WO2021197055A1 - 一种高耐水白性能的丙烯酸酯乳液及其制备方法 - Google Patents

一种高耐水白性能的丙烯酸酯乳液及其制备方法 Download PDF

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WO2021197055A1
WO2021197055A1 PCT/CN2021/081162 CN2021081162W WO2021197055A1 WO 2021197055 A1 WO2021197055 A1 WO 2021197055A1 CN 2021081162 W CN2021081162 W CN 2021081162W WO 2021197055 A1 WO2021197055 A1 WO 2021197055A1
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parts
monomer
emulsion
emulsifier
acrylate
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PCT/CN2021/081162
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English (en)
French (fr)
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曾国红
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上海保立佳新材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers

Definitions

  • the invention relates to the technical field of emulsion paint films, and more specifically relates to an acrylic emulsion with high water whitening resistance and a preparation method thereof.
  • a series of anti-rust coatings have been developed in China, but most of them are solvent-based anti-rust coatings. In addition to containing a large amount of organic solvents, this type of coating also contains a large amount of toxic pigments, causing serious pollution to the environment. To this end, research and development of new environmentally-friendly, water-based anti-rust coatings with excellent anti-rust performance is in line with the current development trend of coatings.
  • Water-based paint refers to the paint that uses water as a solvent or dispersion medium. It has the advantages of good protection and good corrosion resistance. Compared with oil-based paints, the production of water-based paints can save resources and cause less pollution during production and use. The application is more and more extensive.
  • Polyacrylate emulsion uses water as the medium, has the advantages of low cost, safe use, and less environmental pollution. Its film-forming material has the characteristics of flexibility, weather resistance, and good viscosity. Therefore, it has been widely used as a building material in decoration and interior and exterior walls. In the paint.
  • water-based acrylic emulsions are copolymerized with hydroxy monomers and acrylate monomers, and there are still certain problems in terms of water resistance, hardness and weather resistance, especially the phenomenon of water absorption and whitening.
  • the first aspect of the present invention provides an acrylic emulsion with high water whitening resistance.
  • the raw materials include at least 15-40 parts of styrene monomer and acrylic monomer Body 40-70 parts, first organosilicon monomer 1-5 parts, second organosilicon monomer 1-10 parts, first emulsifier 0.5-4 parts, second emulsifier 1-10 parts, first initiator 0.1-5 parts, 0.1-4 parts of the second initiator.
  • the acrylate emulsion with high water whitening resistance described in the present invention in parts by weight, contains at least 20-30 parts of styrene monomer and 50-60 parts of acrylic monomer. , 1-3 parts of the first organosilicon monomer, 2-8 parts of the second organosilicon monomer, 0.6-3.5 parts of the first emulsifier, 2-6 parts of the second emulsifier, 0.1-3 parts of the first initiator, 0.1-2 parts of the second initiator.
  • the acrylic monomer in the present invention is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, and methyl methacrylate monomer; the butyl acrylate monomer, The weight ratio of isooctyl acrylate monomer to methyl methacrylate monomer is 1:(0.5-1.5):(1-3).
  • the first organosilicon monomer in the present invention is selected from the group consisting of dimethyldimethoxysiloxane, methylphenyldimethoxysiloxane, and methylvinyldimethylsiloxane. At least one of oxysiloxane.
  • the second organosilicon monomer in the present invention is selected from ethyltrichlorosilane, propyltrichlorosilane, ⁇ -chloropropyltrichlorosilane, phenylchlorosilane, vinyl trichlorosilane, At least one of chlorosilane, methylvinylchlorosilane, and methylchlorosilane.
  • the first emulsifier in the present invention is alkylphenol polyether sulfosuccinic acid monoester sodium salt, long-chain carboxylate polyoxyethylene, polyoxyethylene carboxylate, carboxylic acid At least one of salt type emulsifier and folded sodium stearate.
  • the second emulsifier in the present invention is at least one of rosin oil soap and long-chain carboxylate polyoxyethylene.
  • the first emulsifier in the present invention is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylate polyoxyethylene; the alkylphenol polyether The weight ratio of sulfosuccinic acid monoester sodium salt and long-chain carboxylate polyoxyethylene is 1: (1-5).
  • the second emulsifier in the present invention is a combination of rosin oil soap and long-chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap and long-chain carboxylate polyoxyethylene is It is 1: (0.1-0.5).
  • the second aspect of the present invention provides a method for preparing the acrylate emulsion with high water whitening resistance, and the steps at least include:
  • Pre-emulsion Add deionized water, first emulsifier, first initiator, styrene monomer, acrylic monomer, first organic silicon monomer, and second organic silicon monomer to the monomer tank , Stir for 20-40 minutes to get the pre-emulsion;
  • reaction kettle Add deionized water, second emulsifier, and second initiator to the reaction kettle, raise the temperature to 80-90°C, stir uniformly, add 1wt%-5wt% of pre-emulsion to the reaction kettle, proceed reaction;
  • the present invention has the following excellent beneficial features:
  • the present invention provides an acrylic emulsion with high water whitening resistance, and a novel water-in-water and sand-in-water emulsion studied.
  • the invention is formed by combining seed technology and nuclear technology.
