Waterproof decorative integrated paint and preparation method thereof

Abstract

The application discloses waterproof and decorative integrated paint and a preparation method thereof. The paint comprises silicone emulsion, acrylic emulsion, pigment, heavy calcium carbonate, sheeted kaolin, silicon powder, modified graphene oxide, nano silicon dioxide, ethylene glycol, ultraviolet absorber, light stabilizer, heat stabilizer, dispersant, hydrophobic agent, film forming aid, defoaming agent, leveling agent, thickening agent, preservative and water. The acrylic emulsion is obtained by polymerization reaction of methyl methacrylate, cyclohexyl methacrylate, butyl acrylate, lauryl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid and KH-570. The modified graphene oxide is obtained by modification of graphene oxide by beta-cyclodextrin and vinyltrimethoxysilane. The waterproof and decorative integrated paint provided by the application has the functions of waterproofing and decoration, and has excellent weather resistance, stain resistance and bonding strength.

Description

Technical Field

[0001] This invention relates to an integrated waterproof and decorative coating and its preparation method, belonging to the field of coating technology. Background Technology

[0002] With the modernization of society and the continuous improvement of people's living standards and quality of life, the requirements for buildings are also increasing. Building wall coatings (including interior and exterior walls) are important materials for building decoration and protection, and their performance and quality directly affect the overall effect and service life of the building. Traditional building wall decoration often uses building coatings such as stone paint and latex paint combined with waterproof layers and putty layers, resulting in cumbersome construction procedures and long construction cycles. Furthermore, due to the numerous procedures and layers, poor adhesion between coatings can easily lead to blistering, bulging, and even cracking. To overcome the drawbacks of traditional building wall decoration materials, integrated waterproof and decorative coatings have emerged.

[0003] Waterproof and decorative integrated coatings not only possess the decorative properties of traditional building coatings but also have waterproof properties. They can be applied directly to various substrates, achieving the dual functions of waterproofing and decoration, greatly reducing the cost and construction difficulty of wall coating.

[0004] While existing waterproof and decorative integrated coatings have both waterproof and decorative functions, their performance in terms of weather resistance, stain resistance, and adhesion strength is insufficient, and they cannot effectively protect building walls. Summary of the Invention

[0005] To address the aforementioned problems in the existing technology, the purpose of this invention is to provide an integrated waterproof and decorative coating and its preparation method.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A waterproof and decorative integrated coating has the following composition and proportions:

[0008] Organosilicon emulsion: 22-28 parts by weight;

[0009] Acrylic emulsion: 18-22 parts by weight;

[0010] Pigment: 10-12 parts by weight;

[0011] Heavy calcium carbonate: 5-8 parts by weight;

[0012] Flake kaolin: 5-7 parts by weight;

[0013] Silica powder: 3-4 parts by weight;

[0014] Modified graphene oxide: 0.8-1.0 parts by weight;

[0015] Nano-silica: 0.2-0.3 parts by weight;

[0016] Ethylene glycol: 1-2 parts by weight;

[0017] Ultraviolet absorber: 0.8-1 parts by weight;

[0018] Light stabilizer: 0.8-1 parts by weight;

[0019] Heat stabilizer: 0.1-0.3 parts by weight;

[0020] Dispersant: 2-3 parts by weight;

[0021] Water-repellent agent: 1.5-2 parts by weight;

[0022] Film-forming aid: 2-2.5 parts by weight;

[0023] Defoamer: 0.4-0.6 parts by weight;

[0024] Leveling agent: 0.4-0.6 parts by weight;

[0025] Thickener: 0.6-0.8 parts by weight;

[0026] Preservative: 0.3-0.5 parts by weight;

[0027] Water: 15-20 parts by weight;

[0028] The acrylic emulsion is obtained by polymerizing methyl methacrylate, cyclohexyl methacrylate, butyl acrylate, lauryl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid, and KH-570.

[0029] The modified graphene oxide is obtained by modifying graphene oxide with β-cyclodextrin and vinyltrimethoxysilane.

[0030] In one embodiment, the acrylic emulsion is obtained by polymerization of 149-151 parts by weight of methyl methacrylate, 49-51 parts by weight of cyclohexyl methacrylate, 99-101 parts by weight of butyl acrylate, 29-31 parts by weight of lauryl methacrylate, 9-11 parts by weight of hydroxyethyl methacrylate, 9-11 parts by weight of glycidyl methacrylate, 4-6 parts by weight of acrylic acid, and 14-16 parts by weight of KH-570.

[0031] In a preferred embodiment, the preparation of the acrylic emulsion includes the following steps:

[0032] 1) In an emulsifying tank, mix 279-281 parts by weight of water, 3.5-4.5 parts by weight of reactive emulsifier and 1.5-2.5 parts by weight of anionic emulsifier evenly, then add 149-151 parts by weight of methyl methacrylate, 49-51 parts by weight of cyclohexyl methacrylate, 99-101 parts by weight of butyl acrylate, 29-31 parts by weight of lauryl methacrylate, 9-11 parts by weight of hydroxyethyl methacrylate, 9-11 parts by weight of glycidyl methacrylate and 4-6 parts by weight of acrylic acid, mix evenly to obtain a stable pre-emulsion;

[0033] Dissolve 5.5-6.5 parts by weight of the initiator in 98-102 parts by weight of water to obtain an initiator solution;

[0034] Dissolve 1.5-2.5 parts by weight of buffer in 18-22 parts by weight of water to obtain a buffer solution;

[0035] Dilute 14-16 parts by weight of KH-570 with 14-16 parts by weight of isopropanol to obtain a KH-570 solution.

[0036] 2) Add 118-122 parts by weight of water and the prepared buffer solution to the reactor, heat to 80°C, and simultaneously add 10% of the pre-emulsion and 10% of the initiator solution. Keep the reaction at this temperature for 20-30 minutes until the system shows a faint blue light, and the seed emulsion is obtained.

