Amino-modified quartz sand, reactive stone paint, and preparation method and application thereof

Abstract

The application provides amino-modified quartz sand, a reactive stone paint and a preparation method and application. The amino-modified quartz sand is urea-modified quartz sand. The reactive stone paint comprises the following components in parts by weight: 12-16 parts of epoxy-modified acrylic emulsion, 8-12 parts of a binder and 65-70 parts of the amino-modified quartz sand. The active quartz sand in the reactive stone paint participates in film-forming reaction, on the basis of emulsion cross-linking and film-forming, promotes the reaction between the quartz sand and the polymer, improves the coating strength of the quartz sand and the polymer, increases the chemical cross-linking density of the stone paint system, and further improves the film-forming quality of the stone paint.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building coatings, in particular to an amino-modified quartz sand, a reaction-type real stone paint, and a preparation method and application thereof. BACKGROUND

[0002] At present, real stone paint is mainly formed by physical film-forming, relying on the mutual penetration and entanglement of polymer molecular chains to form a continuous and uniform coating film. The molecular chains do not undergo crosslinking and curing reactions before and after film formation, and do not form a three-dimensional macromolecular network structure. Therefore, after the real stone paint is immersed in water, it is quickly absorbed and swells due to the influence of hydrophilic substances such as emulsifiers, which destroys the coating film formed by molecular chain entanglement, and the real stone paint loses its resistance strength and adhesion. At the same time, the physical film-forming paint film is not dense enough, has weak environmental resistance, and has adverse effects on the weather resistance, stain resistance, and other properties of the coating, losing its protective and decorative functions for buildings.

[0003] Real stone paint is a synthetic resin prepared by emulsion polymerization, which binds and forms film of each component in the paint, forming a thin film and firmly adhering to the base. The emulsion is an oil-in-water emulsion-like particle formed by wrapping solid polymer particles with an emulsifier, stably dispersed in water. During film formation, the dispersed medium volatilizes, and under the action of capillary force and surface tension, the emulsion is tightly packed and deformed, the particle shell is broken, the interface between particles gradually disappears, the polymer molecular chains penetrate and entangle each other, and a continuous and uniform coating film is formed. Since the emulsion polymer is a linear thermoplastic polymer, after drying and film formation, the coating film will become soft when heated and hard when cooled, so it is inevitable to have problems such as stain resistance, water resistance, and weather resistance.

[0004] CN115558365A discloses a self-film-forming high-strength rock flake paint and a preparation method thereof. The self-film-forming real stone paint emulsion used has a core-shell structure of acrylate emulsion, forming a solid shell layer skeleton and a high crosslinking degree structure, improving the stability, adhesion strength, and rain mark resistance of the coating.

[0005] CN114292547A discloses a thick paste type pull flower multi-color two-in-one coating and a preparation method thereof. The self-crosslinking silicone-acrylate emulsion with a core-shell structure is used in combination with a self-crosslinking acrylate emulsion to form a coating with excellent physical and chemical properties such as water resistance, weather resistance, and stain resistance, ensuring a service life of more than 10 years.

[0006] CN112010589A discloses a sand bag sand multi-color paint and its preparation method and application, which utilizes the crosslinking of the ketone carbonyl introduced by the multi-color base emulsion containing double ketone acrylamide in the sand color particle base with the hydrazine compound in the prilling solution, and the crosslinking of the ketone carbonyl introduced by the real stone paint emulsion containing double ketone acrylamide in the real stone paint with the hydrazine compound in the prilling solution, and forms a three-dimensional network structure, thereby significantly enhancing the film strength of the sand bag sand multi-color paint.

[0007] The above self-crosslinking emulsion relies on the reaction active groups on the polymer molecules to occur crosslinking and curing reaction during film formation, in order to maintain the emulsion from crosslinking and curing at room temperature, the reaction activity of the polymer is often reduced. Therefore, the pure self-crosslinking emulsion can only improve the film performance to a certain extent, and cannot completely solve the film defects.

[0008] In summary, the existing real stone paint mainly relies on the film forming aid to deform the latex particles with high film forming temperature, and the molecular chains diffuse and penetrate each other, so as to be intertwined, coalesce, and belong to a physical film forming mode, the film forming effect is poor, the environmental resistance is weak, and the real stone paint has poor water resistance, weather resistance and stain resistance; the real stone paint prepared by using the self-crosslinking emulsion can only improve the film forming performance to a certain extent due to the low reaction activity, and cannot completely avoid the film defects.

[0009] Therefore, it is urgent to develop a real stone paint which relies on active quartz sand in the real stone paint to participate in the film forming reaction, promotes the reaction between the quartz sand and the polymer on the basis of the emulsion crosslinking and film forming, improves the coating strength of the quartz sand and the polymer, increases the chemical crosslinking density of the real stone paint system, and further improves the film forming quality of the real stone paint, so as to solve a series of problems existing in the real stone paint.

[0010] Therefore, the present application is proposed. SUMMARY

[0011] One of the purposes of the present application is to provide an amino modified quartz sand. The amino modified quartz sand is a urea modified quartz sand. The present application modifies the quartz sand by using urea, and the modified quartz sand can greatly improve the surface physical characteristics and chemical properties, and expand the specific surface area of the quartz sand.

[0012] The second purpose of the present application is to provide a preparation method of the amino modified quartz sand, which comprises the following steps: mixing the quartz sand and an oxidizing agent, and reacting to obtain oxidized quartz sand; mixing the oxidized quartz sand and urea, and reacting to obtain the amino modified quartz sand.

[0013] The third object of the present application is to provide an application of the amino-modified quartz sand in preparing the real stone paint.

[0014] The fourth object of the present application is to provide a reactive real stone paint, which comprises the following components in parts by weight: 12-16 parts of epoxy-modified acrylic emulsion, 8-12 parts of binder, and 65-70 parts of the amino-modified quartz sand.

[0015] The fifth object of the present application is to provide a preparation method of the reactive real stone paint, which comprises the following steps: mixing the epoxy-modified acrylic emulsion, the binder and the amino-modified quartz sand, and reacting to obtain the reactive real stone paint.

