CN109535312B - Core-shell styrene-acrylic emulsion for primer coating and preparation method and application thereof - Google Patents
Core-shell styrene-acrylic emulsion for primer coating and preparation method and application thereof Download PDFInfo
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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
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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
- 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
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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
- 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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The core-shell styrene-acrylic emulsion for the primer coating belongs to the technical field of waterproof coatings, and comprises the following components in parts by weight: 5.07-30 parts of core monomer, 5.07-30 parts of shell monomer, 0.6-12 parts of emulsifier, 0.02-5 parts of initiator, 0.02-5 parts of chain transfer agent, 0.02-5 parts of pH buffer, 0.02-2 parts of first defoaming agent, 0.02-2 parts of first preservative and 40-50 parts of deionized water; the core monomer is main monomer, and the shell monomer includes main monomer 4.93-20 weight portions, polar monomer 0.02-2.55 weight portions, phosphate ester monomer 0.02-2.5 weight portions and carbamido monomer 0.05-5 weight portions. The invention also provides a preparation method of the core-shell styrene-acrylic emulsion for the primer coating and application of the core-shell styrene-acrylic emulsion for the primer coating in the water-based seal primer coating.
Description
Technical Field
The invention belongs to the technical field of waterproof coatings, and relates to a core-shell styrene-acrylic emulsion for a primer coating, and a preparation method and application thereof.
Background
Although the performances of various aspects of the existing water-based paint cannot exceed those of the traditional solvent-based paint, the existing water-based paint has a certain trend of paint development due to no pollution, environmental protection and safety and accordance with the national environmental protection policy, particularly, after new regulations of the paint industry are issued in 2014 and the new regulations are implemented in 2015 2, 1, the water-based paint or the water-based paint is a key for continuous development of enterprises, the original solvent-based paint enterprises are gradually eliminated, more strict regulations are correspondingly issued in a plurality of cities, and the solvent-based paint and the solvent-based adhesive are forbidden to be used, so that the development of the water-based paint resin which has excellent comprehensive performance and can replace the traditional solvent for water proofing has a very wide application prospect and social benefit.
The primer emulsion is coated on the inner and outer wall putty after being made into varnish or emulsion paint, is used for sealing salt and alkali in the putty and simultaneously improving the comprehensive performance of finish paint, particularly for the imitation brick texture paint, has high requirement on meeting the performance of resisting tearing of the masking paper, and compared with similar products on the market, the primer emulsion has good adhesive force, but the sealing property, the water permeability resistance and the tearing resistance of the masking paper are general, and the problems of poor sealing property and poor adhesive force generally exist in the prior inner and outer wall primer emulsion of domestic buildings; the primer is coated on a wall surface, the masking paper is adhered after the primer is quickly dried, and the masking paper is quickly torn off after the texture paint is sprayed or smeared, so that the requirement on the surface hardness of the primer is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention designs the core-shell styrene-acrylic emulsion for the primer coating and the preparation method and the application thereof, and solves the problems of poor film forming compactness, poor sealing property, poor water permeability, poor adhesive force and the like of the existing primer emulsion.
The invention adopts the specific technical scheme that: the core-shell styrene-acrylic emulsion for the primer coating is characterized by comprising the following components in parts by weight: 5.07-30 parts of core monomer, 5.07-30 parts of shell monomer, 0.6-12 parts of emulsifier, 0.02-5 parts of initiator, 0.02-5 parts of chain transfer agent, 0.02-5 parts of pH buffer, 0.02-2 parts of first defoaming agent, 0.02-2 parts of first preservative and 40-50 parts of deionized water; the core monomer is main monomer, and the shell monomer includes main monomer 4.93-20 weight portions, polar monomer 0.02-2.55 weight portions, phosphate ester monomer 0.02-2.5 weight portions and carbamido monomer 0.05-5 weight portions.
The main monomer is at least one of acrylic acid, methacrylic acid, styrene, methyl methacrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, butyl methacrylate, glycidyl methacrylate, diacetone acrylamide and isobornyl acrylate;
the polar monomer is at least one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and vinyl siloxane;
the phosphate ester monomer is at least one of 2-hydroxyethyl methacrylate phosphate, 2-hydroxyethyl methacrylate phosphate diester, a mixture of 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate diester;
the ureido monomer is one of methacrylamide ethyl ethylene urea, allophanate, N- (2-methacryloyloxyethyl) phosphorylcholine, ethylene urea and allyl urea.
The emulsifier comprises 0.1-2 parts of short-chain reactive emulsifier, 0.5-10 parts of long-chain reactive emulsifier and 0.1-2 parts of reactive nonionic emulsifier, wherein the carbon atom number of the short-chain reactive emulsifier is less than or equal to 5, and the carbon atom number of the long-chain reactive emulsifier is more than 5.
