Acrylate emulsion as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer coatings, and particularly relates to an acrylate emulsion as well as a preparation method and application thereof. The acrylate emulsion provided by the invention is divided into a core part and a shell part, organic amine containing three carbon-carbon double bonds and having a cross-linking agent and a neutralizing agent and a mono-ethylenic bond type hydrolysable organosilicon monomer are added into a core layer, a polyethylenic bond unsaturated cross-linking monomer is added into a shell layer, and a three-dimensional network structure formed by multiple double bonds of the core layer and the shell layer is utilized, so that the acrylate emulsion is prepared. The crosslinking degree of the paint film is greatly improved, so that the compactness of the paint film is improved, the bonding strength of the paint film is improved, and the water absorption rate is reduced.

Description

Technical Field

[0001] This application belongs to the field of polymer coating technology, specifically relating to an acrylic emulsion, its preparation method, and its application. Background Technology

[0002] Stone-like paint is a decorative material that uses synthetic resin emulsion as the main binder and sand as aggregate to form a stone-like finish on building surfaces. Compared to traditional exterior wall decorations such as ceramic tiles, stone, and glass, stone-like paint has many advantages, including lower cost, easier application, stronger decorative effect, environmental friendliness, and no risk of peeling. In recent years, stone-like paint has become increasingly popular among builders and the market, and has become one of the leading coating materials in building exterior wall coating systems.

[0003] As the film-forming substance of stone-like paint, the emulsion plays a decisive role in the coating performance. Currently, most emulsions on the market use high glass transition temperatures (Tg) to improve the adhesion strength of the coating. While this results in a hard film, it lacks relative toughness and tends to become brittle at low temperatures and after prolonged use. Cracking is particularly likely at curved edges and in situations involving dynamic changes in the external insulation system, severely hindering the promotion and normal use of stone-like paint. Furthermore, the latest building industry standard, JG / T 24-2018 Synthetic Resin Emulsion Sand-textured Architectural Coatings, has added requirements for water absorption, flexibility, and adhesion strength to stone-like paint coatings, raising the performance standards for stone-like paint.

[0004] However, existing stone-like paints generally cannot simultaneously meet the standard requirements for flexibility and bonding strength. With the market demand driven by decoration trends and cost requirements, there is an urgent need for a high-performance stone-like paint emulsion that can combine flexibility and bonding strength, while meeting the standards of the construction industry in terms of water absorption, water whitening at normal and low temperatures and water whitening recovery, and mechanical stability. This would reduce formulation costs and enhance product competitiveness. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this application is to overcome the shortcomings of existing stone paints, which generally cannot meet the standard requirements of flexibility and bonding strength at the same time, and whose water absorption rate, water whitening at room temperature and low temperature and water whitening recovery, and mechanical stability cannot meet the industry standard requirements, thereby providing an acrylic emulsion and its preparation method and application.

[0006] Therefore, this application provides the following technical solution:

[0007] According to one aspect of this application, an acrylic emulsion is provided having a core-shell structure, wherein...

[0008] (1) The core layer comprises the following parts by weight of raw material:

[0009] Component a): at least one monovinyl aromatic monomer or at least one C1-C4 alkyl ester of methacrylic acid and mixtures thereof, 30.0-50.0 parts; as an example, it can be 30 parts, 33 parts, 35 parts, 37 parts, 40 parts, 42 parts, 45 parts, 50 parts, etc., or within any of the above values, preferably 35.0-45.0 parts;

[0010] Component b): at least one C2-C of acrylic acid 10 Alkyl ester, 30.0-50.0 parts; examples may be 30 parts, 32 parts, 35 parts, 37 parts, 40 parts, 43 parts, 45 parts, 50 parts, etc., or within any range of the above values, preferably 35.0-45.0 parts;

[0011] Component c): at least one α,β-monoolefinic unsaturated C3-C6 monocarboxylic acid, 1.5-3.5 parts; for example, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3.0 parts, 3.5 parts, etc., or within any of the above values, preferably 1.5-3.0 parts;

[0012] Component d): at least one acrylamide and / or acrylamide derivative, 1.5-3.5 parts; for example, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3.0 parts, 3.5 parts, etc., or within any of the above values, preferably 1.5-3.0 parts;

[0013] Component e): at least one mono-olefinic unsaturated sulfonic acid and its salt, 0.1-1.0 parts; for example, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc., or within any of the above values, preferably 0.2-0.8 parts;

[0014] Component f): at least one organic amine having three carbon-carbon double bonds, 0.5-2.0 parts; for example, 0.5 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2.0 parts, etc., or within any of the above values, preferably 0.8-1.6 parts;

[0015] Component g): at least one mono-olefinic unsaturated hydrolyzable organosilicon monomer, 0.1-1.0 parts; for example, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc., or within any of the above values, preferably 0.3-0.8 parts;

[0016] 2) The shell layer comprises the following parts by weight of raw material:

[0017] Component a): at least one monovinyl aromatic monomer or at least one C1-C4 alkyl ester of methacrylic acid and mixtures thereof, 2.0-10.0 parts; for example, 2.0 parts, 3.0 parts, 4.0 parts, 5.0 parts, 6.0 parts, 7.0 parts, 8.0 parts, 9.0 parts, 10.0 parts, etc., or within any range of the above values, preferably 4.0-8.0 parts;

[0018] Component b): at least one C2-C of acrylic acid 10 Alkyl ester, 4.0-12.0 parts; for example, 4.0 parts, 5.0 parts, 7.0 parts, 9.0 parts, 10.0 parts, 11.0 parts, 12.0 parts, etc., or within any range of the above values, preferably 5.0-10.0 parts;

[0019] Component c): at least one α,β-monoolefinic unsaturated C3-C6 monocarboxylic acid, 1.0-5.0 parts; for example, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, etc., or within any of the above values, preferably 1.5-3.5 parts;

[0020] Component h): at least one polyene unsaturated crosslinked monomer, 0.05-0.15 parts; for example, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.15 parts, etc., or within any of the above values, preferably 0.05-0.1 parts.

[0021] In some alternative embodiments, the organic amine having three carbon-carbon double bonds in component f) has the following structural formula:

[0022]

[0023] in:

[0024] R1 and R2 can be the same or different, but at least one of them must be H;

[0025] Optionally, R1 and R2 independently include H, and at least one of a straight-chain, branched, or cyclic saturated or unsaturated group comprising 1 to 20 carbon atoms, substituted with one or more alkoxy carbonyl groups, wherein the alkoxy group comprises 1 to 10 carbon atoms.

