One-component direct-coating waterproof coating and preparation method thereof

Abstract

The present invention discloses a one-component direct-apply waterproof coating, belonging to the technical field of waterproof coatings. The one-component direct-apply waterproof coating comprises the following components, by weight: 50-60 parts of a modified acrylic emulsion, 25-35 parts of a filler, 3-5 parts of a film-forming aid, 0.5-2 parts of a thickener, 0.5-1 part of a defoamer, and 20-30 parts of deionized water. The modified acrylic emulsion is a mixed emulsion of a melamine-modified emulsion and a fluorozine-modified emulsion. The one-component direct-apply waterproof coating provided by the present invention has high weather resistance, water resistance, and thermal insulation properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of waterproof coatings, and in particular relates to a one-component direct-coating waterproof coating and a preparation method thereof. Background Art

[0002] One-component, direct-apply waterproof coatings are applied directly to the substrate. Compared to two-component coatings, they are easier to use and require no mixing or additions. They are quicker to apply and have a wider range of adaptability. These coatings typically come in liquid form and form a continuous, seamless waterproof membrane upon application, achieving the desired waterproofing effect.

[0003] Acrylic resin coatings are high-performance polymer coatings with excellent film-forming properties, adhesion, and aging resistance. However, because traditional acrylic waterproof coatings are based on common acrylate polymers, their molecular chains are primarily composed of carboxyl and ester groups, resulting in coatings with a certain degree of water permeability. This is particularly susceptible to sunlight, wind, rain, and acidic substances, significantly impacting the coating's performance and causing it to degrade. Furthermore, due to the single functional group in the molecular chain, traditional acrylic waterproof coatings typically lack the ability to balance hydrophobicity, weather resistance, and mechanical strength, hindering their further application in the coatings industry. Summary of the Invention

[0004] In order to overcome the deficiencies of the above-mentioned prior art, the present invention provides a one-component direct-coating waterproof coating and a preparation method thereof, which achieves a balance of the coating's weather resistance, waterproofness, mechanical strength and other properties through precise functional group arrangement and substituent regulation.

[0005] The technical solutions for achieving the purpose of the present invention are as follows:

[0006] A one-component direct-coating waterproof coating comprising the following components: 50-60 parts of modified acrylic emulsion, 25-35 parts of filler, 3-5 parts of film-forming aid, 0.5-2 parts of thickener, 0.5-1 part of defoamer, and 20-30 parts of deionized water;

[0007] The filler is selected from one or more of talc powder, mica powder and heavy calcium carbonate powder; the film-forming aid is one or both of propylene glycol butyl ether and dipropylene glycol butyl ether; the thickener is an acrylic thickener; and the defoamer is a silicone defoamer.

[0008] The modified acrylic emulsion is a mixed emulsion formed by blending a melamine modified emulsion and a fluoroquinolone modified emulsion, wherein the mass ratio of the melamine modified emulsion to the fluoroquinolone modified emulsion is (5-10):1;

[0009] The preparation method of the modified acrylic emulsion comprises the following steps:

[0010] The melamine-modified emulsion and the fluoroquinoxaline-modified emulsion were preheated to 50° C. respectively; under a nitrogen atmosphere, the melamine-modified emulsion was slowly added to the fluoroquinoxaline-modified emulsion at a rate of 2 mL / s, and stirred at 800-1000 rpm; an emulsifier was added, and high-speed shearing was continued at 5000 rpm for 20-30 minutes to obtain a premixed emulsion; the pH was adjusted to 5.0-5.5, carbodiimide was added, and stirring was continued at room temperature for 2-3 hours; AMP-95 was added to adjust the pH to 8-9 to inhibit carboxylic acid hydrolysis and strengthen ionic bonds; the mixture was passed through a 200-mesh sieve, homogenized at 50 MPa, and aged at 25° C. for 24 hours to obtain a modified acrylic emulsion;

[0011] The melamine modified emulsion is a mixture of an aqueous solution of a melamine-polyacrylate ammonium ion covalent crosslinking compound and a pure acrylic emulsion, wherein the mass fraction of the aqueous solution of the melamine-polyacrylate ammonium ion covalent crosslinking compound is 10% to 20%;

[0012] The preparation method of the melamine-modified emulsion comprises the following steps:

[0013] (1) Preheat the pure acrylic emulsion to 50-55°C, add 0.1% by mass of ammonium persulfate, and stir at a low speed of 200 rpm for 15 minutes to activate the active sites of the acrylic acid segments in the emulsion;

[0014] (2) preparing a 10% by mass aqueous solution of a melamine-polyacrylate ammonium ion covalent crosslinking compound, and adding it dropwise to a pure acrylic acid solution at a constant rate of 1 to 10 drops per second, maintaining the temperature at 55°C, and stirring at a medium speed of 400 to 450 rpm. During the addition, a 5% by mass sodium hydroxide solution was added dropwise to maintain the system pH at 7 to promote the condensation of carboxylic acid and amino groups;

[0015] (3) After the addition is complete, heat to 60°C and continue stirring for 1 to 2 hours;

[0016] (4) Cooling to 40-45°C, adjusting the pH to 8.5-9.0, adding 0.05% preservative, and aging for 24 hours;

[0017] (5) passing through a 200-mesh filter to remove trace gel particles to form a melamine-modified emulsion;

[0018] The pure acrylic emulsion has a solid content of 40-50% and a pH of 2-4;

[0019] The preparation method of the melamine-polyacrylate ammonium ion covalent cross-linking compound comprises the following steps:

[0020] Under a nitrogen atmosphere, 3 to 5 eq of polyacrylic acid and aqueous ammonia are mixed in a volume ratio of 1:(1.5 to 2), and then 1 eq of melamine is added and stirred for 20 to 30 minutes. The mixture is then dried to remove ammonia and heated to 150° C. to react to obtain a melamine-polyacrylic acid ammonium ion covalent crosslinked compound. The melamine-polyacrylic acid ammonium ion covalent crosslinked compound contains both ionic bonds and covalent bonds, and its structure is shown in Formula 1:

[0021]

[0022] The general structural formula of the fluoroquinolone modified emulsion is shown in Formula 2:

[0023]

[0024] Wherein, R1 is selected from -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 One of, R2 is selected from -H, One of the following: R3 and R4 are selected from one of -H and -CH3; n is selected from any integer between 9 and 54, and the molar ratio of monomer A, monomer B, monomer C, and monomer D is x:y:z:w:=(2-4):(1-3):(3-5):(4-6).

[0025] The monomer A of the fluoroazine modified emulsion is 1H,1H,7H-perfluoroheptyl acrylate; the monomer B is modified monoethyl fumarate; the monomer C is methyl allyl polyoxyethylene ether or allyl polyoxyethylene ether; and the monomer D is acrylic acid or methacrylic acid.

[0026] The synthesis of monomer B comprises the following steps:

[0027] (1) 1 eq of cyanuric chloride and 1.1 eq of diisopropylamine were stirred in tetrahydrofuran for 10 to 15 minutes, and then 2 eq of aliphatic amine was added and reacted for 15 to 20 minutes. The mixture was stirred at room temperature for another 30 minutes. The solvent was removed under reduced pressure and then purified on a silica gel column to obtain an amination intermediate, the structure of which is shown in Formula 3:

[0028]

[0029] (2) The above-mentioned aminated intermediate and N,N-diisopropylethylamine were mixed in THF, tris(hydroxymethyl)aminomethane was added, and the mixture was stirred and heated to 100°C for 30-35 hours to obtain a trihydroxy intermediate, such as

[0030] As shown in formula 4:

[0031]

[0032] (3) 1.2 to 1.5 eq of the above trihydroxy intermediate and 1 to 2 eq of monoethyl fumarate were mixed with toluene, 5 to 10 mol% of p-toluenesulfonic acid was added, and the mixture was stirred and heated to 110 to 120°C for 4 to 6 hours. After the reaction, the mixture was cooled to room temperature and washed with saturated sodium bicarbonate solution. The aqueous phase was extracted with dichloromethane, the organic phases were combined, dried with anhydrous sodium sulfate, and the desiccant was removed by filtration. The solvent was removed under reduced pressure, and monomer B was obtained after silica gel column chromatography. The structure is shown in Formula 5:

[0033]

[0034] The preparation method of the fluoroquinolone modified emulsion comprises the following steps:

[0035] (1) Pre-emulsification: Under nitrogen atmosphere, the emulsifier and deionized water were mixed, a cosolvent was added, and monomer A, monomer B, monomer C, and monomer D were added in order. The mixture was first coarsely dispersed by shearing at 3000 rpm for 20 min, then finely divided by shearing at 3000 rpm for 15 min, and then homogenized by shearing at 4000 rpm for 20 min to obtain a pre-emulsion.