[0016] In order to achieve the above objects of the present application, the following technical solutions are adopted:

[0017] In the first aspect, the present application provides an amino-modified quartz sand, which is a urea-modified quartz sand.

[0018] The main component of the quartz sand is SiO2, which has high density, stable chemical properties and rich color, and is widely used in sand wall coatings such as real stone paint; however, due to the smooth surface and small specific surface area of the ordinary quartz sand, after mixing the emulsion with the quartz sand, the latex particles are continuously extruded into a film during the film-forming process, and the emulsion gradually changes from hydrophilic to hydrophobic, and the hydrophilic quartz sand surface changes from spreading to wetting, and the hydrophobicity of the resin is incompatible with the hydrophilic surface of the quartz sand, which makes the real stone paint resin and sand not firmly wrapped, and affects the film-forming quality of the real stone paint.

[0019] Therefore, the present application modifies the quartz sand with urea, which not only greatly improves the surface physical characteristics and chemical properties of the quartz sand, but also increases the specific surface area of the quartz sand, and makes the surface of the quartz sand loaded with amino active groups, which can react with the epoxy groups in the emulsion to increase the crosslinking density of the paint film, thereby further improving the film-forming quality of the real stone paint.

[0020] Preferably, the raw materials for preparing the amino-modified quartz sand comprise: quartz sand, oxidizing agent and urea.

[0021] Preferably, the mass ratio of the quartz sand, the oxidizing agent and the urea is (0.8-1.2):(0.8-1.2):(1.2-1.5);

[0022] For example, the first "0.8-1.2" can be 0.8, 0.9, 1, 1.1, 1.2, etc.

[0023] For example, the second "0.8-1.2" can be 0.8, 0.9, 1, 1.1, 1.2, etc.

[0024] For example, the "1.2-1.5" can be 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, etc.

[0025] Preferably, the oxidizing agent comprises concentrated nitric acid and / or concentrated sulfuric acid, preferably a mixture of concentrated nitric acid and concentrated sulfuric acid.

[0026] Preferably, the mass ratio of the concentrated nitric acid and the concentrated sulfuric acid is 1:(0.5-2), for example, it can be 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, etc.

[0027] In a second aspect, the present application provides a preparation method of the amino-modified quartz sand according to the first aspect, and the preparation method comprises the following steps:

[0028] Mixing the quartz sand and the oxidizing agent to perform a reaction to obtain oxidized quartz sand;

[0029] Mixing the oxidized quartz sand and the urea to perform a reaction to obtain the amino-modified quartz sand.

[0030] Preferably, the step of mixing the quartz sand and the oxidizing agent is specifically: adding the oxidizing agent into the quartz sand in a stirring state in a spraying manner to complete the mixing.

[0031] Preferably, the spraying speed is 50-100 mL / min, for example, it can be 50 mL / min, 60 mL / min, 70 mL / min, 80 mL / min, 90 mL / min, 100 mL / min, etc.

[0032] Preferably, the stirring speed of the quartz sand is 300-400 r / min, for example, it can be 300 r / min, 320 r / min, 340 r / min, 360 r / min, 380 r / min, 400 r / min, etc.

[0033] Preferably, the reaction time of the quartz sand and the oxidizing agent is 20-40 min, for example, it can be 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min, 40 min, etc.

[0034] Preferably, after obtaining the oxidized quartz sand, the oxidized quartz sand needs to be cleaned and dried.

[0035] Preferably, the cleaning of the oxidized quartz sand is cleaning with water until the pH of the cleaning liquid after cleaning is 6.8-7.2, for example, it can be 6.8, 6.9, 7.0, 7.1, 7.2, etc.

[0036] Preferably, the drying temperature of the oxidized quartz sand is 100-110°C, for example, it can be 100°C, 102°C, 104°C, 106°C, 108°C, 110°C, etc., and the drying time is 2-4 h, for example, it can be 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h, 4 h, etc.

[0037] Preferably, the step of mixing the oxidized quartz sand and urea is specifically adding urea into the stirring oxidized quartz sand to complete the mixing.

[0038] Preferably, the stirring speed of the oxidized quartz sand is 300-500 r / min, for example, it can be 300 r / min, 350 r / min, 400 r / min, 450 r / min, 500 r / min, etc.

[0039] Preferably, the reaction temperature of the oxidized quartz sand and urea is 55-65°C, for example, it can be 55°C, 56°C, 58°C, 60°C, 62°C, 64°C, 65°C, etc., and the reaction time is 1-3 h, for example, it can be 1 h, 1.2 h, 1.4 h, 1.6 h, 1.8 h, 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3 h, etc.

[0040] Preferably, after obtaining the amino-modified quartz sand, the amino-modified quartz sand needs to be cleaned and dried.

[0041] Preferably, the cleaning of the amino-modified quartz is cleaning with water until the pH of the cleaning liquid after cleaning is 6.8-7.2, for example, it can be 6.8, 6.9, 7.0, 7.1, 7.2, etc.

[0042] Preferably, the temperature for drying the amino-modified quartz is 100-110℃, for example, it can be 100℃, 102℃, 104℃, 106℃, 108℃, 110℃, etc., and the drying time is 2-4h, for example, it can be 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, etc.

[0043] As a preferred technical solution of the present application, the preparation method of the amino-modified quartz sand for preparing the real stone paint specifically comprises the following steps:

[0044] (a) The quartz sand is placed in a stirring device and stirred at a speed of 300-400r / min, and in the process of stirring, a mixed solution of concentrated nitric acid and concentrated sulfuric acid is sprayed into the stirring device at a speed of 50-100mL / min, and mixed for 20-40min to obtain oxidized quartz sand (at this time, the surface of the quartz sand is fully oxidized to form silicon hydroxyl groups);

[0045] (b) The oxidized quartz sand is placed in a stirring device and stirred at a speed of 300-500r / min, and in the process of stirring, urea is added and reacted at 55-65℃ for 1-3h to obtain the amino-modified quartz sand.

[0046] In a third aspect, the present application provides a use of the amino-modified quartz sand according to the first aspect in the preparation of real stone paint.

[0047] Preferably, the emulsion of the raw material for preparing the real stone paint is an emulsion containing an epoxy group.