[0026] In this application, the crosslinking agent and neutralizing agent with three carbon-carbon double bonds in component f) can be prepared with reference to patent CN113683523A, and all related prior art can be incorporated into this application; it can also be obtained through commercial channels.

[0027] In some alternative embodiments, the monovinyl aromatic monomer in component a) includes one or more of styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, and 4-n-decylstyrene; optionally, it is styrene.

[0028] And / or, the C1-C4 alkyl ester of methacrylic acid in component a) includes one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate; optionally, it is methyl methacrylate.

[0029] In some alternative embodiments, the C2-C of acrylic acid in component b) 10 Alkyl esters include one or more of ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, and isooctyl acrylate; optionally, they are n-butyl acrylate or isooctyl acrylate.

[0030] And / or, the α,β-monoolefinic unsaturated C3-C6 monocarboxylic acid in component c) includes one or more of acrylic acid, methacrylic acid, butenoic acid, 2-ethylacrylic acid, 2-propylacrylic acid, 2-acryloyloxyacetic acid, and 2-methacryloyloxyacetic acid; optionally, it is acrylic acid or methacrylic acid;

[0031] And / or, the acrylamide compound in component d) includes one or more of acrylamide, methacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, and N-butylacrylamide; optionally, it is acrylamide or methacrylamide;

[0032] And / or, the polyene unsaturated cross-linking monomer of component h) includes one or more of allyl methacrylate, diallyl phthalate, ethylene glycol dimethacrylate, butanediol dimethacrylate, and 1,6-hexanediol diacrylate; optionally, it is ethylene glycol dimethacrylate.

[0033] In some optional embodiments, the mono-olefinic unsaturated sulfonic acid and its salt in component e) include vinyl sulfonic acid, allyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and one or more of their salts, optionally their sodium salts.

[0034] Optionally, the mono-olefinic unsaturated sulfonic acid and its salt in component e) includes one or more of styrene sulfonic acid and its salt, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and its salt, and optionally their sodium salts.

[0035] In some optional embodiments, the monoolefinically unsaturated hydrolyzable organosilicon monomer in component g) includes one or more of vinyltrialkoxysilane, alkylvinyldialkoxysilane and methacryloxyalkyltrialkoxysilane;

[0036] Optionally, the monoolefinically unsaturated hydrolyzable organosilicon monomer in component g) includes one or more of vinyltrimethoxysilane, methylvinyldialkoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane, and may further be methacryloxypropyltrimethoxysilane.

[0037] According to another aspect of this application, a method for preparing the above-mentioned acrylate emulsion is provided, comprising the following steps:

[0038] S1, prepare core layer preemulsion A, shell layer preemulsion B, base liquid C containing polymerization inhibitor, core layer initiator solution and shell layer initiator solution respectively;

[0039] S2, add core layer pre-emulsion A and core layer initiator solution to the base liquid C, and react to obtain core layer reactants;

[0040] S3, add shell pre-emulsion B and shell initiator solution to the core reactant, and react to obtain a core-shell structured polymer. After the reaction is completed, adjust the pH and filter the product through a filter screen (to remove the gel formed during the reaction) to obtain the acrylate emulsion.

[0041] Specifically, in the above-mentioned stages and steps of this application:

[0042] First, seed emulsion and core layer emulsion are prepared. A portion of core layer pre-emulsion A and core layer initiator solution are added to the substrate solution to obtain seed emulsion. Then, the remaining majority of pre-emulsion A and initiator solution are added dropwise simultaneously. The seeds absorb monomers and continue to grow until the emulsion is completely added. The controllable part lies in the composition of core layer pre-emulsion A. The structure of the core layer polymer can be controlled by adjusting the type of pre-emulsion A and the content of each component.

[0043] After the core emulsion (i.e., the core reactant) is prepared, the shell pre-emulsion B and the shell initiator solution are added simultaneously in two drops to prepare polymer segments with a core-shell structure. Crosslinking agent components e) and f) are used in the core pre-emulsion A, and latex crosslinking agent h) is used in the shell pre-emulsion B. By combining multiple crosslinking technologies, the polymer segments are micro-crosslinked with each other to form a three-dimensional network structure, ensuring that the acrylic emulsion has excellent freeze-thaw stability. The stone paint prepared from it has high bonding strength, good flexibility, excellent water absorption, excellent water whitening at room temperature and low temperature and excellent recovery, and excellent overall comprehensive performance.

[0044] In a preferred embodiment, based on the total amount of preemulsion, the kernel layer preemulsion A in the seed portion accounts for 2%-6% of the total preemulsion by mass, and the kernel layer preemulsion A accounts for 40%-60% of the total preemulsion (kernel layer preemulsion A and shell layer preemulsion B) by mass.

[0045] In a preferred embodiment, based on the total amount of initiator solution (core initiator solution and shell initiator solution), the seed initiator solution accounts for 40%-60% of the total initiator solution by mass, the core initiator solution accounts for 70%-90% of the total initiator solution by mass, and the shell initiator solution accounts for 10%-30% of the total initiator solution by mass.

[0046] In this application, the preparation methods of the core layer preemulsion A, shell layer preemulsion B, base solution C, and initiator solution are conventional in the art. As an example, in some preferred embodiments, the method for preparing the core layer preemulsion A includes: taking 0.9-1.8 parts by mass of emulsifier, core layer components d), e), and 35-85 parts by mass of deionized water, and sequentially adding the core layer components a), b), c), f), and g), mixing well, and setting aside.

[0047] In some preferred embodiments, the method for preparing the shell preemulsion B includes: taking 0.3-0.6 parts by weight of emulsifier and 15-25 parts by weight of deionized water, and sequentially adding the shell components a), b), c), and h), mixing them well, and setting them aside.

[0048] In some preferred embodiments, the method for preparing the base liquid C includes: adding 0.15-0.3 parts by weight of emulsifier, 0.001-0.01 parts by weight of polymerization inhibitor and 40-100 parts by weight of deionized water to a reaction vessel, and heating to 82-90°C for later use;

[0049] In some preferred embodiments, the method for preparing the initiator solution (core initiator solution + shell initiator solution) based on the above-mentioned component proportions includes: mixing 0.2-0.8 parts by mass of initiator with 7.0-40 parts by mass of deionized water for later use.

