A hydroxylated acrylic acid dispersion and its preparation method and application

Abstract

The present invention relates to a hydroxy acrylic acid dispersion and a preparation method and application thereof. The raw materials for preparing the hydroxy acrylic acid dispersion include kettle bottom material, a first layer monomer, a second layer monomer and water; the kettle bottom material includes the following components by weight: 5-40 parts of tert-butyl glycidyl carbonate, 0.1-1.5 parts of graphene, 1-10 parts of solvent oil, 0.01-0.5 parts of catalyst, and the first layer monomer and the second layer monomer each independently include an acrylic monomer. The anti-tear primer formed by the hydroxy acrylic acid dispersion of the present invention has excellent adhesion and excellent bonding with a substrate, and the anti-tear primer of the present invention does not need to add coarse sand, has a short curing time, can reinforce the substrate within a shorter curing time, and the formed paint film has excellent tear resistance.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a hydroxy acrylic acid dispersion and a preparation method and application thereof. Background Art

[0002] In the field of architectural coatings, primer, as the first layer of the coating system, plays a role in sealing and resisting salt and alkali for the substrate, preventing the alkali and salt in the substrate from migrating to the surface of the paint film with the volatilization of water, causing the surface of the paint film to bloom. Primer also has important reinforcement properties, which can increase the adhesion between the topcoat and the substrate, ensure the uniform absorption of the topcoat, and make the paint film firmly attached to the wall.

[0003] CN114213592A discloses a real stone paint primer emulsion with good tear resistance and alkali resistance. The raw materials include core layer raw materials, shell layer raw materials, and primer raw materials. The core layer raw materials include the following components in parts by weight: 20-40 parts of water for core layer monomer emulsion, 0.5-4 parts of core emulsifier, 0.5-3 parts of core initiator, 5-6 parts of water for core initiator, 20-50 parts of styrene, 15-35 parts of butyl acrylate, 0.5-3 parts of acrylic acid, 0-0.5 parts of acrylamide, Chain transfer agent 0.5-2 parts; the shell raw material includes the following components by weight: shell monomer emulsion water 25-35 parts, shell emulsifier 1-3 parts, oxidant 0.7-4 parts, oxidant water 4-5 parts, reducing agent 1-3 parts, reducing agent water 15-20 parts, styrene 10-40 parts, methyl methacrylate 5-10 parts, butyl acrylate 25-45 parts, methacrylic acid 1-4 parts, acrylamide 0-0.5 parts, multifunctional crosslinking agent 0.5-3 parts. It solves the problem of poor tear resistance and alkali resistance of primer emulsion used for real stone paint in the related art.

[0004] CN112341875A discloses a transparent primer with super strong water-proof and alkali-proof properties and a preparation method thereof, which contains 50-60% epoxy group-modified acrylic resin emulsion and 0.5-1.0% silicon-containing anti-sticking auxiliary agent. Because the epoxy group-modified acrylic resin emulsion has super strong adhesion and water-proof and alkali-proof properties, the transparent primer disclosed by the invention can play a good shielding role on alkaline substances in new cement wall surfaces and mortar wall surfaces. The transparent primer can be constructed only when the pH value (alkalinity) of the cement base is ≤13 and the moisture content of the base is ≤40%, and the anti-salinity and alkali performance of the transparent primer is not affected, thereby greatly shortening the construction period of the project site; the transparent primer disclosed by the invention can reduce the adhesion of the self-adhesive paper to the primer because of the silicon-containing anti-sticking auxiliary agent, thereby reducing the tearing of the transparent primer film and putty layer by the masking paper, thereby overcoming the defects of the prior art.

[0005] At present, the primer and the substrate are combined together through mechanical connection theory and chemical bond theory. When the paint is applied on the substrate and the adhesion is generated during the drying and curing process, its firmness depends on the properties of the substrate surface and the film-forming material of the primer. However, in actual construction applications, poor adhesion is often caused by a variety of reasons such as loose putty, poor primer adhesion, and short curing time. Especially in some construction processes that require masking tape as a separation seam, poor primer adhesion will cause the paint film to fall off along with the masking tape, which has a great impact on the overall construction effect.

[0006] In summary, it is crucial to develop a primer that has excellent adhesion to the substrate and forms a paint film with excellent tear resistance. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide a hydroxy acrylic dispersion and a preparation method and application thereof. The anti-tear primer for masking paper formed by the hydroxy acrylic dispersion has excellent adhesion and excellent bonding strength with the substrate. Moreover, the anti-tear primer for masking paper of the present invention does not require the addition of coarse sand, has a short curing time, can reinforce the substrate within a shorter curing time, and the formed paint film has excellent tear resistance.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a hydroxy acrylic acid dispersion, wherein the raw materials for preparing the hydroxy acrylic acid dispersion include kettle bottoms, first layer monomers, second layer monomers and water;

[0010] The kettle bottom material comprises the following components in parts by weight:

[0011]

[0012] The first layer monomer and the second layer monomer each independently include an acrylic monomer.

