated graphene powder and 1 part by weight of acrylamide sodium isopropyl sulfonate, and stirring at a high speed at normal temperature for pre-emulsification;
and c, pouring the pre-emulsification system in the step b into a reaction kettle, adding 45 parts by weight of deionized water and 0.1 part by weight of ammonium persulfate solution, starting stirring, heating, controlling the temperature, setting, reacting for 2 hours at the stirring speed of 200r/min and the temperature of 80 ℃, and adjusting the pH value to 7 after the reaction is finished, thus obtaining the pre-modified fluorocarbon resin emulsion.
The concentration of polyvinylpyrrolidone in the ethanol solution in step a was 10mg/ml.
A production process of fluorocarbon resin emulsion modified silicone-acrylic emulsion comprises the following production steps:
step1, pouring the castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, the silane coupling agent and half of deionized water in a reaction kettle, and mixing and stirring;
step2, adding the pre-modified silicone-acrylate emulsion, the pre-modified fluorocarbon resin emulsion and the rest deionized water in the weight part into the system in Step1, and continuously stirring for 3 hours at the rotating speed of 500r/min and the temperature of 65 ℃ to obtain the fluorocarbon resin emulsion modified silicone-acrylate emulsion.
The rotational speed of the mixing and stirring in Step1 is 300r/min, and the stirring time is 30min.
Example 2:
the fluorocarbon resin emulsion modified silicone-acrylate emulsion of the embodiment comprises the following components in parts by weight: 100 parts of pre-modified silicone-acrylic emulsion, 30 parts of pre-modified fluorocarbon resin emulsion, 8 parts of castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, 6 parts of silane coupling agent and 300 parts of deionized water;
the pre-modified silicone-acrylate emulsion is prepared from antibacterial acrylate emulsion, methyl methacrylate, butyl acrylate and gamma-methacryloxypropyl trimethoxy silane.
The preparation method of the antibacterial acrylate emulsion comprises the following steps: adding graphene oxide into deionized water, stirring for 10min to prepare a suspension system, and then performing ultrasonic dispersion and filtration on the suspension system; and (3) drying the filter residues in a vacuum drying oven with the temperature of 60 ℃ and the vacuum degree of 0.08MPa for 24 hours to obtain filler powder, and finally adding 8% of filler powder into the acrylic ester emulsion for mixing, and performing ultrasonic dispersion for 30 minutes after mixing to obtain the antibacterial acrylic ester emulsion.
The power of the ultrasonic dispersion was 150W, and the frequency of the ultrasonic dispersion was 22kHz.
The preparation method of the pre-modified silicone-acrylic emulsion comprises the following steps:
step1, placing the four-neck flask into a controllable water bath pot, weighing 12 parts by weight of surfactant and 200 parts by weight of deionized water, adding the surfactant and the deionized water into the four-neck flask, stirring for 20min, and raising the temperature of the water bath to 80 ℃;
step2, weighing 50 parts by weight of methyl methacrylate and 18 parts by weight of butyl acrylate, uniformly mixing, adding 3 parts by weight of ammonium persulfate solution, stirring for 30min, and pre-emulsifying to obtain a monomer component;
and 3, dropwise adding the monomer component in the step2 and 12 parts by weight of ammonium sulfate solution into the four-neck flask in the step1, controlling the dropwise adding time to be 2 hours, dropwise adding gamma-methacryloxypropyl trimethoxysilane with the weight being 8% of the monomer component into the system, controlling the dropwise adding time to be 30 minutes, immediately pouring 25 parts by weight of antibacterial acrylate emulsion after the dropwise adding is finished, mixing and stirring, and preserving heat for 40 minutes at 85 ℃ after stirring for 20 minutes to obtain the pre-modified silicone-acrylate emulsion.
The surfactant in the step1 is glyceryl monostearate.
The mass fraction of the ammonium persulfate solution in the step2 is 2%.