[0050] In some preferred embodiments, the raw materials comprising the core preemulsion A, shell preemulsion B, base liquid C, and initiator solution are subjected to a free radical emulsion polymerization reaction, including the following steps:

[0051] At 82-90℃, add 2%-6% (by mass) of core layer preemulsion A and 40%-60% (by mass) of initiator solution to the base solution C in one step. After reacting for 5-10 minutes, begin double-dropping (i.e., simultaneous dropping) of the remaining core layer preemulsion A and initiator solution. Stop the dropping when the core layer preemulsion A is completely added, and keep the temperature for 10-30 minutes. Then, double-droppping the shell layer preemulsion B and the remaining initiator solution, ensuring that the initiator dropping time is longer than the total dropping time of core layer preemulsion A and shell layer preemulsion B. After the dropping is completed, keep the temperature for 15-45 minutes and then cool down to 70-75℃.

[0052] Add post-treatment agents (including oxidizing agents and reducing agents) dropwise into the reactor, keep it warm for 15-30 minutes after the addition is complete, and then cool it down to 35-45℃.

[0053] A neutralizing agent is added dropwise to the reaction vessel to adjust the pH to 7.0-9.0. Then, an antifoaming agent and a bactericide are added, and the mixture is filtered to obtain the acrylate emulsion.

[0054] In a preferred embodiment, the emulsifier is an anionic emulsifier, and suitable anionic emulsifiers include at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether disulfonate, and sodium alkyl succinate sulfonate, more preferably sodium alkyl succinate sulfonate.

[0055] Preferably, the initiator is a water-soluble initiator, including but not limited to at least one of ammonium persulfate, sodium persulfate, and potassium persulfate, more preferably ammonium persulfate.

[0056] Preferably, the polymerization inhibitor is one or more selected from 2,2,6,6-tetramethylpiperidine oxide (TEMPO) and hydroquinone. Optionally, the amount of polymerization inhibitor used is 0.001-0.01 parts by weight.

[0057] Preferably, the post-treatment agent includes, but is not limited to, at least one of tert-butyl hydroperoxide (T-BHP), tert-amyl hydroperoxide (T-AHP), sodium bisulfite, sodium dithionite, and isoascorbic acid, preferably tert-butyl hydroperoxide and / or isoascorbic acid, and more preferably tert-butyl hydroperoxide and sodium bisulfite in a mass ratio of 1:0.8. Optionally, the amount of post-treatment agent used is 0.1-1.0 parts by mass.

[0058] Preferably, the defoamer is conventional in the field, including but not limited to at least one of mineral oil defoamer NXZ, BASF A10, Tego825, and BYK028; optionally, BASF A10 is used in an amount of 0.0002-0.001 parts by weight.

[0059] Preferably, the bactericide is conventional in the field, including but not limited to at least one of KATHON LX 150, KORDEK, QK-20, and ROCIMA 640; optionally, KATHON LX150 or KORDEK is used in an amount of 0.000014-0.00039 parts by weight.

[0060] In this application, the preparation processes of the core layer preemulsion A, shell layer preemulsion B, base solution C, and initiator solution are not sequential. Core layer preemulsion A and shell layer preemulsion B comprise mixtures of various monomers and are the main components participating in the polymerization reaction. Base solution C mainly includes process water, a very small amount of polymerization inhibitor, and a portion of emulsifier. This emulsifier primarily controls the particle size of the seed emulsion to obtain the final target particle size emulsion. The polymerization inhibitor prevents premature initiation of some monomers, ensuring uniform particle size distribution and good batch stability. A portion of the stabilizer (component e) in core layer preemulsion A prevents the mixed monomers from being too hydrophilic, which could easily lead to self-polymerization and slag discharge, ensuring stable polymerization and enabling an external circulation process, saving polymerization reaction time. The initiator in the initiator solution decomposes upon heating to generate free radicals, inducing free radical polymerization of the monomers.

[0061] According to another aspect of this application, the application of the above-described acrylic emulsion or the acrylic emulsion prepared by the above-described preparation method in architectural coatings is provided.

[0062] Optionally, the architectural coating includes at least one of stone-like paint, exterior wall emulsion, and interior wall paint.

[0063] The technical solution of this application has the following advantages:

[0064] The acrylic emulsion provided in this application consists of a core and a shell. The core layer contains an organic amine with three carbon-carbon double bonds, acting as both a crosslinking agent and a neutralizing agent, along with a mono-olefinic unsaturated hydrolyzable organosilicon monomer. The shell layer contains a polyolefinic unsaturated crosslinking monomer. Utilizing the three-dimensional network structure formed by the multiple double bonds in the core and shell layers, the density of the paint film is improved, resulting in a significant increase in the degree of crosslinking. This enhances the film's adhesive strength and reduces water absorption. Specifically, during the polymerization process of raw materials containing components a), b), c), and d), a specially structured component f) is added as a crosslinking agent and neutralizing agent, along with two different types of crosslinking agents (g) and h), and component e) as a co-stabilizer to ensure polymerization stability. By combining multiple crosslinking technologies with functional monomers, the acrylic emulsion, when applied in the construction field, forms a micro-reaction system between the emulsion and the base material, increasing the density of the paint film. This results in high adhesive strength, low water absorption, excellent water whitening at room temperature and low temperatures, and excellent water whitening recovery, while maintaining the film's flexibility.

[0065] Specifically, a special structural component f) is used as a crosslinking agent and neutralizer. It can effectively adjust the pH value of the reaction medium during polymerization and regulate the distribution of functional monomers (mainly components c), d), g), and h), so that they are distributed as much as possible on the surface of latex particles, reducing embedding. At the same time, it contains three carbon-carbon double bonds, which can carry out intermolecular crosslinking to form a three-dimensional network structure, which greatly improves the density of the paint film and the dispersibility of the base material, thereby improving the adhesion strength of the paint film, reducing water absorption, and enhancing mechanical stability. The core layer is compounded with carboxylic acid functional monomers (component c) and amino functional monomers (component d). The carboxylic acid functional monomers improve reaction stability, and a small portion of the self-polymerized carboxylic acid oligomers, after neutralization, become carboxylate salts, acting as dispersants and enhancing dispersibility with the base material, thus significantly improving the mechanical stability of the paint film. The amino functional monomers are non-ionizing monomers; the strong hydrophilicity of the amino groups contributes to the stability of latex particles, and their steric hindrance stabilization mechanism greatly contributes to the calcium ion stability of the emulsion. Therefore, the combination of these two monomers results in an emulsion with excellent calcium ion stability and mechanical stability. Component e) mono-olefinic unsaturated sulfonic acid and its salts can greatly improve the polymerization stability of the emulsion during polymerization, enabling external circulation processes, significantly shortening production time, and reducing the processing cost of acrylic emulsions.