[0048] In a fourth aspect, the present application provides a reactive real stone paint, which comprises the following components in parts by weight:

[0049] Epoxy-modified acrylic emulsion 12-16 parts, binder 8-12 parts, amino-modified quartz sand according to the first aspect 65-70 parts.

[0050] Preferably, the raw material for preparing the epoxy-modified acrylic emulsion comprises the following components: tung oil acid, epoxy resin, catalyst, alcohol ether and acrylic monomer.

[0051] By introducing epoxy groups into the polyacrylate molecular chain segments and using compounds containing amino or carboxyl groups as crosslinking agents to carry out crosslinking reactions, self-crosslinking polyacrylate emulsions are obtained. The epoxy groups in waterborne epoxy acrylate resins can react with compounds containing active hydrogen side groups (such as hydroxyl, amino, or other active hydrogen side groups). When waterborne epoxy acrylate resin is mixed with reactive quartz sand, at room temperature, due to the barrier effect of the emulsifier, the epoxy groups have low reactivity with the amino active hydrogen in the quartz sand and can coexist stably. During film formation, as water evaporates and the latex particles deform, epoxy groups are released and crosslink with the active groups on the surface of the quartz sand, increasing the coating strength between the quartz sand and the polymer, increasing the crosslinking density of the polymer, and solving the coating defects caused by poor film formation in stone-like paints.

[0052] Preferably, the mass ratio of tung oil acid, epoxy resin, catalyst, alcohol ether, and acrylic monomer is (1-1.2):(1.5-2):(0.1-0.3):(6-10):(1.5-1.8).

[0053] Among them, "1 to 1.2" can be, for example, 1.02, 1.05, 1.08, 1.1, 1.12, 1.15, 1.18, 1.2, etc.;

[0054] Among them, "1.5~2" can be, for example, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2, etc.;

[0055] Among them, "0.1~0.3" can be, for example, 0.1, 0.15, 0.2, 0.25, 0.3, etc.;

[0056] Among them, "6 to 10" can be, for example, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, etc.;

[0057] Among them, "1.5 to 1.8" can be, for example, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, etc.

[0058] Preferably, the epoxy resin is selected from E-20 and / or E-44.

[0059] Preferably, the catalyst is tetrabutylammonium bromide.

[0060] Preferably, the alcohol ether is selected from ethylene glycol butyl ether and / or propylene glycol methyl ether.

[0061] Preferably, the acrylic monomer is selected from any one or a combination of at least two of acrylic acid, methacrylic acid, styrene, methyl methacrylate, acrylate or N-hydroxymethylacrylamide.

[0062] Preferably, the binder is a silica sol modified by a siloxane coupling agent.

[0063] Preferably, the raw materials for preparing the binder include a silica sol, a siloxane coupling agent, and a small-molecule alcohol compound.

[0064] Preferably, the mass ratio of the silica sol, the siloxane coupling agent, and the small-molecule alcohol compound is (1-1.2):(0.8-1.1):(1.6-1.8).

[0065] For example, "1-1.2" can be 1, 1.02, 1.05, 1.08, 1.1, 1.12, 1.15, 1.18, 1.2, etc.

[0066] For example, "0.8-1.1" can be 0.8, 0.85, 0.9, 0.95, 1, 1.05, 1.1, etc.

[0067] For example, "1.6-1.8" can be 1.6, 1.62, 1.65, 1.7, 1.75, 1.78, 1.8, etc.

[0068] The silica sol is a colloidal solution obtained by uniformly dispersing nano-sized silicon dioxide particles in water or an organic solvent, in which the silanol group has high reactivity and can react with the silicon hydroxyl group on the surface of quartz sand, thereby improving the adhesion between the sand particles in the real stone paint. However, the pure silica sol has too strong reactivity, and the methyl-modified silica sol can reduce the reactivity, increase the steric hindrance between the particles, and improve the stability of the system.

[0069] Preferably, the solid content of the silica sol is 20-40wt%. For example, it can be 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, etc.

[0070] Preferably, the siloxane coupling agent is selected from any one or a combination of at least two of methyl dimethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, tetramethoxy silane, or tetraethoxy silane, preferably methyl trimethoxy silane.

[0071] Preferably, the small-molecule alcohol is selected from C1-C5 linear or branched alkyl alcohol, preferably n-butanol and / or isopropyl alcohol, further preferably a combination of n-butanol and isopropyl alcohol.

[0072] Preferably, the mass ratio of the n-butanol and the isopropyl alcohol is (1-1.2):(5.8-6.2).

[0073] Wherein, "1~1.2" may be 1, 1.02, 1.05, 1.08, 1.1, 1.12, 1.15, 1.18, 1.2, etc. for example;

[0074] Wherein, "5.8~6.2" may be 5.8, 5.9, 6, 6.1, 6.2, etc. for example.

[0075] In a fifth aspect, the present application provides a preparation method of the reaction type real stone paint, which comprises the following steps:

[0076] Mixing the epoxy-modified acrylic emulsion, the binder and the amino-modified quartz sand, and performing a reaction to obtain the reaction type real stone paint.

[0077] Preferably, the reaction temperature is 20~25℃, which may be 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, etc. for example, and the reaction time is 24~48h, which may be 24h, 26h, 28h, 30h, 32h, 36h, 40h, 45h, 48h, etc. for example.

[0078] Preferably, the epoxy-modified acrylic emulsion is prepared by the following method:

[0079] Mixing the tung oil acid, the epoxy resin and the catalyst, and performing an esterification reaction to obtain the unsaturated drying tung oil acid-modified self-drying epoxy ester;

[0080] Mixing the saturated drying tung oil acid-modified self-drying epoxy ester, the alcohol ether and the acrylic monomer, and performing a graft copolymerization reaction to obtain the epoxy-modified acrylic emulsion.

[0081] Preferably, the esterification reaction temperature is 150~250℃, which may be 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, etc. for example.

[0082] Preferably, the esterification reaction ends when the acid value of the system is reduced to below 3mg KOH / g, which may be 3mg KOH / g, 2.9mg KOH / g, 2.8mg KOH / g, 2.7mg KOH / g, 2.6mg KOH / g, 2.5mg KOH / g, etc. for example.