[0036] (2) Initiation and polymerization: Prepare a 5% potassium persulfate aqueous solution, preheat to 50°C, and set aside; prepare a 0.5% azobisisobutyronitrile glycol butyl ether solution, and set aside; take 10% of the pre-emulsion and heat it to 80°C, add one-fifth of the volume of potassium persulfate solution, and keep it warm for 30 minutes; add the remaining emulsion and potassium persulfate solution simultaneously through a constant pressure funnel; heat the pre-emulsion to 85-90°C, slowly add potassium persulfate solution at a rate of 1.5 mL / min, and maintain the temperature at 85°C; when the pre-emulsion is halfway added, slowly inject azobisisobutyronitrile glycol butyl ether solution at a rate of 0.5 mL / min; after the addition is complete, cool to 80°C and keep warm for 1 hour;

[0037] (3) Post-treatment: Cool to 60°C, adjust the pH to 6-7, and stir the reaction for 1 hour; then adjust the pH of the system to 8.5-9 with AMP-95 to inhibit carboxylic acid hydrolysis; pass through a 200-mesh sieve to remove gel particles, and treat with a high-pressure homogenizer at 50 MPa three times to refine the particle size to 80-120 nm; add 0.05% preservative and mature for 24 hours;

[0038] The emulsifier is a compound system of Capstone FS-3100, sodium lauryl sulfate and alkylphenol polyoxyethylene ether; the amount of the emulsifier added is 2% to 4% of the total weight of monomers A to D; the cosolvent is one or more of ethylene glycol butyl ether, propylene glycol phenyl ether, and PEG-400; the amount of the initiator added is 0.5% to 1.0% of the weight of the pre-emulsion; the preservative is BIT preservative;

[0039] Another object of the present invention is to provide a method for preparing the above-mentioned one-component direct-coating waterproof coating, comprising the following steps:

[0040] The filler was pre-dispersed at 3000 rpm for 15 minutes, and the film-forming agent, defoaming agent, thickener, and deionized water were added to the modified acrylic emulsion at intervals of 5 to 10 minutes, and stirred evenly to obtain a one-component direct-coating waterproof coating.

[0041] Beneficial effects

[0042] The present invention has the following beneficial effects:

[0043] The present invention discloses a one-component direct-apply waterproof coating and its preparation method, which features excellent weather resistance and waterproofness. The present invention synthesizes a new modified acrylic polymer through chemical modification. Through precise functional group arrangement and substituent regulation, the coating achieves a balance of waterproofness, mechanical strength, weather resistance, and thermal insulation properties.

[0044] 1. Superior hydrophobicity and self-cleaning properties: By simultaneously introducing fluorinated alkyl chains and long alkyl chains into the molecule, the introduction of fluorine atoms reduces the surface energy of the coating. Simultaneously, the regular arrangement of the long alkyl chains enhances the van der Waals forces between molecules, forming a dense hydrophobic layer that blocks the penetration path of water molecules. Together, they form an ultra-strong hydrophobic barrier. Notably, the introduction of fluorinated alkyl chains imparts self-cleaning capabilities to the coating, allowing rainwater to clean surface stains, reducing maintenance requirements.

[0045] 2. Excellent weather resistance and chemical corrosion resistance: The C-H bond energy in the fluorinated group is much higher than the C-H bond energy in the alkyl group, which can resist environmental erosion such as ultraviolet rays and acid rain. Compared with traditional acrylic coatings that are easily induced by ultraviolet rays to turn yellow and powder, the coating of this invention is widely suitable for outdoor waterproofing operations. The cross-linked network formed by dynamic amide bonds and ester bonds can buffer external stress and resist the penetration of chemical solvents.

[0046] 3. Improved mechanical properties and adhesion: The molecules of this invention achieve synergistic effects through the precise introduction of multiple functional groups. The alternating positive and negative charges of the carboxyl and amino ions can simultaneously bind to the anions and cations on substrates such as concrete and metal surfaces, forming a multi-point ionic bond network. The reversibility of these ionic bonds allows the coating to dynamically adjust to micro-cracks or deformations in the substrate, maintaining adhesion. The nitrogen atoms on the triazine ring can form coordination bonds with the cations of the substrate, synergistically improving adhesion.