  • the emulsion has good transparency, is stable with protective glue, does not thicken afterwards, has excellent paint stability, stain resistance and water whitening resistance, and excellent calcium ion stability. Performance, dilution stability, freeze-thaw stability and mechanical stability.
  • the acrylic emulsion not only has high hardness, especially has super water resistance, anti-whitening, excellent hydrophobicity, and good stain resistance; the formulated water-in-water and sand-in-water have a realistic feeling; because the emulsion contains specific The content and type of silicone form excellent adhesion to the substrate; and the special silane grafting process gives the paint film excellent weather resistance; the acrylic emulsion is an emulsion with excellent comprehensive properties and can be widely used in water Water-in-water, sand-in-water, high-grade real stone paint, high-grade exterior wall silicone acrylic latex paint.
  • the invention provides an acrylate emulsion with high water whitening resistance.
  • the raw materials at least include: 15-40 parts of styrene monomer, 40-70 parts of acrylate monomer, and 1st organosilicon monomer. -5 parts, 1-10 parts of the second silicone monomer, 0.5-4 parts of the first emulsifier, 1-10 parts of the second emulsifier, 0.1-5 parts of the first initiator, 0.1-4 parts of the second initiator .
  • the acrylate emulsion with high water whitening resistance based on parts by weight, the raw materials include at least: 20-30 parts of styrene monomer, 50-60 parts of acrylic monomer, first 1-3 parts of organosilicon monomer, 2-8 parts of second organosilicon monomer, 0.6-3.5 parts of first emulsifier, 2-6 parts of second emulsifier, 0.1-3 parts of first initiator, second initiator Agent 0.1-2 parts.
  • the acrylate emulsion with high water whitening resistance in parts by weight, the raw materials at least include: 25 parts of styrene monomer, 55 parts of acrylate monomer, and the first silicone monomer 2 parts of the second organic silicon monomer, 2 parts of the first emulsifier, 4 parts of the second emulsifier, 1.5 parts of the first initiator, and 1 part of the second initiator.
  • the acrylic monomer is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, and methyl methacrylate monomer; the butyl acrylate monomer, isooctyl acrylate monomer The weight ratio of the monomer to the methyl methacrylate monomer is 1:(0.5-1.5):(1-3).
  • the weight ratio of the butyl acrylate monomer, the isooctyl acrylate monomer, and the methyl methacrylate monomer is 1:1:2.
  • the first organosilicon monomer is selected from dimethyldimethoxysiloxane, methylphenyldimethoxysiloxane, methylvinyldimethoxysiloxane At least one of them.
  • the first organosilicon monomer is dimethyldimethoxysiloxane.
  • the second organosilicon monomer is selected from ethyltrichlorosilane, propyltrichlorosilane, ⁇ -chloropropyltrichlorosilane, phenylchlorosilane, vinyltrichlorosilane, methyl At least one of vinylchlorosilane and methylchlorosilane.
  • the second organosilicon monomer is vinyltrichlorosilane.
  • the first emulsifier is alkylphenol polyether sulfosuccinic acid monoester sodium salt, long-chain carboxylate polyoxyethylene, polyoxyethylene carboxylate, carboxylate type emulsifier, Fold at least one of sodium stearate.
  • the first emulsifier is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylate polyoxyethylene; the alkylphenol polyether sulfosuccinic acid monoester The weight ratio of the ester sodium salt and the long-chain carboxylate polyoxyethylene is 1: (1-5).
  • the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylate polyoxyethylene is 1:2.5.
  • the second emulsifier is at least one of rosin oil soap and long-chain carboxylate polyoxyethylene.
  • the second emulsifier is a combination of rosin oil soap and long-chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap and long-chain carboxylate polyoxyethylene is 1:(0.1 -0.5).
  • the weight ratio of the rosin oil soap to the long-chain carboxylate polyoxyethylene is 1:0.3.
  • the model of the long-chain carboxylate polyoxyethylene described in the present invention is LMEO-18, and the brand is American Sima.
  • the acrylic emulsion prepared in the present invention not only has very excellent hardness, but also has very good anti-whitening ability and excellent hydrophobicity, especially when long-chain carboxylic acid ester poly
  • oxyethylene is used in combination with other rosin oil soaps and alkylphenol polyether sulfosuccinic acid monoester sodium salt
  • the inventor found that it has an outstanding synergistic effect, achieves a good cost performance, and can significantly enhance the paint film formed by the emulsion
  • the inventor believes that it may be because the long-chain carboxylate polyoxyethylene has a special 18-carbon fatty acid ester with an ester group and a double bond structure, which can form a better Dispersion, as well as a water-resistant paint film formed by water-in-water and sand-in-water in the special silane grafting process and the preparation of the coating process, which resists the erosion and penetration of water.
  • the first initiator and the second initiator are the same initiator, and the types of the first initiator and the second initiator are not particularly limited.
  • the first initiator and the second initiator are not particularly limited.
  • the secondary initiators include, but are not limited to, azobisisobutylamidine dihydrochloride and azobisisobuimidazoline hydrochloride.
