CN111285959A - Acrylate emulsion with high water-white resistance and preparation method thereof - Google Patents

Acrylate emulsion with high water-white resistance and preparation method thereof Download PDF

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CN111285959A
CN111285959A CN202010252047.2A CN202010252047A CN111285959A CN 111285959 A CN111285959 A CN 111285959A CN 202010252047 A CN202010252047 A CN 202010252047A CN 111285959 A CN111285959 A CN 111285959A
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parts
monomer
emulsion
water
emulsifier
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曾国红
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Shanghai Baolijia New Material Co ltd
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Shanghai Baolijia New Material Co ltd
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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

Abstract

The invention relates to the technical field of emulsion paint films, and provides an acrylate emulsion with high water-white resistance, which at least comprises the following raw materials in parts by weight: 15-40 parts of styrene monomer, 40-70 parts of acrylate monomer, 1-5 parts of first organic silicon monomer, 1-10 parts of second organic silicon monomer, 0.5-4 parts of first emulsifier, 1-10 parts of second emulsifier, 0.1-5 parts of first initiator and 0.1-4 parts of second initiator. The emulsion has good transparency, is stable with protective glue, is not thick later, has excellent paint forming stability, stain resistance and water-white resistance, and has excellent calcium ion stability, dilution stability, freeze-thaw stability and mechanical stability.

Description

Acrylate emulsion with high water-white resistance and preparation method thereof
Technical Field
The invention relates to the technical field of emulsion paint films, in particular to an acrylate emulsion with high water-white resistance and a preparation method thereof.
Background
A series of antirust coatings are developed successively in China, but most of the antirust coatings are solvent-based antirust coatings. Besides a large amount of organic solvent, the paint also contains a large amount of toxic pigment, which causes serious pollution to the environment. Therefore, the research and development of novel environment-friendly water-based antirust coating with excellent antirust performance accords with the development trend of the current coating. The water-based paint is a paint using water as a solvent or a dispersion medium, has the advantages of good protection property, good corrosion resistance and the like, and compared with an oil-based paint, the water-based paint can save resources in production and has small pollution in the production and use processes, so that the water-based paint is more and more widely applied.
The polyacrylate emulsion takes water as a medium, has the advantages of low cost, safe use, less environmental pollution and the like, and the film forming material has the characteristics of flexibility, weather resistance, good viscosity and the like, so the polyacrylate emulsion is widely applied to decoration and interior and exterior wall coatings as a building material. However, the aqueous acrylic emulsion is prepared by copolymerizing a hydroxyl monomer and an acrylate monomer, and has certain problems in the aspects of water resistance, hardness, weather resistance and the like, particularly serious water-absorbing whitening phenomenon.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides an acrylate emulsion with high water-white resistance, which comprises the following raw materials in parts by weight: 15-40 parts of styrene monomer, 40-70 parts of acrylate monomer, 1-5 parts of first organic silicon monomer, 1-10 parts of second organic silicon monomer, 0.5-4 parts of first emulsifier, 1-10 parts of second emulsifier, 0.1-5 parts of first initiator and 0.1-4 parts of second initiator.
As a preferred technical solution, the acrylate emulsion with high water-white resistance in the invention comprises the following raw materials in parts by weight: 20-30 parts of styrene monomer, 50-60 parts of acrylate monomer, 1-3 parts of first organic silicon monomer, 2-8 parts of second organic silicon monomer, 0.6-3.5 parts of first emulsifier, 2-6 parts of second emulsifier, 0.1-3 parts of first initiator and 0.1-2 parts of second initiator.
As a preferred technical scheme, the acrylic ester monomer is a mixture of a butyl acrylate monomer, an isooctyl acrylate monomer and a methyl methacrylate monomer; the weight ratio of the butyl acrylate monomer to the isooctyl acrylate monomer to the methyl methacrylate monomer is 1: (0.5-1.5): (1-3).
In a preferred embodiment of the present invention, the first organosilicon monomer is at least one selected from the group consisting of dimethyldimethoxysiloxane, methylphenyldimethoxysiloxane, and methylvinyldimethoxysiloxane.
In a preferred embodiment, the second organosilicon monomer is at least one selected from ethyltrichlorosilane, propyltrichlorosilane, γ -chloropropyltrichlorosilane, phenylchlorosilane, vinyltrichlorosilane, methylvinylchlorosilane, and methylchlorosilane.
