CN115572345A - Inorganic hybrid acrylic emulsion, preparation method thereof, coating and application thereof - Google Patents
Inorganic hybrid acrylic emulsion, preparation method thereof, coating and application thereof Download PDFInfo
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- 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
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C08F220/16—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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
- C09D125/00—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 at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- 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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The invention discloses an inorganic hybrid acrylic emulsion and a preparation method thereof, a coating and application thereof, wherein the preparation raw materials of the inorganic hybrid acrylic emulsion comprise an acrylic emulsion base raw material and a hybrid additive; the acrylic emulsion base material comprises: unsaturated acrylate monomer, styrene, monofunctional functional monomer, polyfunctional group crosslinking monomer, emulsifier and initiator; the hybrid additive comprises a silane coupling agent and alkali metal silicate, and the amount of the hybrid additive accounts for 8-15% of the total mass of the preparation raw materials. The addition of the silane coupling agent and the alkali metal silicate can realize hybridization of the acrylic emulsion, the obtained inorganic hybrid acrylic emulsion has high storage stability, the film forming strength can be quickly established when the inorganic hybrid acrylic emulsion is applied to coating and film forming, quick drying is realized, and the formed film has high hardness, good scratch resistance and strong water resistance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an inorganic hybrid acrylic emulsion, a preparation method thereof, a coating and application thereof.
Background
The organic acrylic emulsion is widely applied as a main film forming substance of building coatings and industrial coatings in recent years, and is mainly characterized by good adhesion to pigments and fillers, capability of forming a film by self-drying or drying, and certain water resistance, weather resistance and stain resistance after the film is formed by drying. However, the conventional acrylic emulsion has a slow drying speed, so that the application of the acrylic emulsion in a place requiring a quick-drying coating production line or quick construction is greatly limited.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an inorganic hybrid acrylic emulsion, a preparation method thereof, a coating and application thereof.
In the first aspect of the invention, an inorganic hybrid acrylic emulsion is provided, and the preparation raw materials comprise acrylic emulsion base raw materials and hybrid additives; the acrylic emulsion base material comprises: unsaturated acrylate monomer, styrene, monofunctional functional monomer, polyfunctional group crosslinking monomer, emulsifier and initiator; the hybrid additive comprises a silane coupling agent and alkali metal silicate, and the using amount of the hybrid additive accounts for 8-15% of the total mass of the preparation raw materials.
According to the embodiment of the invention, the inorganic hybrid acrylic emulsion has at least the following beneficial effects: the inorganic hybrid acrylic emulsion is prepared by adding alkali metal silicate and silane coupling agent to acrylic emulsion base raw materials for inorganic hybrid, and when the inorganic hybrid acrylic emulsion is applied to a base material for film formation, the alkali metal silicate in the emulsion can react with carbon dioxide in the air to generate high-modulus silicate, carbonate and silicon dioxide (as shown in the following reaction formula I), so that the film formation strength of an inorganic hybrid emulsion coating can be quickly established, and the quick drying effect is achieved; unlike common emulsion, which needs latex particle deformation, mutual molecular chain diffusion and permeation to intertwine with each other, and can reach physical film forming of coalescence. In addition, if the inorganic hybrid acrylic emulsion is applied to a substrate containing calcium (or calcium ions) and/or silicon dioxide, the aim of quick drying can be further achieved, specifically, alkali metal silicate in the emulsion can react with calcium ions/silicon dioxide in the substrate to generate silicate (as shown in the following reaction formulas II and III), carbon dioxide in air can further promote the reaction of a film formed on the substrate containing the calcium ions, so that the strength can be more quickly established, the performance can be improved, the reaction can be continuously carried out with the calcium ions/silicon dioxide in the substrate, the effect of integrating a coating substrate is achieved, a contact surface can be used as a connecting layer to better receive the substrate and the film, and the inorganic hybrid acrylic emulsion can be used more confidently for occasions needing quick construction.