[0013] In the present invention, the carboxylated dispersion is added with graphene in the bottom material of the kettle, and when it is further applied to the primer, the tear resistance and adhesion to the substrate of the primer can be improved. If the graphene is added to the first layer of monomers, the graphene reaction will be insufficient and the effect will be hindered; if the graphene is added to the second layer of monomers, the graphene will adhere to the surface of the molecular chain, affecting the water-transfer dispersion effect. In addition, the graphene of the present invention is added to the bottom material of the kettle according to a specific ratio. If the addition amount is too high, the graphene reaction will be insufficient; if the addition amount is too low, the tear resistance of the coating will be low.

[0014] In the present invention, the weight proportion of the versatile glycidyl carbonate is 5-40 parts, such as 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.

[0015] The weight proportion of the graphene is 0.1-1.5 parts, for example, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, etc.

[0016] The weight proportion of the solvent oil is 1-10 parts, such as 2 parts, 4 parts, 6 parts, 8 parts, etc.

[0017] The weight portion of the catalyst is 0.01-0.5 parts, such as 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, etc.

[0018] Preferably, the graphene comprises carboxylated graphene.

[0019] In the present invention, the graphene is preferably carboxylated graphene because it can react with monomers and be introduced into the resin molecular chain structure, and the resin performance is stable.

[0020] Preferably, the catalyst comprises potassium hydroxide and / or triethylamine.

[0021] Preferably, the first layer monomers further include styrene and an auxiliary agent.

[0022] Preferably, the acrylic monomer includes any one of hydroxyethyl methacrylate, methyl methacrylate or acrylic acid, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of hydroxyethyl methacrylate and methyl methacrylate, a combination of methyl methacrylate and acrylic acid, a combination of hydroxyethyl methacrylate, methyl methacrylate and acrylic acid, and the like.

[0023] Preferably, the auxiliary agent comprises n-dodecyl mercaptan and / or di-tert-amyl hydroperoxide.

[0024] Preferably, the weight proportion of the acrylic monomer is 1-75 parts, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, etc.

[0025] Preferably, the weight proportion of the hydroxyethyl methacrylate is 10-40 parts, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.

[0026] Preferably, the weight proportion of the methyl methacrylate is 5-25 parts, such as 10 parts, 15 parts, 20 parts, etc.

[0027] Preferably, the weight proportion of the acrylic acid is 1-10 parts, such as 2 parts, 4 parts, 6 parts, 8 parts, etc.

[0028] Preferably, the weight proportion of the styrene is 5-15 parts, for example, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.

[0029] Preferably, the weight proportion of the auxiliary agent is 0.1-1.5 parts, for example, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, etc.

[0030] Preferably, the weight portion of n-dodecyl mercaptan is 0.1-1 part, such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, etc.

[0031] Preferably, the weight proportion of the di-tert-amyl hydroperoxide is 0.1-0.5 parts, such as 0.2 parts, 0.3 parts, 0.4 parts, etc.

[0032] As a preferred technical solution, the first layer monomers include the following components in parts by weight:

[0033]

[0034]

[0035] Preferably, the second layer monomer further comprises an auxiliary agent.

[0036] Preferably, the acrylic monomer includes any one of hydroxyethyl methacrylate, n-butyl methacrylate, methyl methacrylate, acrylic acid or isobornyl methacrylate, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of hydroxyethyl methacrylate and n-butyl methacrylate, a combination of methyl methacrylate, acrylic acid and isobornyl methacrylate, a combination of hydroxyethyl methacrylate, n-butyl methacrylate, methyl methacrylate, acrylic acid and isobornyl methacrylate, and the like.

[0037] Preferably, the auxiliary agent comprises n-dodecyl mercaptan and / or di-tert-amyl hydroperoxide.

[0038] Preferably, the weight proportion of the acrylic monomer is 1-70 parts, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, etc.

[0039] Preferably, the weight proportion of the hydroxyethyl methacrylate is 3-15 parts, for example, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.

[0040] Preferably, the weight proportion of the n-butyl methacrylate is 3-15 parts, for example, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.

[0041] Preferably, the weight proportion of the methyl methacrylate is 5-20 parts, for example, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, etc.

[0042] Preferably, the weight proportion of the acrylic acid is 1-10 parts, such as 2 parts, 4 parts, 6 parts, 8 parts, etc.