The short-chain reaction type emulsifier is at least one of allyloxy hydroxyl sodium sulfonate, 2-acrylamide-2-methyl propyl sodium sulfonate, allyl phosphate ammonium salt, sodium vinyl sulfonate, 2-acrylamide-2-methyl propyl sulfonic acid and methyl propylene sodium sulfonate;
the long-chain reaction type emulsifier is at least one of unsaturated allyl alkyl ammonium sulfate salt, allyloxy allyl alkyl alcohol polyether, allyl-containing alcohol ether sulfate, methacrylic acid ether phosphate, allyl alkyl sulfosuccinate diester sodium, alkyl propenyl phenoxy polyether sulfate, 2-allyl ether 3-hydroxy propane-1-sodium sulfonate, acrylamide isopropyl sodium sulfonate and double-bond sulfosuccinate diester sodium salt;
the reactive nonionic emulsifier is at least one of unsaturated allyl alkylphenol ether, alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene, fatty acid polyoxyethylene ester, fatty acid methyl ester ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, octylphenol ethoxylate and sorbitan ester.
The chain transfer agent is one of n-dodecyl mercaptan and tert-dodecyl mercaptan.
The initiator is one of ammonium persulfate, potassium persulfate or sodium persulfate.
The pH buffer is at least one of ammonia water, liquid alkali, sodium bicarbonate and sodium dihydrogen phosphate.
The preparation method of the core-shell styrene-acrylic emulsion for the primer coating is characterized by comprising the following steps:
(1) preparing materials: weighing the components according to the mass portion ratio in claim 1, and mixing deionized water according to the mass ratio of (1.8-2.2): 1 is divided into core deionized water and shell deionized water, and the core deionized water is mixed according to the mass ratio of (1.8-2.2): 0.1: 0.4: (1.8-2.2) dividing into a first deionized water, a second deionized water, a third deionized water and a fourth deionized water; shell deionized water is added according to the mass ratio of 2: 0.4 part of the deionized water is fifth deionized water and sixth deionized water;
dividing the emulsifier into a core emulsifier and a shell emulsifier, and mixing the core emulsifier with the shell emulsifier according to the mass ratio of (6-7): (1-2) dividing into a first reactive core emulsifier and a second reactive core emulsifier;
and (2) mixing an initiator according to a mass ratio of 1: (1-2) dividing the core initiator into a core initiator and a shell initiator, and dividing the core initiator into a first core initiator and a second core initiator according to the weight ratio of (1.5-2.5) to (2.5-3.5);
and (2) mixing a pH buffering agent according to a mass ratio of 1: (1-2) dividing into a first pH buffer and a second pH buffer;
(2) preparing an emulsifier solution: dissolving a first reactive nuclear emulsifier in first deionized water to obtain a nuclear emulsifier solution;
dissolving a shell emulsifier in fifth deionized water to obtain a shell emulsifier solution;
(3) preparing an initiator solution: dissolving a first nuclear initiator in second deionized water to form a first nuclear initiator solution; dissolving a second nuclear initiator in third deionized water to form a second nuclear initiator solution;
dissolving a shell initiator in sixth deionized water to obtain a shell initiator solution;
(4) preparing a dispersion liquid: adding a nuclear monomer into the nuclear emulsifier solution obtained in the step (2) under the condition of stirring, dispersing to obtain a nuclear dispersion liquid, and dividing the nuclear dispersion liquid into a first nuclear dispersion liquid and a second nuclear dispersion liquid;
adding a main monomer of a shell monomer, a phosphate monomer and a carbamido monomer into the shell emulsifier solution obtained in the step (2) under the stirring condition, and dispersing to obtain a shell dispersion liquid;
(5) preparing a nuclear emulsion: mixing fourth deionized water, a first pH buffer and a second reactive nuclear emulsifier, then placing the mixture into a reactor, stirring and heating the mixture, when the temperature reaches 75-77 ℃, dropwise adding the first nuclear dispersion liquid prepared in the step (4) and the first nuclear initiator solution prepared in the step (3) at a constant speed within 8-12min, after the exothermic reaction is finished, heating the mixture to 80-85 ℃, reacting until blue light appears to obtain a first mixed solution, stirring the mixture for 15-20min, dropwise adding the second nuclear initiator solution prepared in the step (3) and the second nuclear dispersion liquid prepared in the step (4) into the first mixed solution at the same time within 60-90min, and preserving the heat for 0.5-1h after dropwise adding to obtain a nuclear emulsion;
(6) preparing a core-shell styrene-acrylic emulsion: and (3) dropwise adding the shell dispersion liquid prepared in the step (4) and the shell initiator solution prepared in the step (3) into the core emulsion prepared in the step (5) at the temperature of 80-85 ℃, adding a chain transfer agent and a polar monomer of the shell monomer into the residual shell dispersion liquid when the shell dispersion liquid is dropped to 1/5-2/5 of the residual shell dispersion liquid, continuously dropwise adding the shell dispersion liquid and the shell initiator solution into the reactor after uniformly stirring, controlling the whole dropwise adding time of the step to be 60-90min, keeping the temperature for 1-1.5h after dropwise adding, adding a first defoaming agent, a first preservative and a second pH buffer after the solution is cooled to below 40 ℃, and uniformly stirring to obtain the core-shell emulsion.