[0037] 3) Stabilize the temperature of the seed emulsion at 82±1℃, and simultaneously add the remaining 90% pre-emulsion and 90% initiator solution dropwise, completing the dropwise addition within 3-4 hours. During the dropwise addition, maintain the pH of the system between 7 and 8. After the dropwise addition is complete, continue to keep the reaction at the temperature for 25-35 minutes.

[0038] 4) Heat the system to 85℃, slowly add KH-570 solution dropwise, and control the addition to be completed within 1 hour. After the addition is completed, keep it at 85℃ for 1.5-2.5 hours to mature.

[0039] 5) Cool the system to below 40°C, adjust the pH to 7.5-8.0 with ammonia, add 1.6-1.8 parts by weight of defoamer and 1.6-1.8 parts by weight of preservative, stir for 25-35 minutes, filter, and obtain acrylic emulsion (solid content about 50%).

[0040] In a preferred embodiment, during the preparation of the acrylic emulsion, the reactive emulsifier used is DNS-86, the anionic emulsifier is A-102, the initiator is ammonium persulfate, the buffer is sodium bicarbonate, the defoamer is BYK-019, and the preservative is a BIT-based agent (e.g., Acticide MBS, Preventol D7).

[0041] In one embodiment, the mass ratio of β-cyclodextrin:vinyltrimethoxysilane:graphene oxide in the modified graphene oxide is (1.8-2.2):(0.8-1.2):(0.8-1.2), preferably 2:1:1.

[0042] In a preferred embodiment, the preparation of the modified graphene oxide includes the following steps:

[0043] ① Add 98-102 parts by weight of water and 1.8-2.2 parts by weight of β-cyclodextrin to the reactor, heat to 70°C, keep warm and stir to completely dissolve β-cyclodextrin or form a uniform suspension, add 0.08-0.12 parts by weight of phase transfer catalyst, keep warm and stir to mix evenly;

[0044] ② Dilute 0.8-1.2 parts by mass of vinyltrimethoxysilane with 1.4-1.6 parts by mass of anhydrous ethanol, and then slowly add the resulting vinyltrimethoxysilane solution dropwise to the system in step ①, controlling the dropwise addition rate to be completed within 30 minutes. After the addition is completed, continue to keep warm and stir for 3-5 hours.

[0045] ③ Cool the reaction system to room temperature, adjust the pH to 4.5-5.0 with a pH adjuster, add 1.5-2.5 wt% of graphene oxide dispersion, wherein the dry weight of graphene oxide is 0.8-1.2 parts by mass. After the addition is complete, place the reaction system in an ice-water bath and use a probe-type ultrasonic cell disruptor at 400W power for ultrasonic treatment for 25-35 minutes.

[0046] ④ After ultrasonic treatment, remove the ice-water bath, raise the temperature of the reaction system to 85°C, and keep it at this temperature for 7.5-8.5 hours under nitrogen protection. After the reaction is completed, allow it to cool naturally to room temperature, separate the solid and liquid, wash the separated solid with water 2-4 times, dry and grind it to obtain modified graphene oxide.

[0047] In a preferred embodiment, the phase transfer catalyst used in the preparation of modified graphene oxide is tetrabutylammonium bromide, and the pH adjuster is glacial acetic acid.

[0048] In one embodiment, the organosilicon emulsion is obtained by reacting 107 silicone rubber, MQ silicone resin, methyltriethoxysilane and vinyltrimethoxysilane, wherein the mass ratio of 07 silicone rubber:MQ silicone resin:methyltriethoxysilane:vinyltrimethoxysilane is (32-33):(7.6-8):(9-9.2):(1.2-1.4).

[0049] In a preferred embodiment, the preparation of the silicone emulsion includes the following steps:

[0050] 1) Mix 32-33 parts by weight of 107 silicone rubber, 7.6-8 parts by weight of MQ silicone resin, 9-9.2 parts by weight of methyltriethoxysilane and 1.2-1.4 parts by weight of vinyltrimethoxysilane evenly to obtain an oil phase;

[0051] Dissolve 2.2-2.3 parts by weight of AEO-3 (fatty alcohol polyoxyethylene ether), 1.34-1.36 parts by weight of SDS (sodium dodecyl sulfate), and 0.8-1 parts by weight of CO-436 (nonylphenol polyoxyethylene ether ammonium sulfate) in 9-11 parts by weight of water to obtain the emulsifier phase.

[0052] 2) Pour the oil phase into the emulsification tank, and slowly add the emulsifier phase while stirring. Stir for 10-20 minutes to obtain the initial emulsion. Then slowly add 38-42 parts by weight of water and stir for 10-20 minutes. Then transfer the obtained emulsion to a homogenizer and homogenize it 3-5 times at 5 MPa to obtain a stable pre-emulsion.

[0053] 3) Transfer the pre-emulsion to an emulsifying tank, add 0.04-0.06 parts by weight of catalyst while stirring, stir and mix evenly, then add NaOH aqueous solution to adjust the pH of the system to 10-11, raise the temperature to 60℃, keep the reaction at this temperature for 4-6 hours, and monitor the viscosity change of the system until the viscosity is basically stable. After the reaction is completed, cool the system to room temperature, adjust the pH to 6.5-7.5 with glacial acetic acid, then add 1.6-1.8 parts by weight of preservative, stir for 25-35 minutes, filter, and obtain the organosilicon emulsion.

[0054] In a preferred embodiment, the catalyst used in the preparation of the organosilicon emulsion is an organobismuth catalyst (e.g., Cosmolube VPS 3501X, Borchi Kat 24, K-KAT XK-601), the mass concentration of the NaOH aqueous solution is 4-6%, and the preservative used is of the BIT type.