[0043] Preferably, the weight proportion of the isobornyl methacrylate is 1-10 parts, such as 2 parts, 4 parts, 6 parts, 8 parts, etc.

[0044] Preferably, the weight proportion of the auxiliary agent is 0.1-2 parts, for example, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, etc.

[0045] Preferably, the weight portion of n-dodecyl mercaptan is 0.1-1 part, such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, etc.

[0046] Preferably, the weight proportion of the di-tert-amyl hydroperoxide is 0.1-1 part, such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, etc.

[0047] As a preferred technical solution, the second layer monomers include the following components in parts by weight:

[0048]

[0049] Preferably, the raw materials for preparing the hydroxylated acrylic dispersion further include a neutralizing agent.

[0050] Preferably, the neutralizing agent comprises N,N-dimethylethanolamine.

[0051] Preferably, the weight proportion of the neutralizing agent is 1-10 parts, such as 2 parts, 4 parts, 6 parts, 8 parts, etc.

[0052] Preferably, the weight proportion of the water is 80-200 parts, for example, 100 parts, 120 parts, 140 parts, 60 parts, 180 parts, etc.

[0053] As a preferred technical solution, the raw materials for preparing the hydroxylated acrylic acid dispersion include kettle bottom material, first layer monomer, second layer monomer, water and a neutralizing agent;

[0054] The kettle bottom material comprises the following components in parts by weight:

[0055]

[0056] The first layer monomers include the following components in parts by weight:

[0057]

[0058] The second layer monomers include the following components in parts by weight:

[0059]

[0060] The weight proportion of the water is 80-200 parts;

[0061] The weight proportion of the neutralizing agent is 1-10 parts.

[0062] In a second aspect, the present invention provides a method for preparing the hydroxy acrylic acid dispersion according to the first aspect, the preparation method comprising the following steps:

[0063] Glycidyl tert-carbonate, graphene, solvent oil and a catalyst are mixed and reacted to form a kettle bottom material, and then the kettle bottom material is sequentially mixed with the first layer monomer, the second layer monomer and water to obtain the hydroxy acrylic acid dispersion.

[0064] Preferably, the reaction temperature is 100-120°C, for example, 102°C, 104°C, 106°C, 108°C, 110°C, 112°C, 114°C, 116°C, 118°C, etc.

[0065] Preferably, the reaction time is 3-4 h, such as 3.2 h, 3.4 h, 3.6 h, 3.8 h, etc.

[0066] Preferably, the reaction is followed by a heat preservation operation.

[0067] Preferably, the insulation temperature is 140-160°C, for example, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C, etc.

[0068] Preferably, the insulation time is 10-50 minutes.

[0069] Preferably, the first layer monomer is mixed with the kettle bottom material in a manner including: dropping the first layer monomer into the kettle bottom material.

[0070] Preferably, the dropping time is 2-8 hours, for example 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, etc.

[0071] Preferably, the step of heat preservation is further performed after the dropwise adding.

[0072] Preferably, the insulation time is 0.5-1.5h, for example 0.6h, 0.8h, 1h, 1.2h, 1.4h, etc.

[0073] Preferably, the second layer monomer is mixed with the kettle bottom material in a manner including: dropping the second layer monomer into the kettle bottom material.

[0074] Preferably, the dropping time is 1-3 h, for example, 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, etc.

[0075] Preferably, the dropping further includes heat preservation and cooling operations.

[0076] Preferably, the insulation time is 1-5h, for example, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, etc.

[0077] Preferably, the temperature is lowered to 80-110°C, such as 85°C, 90°C, 95°C, 100°C, 105°C, etc.

[0078] Preferably, after the second layer monomer is mixed with the kettle bottom material and before the water is mixed with the kettle bottom material, a neutralizing agent is added to the kettle bottom material.

[0079] Preferably, after the neutralizing agent is added, the neutralization degree of the system is 85%-110%, such as 90%, 95%, 100%, 105%, etc.

[0080] As a preferred technical solution, the preparation method comprises the following steps:

[0081] (1) adding tert-butyl glycidyl carbonate, graphene, solvent oil and a catalyst to the bottom of a kettle, heating to 100-120° C., reacting for 3-4 hours, then heating to 140-160° C., and keeping the temperature for 10-50 minutes to form the bottom of the kettle;

[0082] (2) mixing hydroxyethyl methacrylate, methyl methacrylate, styrene, acrylic acid, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then adding the mixture dropwise to the bottom of the kettle in step (1) over 2-8 hours, and keeping the mixture warm for 0.5-1.5 hours;

[0083] (3) mixing hydroxyethyl methacrylate, n-butyl methacrylate, methyl methacrylate, acrylic acid, isobornyl methacrylate, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then adding the mixture dropwise to the system of step (2) within 1-3 hours, keeping the mixture warm for 1-5 hours, and then cooling to 80-110° C.;

[0084] (4) adding a neutralizing agent to the system of step (3), controlling the degree of neutralization to be 85%-100%, stirring for 10-50 minutes, and then adding water to obtain the hydroxylated acrylic acid dispersion.