[0083] Preferably, the graft copolymerization reaction temperature is 80~120℃, which may be 80℃, 90℃, 95℃, 100℃, 105℃, 110℃, 120℃, etc. for example, and the graft copolymerization reaction time is 3~5h, which may be 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, etc. for example.

[0084] As a preferred technical scheme of the present application, the epoxy-modified acrylic emulsion is prepared by the following method:

[0085] (A) The tung oil acid is heated to 140-160℃ within 0.5-2h, then the epoxy resin is added, after the epoxy resin is melted, the catalyst is added, then heated to 150-250℃ within 1-2h, and the esterification reaction is carried out under insulation; the acid value of the system is monitored, when the acid value of the system is reduced to below 3mg KOH / g, the system is cooled, and then the alcohol ether solution is added for dilution, to obtain the unsaturated dry tung oil acid-modified self-drying epoxy ester;

[0086] (B) The acrylic monomer is dissolved in the alcohol ether solvent, and is added to the above unsaturated dry tung oil acid-modified self-drying epoxy ester within 0.5-2h at 80-120℃, to carry out the graft copolymerization reaction, after the dropping is completed, the reaction is carried out at 80-120℃ for 3-5h, to obtain the epoxy-modified acrylic emulsion.

[0087] Preferably, the siloxane coupling agent-modified silica sol is prepared by the following method:

[0088] The silica sol and the siloxane coupling agent are mixed to carry out the dehydration-condensation reaction, and then mixed with the small molecule alcohol to obtain the siloxane coupling agent-modified silica sol.

[0089] Preferably, before the mixing, the pH of the silica sol is adjusted to 2.5-3.5, for example, it can be 2.5, 2.6, 2.8, 3, 3.2, 3.5, etc.

[0090] Preferably, the dehydration-condensation reaction is carried out at a temperature of 60-70℃, for example, it can be 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, etc., and the dehydration-condensation reaction is carried out for a time of 80-120min, for example, it can be 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min, 120min, etc.

[0091] Preferably, the step of mixing with the small molecule alcohol is specifically: first, n-butanol is added to the reaction system and stirred for 20-40min, for example, it can be 20min, 25min, 30min, 35min, 40min, etc., then isopropyl alcohol is added to the reaction system and continues to be stirred for 20-40min, for example, it can be 20min, 25min, 30min, 35min, 40min, etc.

[0092] As a preferred technical scheme of the present application, the siloxane coupling agent-modified silica sol is prepared by the following method:

[0093] The pH of the silica sol is adjusted to 2.5-3.5, a siloxane coupling agent is added, and after dehydration-condensation reaction at 60-70℃ for 80-120min, n-butanol is added to the reaction system and stirred for 20-40min, and finally isopropyl alcohol is added to the reaction system and stirred for 20-40min, to obtain the siloxane coupling agent modified silica sol.

[0094] In the present application, the addition of n-butanol and then isopropyl alcohol and stirring can promote the reaction of the silane coupling agent with the hydroxyl groups on the surface of nano-SiO2 in the silica sol, and improve the storage stability of the modified silica sol.

[0095] Preferably, the reactive stone paint comprises the following components by weight fraction:

[0096] The epoxy modified acrylic emulsion is 12-16 parts, the binder is 8-12 parts, the amino modified quartz sand of the first aspect is 65-70 parts, water is 0-10 parts, and the auxiliary agent is 0-5 parts.

[0097] The content of the epoxy modified acrylic emulsion is 12-16 parts, for example, it can be 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, 15.5 parts, 16 parts, etc.

[0098] The content of the binder is 8-12 parts, for example, it can be 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, etc.

[0099] The content of the amino modified quartz sand is 65-70 parts, for example, it can be 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, etc.

[0100] The content of water is 0-10 parts, for example, it can be 0 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.

[0101] The content of the auxiliary agent is 0-5 parts, for example, it can be 0 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.

[0102] Preferably, the auxiliary agent is selected from any one or a combination of at least two of bactericides, cellulose, pH regulators, defoamers, antifreezes, or thickening agents.

[0103] Preferably, the auxiliary agent comprises the following components by weight fraction:

[0104] 0-0.3 parts of bactericide, 0-0.3 parts of cellulose, 0-0.2 parts of pH regulator, 0-0.6 parts of defoaming agent, 0-2 parts of anti-freezing agent, 0-1 parts of thickening agent.

[0105] The content of the bactericide is 0-0.3 parts, for example, 0 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, etc.

[0106] The content of the cellulose is 0-0.3 parts, for example, 0 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, etc.

[0107] The content of the pH regulator is 0-0.2 parts, for example, 0 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.15 parts, 0.18 parts, 0.2 parts, etc.

[0108] The content of the defoaming agent is 0-0.6 parts, for example, 0 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.5 parts, 0.6 parts, etc.

[0109] The content of the anti-freezing agent is 0-2 parts, for example, 0 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, etc.

[0110] The content of the thickening agent is 0-1 parts, for example, 0 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, etc.

[0111] Preferably, the cellulose is hydroxyethyl cellulose ether.

[0112] Preferably, the anti-freezing agent is propylene glycol.

[0113] Preferably, the bactericide is selected from any one or a combination of at least two of MIT, CMIT or BIT.

[0114] Preferably, the pH regulator is selected from alkanolamine and / or ammonia water.

[0115] Preferably, the defoaming agent is selected from silicone-based defoaming agent and / or polymer non-silicone defoaming agent.

[0116] Preferably, the thickening agent is selected from alkali-swellable thickening agent and / or polyurethane thickening agent.