The preparation method of the pre-modified fluorocarbon resin emulsion comprises the following steps:
step a, weighing graphite fluoride, dissolving the graphite fluoride in an ethanol solution containing polyvinylpyrrolidone, performing ultrasonic dispersion for 10min to obtain a preparation solution with graphite fluoride concentration of 8mg/ml, then performing high-speed mechanical shearing stirring on the preparation solution, continuously stirring for 10h at a rotating speed of 1200r/min, performing centrifugal treatment on the preparation solution for 10min after stirring, taking supernatant, performing suction filtration to absorb excessive polyvinylpyrrolidone, and finally drying in a vacuum drying oven at 60 ℃ for 12h to obtain the graphene fluoride powder;
step b, weighing 22 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, 2 parts by weight of acrylic acid, 6 parts by weight of chlorotrifluoroethylene, 7 parts by weight of fluorinated graphene powder and 2 parts by weight of acrylamide sodium isopropyl sulfonate, and stirring at a high speed at normal temperature for pre-emulsification;
and c, pouring the pre-emulsification system in the step b into a reaction kettle, adding 48 parts by weight of deionized water and 0.3 part by weight of ammonium persulfate solution, starting stirring, heating, controlling the temperature, setting, reacting for 3 hours at the stirring speed of 300r/min and the temperature of 80 ℃, and adjusting the pH value to 8 after the reaction is finished, thus obtaining the pre-modified fluorocarbon resin emulsion.
The concentration of polyvinylpyrrolidone in the ethanol solution in step a was 10mg/ml.
A production process of fluorocarbon resin emulsion modified silicone-acrylic emulsion comprises the following production steps:
step1, pouring the castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, the silane coupling agent and half of deionized water in a reaction kettle, and mixing and stirring;
step2, adding the pre-modified silicone-acrylate emulsion, the pre-modified fluorocarbon resin emulsion and the rest deionized water in the weight part into the system in Step1, and continuously stirring for 4 hours at the rotating speed of 600r/min and the temperature of 70 ℃ to obtain the fluorocarbon resin emulsion modified silicone-acrylate emulsion.
The rotational speed of the mixing and stirring in Step1 is 400r/min, and the stirring time is 40min.
Example 3:
the fluorocarbon resin emulsion modified silicone-acrylate emulsion of the embodiment comprises the following components in parts by weight: 95 parts of pre-modified silicone-acrylic emulsion, 25 parts of pre-modified fluorocarbon resin emulsion, 7 parts of castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, 5 parts of silane coupling agent and 290 parts of deionized water;
the pre-modified silicone-acrylate emulsion is prepared from antibacterial acrylate emulsion, methyl methacrylate, butyl acrylate and gamma-methacryloxypropyl trimethoxy silane.
The preparation method of the antibacterial acrylate emulsion comprises the following steps: adding graphene oxide into deionized water, stirring for 10min to prepare a suspension system, and then performing ultrasonic dispersion and filtration on the suspension system; and (3) drying the filter residues in a vacuum drying oven with the temperature of 60 ℃ and the vacuum degree of 0.08MPa for 24 hours to obtain filler powder, and finally adding 6% of filler powder into the acrylic ester emulsion for mixing, and performing ultrasonic dispersion for 30 minutes after mixing to obtain the antibacterial acrylic ester emulsion.
The power of the ultrasonic dispersion was 150W, and the frequency of the ultrasonic dispersion was 21kHz.
The preparation method of the pre-modified silicone-acrylic emulsion comprises the following steps:
step1, placing the four-neck flask into a controllable water bath pot, weighing 10 parts by weight of surfactant and 200 parts by weight of deionized water, adding the surfactant and the deionized water into the four-neck flask, stirring for 20min, and raising the temperature of the water bath to 80 ℃;
step2, weighing 48 parts by weight of methyl methacrylate and 16 parts by weight of butyl acrylate, uniformly mixing, adding 3 parts by weight of ammonium persulfate solution, stirring for 30min, and pre-emulsifying to obtain a monomer component;
and 3, dropwise adding the monomer component in the step2 and 10 parts by weight of ammonium sulfate solution into the four-neck flask in the step1, controlling the dropwise adding time to be 2 hours, dropwise adding gamma-methacryloxypropyl trimethoxysilane with the weight being 7% of the monomer component into the system, controlling the dropwise adding time to be 30 minutes, immediately pouring 23 parts by weight of antibacterial acrylate emulsion after the dropwise adding is finished, mixing and stirring, preserving heat for 35 minutes at 83 ℃ after stirring for 20 minutes, and obtaining the pre-modified silicone-acrylate emulsion.
The surfactant in the step1 is glyceryl monostearate.
The mass fraction of the ammonium persulfate solution in the step2 is 2%.