[0055] In one embodiment, the dispersant in the waterproof and decorative integrated coating is composed of polyacid salt and dioxyethylene ether in a mass ratio of 65:35.

[0056] In a preferred embodiment, the polycarboxylate is obtained by reacting methacrylic acid, diallyl dimethyl ammonium chloride, isobornyl methacrylate, methoxy polyethylene glycol methacrylate, and allyl glycidyl ether, wherein the mass ratio of methacrylic acid: diallyl dimethyl ammonium chloride: isobornyl methacrylate: methoxy polyethylene glycol methacrylate: allyl glycidyl ether is (29-31):(14-16):(14-16):(4-6):(9-11).

[0057] In a preferred embodiment, the preparation of the polycarboxylate includes the following steps:

[0058] 1) Dissolve 1.8-2.2 parts by weight of the initiator in 38-42 parts by weight of water to obtain an initiator solution; dissolve 0.8-1.2 parts by weight of the reducing agent in 38-42 parts by weight of water to obtain a reducing agent solution;

[0059] 29-31 parts by weight of methacrylic acid, 14-16 parts by weight of diallyl dimethyl ammonium chloride, 14-16 parts by weight of isobornyl methacrylate, 4-6 parts by weight of methoxy polyethylene glycol methacrylate, 9-11 parts by weight of allyl glycidyl ether, 1.4-1.6 parts by weight of chain transfer agent and 118-122 parts by weight of water / isopropanol mixed solvent are mixed evenly to obtain monomer preemulsion;

[0060] 2) Add 28-32 parts by weight of water / isopropanol mixed solvent and 1 / 5 of monomer pre-emulsion to the reactor, mix well, heat to 60°C under nitrogen protection, add 1 / 5 of initiator solution and 1 / 5 of reducing agent solution dropwise, controlling the dropwise addition to be completed within 10-20 minutes, and continue to keep the temperature for 10-20 minutes after the dropwise addition is completed to obtain seed emulsion;

[0061] 3) Maintain a constant temperature of 60℃, and simultaneously add the remaining monomer pre-emulsion, initiator solution and reducing agent solution dropwise, controlling the dropwise addition to be completed within 3-4 hours. After the dropwise addition is completed, raise the temperature to 70℃, keep the reaction at this temperature for 1-2 hours, and then stop the reaction. Cool the reaction system to below 40℃, and adjust the pH to 7.5-8.5 with a pH adjuster while stirring.

[0062] 4) The obtained product is distilled under reduced pressure at 50°C to remove 150-155 parts by weight of solvent, resulting in a viscous slurry. Then, 150-155 parts by weight of propylene glycol methyl ether is added to the viscous slurry as a substitute solvent, and the mixture is stirred evenly to obtain an emulsion of polyacid salt with a solid content of about 50%.

[0063] In a preferred embodiment, during the preparation of polyacid salts, the initiator used is ammonium persulfate, the reducing agent used is ascorbic acid, the chain transfer agent used is 3-mercaptopropionic acid, the pH adjuster used is aminomethylpropanol, and the water / isopropanol mixed solvent used has a water:isopropanol mass ratio of 4:1.

[0064] In a preferred embodiment, the methoxy polyethylene glycol methacrylate is methoxy polyethylene glycol (1000) methacrylate.

[0065] In a preferred embodiment, the double-tailed polyether is an alkenyl alkylene double-tailed polyoxyethylene ether with the molecular formula C8H. 14 O3(C2H4O) n(C2H4O) m H2, n+m are any natural numbers between 20 and 100.

[0066] In one embodiment, the pigment in the waterproof and decorative integrated coating is selected from at least one of titanium dioxide, iron oxide yellow, iron oxide red, phthalocyanine blue, phthalocyanine green, iron oxide black, and iron oxide brown.

[0067] In one embodiment, the integrated waterproof and decorative coating comprises: an ultraviolet absorber being a benzotriazole, such as Tinuvin 1130 or Tinuvin 384; a light stabilizer being a hindered amine, such as Tinuvin 123, Tinuvin 292, or Chimassorb 2020; a heat stabilizer being a phosphite / phosphonate, such as Irgafos 168 or Weston 399; a water repellent being TEGO® Phobe 1401 or 1650; a defoamer being BYK-019 or BYK-028; a leveling agent being TEGO® Glide 100 or 450; a thickener being a mixture of ASE-60 and RM-2020 NPR at a mass ratio of 65:35; and a preservative being Acticide MBS.

[0068] In one embodiment, the film-forming aid in the waterproof and decorative integrated coating is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0069] In a preferred embodiment, the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate is obtained by reacting 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and isobutyric acid, wherein the mass ratio of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (i.e., dodecyl alcohol ester) to isobutyric acid is (755-765):(430-440).

[0070] In a preferred embodiment, the preparation of the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate comprises the following steps:

[0071] Add 755-765 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 430-440 parts by weight of isobutyric acid, 1-1.4 parts by weight of isopropyl titanate and 175-185 parts by weight of cyclohexane to a reactor equipped with a water separator, and mix thoroughly. The water separator has been pre-filled with cyclohexane.

[0072] First, slowly raise the temperature to 110-120℃ for preliminary dehydration to remove any trace amounts of water that may be present in the system. Then, raise the temperature to 160℃ and maintain this temperature for esterification for 6-7 hours. The water generated in the reaction will form an azeotrope with cyclohexane and be carried out.