[0066] The acrylate emulsion of this application adopts a pre-emulsification semi-continuous dripping process, which can effectively improve polymerization stability and allow the chemical reaction to proceed under relatively mild conditions.

[0067] Other features and advantages of this application will be described in detail in the following specific embodiments. Detailed Implementation

[0068] The following embodiments are provided to better understand this application and are not limited to the preferred embodiments described herein. They do not constitute a limitation on the content and scope of protection of this application. Any product that is the same as or similar to this application, derived by anyone under the guidance of this application or by combining features of this application with other prior art, falls within the scope of protection of this application.

[0069] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0070] Unless otherwise specified, the "%" used in the following examples refers to mass percentage. The following describes some of the raw materials used in the examples and comparative examples:

[0071] 1,1,1-Triallylmethyl ether-2-ethoxyamine (crosslinking agent and neutralizing agent) is a product of Aladdin Company;

[0072] Ethanolamine (MEA) is a product of Aladdin Corporation.

[0073] Sodium hydroxide is a product of Aladdin Company;

[0074] Ethylene glycol dimethacrylate (EGDMA) is a product of Aladdin Company;

[0075] Vinyltriethoxysilane (A-171) is a product of Nanjing Chenggong Organosilicon Materials Co., Ltd.

[0076] DES-30 (Sodium alkyl succinate sulfonate) is a product of Solvay Investment Co., Ltd.

[0077] Sodium dodecyl sulfate (SDS) is a product of Aladdin Company;

[0078] SSS (sodium vinylbenzenesulfonate) is a product of Shandong Xingzhilian Biotechnology Co., Ltd.

[0079] The polymerization inhibitor TEMPO is a product of Aladdin Corporation.

[0080] Defoamer A10 is a product of BASF Chemicals Ltd.

[0081] The bactericides LX 150 and KORDEK are products of Dow Chemical Company.

[0082] Example 1

[0083] This embodiment provides an acrylic emulsion, the composition of which and its specific preparation method are as follows:

[0084] 1) Preparation of core layer preemulsion A: At room temperature and pressure, add 1.0g DES-30, 0.15g sodium vinylbenzenesulfonate, 1.6g acrylamide and 30g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 5g methyl methacrylate, 25g styrene, 24g n-butyl acrylate, 6g isooctyl acrylate, 1.6g acrylic acid, 0.6g 1,1,1-triallylmethyl ether-2-ethoxyamine and 0.15g A-171 in sequence. Stir thoroughly and mix well before use.

[0085] 2) Preparation of shell preemulsion B: At room temperature and pressure, add 0.35g DES-30 and 15g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 1.5g methyl methacrylate, 1.5g styrene, 4.5g n-butyl acrylate, 1.2g methacrylic acid, and 0.06g ethylene glycol dimethacrylate in sequence. Stir thoroughly and mix well before use.

[0086] 3) Preparation of bottom liquid C (bottom liquid): Add 0.16g DES-30, 0.005g TEMPO and 40g deionized water to the polymerization reactor equipped with a stirrer, condenser, constant flow pump feeding device and constant flow drip metering device, stir thoroughly to dissolve, and heat to 82℃ inside the polymerization reactor.

[0087] 4) Preparation of initiator solution: At room temperature and pressure, add 0.2g of ammonium persulfate and 18g of deionized water to an initiator container equipped with a stirrer and a constant flow dripping device, and stir until completely dissolved for later use;

[0088] 5) When the temperature inside the reactor reaches 82℃, add core layer preemulsion A (6% of the total core layer preemulsion) and initiator solution (50% by mass) sequentially to the reactor. React for 5 minutes under stirring. Then, add the remaining core layer preemulsion A and initiator solution dropwise to the reactor using a constant flow pump. Stop adding core layer preemulsion A after it has been added. Keep the temperature for 10 minutes. Then, add shell layer preemulsion B and the remaining initiator solution dropwise (the proportion of the initiator solution in this step is the same as the proportion of shell layer preemulsion B in the total preemulsion, and the same applies below). Ensure that the initiator solution is added for a longer time than the total addition time of core layer preemulsion A and shell layer preemulsion B during the addition process. After the addition is completed, keep the temperature for 15 minutes and then cool down to 70℃.

[0089] 6) Add the post-treatment agent dropwise to the reactor, namely, an aqueous solution of 0.1g tert-butyl hydrogen peroxide and an aqueous solution of 0.08g sodium bisulfite. After the addition is complete, keep the temperature for 20 minutes and then cool down to 45℃.

[0090] 7) Add ammonia water as a neutralizing agent to the reactor to adjust the pH value to 7.5;

[0091] 8) Add 0.06g of defoamer (A10, the same below) and 0.8g of bactericide (LX-150, the same below) to the reaction vessel, and obtain the acrylate emulsion after filtration.

[0092] Example 2

[0093] This embodiment provides an acrylic emulsion, the composition of which and its specific preparation method are as follows:

[0094] 1) Preparation of core layer preemulsion A: At room temperature and pressure, add 1.2g DES-30, 0.5g sodium vinylbenzenesulfonate, 2.5g acrylamide and 60g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 6g methyl methacrylate, 30g styrene, 30g n-butyl acrylate, 7.5g isooctyl acrylate, 2.4g acrylic acid, 1.2g 1,1,1-triallylmethyl ether-2-ethoxyamine and 0.6g A-171 in sequence. Stir thoroughly and mix well before use.

[0095] 2) Preparation of shell preemulsion B: At room temperature and pressure, add 0.45g DES-30 and 20g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 2.5g methyl methacrylate, 2.5g styrene, 8.0g n-butyl acrylate, 2.4g methacrylic acid, and 0.08g ethylene glycol dimethacrylate in sequence. Stir thoroughly and mix well before use.