[0117] Compared with the prior art, the present application has the following beneficial effects:

[0118] (1) the application prepares a reactive quartz sand containing amino active hydrogen by modifying the quartz sand, which can react with water-based epoxy acrylic emulsion, improve the binding force of real stone paint resin and sand and the crosslinking density of coating film, and improve the film forming property of real stone paint;

[0119] (2) the modified reactive quartz sand can greatly improve its surface physical characteristics and chemical properties, enlarge the specific surface area of quartz sand, improve the adhesion and film forming of emulsion on the surface, and the compatibility and film forming type of real stone paint system are more excellent;

[0120] (3) the application prepares a reactive real stone paint by using water-based epoxy acrylic emulsion and reactive quartz sand, which can form a three-dimensional network paint film structure during film forming, improve the environmental resistance and resistance of paint film, and solve the film defect of real stone paint;

[0121] (4) on the basis of emulsion crosslinking film forming, the application promotes the reaction between quartz sand and polymer, improves the coating strength of quartz sand and polymer, increases the chemical crosslinking density of real stone paint system, and further improves the film forming quality of real stone paint;

[0122] (5) the application prepares a reactive real stone paint by using water-based epoxy acrylic emulsion and reactive quartz sand, which is not easy to react during storage due to the blocking of emulsifier, and has better stability. DETAILED DESCRIPTION

[0123] Unless otherwise defined, scientific and technical terms used in connection with the application herein shall have the meanings that are commonly understood by those of ordinary skill in the art. Clear indications to the contrary do not follow, the meaning and scope of the terms should be clear; however, in the event that any potentially ambiguous terms are used, then the definitions provided herein prevail over any dictionary or extrinsic definition. In this application, unless indicated otherwise, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-restrictive.

[0124] It should be noted that specific details are set forth in the following description in order to provide a thorough understanding of the application. However, the application can be practiced with multiple embodiments other than those described herein, and it can be apparent to those skilled in the art that the present application can be practiced with or without the specific details set forth in the following description. Therefore, the present application is not limited to the specific embodiments disclosed in the following description.

[0125] The technical solutions of the application will be described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0126] The application is further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to the existing methods or directly purchased from the market.

[0127] The sources of the raw materials in the following preparation examples and examples are shown as follows:

[0128]

[0129]

[0130] Preparation Example 1

[0131] The present preparation example provides an amino-modified quartz sand prepared by the following method:

[0132] (a) An oxidizing mixed solution is prepared by mixing concentrated nitric acid and concentrated sulfuric acid at a mass ratio of 1:1; an appropriate amount of quartz sand is added to a plastic stirring cylinder, the rotating speed is adjusted to 350 r / min, and the oxidizing mixed solution is slowly added to the plastic stirring cylinder in a spraying manner (the spraying speed is 75 mL / min) according to a solid-liquid mass ratio of 1:1 of the quartz sand and the oxidizing mixed solution, and the mixture is reacted for 30 min, so that the surface of the quartz sand is fully oxidized to form silicon hydroxyl groups; the prepared sand is repeatedly washed with distilled water until the pH of the washing liquid is 7, and is dried at 105 ℃ for 3 h to remove the surface moisture, thereby obtaining oxidized quartz sand;

[0133] (b) An appropriate amount of the oxidized quartz sand is added to a plastic stirring cylinder, the rotating speed is adjusted to 400 r / min, and urea is added according to a solid-liquid mass ratio of 1:1.3 of the quartz sand and the urea, and is dried at 60 ℃ for 2 h; after the reaction, the quartz sand is repeatedly washed with distilled water until the pH of the washing liquid is 7, and is dried at 105 ℃ for 3 h to remove the surface moisture, thereby obtaining the amino-modified quartz sand.

[0134] Preparation Example 2

[0135] The present preparation example provides an epoxy-modified acrylic emulsion prepared by the following method:

[0136] (A) 1 part of tung oil acid is added to a four-necked flask, stirring is started and nitrogen protection is performed, the temperature is raised to 150 ℃ within 1 h, then 1.5 parts of epoxy resin E-20 is added, after the epoxy resin is melted, 0.1 part of catalyst tetrabutylammonium bromide is added, then the temperature is raised to 200 ℃ within 1 h, and the esterification reaction is carried out under temperature preservation; the acid value and the viscosity are measured every 0.5 h; when the acid value is reduced to below 3 mg KOH / g, the temperature is immediately lowered, and when the temperature is reduced to 60 ℃, 1.5 parts of ethylene glycol butyl ether and 1.5 parts of propylene glycol methyl ether are dissolved, thereby obtaining an unsaturated dry oil acid-modified self-drying epoxy ester;

[0137] (B) 1.5 parts of MAA acrylic monomer dissolved in 1.5 parts of ethylene glycol butyl ether and 1.5 parts of propylene glycol methyl ether mixed solvent to obtain an acrylic monomer solution; the above acrylic monomer solution was added dropwise into the self-drying epoxy ester with solid content of 60% at 100°C within 1 h to perform graft copolymerization reaction, and after the dropwise addition was completed, the temperature was increased to 100°C for 4 h of incubation to obtain an epoxy-modified acrylic emulsion.

[0138] Preparation Example 3

[0139] The present preparation example provides an epoxy-modified acrylic emulsion prepared by the following method:

[0140] (A) 1.1 parts of tung oil acid was added into a four-necked flask, stirring was started and nitrogen protection was performed, the temperature was increased to 150°C within 1 h, then 1.8 parts of epoxy resin E-44 was added, after the epoxy resin was melted, 1.2 parts of catalyst tetrabutylammonium bromide was added, then the temperature was increased to 200°C within 1 h, and esterification reaction was performed under incubation, the acid value and viscosity were determined every 0.5 h; when the acid value decreased to below 3 mg KOH / g, the temperature was immediately decreased, and when the temperature decreased to 60°C, 2 parts of ethylene glycol butyl ether and 2 parts of propylene glycol methyl ether were added to obtain an unsaturated dry oil acid-modified self-drying epoxy ester dissolved;

[0141] (B) 1.7 parts of St acrylic monomer dissolved in 2 parts of ethylene glycol butyl ether and 2 parts of propylene glycol methyl ether mixed solvent to obtain an acrylic monomer solution; the above acrylic monomer solution was added dropwise into the self-drying epoxy ester with solid content of 60% at 100°C within 1 h to perform graft copolymerization reaction, and after the dropwise addition was completed, the temperature was increased to 100°C for 4 h of incubation to obtain an epoxy-modified acrylic emulsion.