The mass ratio of the soft monomer to the hard monomer in the core monomer is (20-30): (70-80); the mass ratio of the soft monomer to the hard monomer in the shell monomer is (85-95): (5-15).
The application of the core-shell styrene-acrylic emulsion for the primer coating in the water-based seal primer coating is characterized in that the coating comprises the following components in parts by weight: 215 parts of deionized water 160-containing organic silicon, 1-2 parts of hydroxyethyl cellulose, 0.1-2 parts of 2-amino-2-methyl-1-propanol, 5-20 parts of ethylene glycol, 260 parts of heavy calcium carbonate 150-containing organic silicon, 5-24 parts of a film-forming additive, 450 parts of core-shell styrene-acrylic emulsion, 0.1-2 parts of a second defoaming agent, 0.1-6 parts of a dispersing agent, 0.1-2 parts of a wetting agent, 0.1-4 parts of a thickening agent, 0.1-3 parts of a flatting agent, 0.2-1 part of a second preservative, 0.2-1 part of a mildew inhibitor and 8 parts of color paste carbon black.
The invention has the beneficial effects that: the core-shell interpenetrating technology is adopted, so that the transfer speed and the quantity of moisture, oxygen and electrolyte in a paint film can be effectively reduced, excellent compactness and surface hardness of the paint film can be obtained, the prepared non-toxic, tasteless, non-combustible and low-VOC core-shell styrene-acrylic emulsion has excellent adhesive force, sealing property, water resistance, water permeability and other properties, the adhesive force between the emulsion and a base material can be greatly improved, a high-adhesive-force protective film is formed, and the emulsion can be well matched with other coatings to improve the protective performance. The primer coating prepared from the core-shell styrene-acrylic emulsion can ensure the film forming property, the sealing property and the adhesive force of a paint film, and the paint film has higher surface hardness and anti-tearing capability of the textured paper.
The polar monomer in the invention greatly improves the adhesive force of the core-shell styrene-acrylic emulsion and endows the core-shell styrene-acrylic emulsion with excellent hydrophobicity. The ureido monomer can effectively improve the stability, film forming property, water resistance and adhesive force of the core-shell styrene-acrylic emulsion. The hydrophilic monomer in the main monomer is self-crosslinked in the reaction, so that the tensile strength and the elongation at break of the paint film are improved, and the phosphate ester monomer and the main monomer are crosslinked during polymerization to form a compact protective film, so that the hardness, the tensile strength and the elongation at break of the paint film can be improved again.
The main monomer mainly adopts acrylic self-crosslinking monomer, the phosphate monomer mainly adopts methacrylic self-crosslinking monomer, the acrylic self-crosslinking monomer, the methacrylic self-crosslinking monomer, the polar monomer and the ureido monomer are matched in the polymerization process of the core-shell emulsion, so that a network crosslinking structure is formed between a core layer and a shell layer, and the soap-free polymerization process is adopted to prepare the core-shell styrene-acrylic emulsion, so that the number of migratable small molecules in the core-shell styrene-acrylic emulsion is greatly reduced, and the migration probability of alkali and salt in the wall surface is reduced.
The invention takes acrylic monomers as main raw materials, self-crosslinking monomers such as acrylic acid or methacrylic acid and the like are introduced into a core layer in the polymerization process of a core-shell emulsion, polar monomers and carbamido monomers are introduced into a shell layer, so that the core layer and the shell layer form a net-shaped crosslinking structure, and the core-shell styrene-acrylic emulsion is prepared by adopting a soap-free polymerization process, thereby greatly reducing the number of migratable small molecules in the core-shell styrene-acrylic emulsion and further reducing the migration probability of alkali and salt in a wall surface.
The core-shell emulsion, the shell dispersion, the shell monomer, the emulsifier, the initiator solution, the pH buffer and the deionized water are added at different nodes in batches, the chain transfer agent and the polar monomer of the shell monomer are added into the rest of the shell dispersion of 1/5-2/5, then the shell dispersion and the shell initiator solution are continuously added dropwise, and finally the defoamer, the preservative and the rest of the pH buffer are added dropwise.