  • the second aspect of the present invention provides a method for preparing the acrylate emulsion with high water whitening resistance, and the steps at least include:
  • Pre-emulsion Add deionized water, first emulsifier, first initiator, styrene monomer, acrylic monomer, first organic silicon monomer, and second organic silicon monomer to the monomer tank , Stir for 20-40 minutes to get the pre-emulsion;
  • reaction kettle Add deionized water, second emulsifier, and second initiator to the reaction kettle, raise the temperature to 80-90°C, stir uniformly, add 1wt%-5wt% of pre-emulsion to the reaction kettle, proceed reaction;
  • the method for preparing the acrylic emulsion with high water whitening resistance includes at least:
  • Pre-emulsion Add deionized water, first emulsifier, first initiator, styrene monomer, acrylic monomer, first organic silicon monomer, and second organic silicon monomer to the monomer tank , Stir for 30 minutes to get the pre-emulsion;
  • reaction kettle Add deionized water, second emulsifier, and second initiator to the reaction kettle, raise the temperature to 85°C, stir uniformly, and add 4wt% of the pre-emulsion to the reaction kettle for reaction;
  • the amount of deionized water added in the step (1) is 20-40 of the total mass of styrene monomer, acrylate monomer, first organosilicon monomer, and second organosilicon monomer. %; Preferably, the amount of deionized water added in the step (1) is 30% of the total mass of styrene monomer, acrylate monomer, first organosilicon monomer, and second organosilicon monomer.
  • the amount of deionized water added in the step (2) is 5-20 of the total mass of styrene monomer, acrylate monomer, first organosilicon monomer, and second organosilicon monomer. %; Preferably, the amount of deionized water added in the step (2) is 10% of the total mass of styrene monomer, acrylate monomer, first organosilicon monomer, and second organosilicon monomer.
  • the raw materials at least contain: 25 parts of styrene monomer, 55 parts of acrylate monomer, 2 parts of first organosilicon monomer, and second organosilicon monomer 5 parts, 2 parts of the first emulsifier, 4 parts of the second emulsifier, 1.5 parts of the first initiator, 1 part of the second initiator.
  • the acrylate monomer is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, and methyl methacrylate monomer; the butyl acrylate monomer, isooctyl acrylate monomer, methyl methacrylate monomer
  • the weight ratio of ester monomers is 1:1:2.
  • the first organosilicon monomer is dimethyldimethoxysiloxane.
  • the second organosilicon monomer is vinyltrichlorosilane.
  • the first emulsifier is a mixture of alkylphenol polyether sulfosuccinate monoester sodium salt and long-chain carboxylate polyoxyethylene; the alkylphenol polyether sulfosuccinate monoester sodium salt, long-chain carboxylate
  • the weight ratio of carboxylate polyoxyethylene is 1:2.5.
  • the second emulsifier is a combination of rosin oil soap and long-chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap and long-chain carboxylate polyoxyethylene is 1:0.3.
  • the model of the long-chain carboxylate polyoxyethylene is LMEO-18, and the brand is American Sima.
  • the first initiator and the second initiator are azobisisobutylamidine dihydrochloride.
  • the method for preparing the acrylate emulsion with high water whitening resistance includes at least:
  • Pre-emulsion Add deionized water, first emulsifier, first initiator, styrene monomer, acrylic monomer, first organic silicon monomer, and second organic silicon monomer to the monomer tank , Stir for 30 minutes to get the pre-emulsion;
  • reaction kettle Add deionized water, second emulsifier, and second initiator to the reaction kettle, raise the temperature to 85°C, stir uniformly, and add 4wt% of the pre-emulsion to the reaction kettle for reaction;
  • the amount of deionized water added is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer, and the second organosilicon monomer.
  • the amount of deionized water added is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer, and the second organosilicon monomer.
  • the raw materials at least include: 20 parts of styrene monomer, 50 parts of acrylate monomer, 1 part of first organosilicon monomer, and second organosilicon monomer 2 parts, 0.6 parts of the first emulsifier, 2 parts of the second emulsifier, 0.1 part of the first initiator, 1 part of the second initiator.
  • the acrylate monomer is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, and methyl methacrylate monomer; the butyl acrylate monomer, isooctyl acrylate monomer, methyl methacrylate monomer
  • the weight ratio of ester monomer is 1:0.5:1.
  • the first organosilicon monomer is dimethyldimethoxysiloxane.
  • the second organosilicon monomer is vinyltrichlorosilane.
  • the first emulsifier is a mixture of alkylphenol polyether sulfosuccinate monoester sodium salt and long-chain carboxylate polyoxyethylene; the alkylphenol polyether sulfosuccinate monoester sodium salt, long-chain carboxylate The weight ratio of carboxylate polyoxyethylene is 1:1.
  • the second emulsifier is a combination of rosin oil soap and long-chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap and long-chain carboxylate polyoxyethylene is 1:0.1.
  • the model of the long-chain carboxylate polyoxyethylene is LMEO-18, and the brand is American Sima.
  • the first initiator and the second initiator are azobisisobutylamidine dihydrochloride.