In a preferred embodiment of the present invention, the first emulsifier is at least one of alkylphenol polyether sulfosuccinic acid monoester sodium salt, long-chain carboxylic ester polyoxyethylene, polyoxyethylene carboxylic ester, carboxylate type emulsifier, and sodium stearyl stearate.
In a preferred embodiment, the second emulsifier in the present invention is at least one of rosin oil soap and long-chain carboxylic ester polyoxyethylene.
As a preferable technical scheme, the first emulsifier in the invention is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylic ester polyoxyethylene; the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylic ester polyoxyethylene is 1: (1-5).
As a preferable technical solution, in the present invention, the second emulsifier is a combination of rosin oil soap and long-chain carboxylic ester polyoxyethylene; the weight ratio of the rosin oil soap to the long-chain carboxylic ester polyoxyethylene is 1: (0.1-0.5).
The second aspect of the present invention provides a method for preparing the acrylate emulsion with high water-white resistance, which at least comprises the following steps:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 20-40 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 80-90 ℃, uniformly stirring, adding 1-5 wt% of pre-emulsion into the reaction kettle, and reacting;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 2-4 hours, and after the dripping is finished, the pH value is adjusted to 8 +/-1, thus obtaining the product.
Compared with the prior art, the invention has the following excellent beneficial characteristics:
the invention provides a novel water-in-water and sand-in-water emulsion researched from an acrylic emulsion with high water-white resistance. The invention is polymerized by combining a seed process and a nucleation technology, has good emulsion transparency, is stable with a protective adhesive, is not thick later, has excellent paint forming stability, stain resistance and water-white resistance, and has excellent calcium ion stability, dilution stability, freeze-thaw stability and mechanical stability. In addition, the acrylic emulsion has high hardness, and particularly has super-strong water resistance, whitening resistance, excellent hydrophobicity and good anti-staining property; the prepared water-in-water sand has vivid sense; because the emulsion contains specific content and types of organic silicon, the emulsion forms excellent adhesive force with a substrate; the special silane grafting process endows the paint film with excellent weather resistance; the acrylic emulsion is an emulsion with excellent comprehensive performance, and can be widely used for water-in-water, sand-in-water, high-grade real stone paint and high-grade exterior wall silicone acrylic emulsion paint.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The invention provides an acrylate emulsion with high water-white resistance, which at least comprises the following raw materials in parts by weight: 15-40 parts of styrene monomer, 40-70 parts of acrylate monomer, 1-5 parts of first organic silicon monomer, 1-10 parts of second organic silicon monomer, 0.5-4 parts of first emulsifier, 1-10 parts of second emulsifier, 0.1-5 parts of first initiator and 0.1-4 parts of second initiator.
In some preferred embodiments, the acrylate emulsion with high water-white resistance comprises the following raw materials in parts by weight: 20-30 parts of styrene monomer, 50-60 parts of acrylate monomer, 1-3 parts of first organic silicon monomer, 2-8 parts of second organic silicon monomer, 0.6-3.5 parts of first emulsifier, 2-6 parts of second emulsifier, 0.1-3 parts of first initiator and 0.1-2 parts of second initiator.
In some more preferred embodiments, the acrylate emulsion with high water-white resistance comprises the following raw materials in parts by weight: 25 parts of styrene monomer, 55 parts of acrylate monomer, 2 parts of first organic silicon monomer, 5 parts of second organic silicon monomer, 2 parts of first emulsifier, 4 parts of second emulsifier, 1.5 parts of first initiator and 1 part of second initiator.
In some embodiments, the acrylate monomer is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, methyl methacrylate monomer; the weight ratio of the butyl acrylate monomer to the isooctyl acrylate monomer to the methyl methacrylate monomer is 1: (0.5-1.5): (1-3).
In some preferred embodiments, the weight ratio of the butyl acrylate monomer, the isooctyl acrylate monomer, and the methyl methacrylate monomer is 1: 1: 2.
in some embodiments, the first silicone monomer is selected from at least one of dimethyldimethoxysiloxane, methylphenyldimethoxysiloxane, methylvinyldimethoxysiloxane.
In some preferred embodiments, the first silicone monomer is dimethyldimethoxysiloxane.
