CN110845678A - Fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method and application thereof - Google Patents
Fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion and a preparation method and application thereof, belonging to the technical field of water-based coatings. The invention provides a fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion which is prepared from the following preparation raw materials in parts by weight: 50-90 parts of fluorine modified silica sol; 40-50 parts of styrene; 40-50 parts of acrylic monomers; 4-6 parts of an initiator; 10-20 parts of an emulsifier; 5-10 parts of core layer monomer pre-emulsion; 5-10 parts of a shell layer monomer pre-emulsion; 1-5 parts of a pH regulator; 10-20 parts of a fluorescent whitening agent; 20-30 parts of graphene oxide; 30-50 parts of water. The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion provided by the invention has high silicon content and good water resistance and stability.
Description
Technical Field
The invention relates to the technical field of water-based coatings, in particular to fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion and a preparation method and application thereof.
Background
Acrylic emulsions are generally formed by emulsion polymerization of acrylic monomers, vinyl acetate and styrene in the presence of emulsifiers. The traditional acrylic emulsion has the defect of poor water resistance, and particularly when the acrylic emulsion is used for coating, the residual emulsifier in the acrylic emulsion can cause the water resistance of an acrylic emulsion coating film to be poor, so that the use requirement of people cannot be met.
Disclosure of Invention
The invention aims to provide a fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion as well as a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion which is prepared from the following preparation raw materials in parts by weight:
50-90 parts of fluorine modified silica sol;
40-50 parts of styrene;
40-50 parts of acrylic monomers;
4-6 parts of an initiator;
10-20 parts of an emulsifier;
5-10 parts of core layer monomer pre-emulsion;
5-10 parts of a shell layer monomer pre-emulsion;
1-5 parts of a pH regulator;
10-20 parts of a fluorescent whitening agent;
20-30 parts of graphene oxide;
30-50 parts of water.
Preferably, the particle size of solid particles in the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion is 60-80 nm.
Preferably, the raw materials for preparing the fluorine modified silica sol comprise silica sol, fluorine alkene monomers and an initiator;
the mass ratio of the silica sol to the vinyl fluoride monomer to the initiator is (5-8): (6-7): (1-3).
Preferably, the vinyl fluoride monomer comprises one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisobutyl acrylate, octafluoropentyl acrylate and octafluoropentyl methacrylate.
Preferably, the preparation method of the fluorine modified silica sol comprises the following steps: mixing silica sol, initiator and fluorine alkene monomer, and carrying out modification treatment to obtain fluorine modified silica sol.
Preferably, the temperature of the modification treatment is 85-90 ℃, and the time is 2-3 h.
Preferably, the acrylic monomer comprises one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and iso-glacial methacrylate;
the initiator comprises one or more of azodiisobutyronitrile, ammonium persulfate and sodium thiosulfate;
the emulsifier comprises at least two of allyloxy nonylphenoxy propanol polyoxyethylene ether, allyloxy hydroxypropyl sodium sulfonate, allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate and allyloxy nonylphenoxy propanol polyoxyethylene ether ammonium sulfate, sodium dodecyl benzene sulfonate, sorbitol fatty acid ester and propylene glycol fatty acid ester;
the pH regulator comprises one or more of sodium carbonate, ammonia water and sodium hydroxide.
The invention provides a preparation method of fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion, which comprises the following steps:
mixing fluorine modified silica sol, partial styrene, partial acrylic monomers, partial initiator, emulsifier, core layer monomer pre-emulsion and water in a protective atmosphere, and carrying out in-situ polymerization reaction to obtain seed emulsion;
mixing the seed emulsion, the shell monomer pre-emulsion, the residual styrene, the residual acrylic monomer, the pH regulator, the residual initiator, the fluorescent whitening agent and the graphene oxide, and carrying out shell polymerization reaction to obtain fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion;
the mass ratio of the partial styrene to the residual styrene is (1.5-2.5): 1; the mass ratio of the partial acrylic monomer to the residual acrylic monomer is 1: (1.5-3); the mass ratio of the partial initiator to the rest initiator is (4-5): (5-6).