Reaction formula I:
reaction formula II:
reaction formula III:
in addition, alkali metal silicate itself can undergo a reversible condensation dissociation reaction as shown in the following reaction formula IV, and simultaneously can be easily reacted with polyvalent metal ion Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Fe 3+ 、Al 3+ And the like, undergoes an almost irreversible ionic reaction (similar to the following reaction formula V), generates an insoluble silicate to thicken and even gel-solidify; meanwhile, the inorganic hybrid coating has high pH value, strong alkalinity and high electrolyte concentration, and can easily cause hydrolysis and surface charge neutralization on hydrophilic groups (such as carboxyl and hydroxyl) and other organic matters contained in the emulsion in the coating, and destroy the stability of the emulsion and the like. In this regard, the above inorganic hybrid acrylic emulsion utilizes a silane coupling agent for the alkaliThe metal silicate is subjected to surface modification to carry out stabilization treatment (as shown in the following reaction formula VI), and silicon atoms in the alkali metal silicate are connected with organic groups, so that the number of active functional groups (silanol groups) of the alkali metal silicate can be properly reduced, the reaction activity of the alkali metal silicate can be reduced, and the stability of the alkali metal silicate can be further improved through the steric hindrance of the organic groups; after the alkali metal silicate is modified by the silane coupling agent, double bonds in the silane coupling agent can be grafted on chain links of an acrylic polymer, so that the aim of inorganic hybridization can be fulfilled, the doping amount of the alkali metal silicate in the acrylic emulsion can be further improved, and the hardness of a film layer can be remarkably improved due to the rigidity of silicon-oxygen bonds in the alkali metal silicate after the inorganic hybridization acrylic emulsion is formed into a film, so that the surface scratch resistance of the film layer is further improved; and moreover, when the alkali metal silicate is adopted, the silane coupling agent is added for modification, so that the acrylic emulsion product has good compatibility with the alkali metal silicate and good storage stability, organic and inorganic compounding can be realized, and the defects of hot sticking and cold brittleness of the conventional acrylic emulsion can be overcome.
Reaction formula IV:
the reaction formula V:
reaction formula vi:
in some embodiments of the invention, the hybrid additive comprises 20 to 35% silane coupling agent and 65 to 80% alkali metal silicate, based on the total mass of the hybrid additive.
In some embodiments of the invention, the alkali metal silicate is selected from at least one of potassium silicate, sodium silicate, lithium silicate; the silane coupling agent is at least one selected from vinyl trimethoxy silane, vinyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
In some embodiments of the present invention, the acrylic emulsion base stock comprises, in parts by mass: 10 to 27 portions of unsaturated acrylate monomer, 5 to 15 portions of styrene, 1 to 3.5 portions of monofunctional functional monomer, 0.5 to 5 portions of polyfunctional crosslinking monomer, 0.6 to 2 portions of emulsifier, 0.15 to 0.4 portion of initiator, 1 to 2 portions of pH regulator and 21 to 56 portions of water.
In some embodiments of the present invention, the monofunctional functional monomer is selected from at least one of methacrylic acid, acrylic acid, acrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, itaconic acid. At least one of acrylic acid, acrylamide and hydroxyethyl methacrylate is preferably used.
In some embodiments of the invention, the multifunctional crosslinking monomer is selected from at least one of trimethylolpropane trimethacrylate, ethylene Glycol Dimethacrylate (EGDMA), hydroxyethyl acrylurea.
In some embodiments of the present invention, the acrylate unsaturated monomer is selected from at least one of methyl methacrylate, butyl acrylate, isooctyl acrylate, methyl acrylate, ethyl acrylate, glycidyl methacrylate, butyl methacrylate.
In some embodiments of the invention, the emulsifier is selected from at least one of sodium polyoxyethylene ether sulfate, SR-10, SE-10, sodium 3-allyloxy-2 hydroxy-1-propane sulfonate, sodium lauryl sulfate, alkyl polyoxyethylene ethers with a degree of polymerization of 10 to 40 (i.e., EO =10 to 40). In some embodiments of the invention, the initiator is selected from at least one of sodium persulfate, potassium persulfate; potassium persulfate is preferably used. In addition, sodium hydroxide, ammonia water with a concentration of 25 to 28wt%, and the like can be used as the pH adjuster.
The second aspect of the invention provides a preparation method of any one of the inorganic hybrid acrylic emulsion, which comprises the following steps:
s1, mixing an acrylate unsaturated monomer, styrene, a monofunctional functional monomer, a polyfunctional group crosslinking monomer, a partial emulsifier, a partial initiator and part of water to obtain a component A; mixing the rest of the initiator with the other part of the water to obtain a component B; mixing a silane coupling agent and an alkali metal silicate to prepare a hybrid additive;
s2, mixing the rest of the emulsifier and the rest of the water, heating, adding the component B, then dropwise adding the component A, adding the pH regulator, and carrying out heat preservation reaction; and then adding the hybrid additive thereto to perform a reaction.