In some embodiments, the second organosilicon monomer is selected from at least one of ethyltrichlorosilane, propyltrichlorosilane, gamma-chloropropyltrichlorosilane, phenylchlorosilane, vinyltrichlorosilane, methylvinylchlorosilane, methylchlorosilane.
In some preferred embodiments, the second silicone monomer is vinyltrichlorosilane.
In some embodiments, the first emulsifier is at least one of alkylphenol polyether sulfosuccinic acid monoester sodium salt, long chain carboxylate polyoxyethylene, polyoxyethylene carboxylate, carboxylate type emulsifier, sodium stearyl.
In some embodiments, the first emulsifier is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt, long chain carboxylic acid ester polyoxyethylene; the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylic ester polyoxyethylene is 1: (1-5).
In some preferred embodiments, the weight ratio of alkylphenol polyether sulfosuccinic acid monoester sodium salt to long chain carboxylic acid ester polyoxyethylene is 1: 2.5.
in some embodiments, the second emulsifier is at least one of rosin oil soap, long chain carboxylate polyoxyethylene.
In some embodiments, the second emulsifier is a combination of rosin oil soap, long chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap to the long-chain carboxylic ester polyoxyethylene is 1: (0.1-0.5).
In some preferred embodiments, the weight ratio of rosin oil soap to long chain carboxylate polyoxyethylene is 1: 0.3.
the long-chain carboxylic ester polyoxyethylene is LMEO-18, and the brand is American Hima.
The inventor unexpectedly discovers that the acrylic emulsion prepared in the invention not only has very excellent hardness, but also has very good whitening resistance and very excellent hydrophobicity, and particularly, the acrylic emulsion is prepared by compounding long-chain carboxylic ester polyoxyethylene with other rosin oil soap and alkylphenol polyether sulfosuccinic acid monoester sodium salt, so that the inventor discovers that the acrylic emulsion has an outstanding synergistic effect, achieves good cost performance and can remarkably enhance the whitening resistance effect of a paint film formed by the emulsion; the inventor believes that it is possible that the long chain carboxylic acid ester polyoxyethylene has a specific 18 carbon fatty acid ester, has an ester group and double bond structure, can form better dispersion during emulsion polymerization, and forms a water-in-water and sand-in-water paint film in a specific silane grafting process and a coating preparation process, and resists water erosion and penetration.
In some embodiments, the first initiator and the second initiator are the same initiator, and the type of the first initiator and the second initiator is not particularly limited, and the first initiator and the second initiator include, but are not limited to, azobisisobutylamidine dihydrochloride, and azobisisobutylimidazoline hydrochloride.
In a second aspect of the present invention, there is provided a method for preparing the acrylate emulsion with high water-white resistance, comprising at least the steps of:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 20-40 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 80-90 ℃, uniformly stirring, adding 1-5 wt% of pre-emulsion into the reaction kettle, and reacting;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 2-4 hours, and after the dripping is finished, the pH value is adjusted to 7-9, thus obtaining the product.
In some preferred embodiments, the method for preparing the acrylate emulsion with high water-white resistance at least comprises the following steps:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 30 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 85 ℃, uniformly stirring, and adding 4 wt% of pre-emulsion into the reaction kettle for reaction;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 3 hours, and after the dripping is finished, the pH value is adjusted to 8 +/-1, thus obtaining the product.
In some embodiments, the deionized water is added in the step (1) in an amount of 20 to 40 percent of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer and the second organosilicon monomer; preferably, the adding amount of the deionized water in the step (1) is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer and the second organosilicon monomer.
In some embodiments, the deionized water is added in the step (2) in an amount of 5-20% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer and the second organosilicon monomer; preferably, the adding amount of the deionized water in the step (2) is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organosilicon monomer and the second organosilicon monomer.
The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.
Example 1
The acrylic ester emulsion with high water-white resistance comprises the following raw materials in parts by weight: 25 parts of styrene monomer, 55 parts of acrylate monomer, 2 parts of first organic silicon monomer, 5 parts of second organic silicon monomer, 2 parts of first emulsifier, 4 parts of second emulsifier, 1.5 parts of first initiator and 1 part of second initiator.