According to the invention, the chain transfer agent and the polar monomer are added at the later stage of emulsion polymerization, the chain transfer agent can enable chain growth free radicals to generate free radical transfer, so that the chain length of the polymer, namely the viscosity of the polymer, is adjusted, and the chain transfer agent is matched with the polar monomer, so that the crosslinking density of an emulsion adhesive film can be further improved, and the core-shell styrene-acrylic emulsion-containing paint film has excellent adhesive force.
Detailed Description
The first defoaming agent is one of a metal soap defoaming agent, a mineral oil defoaming agent or an organic silicon defoaming agent; the first preservative is one of 1, 2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
The hard monomer provides hardness and blocking resistance but is unfavorable for low-temperature film forming, the soft monomer provides low-temperature film forming property and flexibility but is unfavorable for hardness and blocking resistance, in order to enable the core-shell styrene-acrylic emulsion to have certain hardness and blocking resistance and good low-temperature film forming property, the mass ratio of the soft monomer to the hard monomer is important, and the mass ratio of the soft monomer to the hard monomer in the core monomer is (20-30): (70-80) and preferably 25: 75, the mass ratio of the soft monomer to the hard monomer in the shell monomer is (85-95): (5-15) and preferably 90: 10.
the present invention will be described in detail with reference to the following specific examples:
example 1, a core-shell styrene-acrylic emulsion for a primer coating, comprising the following components in parts by weight,
main monomers: 36.5 parts of butyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 4 parts and 32.5 parts), 13.5 parts of styrene (wherein the using amounts of the core monomer and the shell monomer are respectively 12 parts and 1.5 parts), 2.4 parts of hydroxyethyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 2.4 parts) and 1 part of butyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 1 part);
polar monomer: 0.2 part of vinyl triethoxysilane;
phosphate ester monomer: 0.4 part of a mixture of 2-hydroxyethyl methacrylate phosphate (60 wt%) and 2-hydroxyethyl methacrylate phosphate diester (40 wt%);
ureido monomer: 0.5 part of methacrylamide ethyl ethylene urea;
short-chain reactive emulsifiers: 0.3 part of allyloxy hydroxy sodium sulfonate;
long chain reactive emulsifier: 0.9 part of unsaturated allyl alkyl ammonium sulfate;
reactive nonionic emulsifiers: 0.1 part of unsaturated allyl alkylphenol ether;
initiator: 0.2 part of potassium persulfate;
chain transfer agent: 0.1 part of n-dodecyl mercaptan (NDM);
pH buffer: 0.45 part of liquid caustic soda and 0.07 part of sodium bicarbonate;
a first defoaming agent: 0.1 part of metal soap defoaming agent;
a first preservative: 0.1 part of 1, 2-benzisothiazolin-3-one;
deionized water: 53.18 parts.
Example 2 the core-shell styrene-acrylic emulsion for the primer coating comprises the following components in parts by weight,
main monomers: 36.5 parts of butyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 4 parts and 32.5 parts), 13.5 parts of styrene (wherein the using amounts of the core monomer and the shell monomer are respectively 12 parts and 1.5 parts), 2.4 parts of hydroxyethyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 2.4 parts) and 1 part of butyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 1 part);
polar monomer: 0.2 part of vinyl triethoxysilane;
phosphate ester monomer: 0.4 part of a mixture of 2-hydroxyethyl methacrylate phosphate (60 wt%) and 2-hydroxyethyl methacrylate phosphate diester (40 wt%);
ureido monomer: 0.5 part of methacrylamide ethyl ethylene urea;
short-chain reactive emulsifiers: 0.3 part of allyloxy hydroxy sodium sulfonate;
long chain reactive emulsifier: 0.9 part of unsaturated allyl alkyl ammonium sulfate;
reactive nonionic emulsifiers: 0.1 part of nonylphenol ethoxylate;
initiator: 0.2 part of potassium persulfate;
chain transfer agent: 0.1 part of n-dodecyl mercaptan (NDM);
pH buffer: 0.45 part of liquid caustic soda and 0.07 part of sodium bicarbonate;
a first defoaming agent: 0.1 part of metal soap defoaming agent;
a first preservative: 0.1 part of 1, 2-benzisothiazolin-3-one;
deionized water: 53.18 parts.