The preparation method of the pre-modified fluorocarbon resin emulsion comprises the following steps:
step a, weighing graphite fluoride, dissolving the graphite fluoride in an ethanol solution containing polyvinylpyrrolidone, performing ultrasonic dispersion for 10min to obtain a preparation solution with graphite fluoride concentration of 8mg/ml, then performing high-speed mechanical shearing stirring on the preparation solution, continuously stirring for 10h at a rotating speed of 1200r/min, performing centrifugal treatment on the preparation solution for 10min after stirring, taking supernatant, performing suction filtration to absorb excessive polyvinylpyrrolidone, and finally drying in a vacuum drying oven at 60 ℃ for 12h to obtain the graphene fluoride powder;
step b, weighing 21 parts by weight of methyl methacrylate, 19 parts by weight of butyl acrylate, 2 parts by weight of acrylic acid, 5 parts by weight of chlorotrifluoroethylene, 6 parts by weight of fluorinated graphene powder and 2 parts by weight of acrylamide sodium isopropyl sulfonate, and stirring at a high speed at normal temperature for pre-emulsification;
and c, pouring the pre-emulsification system in the step b into a reaction kettle, adding 47 parts by weight of deionized water and 0.2 part by weight of ammonium persulfate solution, starting stirring, heating, controlling the temperature, setting, reacting for 3 hours at the stirring speed of 250r/min and the temperature of 80 ℃, and adjusting the pH value to 7 after the reaction is finished, thus obtaining the pre-modified fluorocarbon resin emulsion.
The concentration of polyvinylpyrrolidone in the ethanol solution in step a was 10mg/ml.
A production process of fluorocarbon resin emulsion modified silicone-acrylic emulsion comprises the following production steps:
step1, pouring the castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, the silane coupling agent and half of deionized water in a reaction kettle, and mixing and stirring;
step2, adding the pre-modified silicone-acrylate emulsion, the pre-modified fluorocarbon resin emulsion and the rest deionized water in the weight part into the system in Step1, and continuously stirring for 4 hours at the rotating speed of 600r/min and the temperature of 68 ℃ to obtain the fluorocarbon resin emulsion modified silicone-acrylate emulsion.
The rotational speed of the mixing and stirring in Step1 is 400r/min, and the stirring time is 35min.
Performance testing
1. Antibacterial property detection
The fluorocarbon resin emulsion modified silicone-acrylic emulsion produced in examples 1 to 3 was labeled as example 1, example 2, example 3, and then the antibacterial properties thereof were examined, respectively, and the results of the examination were recorded in the following table:
TABLE 1
2. Corrosion resistance detection
The fluorocarbon resin emulsion modified silicone-acrylate emulsion produced in the examples 1-3 is made into a coating, the coating and the common corrosion-resistant coating on the market are smeared on boards with the same size and dried, the boards are marked as the example 1, the example 2, the example 3 and the comparative example in sequence, finally, the boards are soaked in 0.2mol/L NaOH solution for standing for 12 hours, 24 hours and 36 hours respectively, the boards are taken out and dried after standing is finished, and the detection results are recorded in the following table:
TABLE 2
As shown by the data in tables 1 and 2, the fluorocarbon resin emulsion modified silicone-acrylate emulsion prepared in the embodiment 1-3 has better antibacterial performance, the antibacterial rate can reach more than 99%, and the paint prepared from the fluorocarbon resin emulsion modified silicone-acrylate emulsion has better corrosion resistance, so that the fluorocarbon resin emulsion modified silicone-acrylate emulsion produced by the invention has excellent market popularization value.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The fluorocarbon resin emulsion modified silicone-acrylic emulsion is characterized by comprising the following components in parts by weight: 90-100 parts of pre-modified silicone-acrylic emulsion, 20-30 parts of pre-modified fluorocarbon resin emulsion, 5-8 parts of castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, 3-6 parts of silane coupling agent and 280-300 parts of deionized water;
the pre-modified silicone-acrylate emulsion is prepared from antibacterial acrylate emulsion, methyl methacrylate, butyl acrylate and gamma-methacryloxypropyl trimethoxysilane serving as raw materials;
the preparation method of the antibacterial acrylate emulsion comprises the following steps: adding graphene oxide into deionized water, stirring for 10min to prepare a suspension system, and then performing ultrasonic dispersion and filtration on the suspension system; drying the filter residue in a vacuum drying oven with the temperature of 60 ℃ and the vacuum degree of 0.08MPa for 24 hours to obtain filler powder, adding 5-8% of filler powder into the acrylic ester emulsion, mixing, and performing ultrasonic dispersion for 30 minutes after mixing to obtain the antibacterial acrylic ester emulsion;