  • the method for preparing the acrylate emulsion with high water whitening resistance includes at least:
  • Pre-emulsion Add deionized water, first emulsifier, first initiator, styrene monomer, acrylic monomer, first organic silicon monomer, and second organic silicon monomer to the monomer tank , Stir for 20 minutes to get the pre-emulsion;
  • reaction kettle Add deionized water, second emulsifier, and second initiator to the reaction kettle, raise the temperature to 80°C, stir uniformly, and add 1wt% of the pre-emulsion to the reaction kettle for reaction;
  • the amount of deionized water added is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer, and the second organosilicon monomer.
  • the amount of deionized water added is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer, and the second organosilicon monomer.
  • the raw materials at least include: 30 parts of styrene monomer, 60 parts of acrylate monomer, 3 parts of first organosilicon monomer, and second organosilicon monomer 8 parts, 3.5 parts of the first emulsifier, 6 parts of the second emulsifier, 3 parts of the first initiator, 2 parts of the second initiator.
  • the acrylate monomer is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, and methyl methacrylate monomer; the butyl acrylate monomer, isooctyl acrylate monomer, methyl methacrylate monomer
  • the weight ratio of ester monomers is 1:1.5:3.
  • the first organosilicon monomer is dimethyldimethoxysiloxane.
  • the second organosilicon monomer is vinyltrichlorosilane.
  • the first emulsifier is a mixture of alkylphenol polyether sulfosuccinate monoester sodium salt and long-chain carboxylate polyoxyethylene; the alkylphenol polyether sulfosuccinate monoester sodium salt, long-chain carboxylate
  • the weight ratio of carboxylate polyoxyethylene is 1:5.
  • the second emulsifier is a combination of rosin oil soap and long-chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap and long-chain carboxylate polyoxyethylene is 1:0.5.
  • the model of the long-chain carboxylate polyoxyethylene is LMEO-18, and the brand is American Sima.
  • the first initiator and the second initiator are azobisisobutylamidine dihydrochloride.
  • the method for preparing the acrylate emulsion with high water whitening resistance includes at least:
  • Pre-emulsion Add deionized water, first emulsifier, first initiator, styrene monomer, acrylic monomer, first organic silicon monomer, and second organic silicon monomer to the monomer tank , Stir for 40 minutes to get the pre-emulsion;
  • reaction kettle Add deionized water, second emulsifier, and second initiator to the reaction kettle, raise the temperature to 90°C, stir evenly, and add 5wt% of the pre-emulsion to the reaction kettle for reaction;
  • the amount of deionized water added is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer, and the second organosilicon monomer.
  • the amount of deionized water added is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer, and the second organosilicon monomer.
  • Viscosity test test the initial viscosity, overnight viscosity and viscosity change value of the following conditions, and use Stormer viscometer to test the shear viscosity (test method: in accordance with GB/T 9269-2009 Determination of paint viscosity by Stormer viscometer method ).
  • Test 1 Emulsion and 2% cellulose are mixed in equal proportions: the acrylate emulsion prepared in Example 1 to Example 3 is mixed with a 2% cellulose aqueous solution in a mass ratio of 1:1, and the cellulose model is 250HBR, Yaqualong, the test results are shown in Table 1.
  • Example Example 1 Example 2
  • Example 3 Initial viscosity 86KU 86.3KU 85.8KU
  • Emulsion and 7% protective glue aqueous solution were mixed in equal proportions: the acrylic emulsion prepared in Example 1 to Example 3 was mixed with 7% protective glue at a mass ratio of 1:1; the protective glue was by weight
  • the parts include 240 parts of water, 8.9 parts of modified silicate, 1 part of tackifier, and 0.1 part of bactericide.
  • the acrylic emulsion prepared in Example 1 to Example 3 was applied to prepare a basic paint, and the method of use is as follows:
  • the basic paint in parts by weight includes: 136.7 parts of water and 5.9 parts of film-forming aids , 2 parts bactericide, 2 parts defoamer, 1.5 parts cellulose, 0.5 parts thickening agent, 1.3 strengthening additives, 0.1 parts pH regulator, 5 parts titanium dioxide, 85 parts acrylate emulsion, 100 parts 80 mesh snowflake white , 100 copies of 100 mesh Snow White.
  • Example Example 1 Example 2
  • Example 3 Initial viscosity 102KU 105.4KU 102.2KU Overnight viscosity 107.4KU 111.8KU 107.8KU Viscosity change value 5.4 6.4 5.6
  • Test 4 Application to the continuous phase: The acrylate emulsion prepared in Example 1 to Example 3 was used to prepare the continuous phase.
  • the method of use is as follows: The continuous phase includes 118.1 parts by weight of water and 6.8 parts of film-forming aids. , 5 parts of propylene glycol, 1.5 parts of bactericide, 1 part of defoamer, 3.6 parts of monobutyl ether, 110 parts of acrylate emulsion, 4 parts of thickener.
  • Example Example 1 Example 2
  • Example 3 Initial viscosity 138KU 138.2KU 138.8KU Overnight viscosity 140.3KU 140.5KU 140KU Viscosity change value 2.3 2.3 1.2
  • Test 5 The continuous phase and the protective glue are mixed in equal proportions: the continuous phase in Test 4 and the 7% protective glue aqueous solution are mixed at a weight ratio of 1:1, and the viscosity is tested.