Example 3 the core-shell styrene-acrylic emulsion for the primer coating comprises the following components in parts by weight,
main monomers: 37 parts of butyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 3 parts and 34 parts), 13.4 parts of styrene (wherein the using amounts of the core monomer and the shell monomer are respectively 9 parts and 4.4 parts), 2.4 parts of hydroxypropyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 2.4 parts) and 1 part of butyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 1 part);
polar monomer: 0.2 part of vinyl triethoxysilane;
phosphate ester monomer: 0.4 part of a mixture of 2-hydroxyethyl methacrylate phosphate (60 wt%) and 2-hydroxyethyl methacrylate phosphate diester (40 wt%);
ureido monomer: 0.2 part of allyl urea monomer;
short-chain reactive emulsifiers: 0.3 part of allyloxy hydroxy sodium sulfonate;
long chain reactive emulsifier: 0.7 part of unsaturated allyl alkyl ammonium sulfate;
reactive nonionic emulsifiers: 0.1 part of nonylphenol ethoxylate;
initiator: 0.2 part of potassium persulfate;
chain transfer agent: 0.1 part of n-dodecyl mercaptan (NDM);
pH buffer: 0.45 part of liquid caustic soda and 0.07 part of sodium bicarbonate;
a first defoaming agent: 0.1 part of mineral oil defoaming agent;
a first preservative: 0.1 part of 1, 2-benzisothiazolin-3-one;
deionized water: 53.18 parts.
Example 4 the core-shell styrene-acrylic emulsion for the primer coating comprises the following components in parts by weight,
main monomers: 2 parts of hydroxypropyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 2 parts), 17 parts of methyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 11 parts and 6 parts) and 25 parts of isooctyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 9 parts and 16 parts);
polar monomer: 0.3 part of vinyl trimethoxy silane;
phosphate ester monomer: 0.2 part of a mixture of 2-hydroxyethyl methacrylate phosphate (80 wt%) and 2-hydroxyethyl methacrylate phosphate diester (20 wt%);
ureido monomer: 0.2 part of allyl urea monomer;
short-chain reactive emulsifiers: 0.3 part of allyloxy hydroxy sodium sulfonate;
long chain reactive emulsifier: 1 part of methacrylic ether phosphate and 1.1 parts of sodium allyl alkyl sulfosuccinate diester;
reactive nonionic emulsifiers: 0.3 part of alkylphenol polyoxyethylene;
initiator: 0.2 part of sodium persulfate;
chain transfer agent: 0.2 part of n-dodecyl mercaptan (NDM);
pH buffer: 0.5 part of alkali liquor and 0.05 part of sodium dihydrogen phosphate;
a first defoaming agent: 0.2 part of mineral oil defoaming agent;
a first preservative: 0.1 part of 2-methyl-4-isothiazoline-3-ketone;
deionized water: 53.18 parts.
Example 5, the core-shell styrene-acrylic emulsion for primer coating comprises the following components in parts by weight,
main monomers: 10 parts of hydroxyethyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 2 parts and 8 parts), 17 parts of butyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 5 parts and 12 parts) and 22 parts of methyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 16 parts and 6 parts);
polar monomer: 0.3 part of vinyl triethoxysilane;
phosphate ester monomer: 0.3 part of a mixture of 2-hydroxyethyl methacrylate phosphate (90 wt%) and 2-hydroxyethyl methacrylate phosphate diester (10 wt%);
ureido monomer: 0.5 part of methacrylamide ethyl ethylene urea;
short-chain reactive emulsifiers: 0.3 part of allyloxy hydroxy sodium sulfonate;
long chain reactive emulsifier: 0.2 part of allyloxy allyl alkyl alcohol polyether and 0.85 part of 2-allyl ether 3-hydroxy propane-1-sodium sulfonate;
reactive nonionic emulsifiers: 0.2 part of fatty alcohol ethoxylate;
initiator: 0.2 part of sodium persulfate;
chain transfer agent: 0.2 part of tert-dodecyl mercaptan (TDM);
pH buffer: 0.6 part of ammonia water and 0.2 part of sodium bicarbonate;
a first defoaming agent: 0.2 part of organic silicon defoaming agent;
a first preservative: 0.2 part of 2-methyl-4-isothiazoline-3-ketone;
deionized water: 53.18 parts.
Example 6, the core-shell styrene-acrylic emulsion for primer coating comprises the following components in parts by weight,
main monomers: 22 parts of methyl methacrylate (wherein the using amounts of a core monomer and a shell monomer are respectively 16 parts and 6 parts), 3 parts of glycidyl methacrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 0 part and 3 parts) and 17 parts of isooctyl acrylate (wherein the using amounts of the core monomer and the shell monomer are respectively 6 parts and 11 parts);
polar monomer: 1.5 parts of vinyl triethoxysilane;
phosphate ester monomer: 0.2 part of a mixture of 2-hydroxyethyl methacrylate phosphate (80 wt%) and 2-hydroxyethyl methacrylate phosphate diester (20 wt%);
ureido monomer: 0.5 part of methacrylamide ethyl ethylene urea;
short-chain reactive emulsifiers: 1.2 parts of allyloxy hydroxy sodium sulfonate;
long chain reactive emulsifier: 1 part of double-bond-containing sodium sulfosuccinate;
reactive nonionic emulsifiers: 0.7 part of octyl phenol ethoxylate;
initiator: 0.2 part of ammonium persulfate;
chain transfer agent: 0.8 part of tert-dodecyl mercaptan (TDM);
pH buffer: 0.6 part of ammonia water and 0.5 part of sodium dihydrogen phosphate;
a first defoaming agent: 0.3 part of organic silicon defoaming agent;
a first preservative: 0.2 part of 2-methyl-4-isothiazoline-3-ketone;
deionized water: 53.18 parts.