The acrylate monomer is a mixture of a butyl acrylate monomer, an isooctyl acrylate monomer and a methyl methacrylate monomer; the weight ratio of the butyl acrylate monomer to the isooctyl acrylate monomer to the methyl methacrylate monomer is 1: 1: 2.
the first organic silicon monomer is dimethyl dimethoxy siloxane. The second organosilicon monomer is vinyl trichlorosilane.
The first emulsifier is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylic ester polyoxyethylene; the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylic ester polyoxyethylene is 1: 2.5.
the second emulsifier is a combination of rosin oil soap and long-chain carboxylic ester polyoxyethylene; the weight ratio of the rosin oil soap to the long-chain carboxylic ester polyoxyethylene is 1: 0.3. the long-chain carboxylic ester polyoxyethylene is LMEO-18, and the brand is American Hima.
The first initiator and the second initiator are azobisisobutylamidine dihydrochloride.
The preparation method of the acrylate emulsion with high water-white resistance at least comprises the following steps:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 30 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 85 ℃, uniformly stirring, and adding 4 wt% of pre-emulsion into the reaction kettle for reaction;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 3 hours, and after the dripping is finished, the pH value is adjusted to 8 +/-1, thus obtaining the product.
The adding amount of the deionized water in the step (1) is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organic silicon monomer and the second organic silicon monomer. The adding amount of the deionized water in the step (2) is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organic silicon monomer and the second organic silicon monomer.
Example 2
The acrylic ester emulsion with high water-white resistance comprises the following raw materials in parts by weight: 20 parts of styrene monomer, 50 parts of acrylate monomer, 1 part of first organic silicon monomer, 2 parts of second organic silicon monomer, 0.6 part of first emulsifier, 2 parts of second emulsifier, 0.1 part of first initiator and 1 part of second initiator.
The acrylate monomer is a mixture of a butyl acrylate monomer, an isooctyl acrylate monomer and a methyl methacrylate monomer; the weight ratio of the butyl acrylate monomer to the isooctyl acrylate monomer to the methyl methacrylate monomer is 1: 0.5: 1.
the first organic silicon monomer is dimethyl dimethoxy siloxane. The second organosilicon monomer is vinyl trichlorosilane.
The first emulsifier is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylic ester polyoxyethylene; the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylic ester polyoxyethylene is 1: 1.
the second emulsifier is a combination of rosin oil soap and long-chain carboxylic ester polyoxyethylene; the weight ratio of the rosin oil soap to the long-chain carboxylic ester polyoxyethylene is 1: 0.1. the long-chain carboxylic ester polyoxyethylene is LMEO-18, and the brand is American Hima.
The first initiator and the second initiator are azobisisobutylamidine dihydrochloride.
The preparation method of the acrylate emulsion with high water-white resistance at least comprises the following steps:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 20 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 80 ℃, uniformly stirring, and adding 1 wt% of pre-emulsion into the reaction kettle for reaction;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 2 hours, and after the dripping is finished, the pH value is adjusted to 8 +/-1, thus obtaining the product.
The adding amount of the deionized water in the step (1) is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organic silicon monomer and the second organic silicon monomer. The adding amount of the deionized water in the step (2) is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organic silicon monomer and the second organic silicon monomer.
Example 3
The acrylic ester emulsion with high water-white resistance comprises the following raw materials in parts by weight: 30 parts of styrene monomer, 60 parts of acrylate monomer, 3 parts of first organic silicon monomer, 8 parts of second organic silicon monomer, 3.5 parts of first emulsifier, 6 parts of second emulsifier, 3 parts of first initiator and 2 parts of second initiator.
The acrylate monomer is a mixture of a butyl acrylate monomer, an isooctyl acrylate monomer and a methyl methacrylate monomer; the weight ratio of the butyl acrylate monomer to the isooctyl acrylate monomer to the methyl methacrylate monomer is 1: 1.5: 3.
the first organic silicon monomer is dimethyl dimethoxy siloxane. The second organosilicon monomer is vinyl trichlorosilane.
The first emulsifier is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylic ester polyoxyethylene; the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylic ester polyoxyethylene is 1: 5.
the second emulsifier is a combination of rosin oil soap and long-chain carboxylic ester polyoxyethylene; the weight ratio of the rosin oil soap to the long-chain carboxylic ester polyoxyethylene is 1: 0.5. the long-chain carboxylic ester polyoxyethylene is LMEO-18, and the brand is American Hima.
The first initiator and the second initiator are azobisisobutylamidine dihydrochloride.