[0096] 3) Preparation of bottom liquid C (bottom liquid): Add 0.24g DES-30, 0.007g TEMPO and 80g deionized water to the polymerization reactor equipped with a stirrer, condenser, constant flow pump feeding device and constant flow drip metering device, stir thoroughly to dissolve, and heat to 84℃ inside the polymerization reactor.

[0097] 4) Preparation of initiator solution: At room temperature and pressure, add 0.5g of ammonium persulfate and 31g of deionized water to an initiator container equipped with a stirrer and a constant flow dripping device, and stir until completely dissolved for later use;

[0098] 5) When the temperature inside the reactor reaches 84℃, add 2% of the total amount of core layer preemulsion A and 40% of the initiator solution to the reactor in sequence. React for 10 minutes under stirring. Then, add the remaining core layer preemulsion A and initiator solution dropwise to the reactor through a constant flow pump feeding device. Stop adding the core layer preemulsion A after it is finished. Keep the temperature for 25 minutes. Then, add the shell layer preemulsion B and the remaining initiator solution dropwise in pairs. Ensure that the initiator dropwise time is longer than the total dropwise time of core layer preemulsion A and shell layer preemulsion B during the dropwise process. After the dropwise addition is completed, keep the temperature for 45 minutes and then cool down to 72℃.

[0099] 6) Add the post-treatment agent dropwise to the reactor, namely, an aqueous solution of 0.5g tert-butyl hydrogen peroxide and an aqueous solution of 0.4g sodium bisulfite. After the addition is complete, keep the temperature for 25 minutes and then cool down to 45℃.

[0100] 7) Add ammonia water as a neutralizing agent to the reactor to adjust the pH value to 8.5;

[0101] 8) Add 0.082g of defoamer and 1.0g of bactericide to the reaction vessel, and obtain the acrylate emulsion after filtration.

[0102] Example 3

[0103] This embodiment provides an acrylic emulsion, the composition of which and its specific preparation method are as follows:

[0104] 1) Preparation of core layer preemulsion A: At room temperature and pressure, add 1.7g DES-30, 1.0g sodium vinylbenzenesulfonate, 3.5g acrylamide and 80g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 8g methyl methacrylate, 40g styrene, 36g n-butyl acrylate, 9g isooctyl acrylate, 3.4g acrylic acid, 1.9g 1,1,1-triallylmethyl ether-2-ethoxyamine and 0.95g A-171 in sequence. Stir thoroughly and mix well before use.

[0105] 2) Preparation of shell preemulsion B: At room temperature and pressure, add 0.6g DES-30 and 25g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 4.5g methyl methacrylate, 4.5g styrene, 11.0g n-butyl acrylate, 4.8g methacrylic acid, and 0.14g ethylene glycol dimethacrylate in sequence. Stir thoroughly and mix well before use.

[0106] 3) Preparation of bottom liquid C (bottom liquid): Add 0.3g DES-30, 0.01g TEMPO and 90g deionized water to the polymerization reactor equipped with a stirrer, condenser, constant flow pump feeding device and constant flow drip metering device, stir thoroughly to dissolve, and heat to 90℃ inside the polymerization reactor.

[0107] 4) Preparation of initiator solution: At room temperature and pressure, add 0.8g of ammonium persulfate and 30g of deionized water to an initiator container equipped with a stirrer and a constant flow dripping device, and stir until completely dissolved for later use;

[0108] 5) When the temperature inside the reactor reaches 90℃, add 3% of the total amount of core layer preemulsion A and 60% of the initiator solution to the reactor in sequence. React for 8 minutes under stirring. Then, add the remaining core layer preemulsion A and initiator solution dropwise to the reactor through a constant flow pump feeding device. Stop adding the core layer preemulsion A after it is finished. Keep the temperature for 20 minutes. Then, add the shell layer preemulsion B and the remaining initiator solution dropwise in pairs. Ensure that the initiator dropwise time is longer than the total dropwise time of core layer preemulsion A and shell layer preemulsion B during the dropwise process. After the dropwise addition is completed, keep the temperature for 30 minutes and then cool down to 75℃.

[0109] 6) Add the post-treatment agent dropwise to the reactor, namely, an aqueous solution of 1.0 g tert-butyl hydrogen peroxide and an aqueous solution of 0.8 g sodium bisulfite. After the addition is complete, keep the temperature for 30 min and then cool down to 45°C.

[0110] 7) Add ammonia water as a neutralizing agent to the reactor to adjust the pH value to 9.0;

[0111] 8) Add 0.12g of defoamer and 1.56g of bactericide to the reaction vessel, and obtain the acrylate emulsion after filtration.

[0112] Example 4

[0113] This embodiment provides an acrylic emulsion, the composition of which and its specific preparation method are as follows:

[0114] 1) Preparation of core layer preemulsion A: At room temperature and pressure, add 1.1g DES-30, 0.25g sodium vinylbenzenesulfonate, 1.7g acrylamide and 65g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 6g methyl methacrylate, 30g styrene, 32g n-butyl acrylate, 8.0g isooctyl acrylate, 1.7g acrylic acid, 0.9g 1,1,1-triallylmethyl ether-2-ethoxyamine and 0.4g A-171 in sequence. Stir thoroughly and mix well before use.

[0115] 2) Preparation of shell preemulsion B: At room temperature and pressure, add 0.4g DES-30 and 18g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 2.4g methyl methacrylate, 2.4g styrene, 6.0g n-butyl acrylate, 1.8g methacrylic acid, and 0.07g ethylene glycol dimethacrylate in sequence. Stir thoroughly and mix well before use.

[0116] 3) Preparation of bottom liquid C (bottom liquid): Add 0.2g DES-30, 0.004g TEMPO and 85g deionized water to the polymerization reactor equipped with a stirrer, condenser, constant flow pump feeding device and constant flow drip metering device, stir thoroughly to dissolve, and heat to 86℃ inside the polymerization reactor.