[0047] 4. Improved thermal insulation: The vibration energy of the CF bond in the fluoroalkyl chain absorbs infrared rays with a wavelength of 8 to 14 μm, which is the main concentration area of ​​thermal energy in solar radiation. When the CF bond absorbs the energy in this band, it dissipates the energy through vibration and other means, thereby continuously transferring heat to the interior of the coating, achieving effective reflection of solar radiation heat and improving the thermal insulation performance of the material. In terms of heat conduction barrier, the synergistic effect of the triazine ring and the fluoroalkyl chain forms a complex molecular structure and heat conduction path inside the material. Heat needs to be scattered multiple times in the complex molecular structure, which increases the resistance and path length of heat transfer, effectively reducing the thermal conductivity of the material and improving the thermal insulation effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 Schematic diagram of the synthesis and structure of melamine-polyacrylate ammonium ion covalent cross-linked compound 1;

[0049] Figure 2 Schematic diagram of the synthesis and structure of monomer B1;

[0050] Figure 3 The attenuated total reflection absorption Fourier transform infrared spectra of polyacrylic acid, melamine, and melamine-polyacrylic acid ammonium ion covalent cross-linked compound 1 are shown;

[0051] Figure 4 This is the H NMR spectrum of monomer B1. DETAILED DESCRIPTION

[0052] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0053] In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0054] The raw materials and equipment used in the embodiments and comparative examples are described below:

[0055] Melamine-polyacrylate ammonium ion covalent cross-linked compound 1: homemade, prepared as follows:

[0056] Under a nitrogen atmosphere, 4 eq of polyacrylic acid and aqueous ammonia were mixed in a volume ratio of 1:1.7, and then 1 eq of melamine was added and stirred for 30 minutes. The mixture was then dried to remove ammonia and heated to 150°C to react to obtain a melamine-polyacrylic acid ammonium ion covalent cross-linked compound 1, the structure of which is shown in Formula 1:

[0057]

[0058] Melamine-polyacrylate ammonium ion covalent crosslinking compound 2: homemade. The preparation method is similar to that of melamine-polyacrylate ammonium ion covalent crosslinking compound 1. The difference is that melamine is replaced by 1,3,5-triaminobenzene. Other conditions remain unchanged. Melamine-polyacrylate ammonium ion covalent crosslinking compound 2 is obtained. The structural formula is shown in Formula 6:

[0059]

[0060] Monomer A1: 1H,1H,7H-perfluoroheptyl acrylate, purchased from Shanghai Titan Technology Co., Ltd.;

[0061] Monomer A2: n-heptyl methacrylate, purchased from Shaanxi Didu New Materials Co., Ltd.;

[0062] Monomer B1: Homemade, preparation method is as follows:

[0063] (1) 1 eq of cyanuric chloride and 1.1 eq of diisopropylamine were stirred in tetrahydrofuran for 15 min, and then 2 eq of n-undecylamine was added and reacted for 15 to 20 min. The mixture was stirred at room temperature for another 30 min. The solvent was removed under reduced pressure and then purified on a silica gel column to obtain an amination intermediate, the structure of which is shown in Formula 7:

[0064]

[0065] (2) The above-mentioned aminated intermediate and N,N-diisopropylethylamine were mixed in THF, tris(hydroxymethyl)aminomethane was added, and the mixture was stirred and heated to 100°C. The reaction was carried out for 35 hours to obtain a trihydroxy intermediate, as shown in Formula 8:

[0066]

[0067] (3) 1.3 eq of the above trihydroxy intermediate and 1 eq of monoethyl fumarate were mixed with toluene, 7 mol% of p-toluenesulfonic acid was added, and the mixture was stirred and heated to 110°C for 6 h. After the reaction, the mixture was cooled to room temperature and washed with saturated sodium bicarbonate solution. The aqueous phase was extracted with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, and filtered to remove the desiccant. The solvent was removed under reduced pressure, and the monomer B1 was obtained after silica gel column chromatography. The structure is shown in Formula 9:

[0068]

[0069] Monomer B2: homemade. The preparation method is similar to that of monomer B1, except that the amount of monoethyl fumarate added in step (3) is replaced with 2 eq. Other conditions remain unchanged, yielding monomer B2, whose structural formula is shown in Formula 10:

[0070]

[0071] Monomer B3: monoethyl fumarate, product number 1067577, purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.