In the step S1, the content of the emulsifier in the component A can account for 40-60% of the total amount of the emulsifier, the dosage of the initiator can account for 75-85% of the total amount of the initiator, and the dosage of water can account for 40-50% of the total amount of water; the amount of water in the component B can be 1-5% of the total amount of water. The preparation of the hybrid additive can be realized by slowly dripping the silane coupling agent into the alkali metal silicate which keeps stirring at the temperature of 50-70 ℃, and preserving the heat for 1-1.5 h after the dripping is finished; wherein the dripping time can be controlled between 0.5 and 1.5 hours. Or, the hybrid additive can be prepared by mixing the silane coupling agent and the alkali metal silicate and then dispersing the mixture for 1 to 1.5 hours at a high speed by a dispersion machine. In addition, the formulation order of component A, component B and the hybrid additive is not limited.
In step S2, the temperature may be raised to 83-87 ℃ before adding component B. After the component B is added, the dropping time of the component A can be controlled to be 120-180 min in the process of dropping the component A; and the components A can be dripped at constant speed in different stages according to different dripping speeds, for example, 20 percent of the total amount of the components A can be dripped at constant speed according to the acceleration of the first drop within the first 25min, then 30 percent of the total amount of the components A can be dripped at constant speed according to the second dripping speed within 30min, and the rest of the components A can be dripped at constant speed according to the third dripping speed for the rest time. After the component A is added, a pH regulator is added to regulate the pH of the mixed solution to 5.5-6.5. The reaction temperature is 83-87 ℃, and the reaction time can be controlled within 30-60 min. Then, the hybrid additive is dripped to carry out heat preservation reaction, the heat preservation reaction temperature can be controlled to be 83-87 ℃, and the reaction time can be controlled to be 10-30 min.
In the third aspect of the present invention, the present invention provides a coating, comprising any one of the inorganic hybrid acrylic emulsion provided in the first aspect of the present invention or the inorganic hybrid acrylic emulsion prepared by the preparation method of any one of the inorganic hybrid acrylic emulsion provided in the second aspect of the present invention. The coating may in particular be a coating for a substrate comprising calcium and/or silica.
In a fourth aspect of the invention, there is provided a use of any one of the coatings of the third aspect of the invention for the decoration or protection of a substrate in the construction field.
In some embodiments of the invention, the substrate is a calcium and/or silica containing substrate; the base material can be putty mainly based on calcium or cement base material, such as wall putty layer.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The present example prepares an inorganic hybrid acrylic emulsion, and the preparation raw material components thereof are shown in the following table 1 in parts by mass:
TABLE 1
The preparation method comprises the following steps:
s1, placing each preparation raw material of the component A in an emulsifying cylinder, and dispersing at a high speed for 30min to form a white emulsion to obtain the component A as a pre-emulsion for later use; fully mixing and dissolving the preparation raw materials of the component B to obtain the component B which is used as a primary initiator for standby; mixing the preparation raw materials of the component C and dispersing the mixture for 1 hour at a high speed by a dispersion machine to obtain a component C as a hybrid additive for later use;
s2, placing the preparation raw material of the component D into a normal-pressure reaction kettle with a thermometer, a reflux condenser tube and a stirring device, stirring and heating to 84-86 ℃, and adding the component B; then, dropwise adding the component A for 150min, specifically, dropwise adding at a constant speed 25min before dropwise adding, wherein the dropwise adding amount is 20% of the total amount of the component A at the dropwise adding speed; then dripping at a medium speed at a constant speed for 30min, wherein the dripping amount at the dripping speed is 30 percent of the total amount of the component A; dripping at low speed for the rest 95 min; after the dropwise addition is finished, adding a pH regulator (namely the component E) to regulate the pH of the mixed solution to be between 5.5 and 6.5, and then carrying out heat preservation reaction at the temperature of between 84 and 86 ℃ for 20min to obtain a basic acrylic emulsion;
and S3, slowly dripping the component C into the base acrylic emulsion prepared in the step S2, wherein the application time is 50min, keeping the temperature for reacting for 40min after finishing dripping, and then cooling to below 40 ℃ to obtain the product, namely the inorganic hybrid acrylic emulsion.