[0073] After the reaction was completed, the mixture was cooled to below 60°C, and cyclohexane was recovered by vacuum distillation. The reaction solution was transferred to a separatory funnel and slowly washed with an equal volume of warm saturated sodium bicarbonate solution. After standing, the lower aqueous phase was completely separated. The organic phase was then washed 1-2 times with warm water until the aqueous phase was neutral. The organic phase was collected, dried, filtered, and distilled to obtain 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0074] The preparation of a waterproof and decorative integrated coating includes the following steps:

[0075] a) Add the specified amounts of ethylene glycol, dispersant, 2 / 3 of the specified amount of water, and half of the specified amount of defoamer to the reactor, and stir to mix evenly;

[0076] b) Then add the specified amounts of pigment, heavy calcium carbonate, flake kaolin, silica powder, modified graphene oxide and nano silica, stir and mix evenly, add the resulting mixture to the grinder, use zirconium dioxide as the grinding media ball to grind the mixture, after grinding, separate the resulting grinding liquid from the zirconium beads, use the remaining 1 / 3 of the specified amount of deionized water to clean the grinder, stir and mix the cleaning liquid and grinding liquid evenly;

[0077] c) Then add the specified amounts of silicone emulsion and acrylic emulsion, and stir to mix evenly; then add the specified amounts of film-forming aid, ultraviolet absorber, light stabilizer, heat stabilizer, water repellent, leveling agent and the remaining defoamer, and stir to mix evenly; then add the specified amounts of preservative and thickener, and stir to mix evenly to obtain a waterproof and decorative integrated coating.

[0078] Compared with the prior art, the present invention has the following significant advantages:

[0079] The coating provided by this invention has both waterproof and decorative functions, while also exhibiting excellent weather resistance, stain resistance, and adhesion strength. It can be used as an integrated waterproof and decorative coating for building walls and has extremely high industrial application value. Detailed Implementation

[0080] The technical solution of the present invention will be further described in detail and completely below with reference to the embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the manufacturer. Example 1

[0081] 1) Preparation of Organosilicon Emulsion

[0082] 1) Mix 32.5 parts by weight of 107 silicone rubber, 7.8 parts by weight of MQ silicone resin, 9.1 parts by weight of methyltriethoxysilane and 1.3 parts by weight of vinyltrimethoxysilane evenly to obtain an oil phase;

[0083] 2.25 parts by weight of AEO-3 (fatty alcohol polyoxyethylene ether), 1.35 parts by weight of SDS (sodium dodecyl sulfate), and 0.9 parts by weight of CO-436 (nonylphenol polyoxyethylene ether ammonium sulfate) were dissolved in 10 parts by weight of water to obtain the emulsifier phase.

[0084] 2) Pour the oil phase into the emulsification tank, and slowly add the emulsifier phase while stirring. Stir for 15 minutes to obtain the initial emulsion. Then slowly add 40 parts by weight of water and stir for 15 minutes. Then transfer the obtained emulsion to a homogenizer and homogenize it 4 times at 5 MPa to obtain a stable pre-emulsion.

[0085] 3) Transfer the pre-emulsion to an emulsification vessel, add 0.05 parts by weight of catalyst (Borchi Kat24) while stirring, mix thoroughly, then add 5 wt% NaOH aqueous solution to adjust the pH of the system to 10-11, heat to 60℃, maintain the temperature for 5 hours, and monitor the viscosity change of the system until the viscosity is basically stable. After the reaction is complete, cool the system to room temperature, adjust the pH to 6.5-7.5 with glacial acetic acid, then add 1.7 parts by weight of preservative (Acticide MBS), stir for 30 minutes, filter, and obtain the organosilicon emulsion.

[0086] (ii) Preparation of acrylic emulsion

[0087] 1) In an emulsifying tank, mix 280 parts by weight of water, 4 parts by weight of reactive emulsifier (DNS-86) and 2 parts by weight of anionic emulsifier (A-102) evenly, then add 150 parts by weight of methyl methacrylate, 50 parts by weight of cyclohexyl methacrylate, 100 parts by weight of butyl acrylate, 30 parts by weight of lauryl methacrylate, 10 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of glycidyl methacrylate and 5 parts by weight of acrylic acid, mix evenly to obtain a stable pre-emulsion;

[0088] Dissolve 6 parts by mass of initiator (ammonium persulfate) in 100 parts by mass of water to obtain an initiator solution;

[0089] Dissolve 2 parts by mass of buffer (sodium bicarbonate) in 20 parts by mass of water to obtain a buffer solution;

[0090] 15 parts by mass of KH-570 were diluted with 15 parts by mass of isopropanol to obtain a KH-570 solution.

[0091] 2) Add 120 parts by weight of water and the prepared buffer solution to the reactor, heat to 80°C, and simultaneously add 10% of the pre-emulsion and 10% of the initiator solution. Keep the reaction at this temperature for 25 minutes until the system shows a faint blue light, and the seed emulsion is obtained.

[0092] 3) Stabilize the temperature of the seed emulsion at 82±1℃, and simultaneously add the remaining 90% pre-emulsion and 90% initiator solution dropwise, completing the addition within 3.5 hours. During the addition process, maintain the pH of the system between 7 and 8. After the addition is complete, continue to keep the reaction at the temperature for 30 minutes.

[0093] 4) Heat the system to 85℃, slowly add KH-570 solution dropwise, and control the addition to be completed within 1 hour. After the addition is completed, keep it at 85℃ for 2 hours to mature.

[0094] 5) Cool the system to below 40°C, adjust the pH to 7.5-8.0 with ammonia, add 1.7 parts by weight of defoamer (BYK-019) and 1.7 parts by weight of preservative (Acticide MBS), stir for 30 minutes, filter, and obtain acrylic emulsion (solid content about 50%).

[0095] (III) Preparation of Modified Graphene Oxide

[0096] ① Add 100 parts by weight of water and 2 parts by weight of β-cyclodextrin to the reactor, heat to 70°C, keep warm and stir to completely dissolve β-cyclodextrin or form a uniform suspension, add 0.1 parts by weight of phase transfer catalyst (tetrabutylammonium bromide), keep warm and stir to mix evenly;

[0097] ② Dilute 1 part by mass of vinyltrimethoxysilane with 1.5 parts by mass of anhydrous ethanol, and then slowly add the resulting vinyltrimethoxysilane solution dropwise to the system in step ①, controlling the dropwise addition rate to be completed within 30 minutes. After the addition is completed, continue to keep warm and stir for 4 hours.