[0085] In a third aspect, a primer for resisting tearing of textured paper is provided, wherein the primer for resisting tearing of textured paper comprises a first component and a second component;

[0086] The first component includes the hydroxylated acrylic acid dispersion described in the first aspect, or the hydroxylated acrylic acid dispersion prepared by the preparation method described in the second aspect, an auxiliary agent, a filler and water;

[0087] The second component includes a curing agent.

[0088] In the present invention, the anti-tear primer of the masking paper is provided with the hydroxy acrylic dispersion, and no coarse sand is required. When applied, it can be cured in a short time to complete the reinforcement of the substrate, and the formed paint film has excellent tear resistance. The primer has excellent adhesion to the substrate.

[0089] Preferably, based on 100% of the total mass of the first component, the mass percentage of the hydroxylated acrylic dispersion is 18%-30%, for example, 20%, 22%, 24%, 26%, 28%, etc.

[0090] In the present invention, in the first component, the mass percentage of the hydroxylated acrylic dispersion is preferably in the range of 18%-30%. Too high an addition amount will result in low hardness of the paint film; too low an addition amount will result in low adhesion of the paint film.

[0091] Preferably, the auxiliary agent includes any one of a dispersant, a wetting agent, a defoamer, a thickener, a stabilizer or a mildewproof agent, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of a dispersant and a wetting agent, a combination of a defoamer, a thickener and a stabilizer, a combination of a dispersant, a wetting agent, a defoamer, a thickener, a stabilizer and a mildewproof agent, etc.

[0092] Preferably, based on the total mass of the first component as 100%, the mass percentage of the auxiliary agent is 0.01%-3.3%, for example, 0.1%, 0.2%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% and the like.

[0093] Preferably, the mass percentage of the dispersant is 0.8%-1.6%, such as 1%, 1.2%, 1.4%, etc.

[0094] Preferably, the dispersant comprises a sodium polyacrylic acid dispersant.

[0095] Preferably, the mass percentage of the wetting agent is 0.01%-0.1%, such as 0.02%, 0.04%, 0.06%, 0.08%, etc.

[0096] Preferably, the wetting agent comprises a non-ionic surfactant.

[0097] Preferably, the mass percentage of the defoaming agent is 0.2%-0.5%, such as 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, etc.

[0098] Preferably, the defoaming agent comprises a metal soap defoaming agent and / or a mineral oil defoaming agent.

[0099] Preferably, the mass percentage of the thickener is 0.3%-0.5%, for example, 0.32%, 0.34%, 0.36%, 0.38%, 0.4%, 0.42%, 0.44%, 0.46%, 0.48% and the like.

[0100] Preferably, the thickener comprises hydroxyethyl cellulose.

[0101] Preferably, the mass percentage of the stabilizer is 0.1%-0.3%, for example, 0.12%, 0.14%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, etc.

[0102] Preferably, the stabilizer comprises a potassium silicate stabilizer, and more preferably a cationic stabilizer.

[0103] Preferably, the mass percentage of the mildew inhibitor is 0.1%-0.3%, for example, 0.12%, 0.14%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, etc.

[0104] Preferably, the mildewcide comprises an anionic mildewcide.

[0105] Preferably, the filler includes any one of titanium dioxide, kaolin or other fillers, or a combination of at least two of them.

[0106] In the present invention, the titanium dioxide can be selected from rutile titanium dioxide, and the kaolin can be selected from 1250 mesh calcined kaolin.

[0107] Preferably, the other fillers include heavy calcium.

[0108] Preferably, based on 100% of the total mass of the first component, the mass percentage of the filler is 1%-35%, for example, 5%, 10%, 15%, 20%, 25%, 30% and the like.

[0109] Preferably, the mass percentage of the titanium dioxide is 1%-5%, such as 2%, 3%, 4%, etc.

[0110] Preferably, the mass percentage of the kaolin is 5%-10%, such as 6%, 7%, 8%, 9%, etc.

[0111] Preferably, the mass percentage of the other fillers is 10%-30%, for example, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28% and the like.

[0112] Preferably, the first component further comprises potassium silicate.

[0113] In the present invention, the potassium silicate is subjected to stabilization treatment.