Preferably, the temperature of the in-situ polymerization reaction is 75-80 ℃, and the time is 2-3 h; the polymerization reaction temperature of the shell layer is 80-90 ℃, and the time is 1-2 h.
The invention also provides the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion prepared by the technical scheme or the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion prepared by the preparation method of the technical scheme, which is used as a water-based coating for metal protection.
The invention provides a fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion which is prepared from the following preparation raw materials in parts by weight: 50-90 parts of fluorine modified silica sol; 40-50 parts of styrene; 40-50 parts of acrylic monomers; 4-6 parts of an initiator; 10-20 parts of an emulsifier; 5-10 parts of core layer monomer pre-emulsion; 5-10 parts of a shell layer monomer pre-emulsion; 1-5 parts of a pH regulator; 10-20 parts of a fluorescent whitening agent; 20-30 parts of graphene oxide; 30-50 parts of water. The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion provided by the invention has good core-shell coating property and stability, and a coating film of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion has the performances of high transparency, good water resistance, high hardness, strong adhesive force and the like, and simultaneously has good stain resistance, heat resistance, acid and alkali resistance, environmental protection and flame retardancy. As shown by the results of the embodiments of the invention, the particle size of the solid particles in the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion provided by the invention is 60-80 nm, and the water resistance in hot water at 70 ℃ is 2.5-3 h.
The invention provides a preparation method of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion, which is simple to operate and suitable for large-scale production.
Detailed Description
The invention provides a fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion which is prepared from the following preparation raw materials in parts by weight:
50-90 parts of fluorine modified silica sol;
40-50 parts of styrene;
40-50 parts of acrylic monomers;
4-6 parts of an initiator;
10-20 parts of an emulsifier;
5-10 parts of core layer monomer pre-emulsion;
5-10 parts of a shell layer monomer pre-emulsion;
1-5 parts of a pH regulator;
10-20 parts of a fluorescent whitening agent;
20-30 parts of graphene oxide
30-50 parts of water.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 50-90 parts by weight of fluorine modified silica sol, preferably 50-80 parts by weight of fluorine modified silica sol, and more preferably 60 parts by weight or 70 parts by weight of fluorine modified silica sol.
In the present invention, the raw materials for preparing the fluorine-modified silica sol preferably include silica sol, a fluorine-containing vinyl monomer and an initiator.
In the invention, the average particle size of the silica sol is preferably 10-30 nm, more preferably 10-25 nm, and most preferably 15-20 nm; the pH value of the silica sol is preferably 9-10; the mass percentage of the silica sol is preferably 30-50%, more preferably 35-50%, and most preferably 40-45% calculated by silica.
In the present invention, the vinyl fluoride monomer preferably includes one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisobutyl acrylate, octafluoropentyl acrylate and octafluoropentyl methacrylate, and more preferably includes hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisobutyl acrylate, octafluoropentyl acrylate or octafluoropentyl methacrylate.
In the present invention, the initiator preferably includes one or more of azobisisobutyronitrile, ammonium persulfate and sodium thiosulfate, and more preferably, azobisisobutyronitrile.
In the invention, the mass ratio of the silica sol, the vinyl fluoride monomer and the initiator is preferably (5-8): (6-7): (1-3), more preferably (5.5-7.5): (6.5-7): (1 to 2)
In the present invention, the method for preparing the fluorine-modified silica sol preferably comprises the steps of: mixing silica sol, initiator and fluorine alkene monomer, and carrying out modification treatment to obtain fluorine modified silica sol.
In the present invention, the silica sol, the initiator and the vinyl fluoride monomer are preferably mixed by stirring, and the stirring speed in the present invention is not particularly limited, and may be a stirring speed well known in the art. In the present invention, the order of mixing the silica sol, the initiator and the fluorine-containing vinyl monomer is preferably that the silica sol and a part of the initiator are first mixed, and then a mixed solution of the fluorine-containing vinyl monomer and the remaining initiator is added dropwise to perform a second mixing. In the invention, the temperature of the first mixing is preferably 25-30 ℃, and the time is preferably 0.5-1 h. In the invention, the temperature of the second mixing is preferably 85-90 ℃, and the dropping time of the mixed liquid of the fluorine alkene monomer and the residual initiator is preferably 3-4 h.