[0098] ③ Cool the reaction system to room temperature, adjust the pH to 4.5-5.0 with pH adjuster (glacial acetic acid), add 2wt% graphene oxide dispersion, wherein the dry weight of graphene oxide is 1 part by mass. After the addition is complete, place the reaction system in an ice-water bath and use a probe-type ultrasonic cell disruptor at 400W power for ultrasonic treatment for 30 minutes.

[0099] ④ After ultrasonic treatment, remove the ice-water bath, raise the temperature of the reaction system to 85°C, and keep it at this temperature for 7.5-8.5 hours under nitrogen protection. After the reaction is completed, allow it to cool naturally to room temperature, and then separate the solid and liquid (by centrifugation). Wash the separated solid with water three times, dry it (dry it in an 80°C forced-air drying oven for 12 hours), and grind it to obtain modified graphene oxide.

[0100] IV) Preparation of dispersants (polyacid emulsions)

[0101] 1) Dissolve 2 parts by mass of the initiator (ammonium persulfate) in 40 parts by mass of water to obtain an initiator solution; dissolve 1 part by mass of the reducing agent (ascorbic acid) in 40 parts by mass of water to obtain a reducing agent solution;

[0102] 30 parts by weight of methacrylic acid, 15 parts by weight of diallyl dimethyl ammonium chloride, 15 parts by weight of isobornyl methacrylate, 5 parts by weight of methoxy polyethylene glycol (1000) methacrylate, 10 parts by weight of allyl glycidyl ether, 1.5 parts by weight of chain transfer agent (3-mercaptopropionic acid) and 120 parts by weight of water / isopropanol mixed solvent (water:isopropanol mass ratio of 4:1) were mixed evenly to obtain monomer preemulsion;

[0103] 2) Add 30 parts by mass of water / isopropanol mixed solvent and 1 / 5 of monomer pre-emulsion to the reactor, mix well, heat to 60°C under nitrogen protection, add 1 / 5 of initiator solution and 1 / 5 of reducing agent solution dropwise, control the dropwise addition to be completed within 15 minutes, and continue to keep the temperature for 15 minutes after the dropwise addition is completed to obtain seed emulsion.

[0104] 3) Maintain a constant temperature of 60℃, and simultaneously add the remaining monomer pre-emulsion, initiator solution, and reducing agent solution dropwise, controlling the addition to be completed within 3.5 hours. After the addition is completed, raise the temperature to 70℃, maintain the temperature for 1.5 hours, and then stop the reaction. Cool the reaction system to below 40℃, and adjust the pH to 7.5-8.5 with a pH adjuster (aminomethylpropanol) while stirring.

[0105] 4) The obtained product was distilled under reduced pressure at 50°C to remove about 152 parts by mass of solvent, resulting in a viscous slurry. Then, 152 parts by mass of propylene glycol methyl ether was added to the viscous slurry as a substitute solvent and mixed evenly to obtain an emulsion of polyacid salt with a solid content of about 50%.

[0106] V) Preparation of film-forming aid (2,2,4-trimethyl-1,3-pentanediol diisobutyrate)

[0107] Add 760 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (i.e., dodecyl alcohol ester), 435 parts by weight of isobutyric acid, 1.2 parts by weight of the catalyst isopropyl titanate, and 180 parts by weight of the dehydrating agent cyclohexane to a reactor equipped with a water separator, and mix thoroughly. The water separator has been pre-filled with cyclohexane.

[0108] First, slowly raise the temperature to 115°C for preliminary dehydration to remove any trace amounts of water that may be present in the system. Then, raise the temperature to 160°C and maintain this temperature for esterification for 6.5 hours. The water produced in the reaction will form an azeotrope with cyclohexane and be carried out.

[0109] After the reaction was completed, the mixture was cooled to below 60°C, and cyclohexane was recovered by vacuum distillation. The reaction solution was transferred to a separatory funnel and slowly washed with an equal volume of warm saturated sodium bicarbonate solution. After standing, the lower aqueous phase was completely separated. The organic phase was then washed twice with warm water until the aqueous phase was neutral. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and distilled to obtain 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0110] (vi) Preparation of integrated waterproof and decorative coatings

[0111] a) Add 11 parts by mass of ethylene glycol, 2 parts by mass of dispersant (2.6 parts by mass of polycarboxylate emulsion (i.e., 1.3 parts by mass of polycarboxylate) + 0.7 parts by mass of terminal alkenyl alkylene dioxyethylene ether, wherein the molecular formula of the terminal alkenyl alkylene dioxyethylene ether is: C8H 14 O3(C2H4O) n (C2H4O) m H2 (n+m=43), 10 parts by weight of water and 0.2 parts by weight of defoamer (BYK-019), stir and mix evenly;

[0112] b) Then add 10 parts by weight of pigment (rutile titanium dioxide), 5 parts by weight of heavy calcium carbonate (1250 mesh), 5 parts by weight of flake kaolin, 3 parts by weight of silica powder, 0.8 parts by weight of modified graphene oxide and 0.2 parts by weight of nano silica, stir and mix evenly, add the resulting mixture to a grinder, use zirconium dioxide as the grinding media, and add zirconium beads with a mass of 65% of the mixture mass. During the grinding process, the grinder temperature is ≤30℃ to grind the mixture. After grinding, separate the resulting grinding liquid from the zirconium beads, use the remaining 5 parts by weight of deionized water to clean the grinder, and stir and mix the cleaning liquid and grinding liquid evenly.