[0142] Preparation Example 4

[0143] The present preparation example provides an epoxy-modified acrylic emulsion prepared by the following method:

[0144] (A) 1.2 parts of tung oil acid was added into a four-necked flask, stirring was started and nitrogen protection was performed, the temperature was increased to 150°C within 1 h, then 1 part of epoxy resin E-20 and 1 part of epoxy resin E-44 were added, after the epoxy resin was melted, 1.3 parts of catalyst tetrabutylammonium bromide was added, then the temperature was increased to 200°C within 1 h, and esterification reaction was performed under incubation, the acid value and viscosity were determined every 0.5 h; when the acid value decreased to below 3 mg KOH / g, the temperature was immediately decreased, and when the temperature decreased to 60°C, 2.5 parts of ethylene glycol butyl ether and 2.5 parts of propylene glycol methyl ether were added to obtain an unsaturated dry oil acid-modified self-drying epoxy ester dissolved;

[0145] (B) 1.8 parts of MMA acrylic monomer and NMA acrylic monomer dissolved in 2.5 parts of ethylene glycol butyl ether and 2.5 parts of propylene glycol methyl ether mixed solvent to obtain an acrylic monomer solution; the acrylic monomer solution is added dropwise into the self-drying epoxy ester with a solid content of 60% above at 100°C within 1 h to perform graft copolymerization reaction, and after the dropwise addition is completed, the temperature is increased to 100°C and the reaction is maintained for 4 h, to obtain an epoxy-modified acrylic emulsion.

[0146] Preparation Example 5

[0147] The present preparation example provides a methyl-modified silica sol prepared by the following method:

[0148] 50 g of silica sol is adjusted to a pH of about 3.0 with a pH adjuster, 45 g of methyltrimethoxysilane is added, and stirring is performed in a 65°C water bath to perform dehydration-condensation reaction, after about 100 min of stirring, 12 g of n-butanol is added and stirring is continued for 30 min, then 74 g of isopropyl alcohol is added and stirring is performed for 30 min, to obtain a modified silica sol solution with a solid content of 30%.

[0149] Preparation Example 6

[0150] The present preparation example provides a methyl-modified silica sol prepared by the following method:

[0151] 50 g of silica sol is adjusted to a pH of about 3.0 with a pH adjuster, 45 g of methyltrimethoxysilane is added, and stirring is performed in a 65°C water bath to perform dehydration-condensation reaction, after about 100 min of stirring, 12 g of n-butanol is added and stirring is continued for 30 min, then 74 g of isopropyl alcohol is added and stirring is performed for 30 min, to obtain a modified silica sol solution with a solid content of 30%.

[0152] Comparative Preparation Example 1

[0153] The present comparative preparation example provides a silane coupling agent-modified quartz sand prepared by the following method:

[0154] Quartz sand is placed in a ball mill and 3-aminopropyl triethoxysilane is added for ball milling at 80°C, the added mass of 3-aminopropyl triethoxysilane is 5% of the added mass of the quartz sand, after the ball milling is completed, the temperature is naturally lowered to room temperature, to obtain the quartz sand.

[0155] Comparative Preparation Example 2

[0156] The present preparation example provides an epoxy-modified acrylic emulsion prepared by the following method:

[0157] Mixing 2.5 parts of ethylene glycol butyl ether and 2.5 parts of propylene glycol methyl ether solvent-dissolved 1.6 parts of MAA acrylic monomer to obtain an acrylic monomer solution; add the acrylic monomer solution dropwise to the ethylene glycol butyl ether solution of the above-mentioned E-20 epoxy resin with a solid content of 60% at 100°C within 1h to carry out graft copolymerization reaction, and after the dropwise addition is completed, the temperature is raised to 100°C and the reaction is maintained for 4h to obtain an epoxy-modified acrylic emulsion.

[0158] Example 1

[0159] The example provides a reactive stone paint, the reactive stone paint comprises the following components by weight fraction:

[0160]

[0161] The auxiliary agent comprises the following components by weight fraction: bactericide 0.2 parts, hydroxyethyl cellulose ether 0.2 parts, pH regulator 0.1 part, defoaming agent 0.2 parts, propylene glycol 1 part, thickening agent 0.3 parts.

[0162] The reactive stone paint is prepared by the following steps:

[0163] Mix the epoxy-modified acrylic emulsion, methyl-modified silica sol, amino-modified quartz sand, water and auxiliary agent, and react at 20°C for 24h to obtain the reactive stone paint.

[0164] Example 2

[0165] The example provides a reactive stone paint, the reactive stone paint comprises the following components by weight fraction:

[0166]

[0167] The auxiliary agent comprises the following components by weight fraction: bactericide 0.2 parts, hydroxyethyl cellulose ether 0.2 parts, pH regulator 0.1 part, defoaming agent 0.2 parts, propylene glycol 1 part, thickening agent 0.3 parts.

[0168] The reactive stone paint is prepared by the following steps:

[0169] Mix the epoxy-modified acrylic emulsion, methyl-modified silica sol, amino-modified quartz sand, water and auxiliary agent, and react at 23°C for 36h to obtain the reactive stone paint.

[0170] Example 3

[0171] The example provides a reactive stone paint, the reactive stone paint comprises the following components by weight fraction:

[0172]

[0173] The auxiliary agent comprises 0.2 parts of bactericide, 0.2 parts of hydroxyethyl cellulose ether, 0.1 parts of pH regulator, 0.2 parts of defoaming agent, 1 part of propylene glycol and 0.3 parts of thickening agent by weight.

[0174] The reactive stone paint is prepared by the following steps:

[0175] The epoxy-modified acrylic emulsion, the methyl-modified silica sol, the amino-modified quartz sand, water and the auxiliary agent are mixed, and the reaction is carried out at 25 DEG C for 48 h to obtain the reactive stone paint.

[0176] Example 4

[0177] The example provides a reactive stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided in preparation example 2 is replaced by the epoxy-modified acrylic emulsion provided in preparation example 3 with the same mass, and the content and preparation method of other components are completely consistent with example 1.

[0178] Example 5

[0179] The example provides a reactive stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided in preparation example 2 is replaced by the epoxy-modified acrylic emulsion provided in preparation example 4 with the same mass, and the content and preparation method of other components are completely consistent with example 1.