In the invention, the temperature of the modification treatment is preferably 85-90 ℃, and more preferably 87-89 ℃; the time of the modification treatment is preferably 2-3 h, and more preferably 2.5 h. In the present invention, in the modification treatment process, the styrene, the acrylic monomer, and the vinyl fluoride monomer perform fluorinated surface modification on the silica nanoparticles in the silica sol to obtain a fluorine-modified silica sol. Compared with the silica sol raw material, the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion prepared by taking the fluorine modified silica sol as the raw material has excellent water resistance and stability.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise, by weight, 40-50 parts of styrene, preferably 42-50 parts of styrene, and more preferably 45-50 parts of styrene.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 40-50 parts of acrylic monomers, preferably 42-50 parts, and more preferably 45-50 parts by weight of the fluorine modified silica sol. In the present invention, the acrylic monomer preferably includes one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and iso-glacial methacrylate, and more preferably includes acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate or iso-glacial methacrylate.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 20-30 parts of initiator, preferably 22-28 parts of initiator, and more preferably 25 parts of initiator by weight. In the present invention, the initiator preferably comprises one or more of azobisisobutyronitrile, ammonium persulfate and sodium thiosulfate, and more preferably ammonium persulfate.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 10-20 parts of emulsifier, preferably 12-18 parts, and more preferably 15 parts by weight of the fluorine modified silica sol. In the present invention, the emulsifier includes at least two of allyloxy nonylphenoxypropanol polyoxyethylene ether, allyloxy hydroxypropylsodium sulfonate, allyloxy fatty alcohol ammonium polyoxyethylene ether sulfate and allyloxy nonylphenoxypropanol polyoxyethylene ether ammonium sulfate, sodium lauryl sulfate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate sorbitol fatty acid ester and propylene glycol fatty acid ester. The emulsifier adopted by the invention is a compound emulsifier, has hydrophilicity and lipophilicity, and improves the water resistance, the adhesive strength and the glossiness of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 5-10 parts of core layer monomer pre-emulsion, preferably 6-9 parts, and more preferably 7-8 parts by weight of the fluorine modified silica sol. In the present invention, the core layer monomer pre-emulsion is preferably OP-4 (John's Henry chemical Co., Ltd.), and the main component thereof is preferably a condensate of an alkylphenol and ethylene oxide.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 5-10 parts of shell layer monomer pre-emulsion, preferably 6-9 parts, and more preferably 7-8 parts by weight of the fluorine modified silica sol. In the present invention, the shell monomer pre-emulsion is preferably GMO (yohimbe chemical limited, Jiangsu), and the main component thereof is preferably glycerol monooleate.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 1-5 parts of pH regulator, preferably 3-5 parts, and more preferably 4-4.5 parts by weight of the fluorine modified silica sol. In the invention, the pH regulator preferably comprises one or more of sodium carbonate, ammonia water and sodium hydroxide.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 10-20 parts of fluorescent whitening agent, preferably 12-18 parts of fluorescent whitening agent, and more preferably 15-16 parts of fluorescent whitening agent by weight of the fluorine modified silica sol. In the present invention, the fluorescent whitening agent is preferably fluorescent whitening agent A-1 (manufactured by Ruiche corporation). In the invention, the fluorescent whitening agent is a whitening agent OB-1 (Shanghai Lingbi Fine chemical Co., Ltd.), and the fluorescent whitening agent and other raw materials have the combined action to improve the luster of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion, so that the coating is full and bright in color.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 20-30 parts of graphene oxide, preferably 22-28 parts of graphene oxide, more preferably 24-26 parts of graphene oxide, and most preferably 25 parts of graphene oxide, based on the weight parts of the fluorine modified silica sol. In the invention, the graphene oxide (7782-42-5) can enable the coating to be dispersed more uniformly.
In the invention, the raw materials for preparing the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion comprise 30-50 parts of water, preferably 35-50 parts of water, and more preferably 40-45 parts of water based on the weight parts of the fluorine modified silica sol. The type of water used in the present invention is not particularly limited, and water known in the art may be used, specifically, deionized water or distilled water. The invention takes water as solvent, and is green and environment-friendly.