[0114] In the present invention, the potassium silicate is preferably stabilized potassium silicate because the paint product made from the stabilized potassium silicate has better storage stability.

[0115] Preferably, the mass percentage of the potassium silicate is 1%-5%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.

[0116] As a preferred technical solution, taking the total mass of the first component as 100%, the first component includes the following components in terms of mass percentage:

[0117]

[0118] Preferably, the curing agent comprises an amino curing agent and / or an isocyanate curing agent.

[0119] Preferably, the effective functional group molar mass ratio of the first component to the second component is (0.8-1.2):1, wherein 0.8-1.2 can be 0.9, 1.0, 1.1, etc.

[0120] Compared with the prior art, the present invention has the following beneficial effects:

[0121] (1) The anti-tear primer of masking paper formed by the hydroxy acrylic dispersion of the present invention has excellent adhesion and excellent bonding strength with the substrate.

[0122] (2) The anti-tear primer of the present invention does not need to add coarse sand, has a short curing time, can reinforce the substrate within a shorter curing time, and the formed paint film has excellent tear resistance. DETAILED DESCRIPTION

[0123] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0124] In the present invention, the purchase information of some raw materials in each embodiment is as follows:

[0125] Carboxylated graphene: purchased from Suzhou Kaifa New Materials Co., Ltd., brand BKMK2007;

[0126] Graphene: purchased from Beijing Gaoke New Material Technology Co., Ltd., brand GK-C;

[0127] Solvent oil: 100# solvent oil, purchased from Tiantai Chemical, brand 100#;

[0128] Dispersant: polyacrylic acid sodium salt dispersant, purchased from BASF, brand 4320;

[0129] Wetting agent: nonionic surfactant, purchased from Wellman, brand 7100;

[0130] Defoamer: Metal soap defoamer, purchased from Nopco, brand NXZ;

[0131] Defoamer: mineral oil defoamer, purchased from Wellman, brand 310;

[0132] Thickener: Hydroxyethyl cellulose, purchased from Lotte, South Korea, brand name B30K;

[0133] Stabilizer: Potassium silicate stabilizer, purchased from Clariant, brand name SPS;

[0134] Antifungal agent: Silver ion antifungal agent, purchased from Thor, brand name AGT 2;

[0135] Heavy calcium: purchased from Jiangxi Guangyuan Chemical, brand 116;

[0136] Potassium silicate: Stabilized potassium silicate, purchased from Aorun Chemical, brand K100;

[0137] Curing agent: amino curing agent, purchased from Changxian New Materials, brand DP-03;

[0138] Curing agent: isocyanate curing agent, purchased from Bayer, brand name XP2655.

[0139] Examples 1-5

[0140] Examples 1-5 provide a hydroxylated acrylic dispersion, the formula of which is shown in Table 1.

[0141] Table 1

[0142]

[0143]

[0144] All components in Table 1 are in parts by weight.

[0145] The hydroxylated acrylic acid dispersions described in Examples 1-3 are prepared by the following preparation method, which comprises the following steps:

[0146] (1) adding tert-butyl glycidyl carbonate, graphene, solvent oil and a catalyst to the bottom of a kettle, heating to 110° C., reacting for 3.5 hours, then heating to 150° C., and keeping the temperature for 30 minutes to form the bottom of the kettle;

[0147] (2) mixing hydroxyethyl methacrylate, methyl methacrylate, styrene, acrylic acid, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then adding the mixture dropwise to the bottom of the kettle in step (1) over 6 hours, and keeping the mixture warm for 1 hour;

[0148] (3) Mix hydroxyethyl methacrylate, n-butyl methacrylate, methyl methacrylate, acrylic acid, isobornyl methacrylate, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then drop the mixture into the system of step (2) within 2 hours, keep the mixture warm for 3 hours, and then cool it to 100° C.;

[0149] (4) adding a neutralizing agent to the system of step (3), controlling the neutralization degree to 90%, stirring for 30 minutes, and then adding water to obtain the hydroxylated acrylic acid dispersion.

[0150] The hydroxylated acrylic acid dispersion described in Example 4 is prepared by the following preparation method, which comprises the following steps:

[0151] (1) adding tert-butyl glycidyl carbonate, graphene, solvent oil and a catalyst to the bottom of a kettle, heating to 100° C., reacting for 4 hours, then heating to 140° C., and keeping the temperature for 50 minutes to form the bottom of the kettle;

[0152] (2) mixing hydroxyethyl methacrylate, methyl methacrylate, styrene, acrylic acid, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then adding the mixture dropwise to the bottom of the kettle in step (1) over 8 hours, and keeping the mixture warm for 0.5 hours;

[0153] (3) Mix hydroxyethyl methacrylate, n-butyl methacrylate, methyl methacrylate, acrylic acid, isobornyl methacrylate, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then dropwise add the mixture to the system of step (2) within 1 hour, keep the temperature for 5 hours, and then cool to 110° C.;

[0154] (4) adding a neutralizing agent to the system of step (3), controlling the degree of neutralization to 85%, stirring for 10 minutes, and then adding water to obtain the hydroxylated acrylic acid dispersion.