  • Example Example 1 Example 2 Example 3 Initial viscosity 45.6KU 46.9KU 45.9KU Overnight viscosity 46.7KU 47.9KU 46.8KU Viscosity change value 1.1 1 0.9
  • Test 6 Continuous phase water resistance test: The water resistance test can be divided into emulsion film water resistance test and paint film water resistance test. We usually use emulsion film water resistance test, that is, coat the emulsion film on the glass plate, check the appearance of the wet film, and dry for 24 hours Then check the appearance of the dry film, and soak it in tap water for 4 hours to check whether the emulsion film has changed.
  • emulsion film water resistance test that is, coat the emulsion film on the glass plate, check the appearance of the wet film, and dry for 24 hours Then check the appearance of the dry film, and soak it in tap water for 4 hours to check whether the emulsion film has changed.
  • Example Example 1 Example 2
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Abstract

一种高耐水白性能的丙烯酸酯乳液，涉及乳液漆膜技术领域，按重量份计，原料至少包含：苯乙烯单体15-40份，丙烯酸酯类单体40-70份，第一有机硅单体1-5份，第二有机硅单体1-10份，第一乳化剂0.5-4份，第二乳化剂1-10份，第一引发剂0.1-5份，第二引发剂0.1-4份。该乳液透明性好，与保护胶稳定共存，不后稠，具有极好的成漆稳定性、耐沾污性以及耐水白性，以及极好的钙离子稳定性、稀释稳定性、冻融稳定性和机械稳定性。

Description

一种高耐水白性能的丙烯酸酯乳液及其制备方法 技术领域
本发明涉及乳液漆膜的技术领域，具体的更涉及一种高耐水白性能的丙烯酸酯乳液及其制备方法。
背景技术
国内相继开发了一系列防锈涂料，但大多为溶剂型防锈涂料。这类涂料除了含有大量有机溶剂外，而且还含有大量有毒颜料，给环境造成严重的污染。为此，研究开发新型环保、防锈性能优异的水性防锈涂料符合当前涂料发展的趋势。水性涂料是指用水作溶剂或分散介质的涂料，具有防护性好和耐腐蚀性好等优点，而且与油性涂料相比，水性涂料的生产可以节省资源，生产和使用过程中的污染小，因此应用越来越广泛。
聚丙烯酸酯类乳液以水为介质，具有成本低、使用安全、环境污染少等优点，其成膜物具有柔韧、耐候、粘性好等特点，因此作为建材已广泛应用在装饰和内、外墙涂料中。但是，对于水性丙烯酸乳液均为羟基单体加丙烯酸酯类单体共聚而成，在耐水性、硬度和耐候性等方面还存在一定问题，尤其是吸水泛白现象较为严重。
发明内容
为了解决上述的技术问题，本发明中的第一个方面提供了一种高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体15-40份，丙烯酸酯类单体40-70份，第一有机硅单体1-5份，第二有机硅单体1-10份，第一乳化剂0.5-4份，第二乳化剂1-10份，第一引发剂0.1-5份，第二引发剂0.1-4份。
作为一种优选的技术方案，本发明中所述的高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体20-30份，丙烯酸酯类单体50-60份，第一有机硅单体1-3份，第二有机硅单体2-8份，第一乳化剂0.6-3.5份，第二乳化剂2-6份，第一引发剂0.1-3份，第二引发剂0.1-2份。
作为一种优选的技术方案，本发明中所述丙烯酸酯类单体为丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的混合物；所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：(0.5-1.5)：(1-3)。
作为一种优选的技术方案，本发明中所述第一有机硅单体选自二甲基二甲氧基硅氧烷、甲基苯基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷中的至少一种。
作为一种优选的技术方案，本发明中所述第二有机硅单体选自乙基三氯硅烷、丙基三氯硅烷、γ-氯丙基三氯硅烷、苯基氯硅烷、乙烯基三氯硅烷、甲基乙烯基氯硅烷、甲基氯硅烷中的至少一种。
作为一种优选的技术方案，本发明中所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯、聚氧乙烯羧酸酯、羧酸盐型乳化剂、折叠硬脂酸钠中的至少一种。
作为一种优选的技术方案，本发明中所述的第二乳化剂为松香油皂、长链羧酸酯 聚氧乙烯中的至少一种。
作为一种优选的技术方案，本发明中所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的混合物；所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：(1-5)。
作为一种优选的技术方案，本发明中所述第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯的组合；所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：(0.1-0.5)。
本发明的第二个方面提供了一种所述的高耐水白性能的丙烯酸酯乳液的制备方法，步骤至少包括：
(1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌20-40分钟得到预乳液；
(2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至80-90℃，搅拌均匀，向反应釜中加入1wt％-5wt％的预乳液，进行反应；
(3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为2-4小时，滴加完成后，调pH值至8±1，即得。
与现有技术相比，本发明具有如下优异的有益特点：