The preparation method of the multi-polar monomer modified core-shell styrene-acrylic emulsion for the primer coating comprises the following steps:
(1) preparing materials: weighing the components according to the mass portion ratio in claim 1, and mixing deionized water according to the mass ratio of (1.8-2.2): 1 is divided into core deionized water and shell deionized water, and the core deionized water is mixed according to the mass ratio of (1.8-2.2): 0.1: 0.4: (1.8-2.2) dividing into a first deionized water, a second deionized water, a third deionized water and a fourth deionized water; shell deionized water is added according to the mass ratio of 2: 0.4 part of the deionized water is fifth deionized water and sixth deionized water;
dividing the emulsifier into a core emulsifier and a shell emulsifier, and mixing the core emulsifier with the shell emulsifier according to the mass ratio of (6-7): (1-2) dividing into a first reactive core emulsifier and a second reactive core emulsifier;
and (2) mixing an initiator according to a mass ratio of 1: 1.5 is divided into a core initiator and a shell initiator, and the core initiator is divided into a first core initiator and a second core initiator according to the weight ratio of (1.5-2.5) to (2.5-3.5);
and (2) mixing a pH buffering agent according to a mass ratio of 1: 1.5 into a first pH buffer and a second pH buffer;
(2) preparing an emulsifier solution: dissolving a first reactive nuclear emulsifier in first deionized water to obtain a nuclear emulsifier solution;
dissolving a shell emulsifier in fifth deionized water to obtain a shell emulsifier solution;
(3) preparing an initiator solution: dissolving a first nuclear initiator in second deionized water according to the mass-volume ratio of 0.12g/ml to form a first nuclear initiator solution; dissolving a second nuclear initiator in third deionized water according to the mass-volume ratio of 0.15g/ml to form a second nuclear initiator solution;
dissolving a shell initiator in sixth deionized water to obtain a shell initiator solution;
(4) preparing a dispersion liquid: adding a nuclear monomer into the nuclear emulsifier solution obtained in the step (2) under the stirring condition, dispersing for 20min to obtain a nuclear dispersion liquid, and mixing the nuclear dispersion liquid according to a volume ratio of 1: 4 into a first core dispersion and a second core dispersion;
adding a main monomer of a shell monomer, a phosphate monomer and a carbamido monomer into the shell emulsifier solution obtained in the step (2) under the stirring condition, and dispersing for 20min to obtain a shell dispersion liquid;
(5) preparing a nuclear emulsion: mixing fourth deionized water, a first pH buffer and a second reactive nuclear emulsifier, then placing the mixture into a reactor, stirring and heating the mixture, when the temperature reaches 75-77 ℃, dropwise adding the first nuclear dispersion liquid prepared in the step (4) and the first nuclear initiator solution prepared in the step (3) at a constant speed within 8-12min, after the exothermic reaction is finished, heating the mixture to 80-85 ℃, reacting until blue light appears to obtain a first mixed solution, stirring the mixture for 15-20min, dropwise adding the second nuclear initiator solution prepared in the step (3) and the second nuclear dispersion liquid prepared in the step (4) into the first mixed solution at the same time within 60-90min, and preserving the heat for 0.5-1h after dropwise adding to obtain a nuclear emulsion;
(6) preparing a core-shell styrene-acrylic emulsion: and (3) dropwise adding the shell dispersion liquid prepared in the step (4) and the shell initiator solution prepared in the step (3) into the core emulsion prepared in the step (5) at the temperature of 80-85 ℃, adding a chain transfer agent and a polar monomer of the shell monomer into the residual shell dispersion liquid when the shell dispersion liquid is dropped to 1/5-2/5 of the residual shell dispersion liquid, continuously dropwise adding the shell dispersion liquid and the shell initiator solution into the reactor after uniformly stirring, controlling the whole dropwise adding time of the step to be 60-90min, keeping the temperature for 1-1.5h after dropwise adding, adding a first defoaming agent, a first preservative and a second pH buffer after the solution is cooled to below 40 ℃, and uniformly stirring to obtain the core-shell emulsion.