[0180] Example 6

[0181] The example provides a reactive stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided in preparation example 2 is replaced by the epoxy-modified acrylic emulsion provided in preparation example 4 with the same mass, and the content and preparation method of other components are completely consistent with example 1.

[0182] Comparative example 1

[0183] The example provides a reactive stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided in preparation example 2 is replaced by the epoxy-modified acrylic emulsion provided in preparation example 4 with the same mass, and the content and preparation method of other components are completely consistent with example 1.

[0184] Comparative example 2

[0185] The example provides a reactive stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided in preparation example 2 is replaced by the epoxy-modified acrylic emulsion provided in preparation example 4 with the same mass, and the content and preparation method of other components are completely consistent with example 1.

[0186] Comparative example 3

[0187] The comparative example provides a real stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided by preparation example 2 is replaced by an unmodified acrylic emulsion, and the content and preparation method of other components are completely consistent with example 1.

[0188] Comparative example 4

[0189] The comparative example provides a real stone paint, which is different from example 1 only in that the epoxy-modified acrylic emulsion provided by preparation example 2 is replaced by an unmodified acrylic emulsion, and the content and preparation method of other components are completely consistent with example 1.

[0190] Comparative example 5

[0191] The comparative example provides a real stone paint, which is different from example 1 only in that the methyl-modified silica sol provided by preparation example 4 is replaced by an unmodified silica sol of the same mass, and the content and preparation method of other components are completely consistent with example 1.

[0192] Test example 1

[0193] Test sample: reactive real stone paint provided by examples 1-6, real stone paint provided by comparative examples 1-5;

[0194] Test method:

[0195] (1) Water resistance: test according to JG / T 24-2018 standard, and observe whether the film is soft by hand; Technical requirements: no blistering, cracking, peeling;

[0196] (2) Oil resistance: after soaking in 120# solvent oil for 12h, observe whether the film has blistering, peeling, cracking and other defects; Technical requirements: no blistering, no peeling, no cracking;

[0197] The test results are shown in Table 1 below:

[0198] Table 1

[0199]

[0200]

[0201] It is found by comparing the comparative example 1, the comparative example 2 and the example 1 that the paint film of the comparative examples is soft after the water resistance test, and the money has no strength, because the real stone paint is affected by the hydrophilic substances such as emulsifier after being immersed in water, and the coating film is quickly absorbed and swelled to destroy the molecular chain winding, and the real stone paint loses the resistance strength and the adhesion. Meanwhile, the oil resistance of the comparative example 1 and the comparative example 2 is unqualified, because the real stone paint is mainly a physical film forming method, and relies on the mutual penetration and winding of the polymer molecular chain to form a continuous and uniform coating film, and the molecular chain does not occur crosslinking and curing chemical reaction before and after film forming, and does not form a three-dimensional macromolecular network structure, and after being immersed in solvent oil, the polymer molecules are re-dissolved, and the film forming performance is lost.

[0202] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A reactive stone paint, characterized by, The reactive stone paint comprises the following components in parts by weight: 12-16 parts of epoxy-modified acrylic emulsion, 8-12 parts of binder, and 65-70 parts of amino-modified quartz sand. The amino-modified quartz sand is urea-modified quartz sand. The amino-modified quartz sand is obtained by the following steps: mixing quartz sand and oxidizing agent, and reacting to obtain oxidized quartz sand; mixing the oxidized quartz sand and urea, and reacting to obtain the amino-modified quartz sand. The raw materials for preparing the epoxy-modified acrylic emulsion include tung oil acid, epoxy resin, catalyst, alcohol ether, and acrylic monomer in a mass ratio of (1-1.2):(1.5-2):(0.1-0.3):(6-10):(1.5-1.8). The epoxy-modified acrylic emulsion is prepared by the following method: The tung oil acid, epoxy resin, and catalyst are mixed and subjected to esterification reaction to obtain unsaturated dry oil acid-modified self-drying epoxy ester; the esterification reaction is carried out at a temperature of 150-250 DEG C, and the esterification reaction is ended when the acid value of the system is reduced to below 3 mg KOH / g; The saturated dry oil acid-modified self-drying epoxy ester, alcohol ether, and acrylic monomer are mixed and subjected to graft copolymerization reaction to obtain the epoxy-modified acrylic emulsion; the graft copolymerization reaction is carried out at a temperature of 80-120 DEG C, and the graft copolymerization reaction is carried out for 3-5 h. The binder is a siloxane coupling agent-modified silica sol; and the raw materials for preparing the binder include silica sol, siloxane coupling agent, and small molecular alcohol compound in a mass ratio of (1-1.2):(0.8-1.1):(1.6-1.8).

2. The reactive stone paint according to claim 1, characterized by, The raw materials for preparing the amino-modified quartz sand include quartz sand, oxidizing agent, and urea.

3. The reactive stone paint according to claim 2, characterized by, The mass ratio of the quartz sand, oxidizing agent, and urea is (0.8-1.2):(0.8-1.2):(1.2-1.5).

4. The reactive stone paint according to claim 2 or 3, characterized by, The oxidizing agent includes concentrated nitric acid and / or concentrated sulfuric acid.

5. The reactive stone paint according to claim 4, characterized by, The oxidizing agent is a mixture of concentrated nitric acid and concentrated sulfuric acid.

6. The reactive stone paint according to claim 4, characterized by, The mass ratio of the concentrated nitric acid and the concentrated sulfuric acid is 1:(0.5-2).

7. The reactive stone paint according to claim 1, characterized by, The step of mixing the quartz sand and the oxidizing agent specifically comprises: adding the oxidizing agent to the quartz sand in a stirring state in a spraying manner to complete the mixing.

8. The reactive stone paint according to claim 7, characterized by, The spraying speed is 50-100 mL / min.

9. The reactive stone paint according to claim 7, characterized by, The stirring speed of the quartz sand is 300-400 r / min.

10. The reactive stone paint according to claim 1, characterized by, The reaction time of the quartz sand and the oxidizing agent is 20-40 min.