本发明提供了一种高耐水白性能的丙烯酸乳液，研究的新型水包水、水包砂乳液。本发明结合采用种子工艺，核合技术聚合而成，乳液透明性好，与保护胶稳定，不后稠，极好的成漆稳定性、耐玷污性以及耐水白性，极好的钙离子稳定性、稀释稳定性、冻融稳定性和机械稳定性。此外，该丙烯酸乳液不仅具有高硬度，尤其是具有超强耐水、抗泛白，优异的疏水性，抗玷污性好；配制的水包水，水包砂有逼真感；由于该乳液中含有特定含量和种类的有机硅，与底材形成优异的附着力；而特殊的硅烷接技工艺，赋予漆膜优异耐候性；该丙烯酸乳液是一款具有优异的综合性能的乳液，可广泛用于水包水、水包砂、高级真石漆、高级外墙硅丙乳胶漆。
具体实施方式
下面结合具体实施方式对本发明提供技术方案中的技术特征作进一步清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本技术领域技术人员可以理解，除非另外定义，这里使用的所有术语(包括技术术语和科学术语)具有与本发明所属领域中的普通技术人员的一般理解相同的意义。还应该理解的是，诸如通用字典中定义的那些术语应该被理解为具有与现有技术的上下文中的意义一致的意义，并且除非像这里一样定义，不会用理想化或过于正式的含义来解释。
本发明中的词语“优选的”、“优选地”、“更优选的”等是指，在某些情况下可提供某些有益效果的本发明实施方案。然而，在相同的情况下或其他情况下，其他实施方案也可能是优选的。此外，对一个或多个优选实施方案的表述并不暗示其他实施方案不可用，也并非旨在将其他实施方案排除在本发明的范围之外。
本发明提供了一种高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体15-40份，丙烯酸酯类单体40-70份，第一有机硅单体1-5份，第二有机硅单体1-10 份，第一乳化剂0.5-4份，第二乳化剂1-10份，第一引发剂0.1-5份，第二引发剂0.1-4份。
在一些优选的实施方式中，所述的高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体20-30份，丙烯酸酯类单体50-60份，第一有机硅单体1-3份，第二有机硅单体2-8份，第一乳化剂0.6-3.5份，第二乳化剂2-6份，第一引发剂0.1-3份，第二引发剂0.1-2份。
在一些更优选的实施方式中，所述的高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体25份，丙烯酸酯类单体55份，第一有机硅单体2份，第二有机硅单体5份，第一乳化剂2份，第二乳化剂4份，第一引发剂1.5份，第二引发剂1份。
在一些实施方式中，所述丙烯酸酯类单体为丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的混合物；所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：(0.5-1.5)：(1-3)。
在一些优选的实施方式中，所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：1：2。
在一些实施方式中，所述第一有机硅单体选自二甲基二甲氧基硅氧烷、甲基苯基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷中的至少一种。
在一些优选的实施方式中，所述第一有机硅单体为二甲基二甲氧基硅氧烷。
在一些实施方式中，所述第二有机硅单体选自乙基三氯硅烷、丙基三氯硅烷、γ-氯丙基三氯硅烷、苯基氯硅烷、乙烯基三氯硅烷、甲基乙烯基氯硅烷、甲基氯硅烷中的至少一种。
在一些优选的实施方式中，所述第二有机硅单体为乙烯基三氯硅烷。
在一些实施方式中，所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯、聚氧乙烯羧酸酯、羧酸盐型乳化剂、折叠硬脂酸钠中的至少一种。
在一些实施方式中，所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的混合物；所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：(1-5)。
在一些优选的实施方式中，所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：2.5。
在一些实施方式中，所述的第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯中的至少一种。
在一些实施方式中，所述第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯的组合；所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：(0.1-0.5)。
在一些优选的实施方式中，所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：0.3。
本发明中所述的长链羧酸酯聚氧乙烯的型号为LMEO-18，品牌为美国希马。
发明人意料不到的发现，在本发明中制备的丙烯酸乳液不仅具有非常优异的硬度，而且还具有非常好的抗泛白的能力，疏水性非常的优异，尤其是选用长链羧酸酯聚氧乙烯与其他的松香油皂、烷基酚聚醚磺基琥珀酸单酯钠盐进行复配使用，发明人发现具有出众的协同效应，达到良好的性价比，可以显著的增强乳液形成的漆膜的耐水泛白的效果；发明人认为，可能是由于长链羧酸酯聚氧乙烯具有特殊的18碳脂肪酸酯，具有酯基和双键结 构，在乳液聚合的过程中可以形成更好的分散作用，以及在特殊的硅烷接技工艺和配制涂料过程中形成水包水、水包砂形成的一种耐水性的漆膜，抵抗水的侵蚀渗透作用。
在一些实施方式中，所述第一引发剂和第二引发剂为同一种引发剂，所述第一引发剂和第二引发剂的种类不做特殊的限定，所述第一引发剂和第二引发剂包括但不限于偶氮二异丁基脒二盐酸盐、偶氮二异丁咪唑啉盐酸盐。
本发明中的第二个方面提供了一种所述的高耐水白性能的丙烯酸酯乳液的制备方法，步骤至少包括：
(1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌20-40分钟得到预乳液；
(2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至80-90℃，搅拌均匀，向反应釜中加入1wt％-5wt％的预乳液，进行反应；
(3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为2-4小时，滴加完成后，调pH值至7-9，即得。
在一些优选的实施方式中，所述的高耐水白性能的丙烯酸酯乳液的制备方法，步骤至少包括：
(1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌30分钟得到预乳液；
(2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至85℃，搅拌均匀，向反应釜中加入4wt％的预乳液，进行反应；
(3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为3小时，滴加完成后，调pH值至8±1，即得。
在一些实施方式中，所述步骤(1)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的20-40％；优选的，所述步骤(1)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的30％。