The core-shell styrene-acrylic emulsion obtained in the examples 1 to 6 is used for preparing a water-based seal primer coating, and the core-shell styrene-acrylic emulsion obtained in the example 1 is used for preparing a competitive product coating, wherein the mass parts of the components of each coating are shown in the following table 1:
TABLE 1 parts by weight of the components of the aqueous seal coat paint
The performance parameters for each coating are shown in table 2 below:
TABLE 2 Performance parameters of aqueous seal coat paint
The paint film properties of the water borne seal coat paint are shown in the following table 3:
TABLE 3 film properties of aqueous seal coat paint
As can be seen from tables 2 and 3, the particle size distribution of the water-based seal coat paint prepared in examples 7 to 12 of the present invention is narrower than that of the competitive products, the particle size is more uniform, the properties such as hardness, adhesion (viscosity), water permeability and the like of the paint film are more excellent than those of the competitive products, and other physical parameters and application properties are substantially the same as the level of the competitive product paint.
Claims (7)
1. The core-shell styrene-acrylic emulsion for the primer coating is characterized by comprising the following components in parts by mass: 5.07-30 parts of core monomer, 5.07-30 parts of shell monomer, 0.6-12 parts of emulsifier, 0.02-5 parts of initiator, 0.02-5 parts of chain transfer agent, 0.02-5 parts of pH buffer, 0.02-2 parts of first defoaming agent, 0.02-2 parts of first preservative and 40-50 parts of deionized water; the core monomer is a main monomer, and the shell monomer comprises 4.93-20 parts of the main monomer, 0.02-2.55 parts of polar monomer, 0.02-2.5 parts of phosphate ester monomer and 0.05-5 parts of carbamido monomer;
the preparation method of the core-shell styrene-acrylic emulsion for the primer coating comprises the following steps:
(1) preparing materials: weighing the components according to the mass part ratio, and mixing deionized water according to the mass ratio (1.8-2.2): 1 is divided into core deionized water and shell deionized water, and the core deionized water is mixed according to the mass ratio of (1.8-2.2): 0.1: 0.4: (1.8-2.2) dividing into a first deionized water, a second deionized water, a third deionized water and a fourth deionized water; shell deionized water is added according to the mass ratio of 2: 0.4 part of the deionized water is fifth deionized water and sixth deionized water;
dividing the emulsifier into a core emulsifier and a shell emulsifier, and mixing the core emulsifier with the shell emulsifier according to the mass ratio of (6-7): (1-2) dividing into a first reactive core emulsifier and a second reactive core emulsifier;
and (2) mixing an initiator according to a mass ratio of 1: (1-2) dividing the core initiator into a core initiator and a shell initiator, and dividing the core initiator into a first core initiator and a second core initiator according to the weight ratio of (1.5-2.5) to (2.5-3.5);
and (2) mixing a pH buffering agent according to a mass ratio of 1: (1-2) dividing into a first pH buffer and a second pH buffer;
(2) preparing an emulsifier solution: dissolving a first reactive nuclear emulsifier in first deionized water to obtain a nuclear emulsifier solution;
dissolving a shell emulsifier in fifth deionized water to obtain a shell emulsifier solution;
(3) preparing an initiator solution: dissolving a first nuclear initiator in second deionized water to form a first nuclear initiator solution; dissolving a second nuclear initiator in third deionized water to form a second nuclear initiator solution;
dissolving a shell initiator in sixth deionized water to obtain a shell initiator solution;
(4) preparing a dispersion liquid: adding a nuclear monomer into the nuclear emulsifier solution obtained in the step (2) under the condition of stirring, dispersing to obtain a nuclear dispersion liquid, and dividing the nuclear dispersion liquid into a first nuclear dispersion liquid and a second nuclear dispersion liquid;
adding a main monomer of a shell monomer, a phosphate monomer and a carbamido monomer into the shell emulsifier solution obtained in the step (2) under the stirring condition, and dispersing to obtain a shell dispersion liquid;
(5) preparing a nuclear emulsion: mixing fourth deionized water, a first pH buffer and a second reactive nuclear emulsifier, then placing the mixture into a reactor, stirring and heating the mixture, when the temperature reaches 75-77 ℃, dropwise adding the first nuclear dispersion liquid prepared in the step (4) and the first nuclear initiator solution prepared in the step (3) at a constant speed within 8-12min, after the exothermic reaction is finished, heating the mixture to 80-85 ℃, reacting until blue light appears to obtain a first mixed solution, stirring the mixture for 15-20min, dropwise adding the second nuclear initiator solution prepared in the step (3) and the second nuclear dispersion liquid prepared in the step (4) into the first mixed solution at the same time within 60-90min, and preserving the heat for 0.5-1h after dropwise adding to obtain a nuclear emulsion;