[0113] c) Then add 22 parts by weight of silicone emulsion and 18 parts by weight of acrylic emulsion, and stir to mix evenly; then add 2 parts by weight of film-forming aid (2,2,4-trimethyl-1,3-pentanediol diisobutyrate), 0.8 parts by weight of UV absorber (Tinuvin 1130), 0.8 parts by weight of light stabilizer (Tinuvin 123), 0.1 parts by weight of heat stabilizer (Irgafos 168), 1.5 parts by weight of water repellent (TEGO® Phobe 1401), 0.4 parts by weight of leveling agent (TEGO® Glide 100), and the remaining 0.2 parts by weight of defoamer (BYK-019), and stir to mix evenly; then add 0.3 parts by weight of preservative (Acticide MBS) and 0.6 parts by weight of thickener (ASE-60: RM-2020). A mixture of NPR at a mass ratio of 65:35 is stirred and mixed evenly to obtain an integrated waterproof and decorative coating.

[0114] Example 2

[0115] The difference between this embodiment and Embodiment 1 is that:

[0116] a) Add 1.5 parts by weight of ethylene glycol, 2.5 parts by weight of dispersant (1.25 parts by weight of polycarboxylate emulsion (i.e., 1.625 parts by weight of polycarboxylate) + 0.875 parts by weight of terminal alkenyl alkylene dioxyethylene ether to the reactor, wherein the molecular formula of the terminal alkenyl alkylene dioxyethylene ether is: C8H 14 O3(C2H4O) n (C2H4O) m H2 (n+m=63), 12 parts by weight of water and 0.25 parts by weight of defoamer (BYK-019), stir and mix evenly;

[0117] b) Then add 11 parts by weight of pigment (iron oxide red), 6.5 parts by weight of heavy calcium carbonate (1250 mesh), 6 parts by weight of flake kaolin, 3.5 parts by weight of silica powder, 0.9 parts by weight of modified graphene oxide and 0.25 parts by weight of nano silica, stir and mix evenly, add the resulting mixture to a grinder, use zirconium dioxide as the grinding media, and add zirconium beads with a mass of 65% of the mixture mass. During the grinding process, the grinder temperature is ≤30℃ to grind the mixture. After grinding, separate the resulting grinding liquid from the zirconium beads, use the remaining 6 parts by weight of deionized water to clean the grinder, and stir and mix the cleaning liquid and grinding liquid evenly.

[0118] c) Then add 25 parts by weight of silicone emulsion and 20 parts by weight of acrylic emulsion, and stir to mix evenly; then add 2.25 parts by weight of film-forming aid (2,2,4-trimethyl-1,3-pentanediol diisobutyrate), 0.9 parts by weight of UV absorber (Tinuvin 1130), 0.9 parts by weight of light stabilizer (Tinuvin 123), 0.2 parts by weight of heat stabilizer (Irgafos 168), 1.8 parts by weight of water repellent (TEGO® Phobe 1401), 0.5 parts by weight of leveling agent (TEGO® Glide 100), and the remaining 0.25 parts by weight of defoamer (BYK-019), and stir to mix evenly; then add 0.4 parts by weight of preservative (Acticide MBS) and 0.7 parts by weight of thickener (ASE-60: RM-2020). A mixture of NPR at a mass ratio of 65:35 is stirred and mixed evenly to obtain an integrated waterproof and decorative coating. Example 3

[0119] The difference between this embodiment and Embodiment 1 is that:

[0120] a) Add 2 parts by mass of ethylene glycol, 3 parts by mass of dispersant (3.9 parts by mass of polycarboxylate emulsion (i.e., 1.95 parts by mass of polycarboxylate) + 1.05 parts by mass of terminal alkenyl alkylene dioxyethylene ether, wherein the molecular formula of the terminal alkenyl alkylene dioxyethylene ether is: C8H 14 O3(C2H4O) n (C2H4O) m H2 (n+m=83), 13.3 parts by weight of water and 0.3 parts by weight of defoamer (BYK-019), stir and mix evenly;

[0121] b) Then add 12 parts by weight of pigment (phthalocyanine blue), 8 parts by weight of heavy calcium carbonate (1250 mesh), 7 parts by weight of flake kaolin, 4 parts by weight of silica powder, 1.0 parts by weight of modified graphene oxide and 0.3 parts by weight of nano silica, stir and mix evenly, add the resulting mixture to a grinder, use zirconium dioxide as the grinding media, and add zirconium beads with a mass of 65% of the mixture mass. During the grinding process, the grinder temperature is ≤30℃ to grind the mixture. After grinding, separate the resulting grinding liquid from the zirconium beads, use the remaining 6.7 parts by weight of deionized water to clean the grinder, and stir and mix the cleaning liquid and grinding liquid evenly.

[0122] c) Then add 28 parts by weight of silicone emulsion and 22 parts by weight of acrylic emulsion, and stir to mix evenly; then add 2.5 parts by weight of film-forming aid (2,2,4-trimethyl-1,3-pentanediol diisobutyrate), 1 part by weight of UV absorber (Tinuvin 1130), 1 part by weight of light stabilizer (Tinuvin 123), 0.3 parts by weight of heat stabilizer (Irgafos 168), 2 parts by weight of water repellent (TEGO® Phobe 1401), 0.6 parts by weight of leveling agent (TEGO® Glide 100), and the remaining 0.3 parts by weight of defoamer (BYK-019), and stir to mix evenly; then add 0.5 parts by weight of preservative (Acticide MBS) and 0.8 parts by weight of thickener (a mixture of ASE-60 and RM-2020 NPR at a mass ratio of 65:35), and stir to mix evenly to obtain a waterproof and decorative integrated coating.