The inorganic hybrid acrylic emulsion prepared in the embodiment has the solid content of 40.25 percent, the pH value of 9.8 and the viscosity of 670cps; the particle diameter of the emulsion of the product is 0.75 mu m by the test of a Malvern particle size analyzer. In addition, the emulsion is coated on a transparent glass plate by a frame type membrane making device with the thickness of 100 mu m, and the blue light is obvious in a wet membrane state and is uniform and clear; after the thermal storage at 50 ℃ for 60 days, the test is repeated, the test results are basically consistent, and good storage stability is shown; the product has no problems of thickening, gelling and settling after being stored for 3 months at 50 ℃.
Example 2
The present example prepares an inorganic hybrid acrylic emulsion, which comprises the following raw material components in parts by weight as shown in table 2 below:
TABLE 2
The preparation method comprises the following steps:
s1, placing each preparation raw material of the component A in an emulsifying cylinder, and dispersing at a high speed for 30min to form a white emulsion to obtain the component A as a pre-emulsion for later use; fully mixing and dissolving the preparation raw materials of the component B to obtain the component B which is used as a primary initiator for standby; mixing the preparation raw materials of the component C and dispersing the mixture for 2 hours at a high speed by a dispersion machine to obtain a component C as a hybrid additive for later use;
the operations of steps S2, S3 are the same as those of steps S2, S3 in embodiment 1.
The inorganic hybrid acrylic emulsion prepared in this example was tested to have a solid content of 40.6%, a pH of 9.5, and a viscosity of 430cps. The particle diameter of the emulsion of the product is 0.9 mu m by the test of a Malvern particle size analyzer. In addition, the emulsion is coated on a transparent glass plate by a 100-micron frame type membrane making device, and the blue light is obvious in a wet membrane state and is uniform and clear; after the thermal storage at 50 ℃ for 60 days, the test is repeated, the test results are basically consistent, and good storage stability is shown; the product has no thickening, gelling and settling problems after 3 months of storage at 50 ℃.
Example 3
The inventor prepares raw materials according to the preparation raw material configuration shown in table 3 (in parts by weight) according to the method similar to the above method:
TABLE 3
Wherein, the unsaturated acrylate monomer adopts at least one of methyl methacrylate, butyl acrylate, isooctyl acrylate, methyl acrylate, ethyl acrylate, glycidyl methacrylate and butyl methacrylate; the monofunctional functional monomer is at least one of methacrylic acid, acrylic acid, acrylamide, N-hydroxymethyl acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate and itaconic acid; the polyfunctional group crosslinking monomer is at least one of trimethylolpropane trimethacrylate, ethylene Glycol Dimethacrylate (EGDMA) and hydroxyethyl acryloyl urea; the emulsifier is at least one of polyoxyethylene ether sodium sulfate, SR-10, SE-10, alkyl polyoxyethylene ether, 3-allyloxy-2 hydroxy-1-propane sulfonic acid sodium salt and lauryl sodium sulfate; the initiator adopts at least one of sodium persulfate, persulfuric acid and potassium persulfate; the silane coupling agent is at least one of vinyl trimethoxy silane, vinyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane; the alkali metal silicate is at least one of potassium silicate, sodium silicate and lithium silicate; the pH regulator adopts sodium hydroxide or ammonia water with the concentration of 25-28 wt%.
The preparation method comprises the following steps:
s1, placing each preparation raw material of the component A into an emulsifying cylinder, and dispersing at a high speed for 20-40 min to obtain a white emulsion-like component A as a pre-emulsion for later use; fully mixing and dissolving the preparation raw materials of the component B to obtain the component B which is used as a primary initiator for standby; mixing the preparation raw materials of the component C and dispersing the mixture for 1 to 2 hours at a high speed by a dispersion machine to obtain the component C as a hybrid additive for later use;
s2, placing the preparation raw material of the component D into a normal-pressure reaction kettle with a thermometer, a reflux condenser tube and a stirring device, stirring and heating to 84-86 ℃, and adding the component B; then, dropwise adding the component A for 120-180 min, specifically, dropwise adding at a constant speed 25min before dropwise adding, wherein the dropwise adding amount is 20% of the total amount of the component A at the dropwise adding speed; then dripping at a medium speed at a constant speed for 30min, wherein the dripping amount at the dripping speed is 30 percent of the total amount of the component A; dripping at low speed for the rest time; after the dropwise addition is finished, adding a pH regulator to regulate the pH of the mixed solution to 5.5-6.5, and then carrying out heat preservation reaction at 84-86 ℃ for 10-30 min to obtain a basic acrylic emulsion;
and S3, slowly dripping the component C into the base acrylic emulsion prepared in the step S2, applying for 40-60 min, carrying out heat preservation reaction for 30-60 min after finishing dripping, and then cooling to below 40 ℃ to obtain the product, namely the inorganic hybrid acrylic emulsion.