在一些实施方式中，所述步骤(2)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的5-20％；优选的，所述步骤(2)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的10％。
下面通过实施例对本发明进行具体的描述，以下实施例只能用于本发明做进一步说明，并不能理解为本发明保护的限制，该领域的专业技术人员根据上述发明的内容作出的非本质的改正和调整，仍属于本发明的保护的范围。
实施例1
一种高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体25份，丙烯酸酯类单体55份，第一有机硅单体2份，第二有机硅单体5份，第一乳化剂2份，第二乳化剂4份，第一引发剂1.5份，第二引发剂1份。
所述丙烯酸酯类单体为丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的混合物；所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：1：2。
所述第一有机硅单体为二甲基二甲氧基硅氧烷。所述第二有机硅单体为乙烯基三氯硅烷。
所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的混合物；所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：2.5。
所述第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯的组合；所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：0.3。所述的长链羧酸酯聚氧乙烯的型号为LMEO-18，品牌为美国希马。
所述第一引发剂和第二引发剂为偶氮二异丁基脒二盐酸盐。
所述的高耐水白性能的丙烯酸酯乳液的制备方法，步骤至少包括：
(1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌30分钟得到预乳液；
(2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至85℃，搅拌均匀，向反应釜中加入4wt％的预乳液，进行反应；
(3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为3小时，滴加完成后，调pH值至8±1，即得。
所述步骤(1)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的30％。所述步骤(2)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的10％。
实施例2
一种高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体20份，丙烯酸酯类单体50份，第一有机硅单体1份，第二有机硅单体2份，第一乳化剂0.6份，第二乳化剂2份，第一引发剂0.1份，第二引发剂1份。
所述丙烯酸酯类单体为丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的混合物；所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：0.5：1。
所述第一有机硅单体为二甲基二甲氧基硅氧烷。所述第二有机硅单体为乙烯基三氯硅烷。
所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的混合物；所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：1。
所述第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯的组合；所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：0.1。所述的长链羧酸酯聚氧乙烯的型号为LMEO-18，品牌为美国希马。
所述第一引发剂和第二引发剂为偶氮二异丁基脒二盐酸盐。
所述的高耐水白性能的丙烯酸酯乳液的制备方法，步骤至少包括：
(1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌20分钟得到预乳液；
(2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至80℃，搅拌均匀，向反应釜中加入1wt％的预乳液，进行反应；
(3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为2小 时，滴加完成后，调pH值至8±1，即得。
所述步骤(1)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的30％。所述步骤(2)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的10％。
实施例3
一种高耐水白性能的丙烯酸酯乳液，按重量份计，原料至少包含：苯乙烯单体30份，丙烯酸酯类单体60份，第一有机硅单体3份，第二有机硅单体8份，第一乳化剂3.5份，第二乳化剂6份，第一引发剂3份，第二引发剂2份。
所述丙烯酸酯类单体为丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的混合物；所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：1.5：3。
所述第一有机硅单体为二甲基二甲氧基硅氧烷。所述第二有机硅单体为乙烯基三氯硅烷。
所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的混合物；所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：5。
所述第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯的组合；所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：0.5。所述的长链羧酸酯聚氧乙烯的型号为LMEO-18，品牌为美国希马。
所述第一引发剂和第二引发剂为偶氮二异丁基脒二盐酸盐。
所述的高耐水白性能的丙烯酸酯乳液的制备方法，步骤至少包括：
(1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌40分钟得到预乳液；
(2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至90℃，搅拌均匀，向反应釜中加入5wt％的预乳液，进行反应；
(3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为4小时，滴加完成后，调pH值至8±1，即得。