[0155] The hydroxylated acrylic acid dispersion described in Example 5 is prepared by the following preparation method, which comprises the following steps:

[0156] (1) adding tert-butyl glycidyl carbonate, graphene, solvent oil and a catalyst to the bottom of a kettle, heating to 120° C., reacting for 3 h, then heating to 160° C., and keeping the temperature for 10 min to form the bottom material of the kettle;

[0157] (2) mixing hydroxyethyl methacrylate, methyl methacrylate, styrene, acrylic acid, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then adding the mixture dropwise to the bottom of the kettle in step (1) over 2 hours, and keeping the mixture warm for 1.5 hours;

[0158] (3) Mix hydroxyethyl methacrylate, n-butyl methacrylate, methyl methacrylate, acrylic acid, isobornyl methacrylate, n-dodecyl mercaptan and di-tert-amyl hydroperoxide, and then add the mixture dropwise to the system of step (2) within 3 hours, keep the temperature for 1 hour, and then cool to 80° C.;

[0159] (4) adding a neutralizing agent to the system of step (3), controlling the neutralization degree to 100%, stirring for 50 minutes, and then adding water to obtain the hydroxylated acrylic acid dispersion.

[0160] Example 6

[0161] The difference between this embodiment and embodiment 2 is that the carboxylated graphene is replaced with graphene of equal mass, and the rest is the same as embodiment 2.

[0162] Comparative Example 1

[0163] The difference between this comparative example and Example 2 is that the kettle bottom material does not include carboxylated graphene and catalyst, and the rest is the same as Example 2.

[0164] Comparative Example 2

[0165] The difference between this comparative example and Example 2 is that the kettle bottom material does not include carboxylated graphene, the first layer monomer includes 0.1 parts of carboxylated graphene, and the rest is the same as Example 1.

[0166] Comparative Example 3

[0167] The difference between this comparative example and Example 2 is that the kettle bottom material does not include carboxylated graphene, the second layer monomer includes 0.1 parts of carboxylated graphene, and the rest is the same as Example 1.

[0168] Application Examples 1-5

[0169] Application Example 1-5 provides an anti-tear primer for masking paper. The formula of the first component in the anti-tear primer for masking paper is shown in Table 2.

[0170] Table 2

[0171]

[0172] The contents of the first component in Table 2 are in percentage by mass, with the unit being "%".

[0173] Application Example 1: The effective functional group molar mass ratio of the first component to the second component is 0.8:1, the second component is an amino curing agent, and the hydroxylated acrylic dispersion is the hydroxylated acrylic dispersion described in Example 1;

[0174] Application Example 2: The effective functional group molar mass ratio of the first component to the second component is 1:1, the second component is an amino curing agent and an isocyanate curing agent of equal mass, and the hydroxylated acrylic dispersion is the hydroxylated acrylic dispersion described in Example 2;

[0175] Application Example 3: The mass ratio of the first component to the second component is 1.2:1, the second component is an isocyanate curing agent, and the hydroxylated acrylic dispersion is the hydroxylated acrylic dispersion described in Example 3.

[0176] Application Example 6

[0177] The difference between this application example and application example 2 is that the hydroxylated acrylic dispersion described in example 2 is replaced with an equal mass of the hydroxylated acrylic dispersion described in example 6, and the rest is the same as application example 2.

[0178] Application Example 7

[0179] The difference between this application example and application example 2 is that potassium silicate is not included, and the rest is the same as application example 2.

[0180] Application Example 8

[0181] The difference between this application example and application example 2 is that the potassium silicate is replaced with potassium silicate that has not been stabilized, and the rest is the same as application example 2.

[0182] Application Comparative Examples 1-3

[0183] The difference between Application Examples 1-3 and Application Example 2 is that the hydroxylated acrylic acid dispersion described in Example 2 is replaced with an equal mass of the hydroxylated acrylic acid dispersion described in Comparative Examples 1-3, and the rest is the same as Application Example 2.

[0184] Application Comparative Example 4

[0185] The difference between this comparative example and Application Example 2 is that the raw materials of the hydroxy acrylic dispersion are directly mixed with the raw materials of the first component of the anti-tear primer to form the anti-tear primer, and the rest is the same as Application Example 2.