[0117] 4) Preparation of initiator solution: At room temperature and pressure, add 0.6g of ammonium persulfate and 24g of deionized water to an initiator container equipped with a stirrer and a constant flow dripping device, and stir until completely dissolved for later use;

[0118] 5) When the temperature inside the reactor reaches 86℃, add 5% of the total amount of core layer preemulsion A and 33% of the initiator solution to the reactor in sequence. React for 7 minutes under stirring. Then, add the remaining core layer preemulsion A and initiator solution dropwise to the reactor through a constant flow pump feeding device. Stop adding the core layer preemulsion A after it is finished. Keep the temperature for 15 minutes. Then, add the shell layer preemulsion B and the remaining initiator solution dropwise in pairs. Ensure that the initiator dropwise time is longer than the total dropwise time of core layer preemulsion A and shell layer preemulsion B during the dropwise process. After the dropwise addition is completed, keep the temperature for 25 minutes and then cool down to 71℃.

[0119] 6) Add the post-treatment agent dropwise to the reactor, namely, an aqueous solution of 0.3g tert-butyl hydrogen peroxide and an aqueous solution of 0.24g sodium bisulfite. After the addition is complete, keep the temperature at 15min and then cool it down to 45℃.

[0120] 7) Add ammonia water as a neutralizing agent to the reactor to adjust the pH value to 8.0;

[0121] 8) Add 0.076g of defoamer and 0.92g of bactericide to the reaction vessel, and obtain the acrylate emulsion after filtration.

[0122] Example 5

[0123] This embodiment provides an acrylic emulsion, the composition of which and its specific preparation method are as follows:

[0124] 1) Preparation of core layer preemulsion A: At room temperature and pressure, add 1.5g DES-30, 0.75g sodium vinylbenzenesulfonate, 2.8g acrylamide and 70g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 7g methyl methacrylate, 35g styrene, 34g n-butyl acrylate, 8.5g isooctyl acrylate, 2.8g acrylic acid, 1.5g 1,1,1-triallylmethyl ether-2-ethoxyamine and 0.75g A-171 in sequence. Stir thoroughly and mix well before use.

[0125] 2) Preparation of shell preemulsion B: At room temperature and pressure, add 0.55g DES-30 and 22g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 3.6g methyl methacrylate, 3.6g styrene, 9.5g n-butyl acrylate, 3.2g methacrylic acid, and 0.09g ethylene glycol dimethacrylate in sequence. Stir thoroughly and mix well before use.

[0126] 3) Preparation of bottom liquid C (bottom liquid): Add 0.27g DES-30, 0.008g TEMPO and 85g deionized water to the polymerization reactor equipped with a stirrer, condenser, constant flow pump feeding device and constant flow drip metering device, stir thoroughly to dissolve, and heat to 85℃ inside the polymerization reactor.

[0127] 4) Preparation of initiator solution: At room temperature and pressure, add 0.7g of ammonium persulfate and 27g of deionized water to an initiator container equipped with a stirrer and a constant flow dripping device, and stir until completely dissolved for later use;

[0128] 5) When the temperature inside the reactor reaches 85℃, add 4% of the total amount of core layer preemulsion A and 50% of the initiator solution to the reactor in sequence. React under stirring for 6 minutes. Then, add the remaining core layer preemulsion A and initiator solution dropwise to the reactor through a constant flow pump feeding device. Stop adding the core layer preemulsion A after it is finished. Keep the temperature for 20 minutes. Then, add the shell layer preemulsion B and the remaining initiator solution dropwise in pairs. Ensure that the initiator dropwise time is longer than the total dropwise time of core layer preemulsion A and shell layer preemulsion B during the dropwise process. After the dropwise addition is completed, keep the temperature for 35 minutes and then cool down to 73℃.

[0129] 6) Add the post-treatment agent dropwise into the reactor, namely, an aqueous solution of 0.7g tert-butyl hydrogen peroxide and an aqueous solution of 0.56g sodium bisulfite. After the addition is complete, keep the temperature for 20 minutes and then cool down to 45℃.

[0130] 7) Add ammonia water as a neutralizing agent to the reactor to adjust the pH value to 8.0;

[0131] 8) Add 0.102g of defoamer and 1.22g of bactericide to the reaction vessel, and obtain the acrylate emulsion after filtration.

[0132] Example 6

[0133] This embodiment provides an acrylate emulsion. Compared with Example 2, the only difference is that in the preparation of the core layer preemulsion A, butyl methacrylate is used instead of methyl methacrylate and dimethylstyrene is used instead of styrene. In the preparation of the shell layer preemulsion B, butyl methacrylate is used instead of methyl methacrylate and dimethylstyrene is used instead of styrene. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0134] Example 7

[0135] This embodiment provides an acrylate emulsion. Compared with Example 2, the only difference is that 1.1g of 1,1,1-triallylmethyl ether-2-ethoxyamine is added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0136] Example 8

[0137] This embodiment provides an acrylate emulsion. Compared with Example 2, the only difference is that 1.4g of 1,1,1-triallylmethyl ether-2-ethoxyamine is added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0138] Example 9

[0139] This embodiment provides an acrylic emulsion. Compared with Example 2, the only difference is that 0.45g of A-171 is added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0140] Example 10

[0141] This embodiment provides an acrylic emulsion. Compared with Example 2, the only difference is that 0.65g of A-171 is added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0142] Example 11

[0143] This embodiment provides an acrylate emulsion. Compared with Example 2, the only difference is that 0.07g of ethylene glycol dimethacrylate is added to the shell pre-emulsion B. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0144] Example 12

[0145] This embodiment provides an acrylate emulsion. Compared with Example 2, the only difference is that 0.085g of ethylene glycol dimethacrylate is added to the shell pre-emulsion B. The other components and the emulsion preparation method are exactly the same as in Example 2.

[0146] Comparative Example 1

[0147] This comparative example provides an acrylate emulsion, which differs from Example 3 only in that 1,1,1-triallylmethyl ether-2-ethoxyamine is not added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 3.

[0148] Comparative Example 2

[0149] This comparative example provides an acrylate emulsion. The only difference from Example 3 is that the core layer pre-emulsion A uses an equal mass of ethanolamine instead of 1,1,1-triallylmethyl ether-2-ethoxyamine. The other components and the emulsion preparation method are exactly the same as in Example 3.

[0150] Comparative Example 3

[0151] This comparative example provides an acrylic emulsion. The only difference from Example 3 is that the core layer pre-emulsion A uses an equal mass of sodium hydroxide instead of 1,1,1-triallylmethyl ether-2-ethoxyamine. The other components and the emulsion preparation method are exactly the same as in Example 3.