[0072] Monomer C: methyl allyl polyoxyethylene ether, molecular weight 2000, product number PA290222, purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0073] Monomer D: methacrylic acid, product number R013090, purchased from Shanghai Yien Chemical Technology Co., Ltd.;

[0074] Filler: talc powder, product number 8402, purchased from Shandong Xiya Chemical Co., Ltd.

[0075] Film-forming aid: propylene glycol butyl ether, product number P874807, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0076] Defoaming agent: Tego Foamex 840, purchased from Hubei Zhonglong Kangsheng Fine Chemical Co., Ltd.;

[0077] Thickener: Carbomer 940, product number R1895, purchased from Nanjing Dulai Biotechnology Co., Ltd.;

[0078] Preservatives: BIT preservative, purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0079] n-Undecylamine: Product No. 94200, purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0080] Polyacrylic acid: molecular weight 2000, product number P890198, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0081] Ammonia water: content 25-28%, product number M813390, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0082] Melamine: Product No. M813390, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0083] Cyanuric chloride: product number C805716, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0084] Diisopropylamine: product number R004012, purchased from Shanghai Yien Chemical Technology Co., Ltd.;

[0085] N,N-Diisopropylethylamine: Product No. E-81416, purchased from Tianjin Xiens Biochemical Technology Co., Ltd.;

[0086] Tris(hydroxymethyl)aminomethane: product number E-81416, purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.

[0087] p-Toluenesulfonic acid: product number 4729, purchased from Shandong West Asia Chemical Co., Ltd.

[0088] Pure acrylic emulsion: solid content 48%, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0089] AMP-95: 2-amino-2-methyl-1-propanol, product number R017802, purchased from Shanghai Yien Chemical Technology Co., Ltd.;

[0090] Unless otherwise specified, the components and raw materials used in the examples and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0091] Preparation Example

[0092] Preparation Example 1

[0093] Melamine modified emulsion I: homemade, the preparation method includes the following steps:

[0094] (1) preparing a 10% by mass aqueous solution of the melamine-polyacrylate ammonium ion covalent crosslinking compound 1 for later use;

[0095] (2) Preheat the pure acrylic emulsion with a mass ratio of 1:1 to the above aqueous solution to 55°C, add 0.1% ammonium persulfate, and stir at a low speed of 200 rpm for pre-initiation for 15 minutes;

[0096] (2) wherein the mixture was added dropwise to the pure propane solution at a constant rate of 1 drop / second, the temperature was maintained at 55°C, and the mixture was stirred at a medium speed of 400 rpm. During the addition, a 5% sodium hydroxide solution was added dropwise to maintain the pH of the system at 7;

[0097] (3) After the addition is complete, heat to 60°C and continue stirring for 2 h;

[0098] (4) Cooling to 45°C, adjusting the pH to 8.5, adding 0.05% preservative, and aging for 24 hours;

[0099] (5) passing through a 200-mesh filter to remove trace gel particles to obtain modified emulsion I;

[0100] Preparation Example II

[0101] Melamine-modified emulsion II: homemade. The preparation method is similar to that of Preparation Example I, except that melamine-polyacrylate ammonium ion covalent crosslinking compound 1 is replaced with melamine-polyacrylate ammonium ion covalent crosslinking compound 2. Other conditions remain unchanged to obtain modified emulsion II.

[0102] Preparation Example 1

[0103] Fluoxazine modified emulsion 1: Homemade, the preparation method includes the following steps:

[0104] (1) Pre-emulsification: Under nitrogen atmosphere, the emulsifier and deionized water were mixed, a cosolvent was added, and monomer A1, monomer B1, monomer C, and monomer D were added in a molar ratio of 3:2:4:5. The mixture was first coarsely dispersed at 3000 rpm for 20 min, then refined at 3000 rpm for 15 min, and then homogenized at 4000 rpm for 20 min to obtain a pre-emulsion.