[0123] Comparative Example 1

[0124] The difference between this comparative example and Example 1 is as follows:

[0125] The acrylic emulsion used in the coating is prepared as follows:

[0126] 1) In an emulsifying tank, add 280 parts by weight of water, 4 parts by weight of SDS, and 4 parts by weight of OP-10, and stir to dissolve; add 180 parts by weight of methyl methacrylate, 120 parts by weight of butyl acrylate, and 3 parts by weight of acrylic acid, and mix evenly to obtain a pre-emulsion.

[0127] Dissolve 6 parts by mass of ammonium persulfate in 100 parts by mass of water to obtain an initiator solution;

[0128] Dissolve 2 parts by mass of sodium bicarbonate in 20 parts by mass of water to obtain a buffer solution;

[0129] 2) Add 120 parts by weight of water and buffer solution to the reactor, heat to 80°C, add about 10% of pre-emulsion and 10% of initiator solution, and keep the reaction at this temperature for 25 minutes.

[0130] 3) Stabilize the temperature at 82±1℃, and simultaneously add the remaining pre-emulsion and initiator solution, completing the addition within 3.5 hours. After the addition is complete, keep the reaction at this temperature for 30 minutes.

[0131] 4) Cool the system to below 40℃, adjust the pH to 7.5-8.0 with ammonia, add 1.7 parts by weight of defoamer (BYK-019) and 1.7 parts by weight of preservative (Acticide MBS), stir for 30 minutes, filter, and discharge to obtain the comparative acrylic emulsion;

[0132] The graphene used in the coating is ordinary graphene oxide that has not undergone modification.

[0133] The dispersant used in the coating is 1.3 parts by weight of linear polycarboxylate dispersant SN-5040 from Nopco Japan and 0.7 parts by weight of single-tailed fatty alcohol polyoxyethylene ether AEO-9.

[0134] The film-forming aid used in the coating is dodecyl alcohol ester.

[0135] Comparative Example 2

[0136] The difference between this comparative example and Example 1 is as follows:

[0137] The acrylic emulsion used in the coating is the same as the acrylic emulsion in Comparative Example 1;

[0138] The coating does not contain modified graphene oxide or nano-silica;

[0139] The dispersant used in the coating is 2 parts by weight of SN-5040 linear polycarboxylate dispersant from Nopco Japan. That is, the dispersant is a common polycarboxylate dispersant and does not contain polyoxyethylene ether dispersants.

[0140] The film-forming aid used in the coating is dodecyl alcohol ester.

[0141] Performance testing

[0142] The stain resistance and artificial weathering resistance of the coatings prepared in Examples 1-3 and Comparative Examples 1-2 were tested according to the standard of GB / T 9755-2024 "Synthetic Resin Emulsion Wall Coatings" for exterior wall paints.

[0143] The impermeability pressure / MPa of the coatings prepared in Examples 1-3 and Comparative Examples 1-2 was tested according to the standard of JC / T 2090-2011 "Polymer Cement Waterproofing Grout".

[0144] The tensile strength, bond strength (untreated), impermeability (back side of mortar), and water impermeability (0.3 MPa, 30 min) of the coatings prepared in Examples 1-3 and Comparative Examples 1-2 were tested according to the standard GB / T 23445-2009 "Polymer Cement Waterproof Coatings".

[0145] According to the standard JG / T 309-2011 "Determination and Classification of Water Vapor Transmission Rate of Exterior Wall Coatings", the water vapor transmission rate V / g / (m) of the coatings prepared in Examples 1-3 and Comparative Examples 1-2 was determined. 2 ·d) Conduct the test;

[0146] The test results are shown in Table 1.

[0147] Table 1 Performance test data of the coatings prepared in Examples 1-3 and Comparative Examples 1-2

[0148]

[0149] As shown in Table 1, the coatings prepared in the examples exhibit the following characteristics: stain resistance <10%, artificial weathering resistance >2000 hours, impermeability pressure >1 MPa, tensile strength ≥3 MPa, bond strength (untreated) >2.5 MPa, impermeability (mortar back side) ≥1.5 MPa, impermeability at 0.3 MPa for 30 minutes, and water vapor transmission rate >35V / g / (m²). 2 •d) It possesses excellent water resistance, stain resistance, weather resistance, and bonding strength, exhibiting superior overall performance. It can be used as an integrated waterproof and decorative coating for building walls, especially exterior walls. Furthermore, as can be seen from the table, the coatings prepared in Examples 1-3 exhibit significantly better performance than those prepared in Comparative Examples 1-2. This may be because:

[0150] 1) The acrylic emulsion used in the examples is a modified acrylic emulsion. The glycidyl methacrylate used can provide crosslinking points, enhancing water resistance and adhesion. The KH-570 silane coupling agent can improve the adhesion to inorganic fillers and substrates. The cyclohexyl methacrylate and lauryl methacrylate used can improve the rigidity of chain segments, weather resistance, and hydrophobicity. The final acrylic emulsion can form a core-shell structure, enhancing film-forming properties and mechanical strength. In contrast, the acrylic emulsion used in the comparative example is a common acrylic emulsion, containing only basic monomers (methyl methacrylate, butyl acrylate, and acrylic acid), lacking crosslinking structure and silane modification. As a result, the coating using this acrylic emulsion has poor water resistance, low adhesion strength, poor aging performance, and is prone to chalking and yellowing.

[0151] 2) The graphene oxide used in the examples is modified with β-cyclodextrin and vinyltrimethoxysilane, which can effectively improve its dispersibility in emulsions, enhance the interfacial bonding with the polymer matrix, form a physical barrier layer, block water, oxygen and ion penetration, and improve the coating's impermeability, mechanical strength and aging resistance; while the unmodified graphene oxide used in Comparative Example 1 is prone to agglomeration, has poor dispersibility, and may even become a defect point; Comparative Example 2 does not use graphene oxide and nano silica, lacks nano-reinforcing effect, and has poor coating density.