[0152] Comparative Example 4

[0153] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that A-171 is not added to the core layer pre-emulsion A, while the other components and the emulsion preparation method are exactly the same as in Example 3.

[0154] Comparative Example 5

[0155] This comparative example provides an acrylate emulsion, which differs from Example 3 only in that ethylene glycol dimethacrylate is not added to the shell pre-emulsion B; the other components and the emulsion preparation method are exactly the same as in Example 3.

[0156] Comparative Example 6

[0157] This comparative example provides an acrylic emulsion, the specific composition and preparation method of which are as follows:

[0158] 1) Preparation of preemulsion A: At room temperature and pressure, add 2.3g DES-30, 1.0g sodium vinylbenzenesulfonate, 3.5g acrylamide and 105g deionized water to a preemulsion tank equipped with a monomer metering tank and a stirrer. After stirring and dissolving thoroughly, add 12.5g methyl methacrylate, 44.5g styrene, 47g n-butyl acrylate, 9g isooctyl acrylate, 3.4g acrylic acid, 4.8g methacrylic acid, 1.9g 1,1,1-triallylmethyl ether-2-ethoxyamine, 0.95g A-171 and 0.14g ethylene glycol dimethacrylate. Stir thoroughly and mix well before use.

[0159] 2) Preparation of bottom liquid C (bottom liquid): Add 0.3g DES-30, 0.01g TEMPO and 90g deionized water to the polymerization reactor equipped with a stirrer, condenser, constant flow pump feeding device and constant flow drip metering device, stir thoroughly to dissolve, and heat to 90℃ inside the polymerization reactor.

[0160] 3) Preparation of initiator solution: At room temperature and pressure, add 0.8g of ammonium persulfate and 30g of deionized water to an initiator container equipped with a stirrer and a constant flow dripping device, and stir until completely dissolved for later use;

[0161] 4) When the temperature inside the reactor reaches 90℃, add 3% of the total amount of pre-emulsion A and 60% of the initiator solution to the reactor in sequence. React for 8 minutes under stirring. Then, add the remaining pre-emulsion A and initiator solution dropwise to the reactor through a constant flow pump feeding device. Ensure that the initiator dropwise time is longer than the total dropwise time of pre-emulsion A during the dropwise addition process. After the dropwise addition is completed, keep the temperature for 30 minutes and then cool down to 75℃.

[0162] 5) Add the post-treatment agent dropwise to the reactor, namely, an aqueous solution of 1.0 g tert-butyl hydrogen peroxide and an aqueous solution of 0.8 g sodium bisulfite. After the addition is complete, keep the temperature at 30 min and then lower it to 45 °C.

[0163] 6) Add ammonia water as a neutralizing agent to the reactor to adjust the pH value to 9.0;

[0164] 7) Add 0.12g of defoamer and 1.56g of bactericide to the reaction vessel, and obtain the acrylate emulsion after filtration.

[0165] Comparative Example 7

[0166] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that components g) and h) are replaced with component f), while the other components and the emulsion preparation method are exactly the same as in Example 3.

[0167] Comparative Example 8

[0168] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that components f) and h) are replaced with component g), while the other components and the emulsion preparation method are exactly the same as in Example 3.

[0169] Comparative Example 9

[0170] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that components f) and g) are replaced with component h), while the other components and the emulsion preparation method are exactly the same as in Example 3.

[0171] Comparative Example 10

[0172] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that component e) is not added, while the other components and the emulsion preparation method are exactly the same as in Example 3.

[0173] Comparative Example 11

[0174] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that: 0.8g acrylamide, 7.0g methyl methacrylate, 18g styrene, 40g n-butyl acrylate, 20g isooctyl acrylate, and 1.0g acrylic acid are added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 3.

[0175] Comparative Example 12

[0176] This comparative example provides an acrylic emulsion, which differs from Example 3 only in that: 4.0g of acrylamide, 15g of methyl methacrylate, 40g of styrene, 15g of n-butyl acrylate, 10g of isooctyl acrylate, and 4.0g of acrylic acid are added to the core layer pre-emulsion A. The other components and the emulsion preparation method are exactly the same as in Example 3.

[0177] Test case

[0178] Performance testing methods: The bonding strength, flexibility, and water absorption of the real stone paints prepared from the acrylic emulsions provided in each example and comparative example were tested according to the test methods for bonding strength, flexibility, and water absorption in JG / T24-2018 "Synthetic Resin Emulsion Sand-textured Architectural Coatings".

[0179] Mechanical stability: Weigh 500g of stone paint into a 500ml paint can, place the dispersion plate in the middle of the paint, adjust the speed to 2500rpm, and record the time when the paint surface in the can loses its gloss and becomes noticeably thicker.

[0180] Low-Temperature Water-Whitening and Restoration of Stone Paint: A layer of stone paint approximately 2mm thick was applied to an A4 asbestos-free cement board and cured for 18 hours in a constant temperature and humidity chamber at 25℃ or 5℃ and 50% humidity. The board was then rinsed with water for 6 hours, and the water-whitening effect of the water-soaked areas was compared. After restoring to room temperature for 24 hours, the water-whitening recovery and watermarks on the water-soaked areas were compared.

[0181] The performance test results are shown in Table 1 below:

[0182] Table 1

[0183]

[0184]

[0185] Note: 1 point is the worst, the skin turns white and cannot be restored; 5 points is the best, the skin does not turn white and can be fully restored.

[0186] As shown in Table 1, the emulsion prepared using the embodiments of the present invention, when formulated into a real stone paint, exhibits good flexibility, excellent bonding strength, low water absorption, and high mechanical stability. Furthermore, the real stone paint demonstrates excellent low-temperature water whitening and water whitening recovery.

[0187] Compared with the reaction system of the embodiments of the present invention, no organic amine was added to the raw material components of Comparative Example 1, an organic amine without double bonds was used in the raw material components of Comparative Example 2, a conventional strong base was used in the raw material components of Comparative Example 3, A-171 was not added to the core layer of Comparative Example 4, ethylene glycol dimethacrylate was not added to the shell layer of Comparative Example 5, a uniform structure was adopted in Comparative Example 6, a single crosslinking agent was used in Comparative Examples 7-9, component e) was not added to the core layer of Comparative Example 10, and the core layer components of Comparative Examples 11-12 were not within the scope of the specification. As can be seen from Table 1, the stone paint formulated from the emulsions prepared by Comparative Examples 1-12 cannot simultaneously achieve properties such as bonding strength, flexibility, water absorption, mechanical stability, room temperature and low temperature water whitening and water whitening recovery.