[0105] (2) Initiation and polymerization: Prepare a 5% potassium persulfate aqueous solution, preheat to 50°C, and set aside; prepare a 0.5% azobisisobutyronitrile ethylene glycol butyl ether solution, and set aside; take 10% of the pre-emulsion and heat it to 80°C, add one-fifth of the volume of potassium persulfate solution, and keep warm for 30 minutes; add the remaining emulsion and potassium persulfate solution simultaneously through a constant pressure funnel, dissolve potassium persulfate in deionized water to prepare a 5% solution; heat the pre-emulsion to 85°C, slowly add potassium persulfate solution at a rate of 1.5 mL / min, and maintain the temperature at 85°C; when half of the pre-emulsion is added, slowly inject azobisisobutyronitrile solution at a rate of 0.5 mL / min; after the addition is completed, cool to 80°C and keep warm for 1 hour;

[0106] (3) Post-treatment: Cool to 60°C, adjust pH to 6.5, and stir for 1 hour; then adjust pH of the system to 8.5 with AMP-95 to inhibit carboxylic acid hydrolysis; pass through a 200-mesh sieve to remove gel particles, and treat with a high-pressure homogenizer at 50 MPa three times to refine the particle size to 80-120 nm; add 0.05% preservative and mature for 24 hours to obtain fluoroquinolone modified emulsion 1;

[0107] Preparation Example 2

[0108] Fluoxazine modified emulsion 2: homemade. The preparation method is the same as that of Preparation Example 1, except that the molar ratio of monomer A1, monomer B1, monomer C, and monomer D is replaced with 2:1:3:4. Other conditions remain unchanged to obtain Fluoxazine modified emulsion 2.

[0109] Preparation Example 3

[0110] Fluoxazine modified emulsion 3: homemade, the preparation method is compared with Preparation Example 1, the difference is that the molar ratio of monomer A1, monomer B1, monomer C, and monomer D is replaced with 4:3:5:6, and other conditions remain unchanged, to obtain Fluoxazine modified emulsion 3;

[0111] Preparation Example 4

[0112] Fluoxazine modified emulsion 3: homemade, the preparation method is compared with Preparation Example 1, the difference is that monomer A1 is replaced by monomer A2, and other conditions remain unchanged, to obtain Fluoxazine modified emulsion 4;

[0113] Preparation Example 5

[0114] Fluoxazine modified emulsion 5: homemade. The preparation method is the same as that of Preparation Example 1, except that monomer B1 is replaced by monomer B2. Other conditions remain unchanged to obtain Fluoxazine modified emulsion 5.

[0115] Preparation Example 6

[0116] Fluoxazine modified emulsion 6: homemade. The preparation method is the same as that of Preparation Example 1, except that monomer B1 is replaced by monomer B3. Other conditions remain unchanged to obtain Fluoxazine modified emulsion 6.

[0117] Table 1 Monomer molar ratio of fluoroazine modified emulsion

[0118] Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Monomer A1 3 2 4 3 3 Monomer A2 3 Monomer B1 2 1 3 2 Monomer B2 2 Monomer B3 2 Monomer C 4 3 5 4 4 4 Monomer D 5 4 6 5 5 5

[0119] Example

[0120] Example 1

[0121] One-component direct-coating waterproof coating 1: Homemade, the preparation method is as follows:

[0122] 1. Synthesis of Modified Acrylic Emulsion 1: 43.75 parts by weight of Preparation Example 1 and 6.25 parts by weight of Preparation Example 1 were preheated to 50° C.; under a nitrogen atmosphere, Preparation Example 1 was slowly added to the fluorozine modified emulsion at 2 mL / s, and stirred at 800 rpm; an emulsifier and a cosolvent were added, and high-speed shearing was continued at 5000 rpm for 30 minutes to obtain a premixed emulsion; the pH was adjusted to 5.5, carbodiimide was added, and stirred at room temperature for 2 hours; AMP-95 was added to adjust the pH to 8.5 to inhibit carboxylic acid hydrolysis and strengthen ionic bonds; the mixture was passed through a 200-mesh sieve, homogenized at 50 MPa, and aged at 25° C. for 24 hours to obtain Modified Acrylic Emulsion 1;

[0123] 2. Pre-disperse 25 parts of filler at 3000 rpm for 15 minutes, then add 4 parts of film-forming aid, 0.5 parts of defoamer, 0.5 parts of thickener, and 20 parts of deionized water to the modified acrylic emulsion 1 at 5-minute intervals and stir evenly to obtain a one-component direct-coating waterproof coating 1;