In the invention, the solid content of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion is preferably 30-60%, and more preferably 40-60%. In the invention, the particle size of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion is preferably 60-80 nm, more preferably 60-75 nm, and most preferably 60-70 nm.
The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion prepared by using the fluorine modified silica sol, styrene and acrylic monomers as main bodies and matching with the core-shell monomer pre-emulsion and under the combined action of an initiator, an emulsifier, a pH regulator, a fluorescent whitening agent and graphene oxide has a core-shell structure, namely, the fluorine modified nano silica sol/polystyrene-acrylate nano core-shell emulsion is used as a core and a styrene-acrylate copolymer is used as a shell, and has small granularity, high silicon content, high coating property, excellent water resistance and excellent stability.
The invention provides a preparation method of fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion, which comprises the following steps:
mixing fluorine modified silica sol, partial styrene, partial acrylic monomers, partial initiator, emulsifier, core layer monomer pre-emulsion and water in a protective atmosphere, and carrying out in-situ polymerization reaction to obtain seed emulsion;
mixing the seed emulsion, the shell monomer pre-emulsion, the residual styrene, the residual acrylic monomer, the pH regulator, the residual initiator, the fluorescent whitening agent and the graphene oxide, and carrying out shell polymerization reaction to obtain fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion;
the mass ratio of the partial styrene to the residual styrene is (1.5-2.5): 1; the mass ratio of the partial acrylic monomer to the residual acrylic monomer is 1: (1.5-3); the mass ratio of the partial initiator to the rest initiator is (4-5): (5-6).
In the invention, under the protective atmosphere, fluorine modified silica sol, part of styrene, part of acrylic monomers, part of initiator, emulsifier, core layer monomer pre-emulsion and water are mixed for in-situ polymerization reaction to obtain seed emulsion.
The protective atmosphere in the present invention is not particularly limited, and a protective atmosphere known in the art may be used, specifically, nitrogen or argon.
In the present invention, the fluorine-modified silica sol, part of styrene, part of acrylic monomer, part of initiator, emulsifier, core layer monomer pre-emulsion, pH adjuster and water are preferably mixed by stirring, and the stirring speed in the present invention is not particularly limited, and may be a stirring speed well known in the art.
In the invention, the temperature of the in-situ polymerization reaction is preferably 75-80 ℃, and more preferably 76-78 ℃; the time of the in-situ polymerization reaction is preferably 2-3 h, and more preferably 2.5 h. In the invention, in the in-situ polymerization reaction process, under the action of an emulsifier, styrene and acrylic monomers are subjected to in-situ polymerization on the surface of fluorine modified silica sol (mainly fluorine modified silica particles) to obtain the seed emulsion taking fluorine modified silica as a core.
After obtaining the seed emulsion, mixing the seed emulsion, the shell monomer pre-emulsion, the residual styrene, the residual acrylic monomer, the sodium carbonate and the residual initiator to perform shell polymerization reaction to obtain the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion; the mass ratio of the partial styrene to the residual styrene is (1.5-2.5): 1, preferably (1.8-2.2): 1, more preferably 2: 1; the mass ratio of the partial acrylic monomer to the residual acrylic monomer is 1: (1.5-3), preferably 1: (2-3), more preferably 1: 2.5; the mass ratio of the partial initiator to the rest initiator is (4-5): (5-6), preferably (4.2-4.8): (5.2-5.8), more preferably 4.5: 5.5.
In the present invention, the pH adjuster is preferably used in the form of a sodium carbonate solid or a sodium carbonate aqueous solution; the concentration of the sodium carbonate aqueous solution is preferably 1-5 g/mL, more preferably 2-4 g/mL, and the water in the sodium carbonate aqueous solution is not counted in the amount of the water.
In the present invention, the initiator is preferably used in the form of an initiator solid or an initiator aqueous solution; the concentration of the initiator aqueous solution is preferably 2-3 g/mL, and more preferably 2.5 g/mL; the water in the aqueous initiator solution is not counted in the amount of water used.