[0188] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An acrylic emulsion, characterized in that, It has a core-shell structure, in which, (1) The core layer comprises the following parts by weight of raw material: Component a): 30.0-50.0 parts of at least one monovinyl aromatic monomer or at least one C1-C4 alkyl ester of methacrylic acid and mixtures thereof; Component b): at least one C2-C of acrylic acid 10 Alkyl esters, 30.0-50.0 parts; Component c): at least one α,β-monoene bond unsaturated C3-C6 monocarboxylic acid, 1.5-3.5 parts; Component d): at least one acrylamide and / or acrylamide derivative, 1.5-3.5 parts; Component e): at least one mono-olefinic unsaturated sulfonic acid and its salt, 0.1-1.0 parts; Component f): at least one organic amine having three carbon-carbon double bonds, 0.5-2.0 parts; Component g): at least one mono-olefinic unsaturated hydrolyzable organosilicon monomer, 0.1-1.0 parts; 2) The shell layer comprises the following parts by weight of raw material: Component a): 2.0-10.0 parts of at least one monovinyl aromatic monomer or at least one C1-C4 alkyl ester of methacrylic acid and mixtures thereof; Component b): at least one C2-C of acrylic acid 10 Alkyl esters, 4.0-12.0 parts; Component c): at least one α,β-monoene bond unsaturated C3-C6 monocarboxylic acid, 1.0-5.0 parts; Component h): at least one polyene-bonded unsaturated crosslinked monomer, 0.05-0.15 parts.

2. The acrylate emulsion according to claim 1, characterized in that, The core layer comprises the following raw materials in parts by weight: component a) is 35.0-45.0 parts, component b) is 35.0-45.0 parts; component c) is 1.5-3.0 parts, component d) is 1.5-3.0 parts, component e) is 0.2-0.8 parts, component f) is 0.8-1.6 parts, and component g) is 0.3-0.8 parts; The shell layer comprises the following raw materials in parts by weight: component a) is 4.0-8.0 parts, component b) is 5.0-10.0 parts, component c) is 1.5-3.5 parts, and component h) is 0.05-0.1 parts.

3. The acrylate emulsion according to claim 1 or 2, characterized in that, The structural formula of the organic amine with three carbon-carbon double bonds in component f) is as follows: in: R1 and R2 may be the same or different, but at least one of them is H; Optionally, R1 and R2 independently include H, and at least one of a straight-chain, branched, or cyclic saturated or unsaturated group comprising 1 to 20 carbon atoms, substituted with one or more alkoxy carbonyl groups, wherein the alkoxy group comprises 1 to 10 carbon atoms.

4. The acrylate emulsion according to claim 1 or 2, characterized in that, The monovinyl aromatic monomer in component a) includes one or more of styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, and 4-n-decylstyrene; optionally, it is styrene. And / or, the C1-C4 alkyl ester of methacrylic acid in component a) includes one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate; optionally, it is methyl methacrylate.

5. The acrylate emulsion according to claim 1 or 2, characterized in that, The C2-C of acrylic acid in component b) 10 Alkyl esters include one or more of ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, and isooctyl acrylate; optionally, they are n-butyl acrylate or isooctyl acrylate. And / or, the α,β-monoolefinic unsaturated C3-C6 monocarboxylic acid in component c) includes one or more of acrylic acid, methacrylic acid, butenoic acid, 2-ethylacrylic acid, 2-propylacrylic acid, 2-acryloyloxyacetic acid, and 2-methacryloyloxyacetic acid; optionally, it is acrylic acid or methacrylic acid; And / or, the acrylamide and / or acrylamide derivative in component d) include one or more of acrylamide, methacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, and N-butylacrylamide; optionally, it is acrylamide or methacrylamide; And / or, the polyene unsaturated cross-linking monomer of component h) includes one or more of allyl methacrylate, diallyl phthalate, ethylene glycol dimethacrylate, butanediol dimethacrylate, and 1,6-hexanediol diacrylate; optionally, it is ethylene glycol dimethacrylate.

6. The acrylate emulsion according to claim 1 or 2, characterized in that, The mono-olefinic unsaturated sulfonic acids and their salts in component e) include vinyl sulfonic acid, allyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and one or more of their salts, optionally their sodium salts. Optionally, the mono-olefinic unsaturated sulfonic acid and its salt in component e) includes one or more of styrene sulfonic acid and its salt, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and its salt, and optionally their sodium salts.

7. The acrylate emulsion according to claim 1 or 2, characterized in that, The monoolefinic unsaturated hydrolyzable organosilicon monomers in component g) include one or more of vinyltrialkoxysilane, alkylvinyldialkoxysilane and methacryloxyalkyltrialkoxysilane. Optionally, the monoolefinically unsaturated hydrolyzable organosilicon monomer in component g) includes one or more of vinyltrimethoxysilane, methylvinyldialkoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane, and may further be methacryloxypropyltrimethoxysilane.

8. A method for preparing an acrylic emulsion according to any one of claims 1-7, characterized in that, Includes the following steps: S1, prepare core layer preemulsion A, shell layer preemulsion B, base liquid C containing polymerization inhibitor, core layer initiator solution and shell layer initiator solution respectively; S2, add core layer pre-emulsion A and core layer initiator solution to the base liquid C, and react to obtain core layer reactants; S3, add shell pre-emulsion B and shell initiator solution to the core reactant, and react to obtain a core-shell structured polymer. After the reaction is completed, adjust the pH and discharge the material to obtain the acrylate emulsion.

9. The method for preparing the acrylate emulsion according to claim 8, characterized in that, Based on the total mass of the core layer preemulsion A and the shell layer preemulsion B, the amount of core layer preemulsion A accounts for 70%-90%.

10. The application of an acrylic emulsion according to any one of claims 1-7 or an acrylic emulsion prepared by the preparation method according to claim 8 or 9 in architectural coatings; Optionally, the architectural coating includes at least one of stone-like paint, exterior wall emulsion, and interior wall paint.

Images