The preparation experiment is carried out according to the raw material configuration and the preparation method, the solid content of the prepared inorganic hybrid acrylic emulsion is 40 +/-1 percent, the pH value is 9.5-10.5, the viscosity is 100-1000 cps, and the particle diameter of the product emulsion is 0.05-0.1 mu m as shown by the test of a Malvern particle size analyzer. In addition, the emulsion is coated on a transparent glass plate by a frame type membrane making device with the thickness of 100 mu m, and the blue light is obvious in a wet membrane state and is uniform and clear; after the thermal storage at 50 ℃ for 60 days, the test is repeated, the test results are basically consistent, and good storage stability is shown; the product has no problems of thickening, gelling and settling after being stored for 3 months at 50 ℃.
Comparative example 1
In the comparative example, potassium silicate with different proportions (accounting for 2%, 4%, 6% and 8% of the total mass of the emulsion) is directly added into a styrene-acrylate copolymer emulsion (RS-998A styrene-acrylic emulsion of Guangdong Badhucao limited company), a pure acrylate copolymer emulsion (RS-9689 AS pure acrylic emulsion of Guangdong Badhucao limited company) and a vinyl acetate-acrylate copolymer emulsion (VAE emulsion 707 of Guangxi Sichuan vitamin) respectively, the potassium silicate and the pure acrylate copolymer emulsion are mixed uniformly and then are placed at normal temperature and 50 ℃ respectively, and AS a result, the emulsion is thickened obviously within one week at the temperature of 50 ℃; the blended emulsion left at normal temperature also obviously thickens within 20 days, so that the blended emulsion cannot be used.
Comparative example 3
This comparative example, which was prepared as an acrylic emulsion, differs from example 1 in that: in this comparative example, the addition of the silane coupling agent vinyltrimethoxysilane and the alkali metal silicate potassium silicate was eliminated, and the other operations were the same as in example 1. Namely, the preparation of the component C is cancelled in the step S1 of the embodiment 1 and the addition of the component C in the step S3 is cancelled, and after the operation of the step S2 is completed, the temperature is directly reduced to below 40 ℃, so that the acrylic emulsion product is prepared. The solid content is 39.5%, the pH value is 8, the viscosity is 450cps, and tests show that the emulsion has good condition after being stored for 60 days at normal temperature and 50 ℃, and has no conditions of layering, bottom sinking, thickening and the like.
Example 4
This example prepares a clear coat paint prepared using the inorganic hybrid acrylic emulsion prepared in example 1. The preparation raw materials specifically comprise the following components in percentage by weight: 80% of inorganic hybrid acrylic emulsion, 0.3% of wetting agent LCN-407, 0.2% of defoaming agent BYK-024, 0.5% of thickening agent RM-12W, 4% of dodecyl alcohol ester and 15% of deionized water. The preparation method comprises the following steps: quantitatively weighing inorganic hybrid acrylic emulsion, placing the inorganic hybrid acrylic emulsion on a dispersion machine, starting stirring to 500rpm, sequentially and slowly adding other preparation raw materials, and keeping the dispersion state for 40min to obtain the varnish coating.
Comparative example 4
This comparative example, which differs from example 4 in that a clear coat paint was prepared: in the comparative example, the acrylic emulsion prepared in the comparative example 3 is used to replace the inorganic hybrid acrylic emulsion used in the example 4, and the preparation method of other raw materials is the same as that of the example 4.
Application effect testing
The varnish coatings prepared in example 4 and comparative example 4 were applied to a calcium putty based on loose calcium and then the drying time was tested at 25 ℃ and 50% RH and the hardness and water resistance of the paint film after curing for various days (3 d, 7d, 14 d); the varnish coatings of example 4 and comparative example 4 were then applied to the open calcium-based putty and the cement-based putty, respectively, in a similar manner as above, and the drying time was measured at 8 ℃ and 75% RH, and the hardness and water resistance of the paint film after curing for different days (3 d, 7d, 14 d). The specific test method comprises the following steps:
test method of drying time: the surface dry time is tested by a finger touch method according to GBT 1728-1979 (1989) determination method for the dry time of paint films and putty films;
hardness test method: performing hardness test according to GB/T6739-2006 determination of paint film hardness by a pencil method;
and (3) testing water resistance: after the paint film is cured according to the specified curing time, a water resistance test is carried out according to GB/T1733-1993 paint film water resistance determination method.