In the present invention, the seed emulsion, the shell monomer pre-emulsion, the residual styrene, the residual acrylic monomer, the pH adjuster, the fluorescent whitening agent, the graphene oxide, and the residual initiator are preferably mixed by stirring, and the stirring speed in the present invention is not particularly limited, and may be a stirring speed well known in the art. In the present invention, the seed emulsion, the shell monomer pre-emulsion, the residual styrene, the residual acrylic monomer, the pH adjuster, and the residual initiator are preferably mixed by sequentially adding the shell monomer pre-emulsion, the aqueous sodium carbonate solution, and the aqueous initiator solution to the seed emulsion to obtain a mixed solution, mixing the residual styrene and the residual acrylic monomer to obtain a mixed monomer, and adding the mixed monomer to the mixed solution. The dropping rate in the present invention is not particularly limited, and a dropping rate well known in the art may be used.
In the invention, the polymerization reaction temperature of the shell layer is preferably 80-90 ℃, and more preferably 80-85 ℃; the polymerization reaction time of the shell layer is preferably 1-2 hours, and more preferably 1-1.5 hours. In the invention, in the shell polymerization reaction process, the residual styrene and the residual acrylic monomer are subjected to shell polymerization on the surface of the seed with the core layer structure, and the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion has excellent water resistance and stability.
After the shell polymerization reaction is completed, the method preferably further comprises the steps of reducing the temperature of the obtained emulsion system to room temperature, and then adjusting the pH value of the obtained emulsion to 7-8. The pH regulator used for adjusting the pH value in the present invention is not particularly limited, and any pH regulator known in the art may be used, specifically sodium carbonate or sodium hydroxide.
The preparation method of the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion provided by the invention is simple to operate and suitable for large-scale production.
The invention also provides the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion or the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion prepared by the preparation method, which is used as a water-based coating for metal protection.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
(1) Uniformly mixing 200g of silica sol and 30g of azobisisobutyronitrile, preserving heat for 0.5h at 25 ℃, then heating to 82 ℃, dropwise adding a mixed solution consisting of 150g of hexafluorobutyl acrylate and 30g of azobisisobutyronitrile for 3h, heating to 85 ℃ after dropwise adding, and preserving heat for 1h to obtain fluorine modified silica sol;
(2) under the protection of nitrogen, 50g of fluorine modified silica sol, 40g of styrene, 40g of acrylic monomer, 50g of deionized water, 3g of ammonium persulfate, 10g of a mixture of allyloxy nonyl phenoxypropanol polyoxyethylene ether and allyloxy hydroxypropyl sodium sulfonate (the mass ratio is 1:1), 5g of nuclear layer monomer pre-emulsion and 4g of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate are mixed and reacted for 2 hours at the temperature of 80 ℃ to obtain seed emulsion;
(3) and (2) dropwise adding 5g of shell monomer pre-emulsion, 11.5g of sodium carbonate solution (1.5g of sodium carbonate +10g of deionized water) and 1g of initiator solution (prepared according to the proportion of 1g of initiator to 10g of water) into the seed solution in sequence, uniformly mixing, dropwise adding 50g of mixed monomer consisting of styrene and 50g of acrylate, 10g of fluorescent brightener and 20g of graphene oxide into the obtained mixed solution, polymerizing the shells at 85 ℃ for 3 hours, cooling the temperature of the reaction system to room temperature, and adjusting the pH value of the obtained system to 7 by using sodium carbonate to obtain the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion.
The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion is bluish and semitransparent in appearance, the average particle size is 65nm, and the coating is sprayed on a clean iron plate to form a coating and then placed in distilled water at 70 ℃ for 3 hours without change.