[0124] Example 2

[0125] One-component direct-coating waterproof coating 2: homemade, the preparation method is compared with Example 1, except that the number of parts added in Preparation Example 1 is replaced by 41.67 parts, and the number of parts added in Preparation Example 1 is replaced by 8.33 parts, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 2;

[0126] Example 3

[0127] One-component direct-coating waterproof coating 3: homemade, the preparation method is compared with Example 1, except that the number of parts added in Preparation Example 1 is replaced by 45.45 parts, and the number of parts added in Preparation Example 1 is replaced by 4.55 parts, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 3;

[0128] Example 4

[0129] One-component direct-coating waterproof coating 4: homemade, the preparation method is compared with Example 1, the difference is that the added Preparation Example 1 is replaced by Preparation Example 2, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 4;

[0130] Example 5

[0131] One-component direct-coating waterproof coating 5: homemade, the preparation method is compared with Example 1, except that the added Preparation Example 1 is replaced with Preparation Example 3, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 5;

[0132] Example 6

[0133] One-component direct-coating waterproof coating 6: homemade, the preparation method is compared with Example 1, the difference is that the added Preparation Example 1 is replaced with Preparation Example 4, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 6;

[0134] Example 7

[0135] One-component direct-coating waterproof coating 7: homemade, the preparation method is compared with Example 1, except that the added Preparation Example 1 is replaced with Preparation Example 5, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 7;

[0136] Example 8

[0137] One-component direct-coating waterproof coating 8: homemade, the preparation method is compared with Example 1, except that the added Preparation Example 1 is replaced with Preparation Example 6, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 8;

[0138] Example 9

[0139] One-component direct-coating waterproof coating 9: homemade, the preparation method is compared with Example 1, except that the added Preparation Example I is replaced with Preparation Example II, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 9;

[0140] Comparative Example

[0141] One-component direct-coating waterproof coating 10: homemade, the preparation method is compared with Example 1, except that the added Preparation Example 1 and Preparation Example 1 are replaced with 50 parts of pure acrylic emulsion, and other conditions remain unchanged to obtain a one-component direct-coating waterproof coating 10;

[0142] Table 2: Formulas of Examples 1 to 9 and Comparative Examples (parts by weight)

[0143]

[0144]

[0145] The following are the test methods for the performance parameters involved in the present invention:

[0146] The one-component direct-coating waterproof coatings prepared in Examples 1 to 10 and the comparative example were subjected to the following tests:

[0147] 1. Scrub resistance: Tested according to GB / T 9266-2009 "Determination of Scrub Resistance of Architectural Paints";

[0148] 2. Resistance to artificial weathering: Tested according to GB / T 1865-2009 "Paints and varnishes - Artificial weathering and artificial radiation exposure - filtered xenon arc radiation";

[0149] 3. Scratch resistance: Tested according to GB / T 9279-2007 "Paints and varnishes scratch test";

[0150] 4. Thermal insulation temperature difference test: Apply the paint on a 10mm x 10mm iron plate to make a sample. Place the prepared test sample and reference sample into the temperature difference tester. The reference sample is painted with Hong brand ordinary exterior wall acrylic resin paint. Heat the two samples simultaneously, and record the heating box temperature, the sample back box temperature, and the reference sample back box temperature in real time. Calculate and record the temperature difference between the test sample and reference sample back boxes.

[0151] 5. Tensile strength: Tested according to Chapter 9 of GB / T 16777-2008 "Test methods for building waterproof coatings" at a tensile speed of 500 mm / min ± 50 mm / min. The test results are the average of 5 specimens.