11. The reactive stone paint according to claim 1, characterized by, After obtaining the oxidized quartz sand, the oxidized quartz sand needs to be cleaned and dried. 12.The reactive stone paint according to claim 11, characterized by, The cleaning is performed by using water until the pH of the washing liquid after cleaning is 6.8-7.

2.

13. The reactive stone paint according to claim 11, characterized by, The drying temperature is 100-110 DEG C, and the drying time is 2-4 h.

14. The reactive stone paint according to claim 1, characterized by, The step of mixing the oxidized quartz sand and urea specifically comprises: adding urea to the oxidized quartz sand in a stirring state to complete the mixing.

15. The reactive stone paint according to claim 14, characterized by, The stirring speed of the oxidized quartz sand is 300-500 r / min.

16. The reactive stone paint according to claim 1, characterized by, The reaction temperature of the oxidized quartz sand and urea is 55-65 DEG C, and the reaction time is 1-3 h.

17. The reactive stone paint according to claim 1, characterized by, After obtaining the amino-modified quartz sand, the amino-modified quartz sand needs to be cleaned and dried. 18.The reactive stone paint according to claim 17, characterized by, The cleaning is performed by using water until the pH of the washing liquid after cleaning is 6.8-7.

2.

19. The reactive stone paint according to claim 17, characterized by, The drying temperature is 100-110℃, and the drying time is 2-4 h.

20. The reactive stone paint according to claim 1, characterized by, The reaction type true stone paint further comprises: water 0-10 parts.

21. The reactive stone paint according to claim 1, characterized by, The reaction type true stone paint further comprises: auxiliary 0-5 parts. 22.The reactive stone paint according to claim 21, characterized by, The auxiliary is selected from any one or a combination of at least two of bactericides, cellulose, pH regulators, defoamers, antifreezes or thickening agents. 23.The reactive stone paint according to claim 22, characterized by, The auxiliary comprises the following components by weight fraction: bactericides 0-0.3 parts, cellulose 0-0.3 parts, pH regulators 0-0.2 parts, defoamers 0-0.6 parts, antifreezes 0-2 parts, thickening agents 0-1 parts. 24.The reactive stone paint according to claim 22 or 23, characterized in that, The cellulose is hydroxyethyl cellulose ether. 25.The reactive stone paint according to claim 22 or 23, characterized in that, The antifreeze is propylene glycol.

26. The reactive stone paint according to claim 1, characterized by, The epoxy resin is selected from E-20 and / or E-44.

27. The reactive stone paint according to claim 1, characterized by, The catalyst is tetrabutylammonium bromide.

28. The reactive stone paint according to claim 1, characterized by, The alcohol ether is selected from ethylene glycol butyl ether and / or propylene glycol methyl ether.

29. The reactive stone paint according to claim 1, characterized by, The acrylic monomer is selected from acrylic acid, methacrylic acid, styrene, methyl methacrylate, acrylate or N - any one of hydroxymethyl acrylamide, methacrylamide, acrylamide, methacrylamide, acrylamide, methacrylamide, or a combination of at least two of them.

30. The reactive stone paint according to claim 1, characterized by, The solid content of the silica sol is 20-40wt%.

31. The reactive stone paint according to claim 1, characterized by, The siloxane coupling agent is selected from any one or a combination of at least two of methyl dimethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, tetramethoxy silane or tetraethoxy silane. 32.The reactive stone paint according to claim 31, characterized by, The siloxane coupling agent is methyl trimethoxy silane.

33. The reactive stone paint according to claim 1, characterized by, The small molecule alcohol is selected from C1-C5 straight chain or branched chain alkyl alcohol. 34.The reactive stone paint according to claim 33, characterized by, The small molecule alcohol is n-butanol and / or isopropyl alcohol. 35.The reactive stone paint according to claim 34, characterized in that, The small molecule alcohol is a combination of n-butanol and isopropyl alcohol. 36.The reactive stone paint according to claim 35, characterized by, The mass ratio of n-butanol and isopropyl alcohol is (1-1.2):(5.8-6.2).

37. A method of preparing the reactive stone paint according to any one of claims 1 to 36, characterized by, The preparation method comprises the following steps: mixing the epoxy-modified acrylic emulsion, the binder and the amino-modified quartz sand to perform a reaction to obtain the reaction type true stone paint; wherein the epoxy-modified acrylic emulsion is prepared by the following method: mixing tung oil acid, epoxy resin and catalyst to perform esterification reaction to obtain unsaturated dry tung oil acid modified self-drying epoxy ester; the esterification reaction temperature is 150-250℃, and the esterification reaction ends when the acid value of the system is reduced to below 3 mg KOH / g; mixing the saturated dry tung oil acid modified self-drying epoxy ester, alcohol ether and acrylic monomer to perform graft copolymerization reaction to obtain the epoxy-modified acrylic emulsion; the graft copolymerization reaction temperature is 80-120℃, and the graft copolymerization reaction time is 3-5 h.

38. The preparation method of the reactive stone paint according to claim 37, characterized in that, The reaction temperature is 20-25℃, and the reaction time is 24-48 h.

39. The preparation method of the reactive stone paint according to claim 37, characterized in that, Water and / or auxiliary need to be added during the mixing.

40. The preparation method of the reactive stone paint according to claim 37, characterized in that, The siloxane coupling agent modified silica sol is prepared by the following method: mixing the silica sol and the siloxane coupling agent to perform dehydration-condensation reaction; and then mixing with small molecule alcohol to obtain the siloxane coupling agent modified silica sol.

41. The preparation method of the reactive stone paint according to claim 40, characterized in that, Before the mixing, the pH of the silica sol needs to be adjusted to 2.5-3.

5.

42. The preparation method of the reactive stone paint according to claim 40, characterized in that, The dehydration-condensation reaction temperature is 60-70℃, and the dehydration-condensation reaction time is 80-120 min.

43. The preparation method of the reactive stone paint according to claim 40, characterized in that, The step of mixing with small molecule alcohol is specifically: first, adding n-butanol into the reaction system and stirring for 20-40 min, and then adding isopropyl alcohol into the reaction system and continuing to stir for 20-40 min.

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