(6) preparing a core-shell styrene-acrylic emulsion: dropwise adding the shell dispersion liquid prepared in the step (4) and the shell initiator solution prepared in the step (3) into the core emulsion prepared in the step (5) at the temperature of 80-85 ℃, adding a chain transfer agent and a polar monomer of the shell monomer into the residual shell dispersion liquid when the shell dispersion liquid is dropped to 1/5-2/5 which is the rest of the shell dispersion liquid, continuously dropwise adding the shell dispersion liquid and the shell initiator solution into the reactor after uniformly stirring, controlling the whole dropwise adding time of the step to be 60-90min, keeping the temperature for 1-1.5h after dropwise adding, adding a first defoaming agent, a first preservative and a second pH buffer after the solution is cooled to below 40 ℃, and uniformly stirring to obtain a core-shell emulsion;
the main monomer is at least one of acrylic acid, methacrylic acid, styrene, methyl methacrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, butyl methacrylate, glycidyl methacrylate, diacetone acrylamide and isobornyl acrylate;
the polar monomer is vinyl siloxane;
the phosphate ester monomer is at least one of 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate diester;
the ureido monomer is one of methacrylamide ethyl ethylene urea and allyl urea;
the mass ratio of the soft monomer to the hard monomer in the core monomer is (20-30): (70-80); the mass ratio of the soft monomer to the hard monomer in the shell monomer is (85-95): (5-15);
the emulsifier comprises 0.1-2 parts of short-chain reactive emulsifier, 0.5-10 parts of long-chain reactive emulsifier and 0.1-2 parts of reactive nonionic emulsifier, wherein the carbon atom number of the short-chain reactive emulsifier is less than or equal to 5, and the carbon atom number of the long-chain reactive emulsifier is more than 5.
2. The core-shell styrene-acrylic emulsion for a primer coating according to claim 1, characterized in that: the short-chain reaction type emulsifier is at least one of allyloxy hydroxyl sodium sulfonate, 2-acrylamide-2-methyl propyl sodium sulfonate, allyl phosphate ammonium salt, sodium vinyl sulfonate, 2-acrylamide-2-methyl propyl sulfonic acid and methyl propylene sodium sulfonate;
the long-chain reaction type emulsifier is at least one of unsaturated allyl alkyl ammonium sulfate salt, allyloxy allyl alkyl alcohol polyether, allyl-containing alcohol ether sulfate, methacrylic acid ether phosphate, alkyl propenyl phenoxy polyether sulfate, 2-allyl ether 3-hydroxy propane-1-sodium sulfonate, acrylamide isopropyl sodium sulfonate and double-bond-containing sulfo succinic acid diester sodium salt;
the reactive nonionic emulsifier is unsaturated allyl alkylphenol ether.
3. The core-shell styrene-acrylic emulsion for a primer coating according to claim 2, characterized in that: the double-bond-containing sodium diester sulfosuccinate is allyl alkyl sodium diester sulfosuccinate.
4. The core-shell styrene-acrylic emulsion for a primer coating according to claim 1, characterized in that: the chain transfer agent is one of n-dodecyl mercaptan and tert-dodecyl mercaptan.
5. The core-shell styrene-acrylic emulsion for a primer coating according to claim 1, characterized in that: the initiator is one of ammonium persulfate, potassium persulfate or sodium persulfate.
6. The core-shell styrene-acrylic emulsion for a primer coating according to claim 1, characterized in that: the pH buffer is at least one of ammonia water, liquid alkali, sodium bicarbonate and sodium dihydrogen phosphate.
7. The application of the core-shell styrene-acrylic emulsion for the primer coating in the water-based seal primer coating according to claim 1, wherein the coating comprises the following components in parts by mass: 215 parts of deionized water 160-containing organic silicon, 1-2 parts of hydroxyethyl cellulose, 0.1-2 parts of 2-amino-2-methyl-1-propanol, 5-20 parts of ethylene glycol, 260 parts of heavy calcium carbonate 150-containing organic silicon, 5-24 parts of a film-forming additive, 450 parts of core-shell styrene-acrylic emulsion, 0.1-2 parts of a second defoaming agent, 0.1-6 parts of a dispersing agent, 0.1-2 parts of a wetting agent, 0.1-4 parts of a thickening agent, 0.1-3 parts of a flatting agent, 0.2-1 part of a second preservative, 0.2-1 part of a mildew inhibitor and 8 parts of color paste carbon black.
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| CN110078867B (en) * | 2019-05-13 | 2021-11-02 | 衡水新光新材料科技有限公司 | Core-shell pure acrylic emulsion for exterior wall coating and preparation method and application thereof |
| CN110819143A (en) * | 2019-11-07 | 2020-02-21 | 盛世生态环境股份有限公司 | Water-permeable anticorrosive coating for water-permeable pavement and preparation method thereof |
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Denomination of invention: Core-shell styrene acrylic lotion for primer coating and its preparation method and application Effective date of registration: 20230506 Granted publication date: 20220215 Pledgee: Agricultural Bank of China Limited Nanxiong Sub branch Pledgor: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980039881 |