[0186] Performance Testing

[0187] The anti-tear primers of application examples 1-8 and comparative application examples 1-4 were tested as follows:

[0188] (1) Adhesion: Roll a layer of primer on the putty layer, wait for it to dry completely, and then test it with masking paper. If there is no paint film peeling, the adhesion is rated as 0; if there is a small amount of paint film peeling (less than 5% of the test area), the adhesion is rated as 1; if the paint film peeling area is greater than 5% and less than 15%, the adhesion is rated as 2; if the paint film peeling area is greater than 15% and less than 35%, the adhesion is rated as 3; if the paint film peeling area is greater than 35% and less than 65%, the adhesion is rated as 4; if the paint film peeling area is greater than 65%, the adhesion is rated as 5.

[0189] The test results are summarized in Table 3.

[0190] Table 3

[0191]

[0192]

[0193] Analysis of the data in Table 3 shows that the anti-tear primer formed by the hydroxy acrylic dispersion of the present invention has excellent adhesion and excellent bonding strength with the substrate, and the paint film formed by the anti-tear primer does not require the addition of coarse sand, has a short curing time, and has excellent tear resistance. In the present invention, the anti-tear primer formed by the hydroxy acrylic dispersion has an adhesion of more than level 1 with the substrate.

[0194] Analysis of application examples 1-3 and application example 2 shows that the performance of application examples 1-3 is not as good as that of application example 2, which proves that the hydroxyl acrylic acid dispersion formed by setting graphene in the bottom material of the kettle has better performance.

[0195] Analysis of Application Example 4 and Application Example 2 shows that the performance of Application Example 4 is not as good as that of Application Example 2, which proves that the performance of the anti-tear primer with hydroxyl acrylic dispersion is better.

[0196] Analysis of Application Example 6 and Application Example 2 shows that the performance of Application Example 6 is not as good as that of Application Example 2, which proves that the hydroxyl acrylic acid dispersion formed by the graphene, preferably carboxylated graphene, has better performance.

[0197] Analysis of Application Examples 7-8 and Application Example 2 shows that the performance of Application Examples 7-8 is not as good as that of Application Example 2, which proves that the addition of potassium silicate to the anti-tear primer, especially the stabilized potassium silicate, has better performance.

[0198] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A hydroxylated acrylic dispersion, It is characterized in that The raw materials for preparing the hydroxy acrylic acid dispersion include kettle bottom material, first layer monomer, second layer monomer and water; The kettle bottom material comprises the following components in parts by weight: The first layer monomers include the following components in parts by weight: The second layer monomers include the following components in parts by weight: The hydroxylated acrylic acid dispersion is prepared by the following method, which comprises the following steps: The tert-butyl glycidyl carbonate, carboxylated graphene, solvent oil and a catalyst are mixed, reacted at 100-120° C., and kept warm at 140-160° C. to form a kettle bottom material, and the kettle bottom material is sequentially mixed with the first layer monomer, the second layer monomer and water to obtain the hydroxy acrylic acid dispersion; The method of mixing the first layer monomer with the kettle bottom material comprises: dropping the first layer monomer into the kettle bottom material; and further comprising heat preservation after the dropping; The method of mixing the second layer monomer with the kettle bottom material comprises: dropping the second layer monomer into the kettle bottom material; and sequentially including heat preservation and temperature reduction operations after the dropping.

2. The hydroxy acrylic dispersion according to claim 1, It is characterized in that The catalyst includes potassium hydroxide and / or triethylamine.

3. The hydroxy acrylic dispersion according to claim 1, It is characterized in that The raw materials for preparing the hydroxylated acrylic acid dispersion also include a neutralizing agent.

4. The hydroxy acrylic dispersion according to claim 3, It is characterized in that The neutralizing agent includes N,N-dimethylethanolamine.

5. The hydroxy acrylic dispersion according to claim 3, It is characterized in that The weight proportion of the neutralizing agent is 1-10 parts.

6. The hydroxy acrylic dispersion according to claim 1, It is characterized in that The weight proportion of the water is 80-200 parts.

7. A method for preparing the hydroxy acrylic acid dispersion according to any one of claims 1 to 6, It is characterized in that The preparation method comprises the following steps: The tert-butyl glycidyl carbonate, carboxylated graphene, solvent oil and a catalyst are mixed, reacted at 100-120° C., and kept warm at 140-160° C. to form a kettle bottom material, and the kettle bottom material is sequentially mixed with the first layer monomer, the second layer monomer and water to obtain the hydroxy acrylic acid dispersion; The method of mixing the first layer monomer with the kettle bottom material comprises: dropping the first layer monomer into the kettle bottom material; and further comprising heat preservation after the dropping; The method of mixing the second layer monomer with the kettle bottom material comprises: dropping the second layer monomer into the kettle bottom material; and sequentially including heat preservation and temperature reduction operations after the dropping.