Example 2
(1) Uniformly mixing 200g of silica sol and 30g of azobisisobutyronitrile, preserving heat for 0.5h at 25 ℃, then heating to 82 ℃, dropwise adding a mixed solution consisting of 150g of hexafluorobutyl methacrylate and 30g of azobisisobutyronitrile, wherein the dropwise adding time is 3h, heating to 85 ℃ after the dropwise adding is finished, and preserving heat for 1h to obtain fluorine modified silica sol;
(2) under the protection of nitrogen, 50g of fluorine modified silica sol, 40g of styrene, 40g of acrylic monomer, 50g of deionized water, 3g of ammonium persulfate, 10g of a mixture of allyloxy nonyl phenoxypropanol polyoxyethylene ether and allyloxy hydroxypropyl sodium sulfonate (the mass ratio is 1:1), 5g of nuclear layer monomer pre-emulsion and 4g of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate are mixed and reacted for 2 hours at the temperature of 80 ℃ to obtain seed emulsion;
(3) and (2) dropwise adding 5g of shell monomer pre-emulsion, 11.5g of sodium carbonate solution (1.5g of sodium carbonate +10g of deionized water) and 1g of initiator solution (prepared according to the proportion of 1g of initiator to 10g of water) into the seed solution in sequence, uniformly mixing, dropwise adding 50g of mixed monomer consisting of styrene and 50g of acrylate, 10g of fluorescent brightener and 20g of graphene oxide into the obtained mixed solution, polymerizing the shells at 85 ℃ for 2 hours, cooling the temperature of the reaction system to room temperature, and adjusting the pH value of the obtained system to 8 by using sodium carbonate to obtain the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion.
The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion is light white, bluish and semitransparent, has the average particle size of 70nm, is sprayed on a clean iron plate to form a coating, and is placed in distilled water at 70 ℃ for 2.5 hours without change. .
Example 3
(1) Uniformly mixing 200g of silica sol and 30g of azobisisobutyronitrile, preserving heat for 0.5h at 25 ℃, then heating to 82 ℃, dropwise adding a mixed solution consisting of 150g of hexafluoroisobutyl acrylate and 30g of azobisisobutyronitrile, wherein the dropwise adding time is 3h, heating to 85 ℃ after the dropwise adding is finished, and preserving heat for 1h to obtain fluorine modified silica sol;
(2) under the protection of nitrogen, 60g of fluorine modified silica sol, 50g of styrene, 40g of acrylic monomer, 50g of deionized water, 3g of ammonium persulfate, 10g of a mixture of allyloxy nonyl phenoxypropanol polyoxyethylene ether and allyloxy hydroxypropyl sodium sulfonate (the mass ratio is 1:1), 5g of nuclear layer monomer pre-emulsion and 4g of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate are mixed and reacted for 2 hours at the temperature of 80 ℃ to obtain seed emulsion;
(3) and (2) dropwise adding 5g of shell monomer pre-emulsion, 11.5g of sodium carbonate solution (1.5g of sodium carbonate +10g of deionized water) and 1g of initiator solution (prepared according to the proportion of 1g of initiator to 10g of water) into the seed solution in sequence, uniformly mixing, dropwise adding 50g of mixed monomer consisting of styrene and 50g of acrylate, 10g of fluorescent brightener and 20g of graphene oxide into the obtained mixed solution, polymerizing the shells at 85 ℃ for 2 hours, cooling the temperature of the reaction system to room temperature, and adjusting the pH value of the obtained system to 7.5 by using sodium carbonate to obtain the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion.
The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion is white, bluish and semitransparent, has an average particle size of 72nm, is sprayed on a clean iron plate to form a coating, and is placed in distilled water at 70 ℃ for 2.5 hours without change. .
Comparative example 1
An emulsion was prepared by following the procedures of steps (2) to (3) of example 1, differing from the examples in that: the silica sol was directly used in place of the fluorine-modified silica sol.
The obtained silica sol/polystyrene-acrylate nano core-shell emulsion is bluish and semitransparent in appearance, the average particle size is 100nm, and after the coating is sprayed on a clean iron plate to form a coating, the coating begins to fall off after being placed in distilled water at the temperature of 70 ℃ for 2 hours.
Comparative example 2
The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion was prepared according to the method of example 1, which is different from example 1 in that: graphene oxide was not added.
The obtained silica sol/polystyrene-acrylate nano core-shell emulsion is light white, bluish and semitransparent, has the average particle size of 80nm, and is sprayed on a clean iron plate to form a coating which is then placed in distilled water at 70 ℃ for 1.8h and then begins to fall off.