[0152] 6. Elongation at break: Tested in accordance with GB / T 528-2009 "Rubber, vulcanized or thermoplastic. Determination of tensile stress-strain properties";

[0153] 7. Tear strength test: According to GB / T529-2008 "Vulcanized rubber or thermoplastic rubber - Determination of tear strength (trouser-shaped, right-angled and crescent-shaped test specimens)", the test is conducted on a right-angled specimen without a cut, and the tensile speed is 500mm / min±50mm / min. The test results are the average of 5 specimens;

[0154] 8. Bond strength: Test according to Method A in 7.1 of GB / T16777-2008 "Test methods for building waterproof coatings";

[0155] 9. Waterproofness: According to Chapter 15 of GB / T16777-2008 "Test Methods for Building Waterproof Coatings";

[0156] 10. Nuclear magnetic resonance (H-NMR): 400 MHz NMR spectrometer, Bruker, Germany;

[0157] 11. Attenuated total reflection absorption Fourier transform infrared spectroscopy: Model Spectrum two, PerkinElmer, USA;

[0158] Table 3 Performance test results of one-component direct-coating waterproof coatings of Examples 1 to 9 and Comparative Examples

[0159]

[0160]

[0161] From the test data of Examples 1 to 9 and the comparative example in Table 3, it can be seen that the combination of melamine-modified emulsion and fluoroazine-modified emulsion improves the performance of the waterproof coating, among which the synergistic effect of perfluoroheptyl acrylate and triazine ring monomer improves the mechanical properties of the coating; compared with Example 1 and Example 9, the melamine-polyacrylate ammonium ion covalent cross-linking compound 1 in the preparation example is replaced by melamine-polyacrylate ammonium ion covalent cross-linking compound 2. It can be inferred from the experimental results that the three nitrogen atoms of the triazine ring provide three hydrogen bond acceptor sites, thereby improving the cross-linking density, and its electron deficiency enhances the exposure of lone pair electrons. In contrast, the carbon atoms in the benzene ring have no lone pair electrons and only form a conjugated system through π electron delocalization, which cannot serve as a hydrogen bond acceptor; the construction of the hydrogen bond network makes Example 1 have good wash resistance, the CN bond vibration of the triazine ring matches the mid-infrared band, and the benzene ring only reflects visible light. In summary, the present invention synthesizes a new modified acrylic polymer through chemical modification, and achieves a balance of properties such as waterproofness, mechanical strength, weather resistance, and thermal insulation through precise functional group arrangement and substituent regulation.

[0162] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A one-component direct-coating waterproof coating, characterized in that: The invention comprises the following components in parts by weight: 50-60 parts of modified acrylic emulsion, 25-35 parts of filler, 3-5 parts of film-forming aid, 0.5-2 parts of thickener, 0.5-1 part of defoamer, and 20-30 parts of deionized water; the modified acrylic emulsion is a mixed emulsion formed by blending melamine-modified emulsion and fluoroquinolone-modified emulsion in a mass ratio of (5-10):1; the melamine-modified emulsion is a mixture of an aqueous solution of a melamine-polyacrylic acid ammonium ion covalent cross-linking compound and a pure acrylic emulsion in a mass ratio of 1:(1-3); the structure of the melamine-polyacrylic acid ammonium ion covalent cross-linking compound is shown in Formula 1, and the mass fraction of the aqueous solution is 10%-20%; the general structural formula of the fluoroquinolone-modified emulsion is shown in Formula 2: Wherein, R1 is selected from -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 One of the monomers A, B, C and D, wherein R2 is selected from one of -H, R3 and R4 are selected from one of -H and -CH3; n is selected from any integer between 9 and 54, and the molar ratio of monomer A, monomer B, monomer C and monomer D, x:y:z:w:=(2-4):(1-3):(3-5):(4-6).

2. The one-component direct-coating waterproof coating according to claim 1, characterized in that: The monomer A is 1H,1H,7H-perfluoroheptyl acrylate; the monomer B is modified monoethyl fumarate; the monomer C is methyl allyl polyoxyethylene ether or allyl polyoxyethylene ether; and the monomer D is acrylic acid or methacrylic acid.

3. The one-component direct-coating waterproof coating according to claim 1, characterized in that: The filler is selected from one or more of talc powder, mica powder and heavy calcium carbonate powder; the film-forming aid is one or both of propylene glycol butyl ether and dipropylene glycol butyl ether; the thickener is an acrylic thickener; and the defoamer is a silicone defoamer.

4. The method for preparing a one-component direct-coating waterproof coating according to any one of claims 1 to 3, characterized in that: The following steps are involved: The filler was pre-dispersed at 3000 rpm for 15 minutes, and the film-forming agent, defoaming agent, thickener, and deionized water were added to the modified acrylic emulsion at intervals of 5 to 10 minutes, and stirred evenly to obtain a one-component direct-coating waterproof coating.

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