The preparation method of the acrylate emulsion with high water-white resistance at least comprises the following steps:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 40 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 90 ℃, uniformly stirring, and adding 5 wt% of pre-emulsion into the reaction kettle for reaction;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 4 hours, and after the dripping is finished, the pH value is adjusted to 8 +/-1, thus obtaining the product.
The adding amount of the deionized water in the step (1) is 30% of the total mass of the styrene monomer, the acrylate monomer, the first organic silicon monomer and the second organic silicon monomer. The adding amount of the deionized water in the step (2) is 10% of the total mass of the styrene monomer, the acrylate monomer, the first organic silicon monomer and the second organic silicon monomer.
Performance testing
And (3) viscosity testing: the initial viscosity, overnight viscosity and viscosity change values were measured for several cases, shear viscosity in a Stormer type viscometer test (test method: Stormer viscometer method for determination of coating viscosity according to GB/T9269-.
Test 1. mixing the emulsion with 2% cellulose in equal proportion: the acrylic ester emulsions prepared in examples 1 to 3 were mixed with a 2% cellulose aqueous solution at a mass ratio of 1: 1, the cellulose type number is 250HBR, quartolon, and the test results are shown in table 1.
Table 1 test results
Examples Example 1 Example 2 Example 3
Initial viscosity 86KU 86.3KU 85.8KU
Viscosity at night 87.2KU 87.8KU 87.1KU
Value of change in viscosity 1.2 1.5 1.3
Test 2. mixing the emulsion with 7% protective glue solution in equal proportion: respectively mixing the acrylate emulsion prepared in the embodiment 1-the embodiment 3 with 7% of protective glue according to the mass ratio of 1: 1, mixing; the protective adhesive comprises, by weight, 240 parts of water, 8.9 parts of modified silicate, 1 part of tackifier and 0.1 part of bactericide.
Table 2 test results of test 2
Test 3. application to base paint: the acrylate emulsions prepared in examples 1 to 3 were used to prepare base paints by the following method: the base paint comprises the following components in parts by weight: 136.7 parts of water, 5.9 parts of film-forming additive, 2 parts of bactericide, 2 parts of defoaming agent, 1.5 parts of cellulose, 0.5 part of thickening agent, 1.3 parts of reinforcing additive, 0.1 part of PH regulator, 5 parts of titanium dioxide, 85 parts of acrylate emulsion, 100 parts of 80-mesh snowflake white and 100 parts of 100-mesh snowflake white.
Table 3 test results of test 3
Examples Example 1 Example 2 Example 3
Initial viscosity 102KU 105.4KU 102.2KU
Viscosity at night 107.4KU 111.8KU 107.8KU
Value of change in viscosity 5.4 6.4 5.6
Test 4. application to continuous phase: the acrylate emulsions prepared in examples 1 to 3 were used to prepare the continuous phase by the following method: the continuous phase comprises the following components in parts by weight: 118.1 parts of water, 6.8 parts of film forming additive, 5 parts of propylene glycol, 1.5 parts of bactericide, 1 part of defoaming agent, 3.6 parts of monobutyl ether, 110 parts of acrylate emulsion and 4 parts of thickening agent.
Table 4 test results of test 4
Examples Example 1 Example 2 Example 3
Initial viscosity 138KU 138.2KU 138.8KU
Viscosity at night 140.3KU 140.5KU 140KU
Value of change in viscosity 2.3 2.3 1.2
Test 5. blending the continuous phase and the protective adhesive in equal proportion: the continuous phase from test 4 was mixed with a 7% protective glue solution in a weight ratio of 1: 1, mixing and testing the viscosity.
Table 5 test results of test 5
Examples Example 1 Example 2 Example 3
Initial viscosity 45.6KU 46.9KU 45.9KU
Viscosity at night 46.7KU 47.9KU 46.8KU
Value of change in viscosity 1.1 1 0.9
Test 6. continuous phase water resistance test: the water resistance test can be divided into an emulsion film water resistance test and a paint film water resistance test, and the emulsion film water resistance test is generally adopted, namely the emulsion film is coated on a glass plate, the appearance of a wet film is checked, the appearance of a dry film is checked after the wet film is dried for 24 hours, and whether the emulsion film has change or not is checked after the emulsion film is placed into tap water for soaking for 4 hours.