The results obtained by performing the tests according to the above method are shown in Table 4:
TABLE 4
As can be seen from table 4 above, the varnish coating prepared by using the inorganic hybrid acrylic emulsion prepared in example 4 in the conventional or harsh condition can exhibit the characteristic of quick drying, and can continuously react with calcium ions in the substrate under the condition that the coated substrate has established good strength, so as to further improve the physical and mechanical properties of the coating film, which further guarantees the subsequent quick construction requirements and the quality of the whole coating system.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention.
Claims (10)
1. The inorganic hybrid acrylic emulsion is characterized in that the preparation raw materials comprise acrylic emulsion base raw materials and hybrid additives; the acrylic emulsion base material comprises: unsaturated acrylate monomer, styrene, monofunctional functional monomer, polyfunctional group crosslinking monomer, emulsifier and initiator; the hybrid additive comprises a silane coupling agent and alkali metal silicate, and the amount of the hybrid additive accounts for 8-15% of the total mass of the preparation raw material.
2. The inorganic hybrid acrylic emulsion of claim 1 wherein the hybrid additive comprises 10-20% silane coupling agent and 80-90% alkali metal silicate based on the total mass of the hybrid additive.
3. The inorganic hybrid acrylic emulsion according to claim 1, wherein the alkali metal silicate is at least one selected from the group consisting of potassium silicate, sodium silicate and lithium silicate; the silane coupling agent is at least one selected from vinyl trimethoxy silane, vinyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
4. The inorganic hybrid acrylic emulsion according to any one of claims 1 to 3, wherein the acrylic emulsion base material comprises, in parts by mass: 10 to 27 parts of unsaturated acrylate monomer, 5 to 15 parts of styrene, 1 to 3.5 parts of monofunctional functional monomer, 0.5 to 5 parts of polyfunctional crosslinking monomer, 0.6 to 2 parts of emulsifier, 0.15 to 0.4 part of initiator, 1 to 2 parts of pH regulator and 21 to 56 parts of water.
5. The inorganic hybrid acrylic emulsion according to claim 4, wherein the monofunctional functional monomer is at least one selected from the group consisting of methacrylic acid, acrylic acid, acrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, and itaconic acid; preferably, the multifunctional crosslinking monomer is selected from at least one of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate and hydroxyethyl acrylurea; preferably, the acrylate unsaturated monomer is selected from at least one of methyl methacrylate, butyl acrylate, isooctyl acrylate, methyl acrylate, ethyl acrylate, glycidyl methacrylate and butyl methacrylate.
6. The inorganic hybrid acrylic emulsion according to claim 4, wherein the emulsifier is at least one selected from the group consisting of sodium polyoxyethylene ether sulfate, SR-10, SE-10, sodium 3-allyloxy-2 hydroxy-1-propanesulfonate, sodium lauryl sulfate, and alkyl polyoxyethylene ether having a degree of polymerization of 10 to 40; the initiator is at least one of sodium persulfate, persulfuric acid and potassium persulfate.
7. The method for preparing the inorganic hybrid acrylic emulsion according to any one of claims 1 to 6, comprising the steps of:
s1, mixing an acrylate unsaturated monomer, styrene, a monofunctional functional monomer, a polyfunctional group crosslinking monomer, a partial emulsifier, a partial initiator and part of water to obtain a component A; mixing the rest of the initiator with the other part of the water to obtain a component B; mixing a silane coupling agent and an alkali metal silicate to prepare a hybrid additive;
s2, mixing the rest of the emulsifier and the rest of the water, heating, adding the component B, then dropwise adding the component A, adding the pH regulator, and carrying out heat preservation reaction; and then the hybrid additive is added dropwise thereto for reaction.
8. A paint, which is characterized in that the paint comprises the inorganic hybrid acrylic emulsion as described in any one of claims 1 to 6 or the inorganic hybrid acrylic emulsion prepared by the preparation method of the inorganic hybrid acrylic emulsion as described in claim 7.
9. Use of the coating according to claim 8 for the surface modification or protection of substrates in the construction sector.
10. Use according to claim 9, wherein the substrate is a calcium and/or silica containing substrate.
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