8. The preparation method according to claim 7, It is characterized in that The reaction time is 3-4h.

9. The preparation method according to claim 7, It is characterized in that The heat preservation time after the reaction is 10-50 minutes.

10. The preparation method according to claim 7, It is characterized in that The first layer monomer is added dropwise for 2-8 hours.

11. The preparation method according to claim 7, It is characterized in that The insulation time after the first layer of monomers is added dropwise is 0.5-1.5 hours.

12. The preparation method according to claim 7, It is characterized in that The time for dropping the second layer monomer is 1-3 hours.

13. The preparation method according to claim 7, It is characterized in that The insulation time after the second layer monomer is added dropwise is 1-5 hours.

14. The preparation method according to claim 7, It is characterized in that The temperature is lowered to 80-110°C.

15. The preparation method according to claim 7, It is characterized in that After the second layer monomer is mixed with the kettle bottom material and before the water is mixed with the kettle bottom material, a neutralizing agent is added to the kettle bottom material.

16. The preparation method according to claim 15, It is characterized in that After the neutralizing agent is added, the neutralization degree of the system is 85%-100%.

17. A primer that resists tearing of textured paper. It is characterized in that The anti-tear primer for textured paper comprises a first component and a second component; The first component comprises the hydroxylated acrylic dispersion according to any one of claims 1 to 6, or the hydroxylated acrylic dispersion prepared by the preparation method according to any one of claims 7 to 16, an auxiliary agent, a filler and water; The second component includes a curing agent; The curing agent includes an amino curing agent and / or an isocyanate curing agent.

18. The anti-tear primer for masking paper according to claim 17, It is characterized in that Based on 100% of the total mass of the first component, the mass percentage of the hydroxylated acrylic dispersion is 18%-30%.

19. The anti-tear primer for masking paper according to claim 17, It is characterized in that The auxiliary agent includes any one of a dispersant, a wetting agent, a defoaming agent, a thickener, a stabilizer or a mildewproofing agent, or a combination of at least two of them.

20. The anti-tear primer for masking paper according to claim 17, It is characterized in that Based on the total mass of the first component being 100%, the mass percentage of the auxiliary agent is 0.01%-3.3%.

21. The anti-tear primer for masking paper according to claim 19, It is characterized in that The mass percentage of the dispersant is 0.8%-1.6%.

22. The anti-tear primer for masking paper according to claim 19, It is characterized in that The mass percentage of the wetting agent is 0.01%-0.1%.

23. The anti-tear primer of claim 19, It is characterized in that The mass percentage of the defoaming agent is 0.2%-0.5%.

24. The anti-tear primer of claim 19, It is characterized in that The mass percentage of the thickener is 0.3%-0.5%.

25. The anti-tear primer of claim 19, It is characterized in that The mass percentage of the stabilizer is 0.1%-0.3%.

26. The anti-tear primer of claim 19, It is characterized in that The mass percentage of the mildew inhibitor is 0.1%-0.3%.

27. The anti-tear primer for masking paper according to claim 17, It is characterized in that The filler includes any one of titanium dioxide, kaolin or other fillers or a combination of at least two of them.

28. The anti-tear primer of claim 27, It is characterized in that The other fillers include heavy calcium.

29. The anti-tear primer for masking paper according to claim 17, It is characterized in that Based on the total mass of the first component being 100%, the mass percentage of the filler is 1%-35%.

30. The anti-tear primer of claim 27, It is characterized in that Based on the total mass of the first component being 100%, the mass percentage of the titanium dioxide is 1%-5%.

31. The anti-tear primer of claim 27, It is characterized in that Based on the total mass of the first component being 100%, the mass percentage of the kaolin is 5%-10%.

32. The anti-tear primer of claim 27, It is characterized in that Based on the total mass of the first component being 100%, the mass percentage of the other fillers is 10%-30%.

33. The anti-tear primer of claim 17, It is characterized in that The first component also includes potassium silicate.

34. The anti-tear primer of claim 33, It is characterized in that Based on the total mass of the first component being 100%, the mass percentage of the potassium silicate is 1%-5%.

35. The anti-tear primer of claim 17, It is characterized in that Taking the total mass of the first component as 100%, the first component includes the following components in terms of mass percentage:

36. The anti-tear primer of claim 17, It is characterized in that The molar mass ratio of the effective functional groups of the first component and the second component is (0.8-1.2):1.

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