所述步骤(1)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的30％。所述步骤(2)中去离子水的加入量为苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体总质量的10％。
性能测试
粘度测试：测试以下几种情况的初始粘度、隔夜粘度和粘度变化值，用Stormer型粘度计测试中剪切粘度(测试方法：按照GB/T 9269-2009涂料粘度的测定斯托默粘度计法)。
测试1.乳液与2％纤维素等比例混拼：将实施例1-实施例3制备的丙烯酸酯乳液分别与2％纤维素水溶液按照质量比为1：1进行混合，所述纤维素型号为250HBR，亚夸龙，测试结果如表1所示。
表1测试1测试结果
实施例 实施例1 实施例2 实施例3
初始粘度 86KU 86.3KU 85.8KU
隔夜粘度 87.2KU 87.8KU 87.1KU
粘度变化值 1.2 1.5 1.3
测试2.乳液与7％保护胶水溶液等比例混拼：将实施例1-实施例3制备的丙烯酸酯乳液分别与7％保护胶按照质量比为1：1进行混合；所述保护胶按重量份包括240份水、8.9份改性硅酸盐、1份增粘剂、0.1份杀菌剂。
表2测试2的测试结果
Figure PCTCN2021081162-appb-000001
测试3.应用到基础漆：将实施例1-实施例3制备的丙烯酸酯乳液应用制备基础漆，使用方法如下：所述基础漆按重量份计包括：136.7份水、5.9份成膜助剂、2份杀菌剂、2份消泡剂、1.5份纤维素、0.5份增厚剂、1.3增强添加剂、0.1份PH调节剂、5份钛白粉、85份丙烯酸酯乳液、100份80目雪花白、100份100目雪花白。
表3测试3的测试结果
实施例 实施例1 实施例2 实施例3
初始粘度 102KU 105.4KU 102.2KU
隔夜粘度 107.4KU 111.8KU 107.8KU
粘度变化值 5.4 6.4 5.6
测试4.应用到连续相：将实施例1-实施例3制备的丙烯酸酯乳液应用制备连续相，使用方法如下：所述连续相按重量份计包括：118.1份水、6.8份成膜助剂、5份丙二醇、1.5份杀菌剂、1份消泡剂、3.6份单丁醚、110份丙烯酸酯乳液、4份增稠剂。
表4测试4的测试结果
实施例 实施例1 实施例2 实施例3
初始粘度 138KU 138.2KU 138.8KU
隔夜粘度 140.3KU 140.5KU 140KU
粘度变化值 2.3 2.3 1.2
测试5.连续相与保护胶等比例混拼：将测试4中的连续相与7％保护胶水溶液进行重量比为1：1进行混合，测试其粘度。
表5测试5的测试结果
实施例 实施例1 实施例2 实施例3
初始粘度 45.6KU 46.9KU 45.9KU
隔夜粘度 46.7KU 47.9KU 46.8KU
粘度变化值 1.1 1 0.9
测试6.连续相耐水测试：耐水测试可分为乳液膜耐水测试，成漆膜耐水测试，我们通常采用乳液膜耐水测试，即将乳液膜涂布在玻璃板上，查看湿膜外观，干燥24小时后查看干膜外观，及放入自来水中浸泡4小时再查看乳液膜是否有无变化。
表6测试6的测试结果
实施例 实施例1 实施例2 实施例3
湿膜外观 白相 白相 白相
干膜外观 无色透明 无色透明 无色透明
常温干燥24H，常温耐水4H 无色透明 无色透明 无色透明
以上所述仅是本发明的较佳实施例而已，并非是对发明作其他形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或更改为等同变化的等效实施例，但凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改，等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (10)

  1. 一种高耐水白性能的丙烯酸酯乳液，其特征在于，按重量份计，原料至少包含：苯乙烯单体15-40份，丙烯酸酯类单体40-70份，第一有机硅单体1-5份，第二有机硅单体1-10份，第一乳化剂0.5-4份，第二乳化剂1-10份，第一引发剂0.1-5份，第二引发剂0.1-4份。
  2. 如权利要求1所述的高耐水白性能的丙烯酸酯乳液，其特征在于，按重量份计，原料至少包含：苯乙烯单体20-30份，丙烯酸酯类单体50-60份，第一有机硅单体1-3份，第二有机硅单体2-8份，第一乳化剂0.6-3.5份，第二乳化剂2-6份，第一引发剂0.1-3份，第二引发剂0.1-2份。
  3. 如权利要求1或2所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述丙烯酸酯类单体为丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的混合物；所述丙烯酸丁酯单体、丙烯酸异辛酯单体、甲基丙烯酸甲酯单体的重量比为1：(0.5-1.5)：(1-3)。
  4. 如权利要求1或2所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述第一有机硅单体选自二甲基二甲氧基硅氧烷、甲基苯基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷中的至少一种。
  5. 如权利要求1或2所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述第二有机硅单体选自乙基三氯硅烷、丙基三氯硅烷、γ-氯丙基三氯硅烷、苯基氯硅烷、乙烯基三氯硅烷、甲基乙烯基氯硅烷、甲基氯硅烷中的至少一种。
  6. 如权利要求1或2所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯、聚氧乙烯羧酸酯、羧酸盐型乳化剂、折叠硬脂酸钠中的至少一种。
  7. 如权利要求1或2所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述的第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯中的至少一种。
  8. 如权利要求6所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述第一乳化剂为烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的混合物；所述烷基酚聚醚磺基琥珀酸单酯钠盐、长链羧酸酯聚氧乙烯的重量比为1：(1-5)。
  9. 如权利要求7所述的高耐水白性能的丙烯酸酯乳液，其特征在于，所述所述第二乳化剂为松香油皂、长链羧酸酯聚氧乙烯的组合；所述所述松香油皂、长链羧酸酯聚氧乙烯的重量比为1：(0.1-0.5)。
  10. 一种如权利要求1-9任一项所述的高耐水白性能的丙烯酸酯乳液的制备方法，其特征在于，步骤至少包括：
    (1)预乳液：在单体罐中加入去离子水、第一乳化剂、第一引发剂、苯乙烯单体、丙烯酸酯类单体、第一有机硅单体、第二有机硅单体，搅拌20-40分钟得到预乳液；
    (2)反应釜：在反应釜中加入去离子水、第二乳化剂、第二引发剂，升温至80-90℃，搅拌均匀，向反应釜中加入1wt％-5wt％的预乳液，进行反应；
    (3)回温反应：反应釜回升至常温，开始匀速滴加入剩余的预乳液。滴加时间为2-4小时，滴加完成后，调pH值至8±1，即得。
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