In conclusion, the fluorine modified silica sol is subjected to fluorine modification, and then the obtained fluorine modified silica sol is used as a raw material, so that the water resistance of the prepared fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion can be improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The fluorine modified silica sol/polystyrene-acrylate nanometer core-shell emulsion is characterized by comprising the following preparation raw materials in parts by weight:
50-90 parts of fluorine modified silica sol;
40-50 parts of styrene;
40-50 parts of acrylic monomers;
4-6 parts of an initiator;
10-20 parts of an emulsifier;
5-10 parts of core layer monomer pre-emulsion;
5-10 parts of a shell layer monomer pre-emulsion;
1-5 parts of a pH regulator;
10-20 parts of a fluorescent whitening agent;
20-30 parts of graphene oxide;
30-50 parts of water.
2. The fluorine-modified silica sol/polystyrene-acrylate nano core-shell emulsion according to claim 1, wherein the particle size of solid particles in the fluorine-modified silica sol/polystyrene-acrylate nano core-shell emulsion is 60-80 nm.
3. The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion according to claim 1 or 2, wherein the raw materials for preparing the fluorine modified silica sol comprise silica sol, fluorine vinyl monomers and an initiator; the mass ratio of the silica sol to the vinyl fluoride monomer to the initiator is (5-8): (6-7): (1-3).
4. The fluorine-modified silica sol/polystyrene-acrylate nano core-shell emulsion according to claim 3, wherein the fluorine-containing vinyl monomer comprises one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisobutyl acrylate, octafluoropentyl acrylate and octafluoropentyl methacrylate.
5. The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion according to claim 3, wherein the preparation method of the fluorine modified silica sol comprises the following steps: mixing silica sol, initiator and fluorine alkene monomer, and carrying out modification treatment to obtain fluorine modified silica sol.
6. The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion according to claim 5, wherein the temperature of the modification treatment is 85-90 ℃ and the time is 2-3 h.
7. The fluorine-modified silica sol/polystyrene-acrylate nano core-shell emulsion according to claim 1 or 2, wherein the acrylic monomer comprises one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and iso-glacial methacrylate;
the initiator comprises one or more of azodiisobutyronitrile, ammonium persulfate and sodium thiosulfate;
the emulsifier comprises at least two of allyloxy nonylphenoxy propanol polyoxyethylene ether, allyloxy hydroxypropyl sodium sulfonate, allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate and allyloxy nonylphenoxy propanol polyoxyethylene ether ammonium sulfate, sodium dodecyl benzene sulfonate, sorbitol fatty acid ester and propylene glycol fatty acid ester;
the pH regulator is one or more of sodium carbonate, ammonia water and sodium hydroxide.
8. The preparation method of the fluorine modified silica sol/polystyrene-acrylate nanometer core-shell emulsion according to any one of claims 1 to 7, which is characterized by comprising the following steps:
mixing fluorine modified silica sol, partial styrene, partial acrylic monomers, partial initiator, emulsifier, core layer monomer pre-emulsion and water in a protective atmosphere, and carrying out in-situ polymerization reaction to obtain seed emulsion;
mixing the seed emulsion, the shell monomer pre-emulsion, the residual styrene, the residual acrylic monomer, the pH regulator, the residual initiator, the fluorescent whitening agent and the graphene oxide, and carrying out shell polymerization reaction to obtain fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion;
the mass ratio of the partial styrene to the residual styrene is (1.5-2.5): 1; the mass ratio of the partial acrylic monomer to the residual acrylic monomer is 1: (1.5-3); the mass ratio of the partial initiator to the rest initiator is (4-5): (5-6).
9. The preparation method according to claim 8, wherein the temperature of the in-situ polymerization reaction is 75-80 ℃ and the time is 2-3 h; the polymerization reaction temperature of the shell layer is 80-90 ℃, and the time is 1-2 h.
10. The fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion according to any one of claims 1 to 7 or the fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion prepared by the preparation method according to any one of claims 8 to 9 is used as a water-based coating for metal protection.
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