Table 6 test results of test 6
Examples Example 1 Example 2 Example 3
Appearance of Wet film White phase White phase White phase
Appearance of Dry film Colorless and transparent Colorless and transparent Colorless and transparent
Drying at room temperature for 24H, and resisting water at room temperature for 4H Colorless and transparent Colorless and transparent Colorless and transparent
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (10)

1. The acrylic ester emulsion with high water-white resistance is characterized by comprising the following raw materials in parts by weight: 15-40 parts of styrene monomer, 40-70 parts of acrylate monomer, 1-5 parts of first organic silicon monomer, 1-10 parts of second organic silicon monomer, 0.5-4 parts of first emulsifier, 1-10 parts of second emulsifier, 0.1-5 parts of first initiator and 0.1-4 parts of second initiator.
2. The acrylate emulsion with high water-white resistance of claim 1, wherein the raw materials at least comprise, by weight: 20-30 parts of styrene monomer, 50-60 parts of acrylate monomer, 1-3 parts of first organic silicon monomer, 2-8 parts of second organic silicon monomer, 0.6-3.5 parts of first emulsifier, 2-6 parts of second emulsifier, 0.1-3 parts of first initiator and 0.1-2 parts of second initiator.
3. The acrylate emulsion with high water-white resistance of claim 1 or 2, wherein the acrylate monomer is a mixture of butyl acrylate monomer, isooctyl acrylate monomer, methyl methacrylate monomer; the weight ratio of the butyl acrylate monomer to the isooctyl acrylate monomer to the methyl methacrylate monomer is 1: (0.5-1.5): (1-3).
4. The acrylate emulsion with high water-white resistance of claim 1 or 2, wherein the first organosilicon monomer is at least one selected from dimethyl dimethoxy siloxane, methyl phenyl dimethoxy siloxane and methyl vinyl dimethoxy siloxane.
5. The acrylate emulsion with high water-white resistance according to claim 1 or 2, wherein the second organosilicon monomer is selected from at least one of ethyltrichlorosilane, propyltrichlorosilane, gamma-chloropropyltrichlorosilane, phenylchlorosilane, vinyltrichlorosilane, methylvinylchlorosilane and methylchlorosilane.
6. The acrylate emulsion with high water-white resistance of claim 1 or 2, wherein the first emulsifier is at least one of alkylphenol polyether sulfosuccinic acid monoester sodium salt, long-chain carboxylic ester polyoxyethylene, polyoxyethylene carboxylic ester, carboxylic ester type emulsifier, and sodium stearyl.
7. The acrylate emulsion with high water-white resistance of claim 1 or 2, wherein the second emulsifier is at least one of rosin oil soap and long-chain carboxylic ester polyoxyethylene.
8. The acrylate emulsion with high water-white resistance of claim 6, wherein the first emulsifier is a mixture of alkylphenol polyether sulfosuccinic acid monoester sodium salt and long-chain carboxylic ester polyoxyethylene; the weight ratio of the alkylphenol polyether sulfosuccinic acid monoester sodium salt to the long-chain carboxylic ester polyoxyethylene is 1: (1-5).
9. The high water-white resistance acrylate emulsion of claim 7 wherein the second emulsifier is a combination of rosin oil soap, long chain carboxylate polyoxyethylene; the weight ratio of the rosin oil soap to the long-chain carboxylic ester polyoxyethylene is 1: (0.1-0.5).
10. A method for preparing the acrylate emulsion with high water-white resistance according to any one of claims 1 to 9, characterized by comprising at least the steps of:
(1) pre-emulsion: adding deionized water, a first emulsifier, a first initiator, a styrene monomer, an acrylate monomer, a first organic silicon monomer and a second organic silicon monomer into a monomer tank, and stirring for 20-40 minutes to obtain a pre-emulsion;
(2) a reaction kettle: adding deionized water, a second emulsifier and a second initiator into a reaction kettle, heating to 80-90 ℃, uniformly stirring, adding 1-5 wt% of pre-emulsion into the reaction kettle, and reacting;
(3) and (3) temperature return reaction: the reaction kettle is raised back to normal temperature, and the residual pre-emulsion is added dropwise at a constant speed. The dripping time is 2-4 hours, and after the dripping is finished, the pH value is adjusted to 8 +/-1, thus obtaining the product.
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