the preparation method of the pre-modified silicone-acrylic emulsion comprises the following steps:
step1, placing the four-neck flask into a controllable water bath kettle, weighing 8-12 parts by weight of surfactant and 200 parts by weight of deionized water, adding the surfactant and the 200 parts by weight of deionized water into the four-neck flask, stirring for 20min, and raising the water bath temperature to 80 ℃;
step2, weighing 45-50 parts by weight of methyl methacrylate and 15-18 parts by weight of butyl acrylate, uniformly mixing, adding 2-3 parts by weight of ammonium persulfate solution, stirring for 30min, and pre-emulsifying to obtain a monomer component;
step 3, dropwise adding the monomer component in the step2 and 8-12 parts by weight of ammonium sulfate solution into the four-neck flask in the step1, controlling the dropwise adding time to be 2 hours, then dropwise adding gamma-methacryloxypropyl trimethoxysilane with the weight of 6-8% of the monomer component into the system, controlling the dropwise adding time to be 30 minutes, immediately pouring 22-25 parts by weight of antibacterial acrylate emulsion after the dropwise adding is finished, mixing and stirring, and preserving heat for 30-40 minutes at 80-85 ℃ after stirring for 20 minutes to obtain the pre-modified silicone-acrylate emulsion;
the preparation method of the pre-modified fluorocarbon resin emulsion comprises the following steps:
step a, weighing graphite fluoride, dissolving the graphite fluoride in an ethanol solution containing polyvinylpyrrolidone, performing ultrasonic dispersion for 10min to obtain a preparation solution with graphite fluoride concentration of 8mg/ml, then performing high-speed mechanical shearing stirring on the preparation solution, continuously stirring for 10h at a rotating speed of 1200r/min, performing centrifugal treatment on the preparation solution for 10min after stirring, taking supernatant, performing suction filtration to absorb excessive polyvinylpyrrolidone, and finally drying in a vacuum drying oven at 60 ℃ for 12h to obtain the graphene fluoride powder;
step b, weighing 20-22 parts by weight of methyl methacrylate, 18-20 parts by weight of butyl acrylate, 1-2 parts by weight of acrylic acid, 5-6 parts by weight of chlorotrifluoroethylene, 6-7 parts by weight of fluorinated graphene powder and 1-2 parts by weight of acrylamide sodium isopropyl sulfonate, and stirring at a high speed at normal temperature for pre-emulsification;
and c, pouring the pre-emulsification system in the step b into a reaction kettle, adding 45-48 parts by weight of deionized water and 0.1-0.3 part by weight of ammonium persulfate solution, starting stirring, heating, controlling the temperature, and reacting for 2-3 hours under the conditions of the stirring speed of 200-300r/min and the temperature of 80 ℃, and adjusting the pH value to 7-8 after the reaction is finished, thus obtaining the pre-modified fluorocarbon resin emulsion.
2. A fluorocarbon resin emulsion modified silicone-acrylic emulsion as claimed in claim 1, wherein the power of said ultrasonic dispersion is 150W and the frequency of ultrasonic dispersion is 20-22kHz.
3. A fluorocarbon resin emulsion modified silicone-acrylic emulsion as set forth in claim 1, wherein said surfactant in step1 is glyceryl monostearate.
4. The fluorocarbon resin emulsion modified silicone-acrylic emulsion as claimed in claim 1, wherein the mass fraction of ammonium persulfate solution in said step2 is 2%.
5. A fluorocarbon resin emulsion modified silicone-acrylic emulsion as claimed in claim 1, wherein the concentration of polyvinylpyrrolidone in the ethanol solution in step a is 10mg/ml.
6. A process for producing a fluorocarbon resin emulsion modified silicone-acrylic emulsion as claimed in any one of claims 1 to 5, characterized by comprising the following production steps:
step1, pouring the castor oil amide propyl ethyl dimethyl ethyl ammonium sulfate, the silane coupling agent and half of deionized water in a reaction kettle, and mixing and stirring;
step2, adding the pre-modified silicone-acrylate emulsion, the pre-modified fluorocarbon resin emulsion and the rest deionized water in the weight part into the system in Step1, and continuously stirring for 3-4 hours at the rotating speed of 500-600r/min and the temperature of 65-70 ℃ to obtain the fluorocarbon resin emulsion modified silicone-acrylate emulsion.
7. The process for producing a fluorocarbon resin emulsion modified silicone-acrylate emulsion as claimed in claim 6, wherein the rotational speed of mixing and stirring in Step1 is 300-400r/min, and the stirring time is 30-40min.
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