[0152] 3) The dispersant system used in the examples is a composite of a self-made polycarboxylate emulsion and a terminal alkenyl alkylene double-tailed polyoxyethylene ether. The self-made polycarboxylate has good dispersibility, and the double-tailed structure of the terminal alkenyl alkylene double-tailed polyoxyethylene ether can provide steric stability. The terminal alkenyl groups participate in polymerization, which enhances the compatibility between the dispersant and the emulsion. Overall, this dispersant system can effectively disperse pigments and fillers and prevent sedimentation and flocculation. In contrast, the dispersant system used in Comparative Example 1 is a common linear polycarboxylate and a single-tailed polyether, which has low dispersion efficiency, easily leads to filler agglomeration, cannot participate in film formation, and reduces the density of the coating. The dispersant used in Comparative Example 2 is a common linear polycarboxylate, which has even lower dispersion efficiency.

[0153] 4) The film-forming aid used in the examples is a self-made 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, which has high film-forming efficiency, moderate evaporation rate, good compatibility with organosilicon and acrylic emulsion, and promotes the formation of a continuous and dense coating film; while the film-forming aid used in the comparative example is dodecyl alcohol ester, which has lower film-forming efficiency, is easy to leave residues, affects water resistance, has poor compatibility with silicone resin, and may lead to microphase separation.

[0154] In summary, the coating in the embodiments achieves a good synergistic effect among its components through a comprehensive approach including self-made acrylic emulsion, modified graphene oxide, special dispersant, self-made film-forming aid, and nanofiller composite system, thereby realizing a waterproof and decorative integrated coating with high weather resistance, high impermeability, strong adhesion, and good breathability.

[0155] Finally, it should be noted that the above are only some preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention shall fall within the scope of protection of the present invention.

Claims

1. A waterproof and decorative integrated coating, characterized in that, It has the following composition and proportions: Organosilicon emulsion: 22-28 parts by weight; Acrylic emulsion: 18-22 parts by weight; Pigment: 10-12 parts by weight; Heavy calcium carbonate: 5-8 parts by weight; Flake kaolin: 5-7 parts by weight; Silica powder: 3-4 parts by weight; Modified graphene oxide: 0.8-1.0 parts by weight; Nano-silica: 0.2-0.3 parts by weight; Ethylene glycol: 1-2 parts by weight; Ultraviolet absorber: 0.8-1 parts by weight; Light stabilizer: 0.8-1 parts by weight; Heat stabilizer: 0.1-0.3 parts by weight; Dispersant: 2-3 parts by weight; Water-repellent agent: 1.5-2 parts by weight; Film-forming aid: 2-2.5 parts by weight; Defoamer: 0.4-0.6 parts by weight; Leveling agent: 0.4-0.6 parts by weight; Thickener: 0.6-0.8 parts by weight; Preservative: 0.3-0.5 parts by weight; Water: 15-20 parts by weight; The acrylic emulsion is obtained by polymerizing methyl methacrylate, cyclohexyl methacrylate, butyl acrylate, lauryl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid, and KH-570. The modified graphene oxide is obtained by modifying graphene oxide with β-cyclodextrin and vinyltrimethoxysilane; The dispersant is composed of a polycarboxylate and a di-tailed polyoxyethylene ether in a mass ratio of 65:35; the polycarboxylate is obtained by reacting methacrylic acid, diallyl dimethyl ammonium chloride, isobornyl methacrylate, methoxy polyethylene glycol methacrylate, and allyl glycidyl ether, wherein the mass ratio of methacrylic acid: diallyl dimethyl ammonium chloride: isobornyl methacrylate: methoxy polyethylene glycol methacrylate: allyl glycidyl ether is (29-31):(14-16):(14-16):(4-6):(9-11); the di-tailed polyoxyethylene ether is an alkenyl alkyl di-tailed polyoxyethylene ether with the molecular formula: C8H 14 O3(C2H4O) n (C2H4O) m H2, n+m are any natural numbers between 20 and 100; The film-forming aid is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

2. The waterproof and decorative integrated coating according to claim 1, characterized in that: The acrylic emulsion is obtained by polymerization of 149-151 parts by weight of methyl methacrylate, 49-51 parts by weight of cyclohexyl methacrylate, 99-101 parts by weight of butyl acrylate, 29-31 parts by weight of lauryl methacrylate, 9-11 parts by weight of hydroxyethyl methacrylate, 9-11 parts by weight of glycidyl methacrylate, 4-6 parts by weight of acrylic acid, and 14-16 parts by weight of KH-570.

3. The waterproof and decorative integrated coating according to claim 1, characterized in that, In the modified graphene oxide, the mass ratio of β-cyclodextrin:vinyltrimethoxysilane:graphene oxide is (1.8-2.2):(0.8-1.2):(0.8-1.2).

4. The waterproof and decorative integrated coating according to claim 1, characterized in that, The organosilicon emulsion is obtained by reacting 107 silicone rubber, MQ silicone resin, methyltriethoxysilane and vinyltrimethoxysilane, wherein the mass ratio of 107 silicone rubber:MQ silicone resin:methyltriethoxysilane:vinyltrimethoxysilane is (32-33):(7.6-8):(9-9.2):(1.2-1.4).

5. The waterproof and decorative integrated coating according to claim 1, characterized in that: In the waterproof and decorative integrated coating, the pigment is selected from at least one of titanium dioxide, iron oxide yellow, iron oxide red, phthalocyanine blue, phthalocyanine green, iron oxide black, and iron oxide brown.

6. The waterproof and decorative integrated coating according to claim 1, characterized in that: In the waterproof and decorative integrated coating, the ultraviolet absorber is a benzotriazole; the light stabilizer is a hindered amine; the heat stabilizer is a phosphite / phosphonate; the water repellent is TEGO® Phobe 1401 or 1650; the defoamer is BYK-019 or BYK-028; the leveling agent is TEGO® Glide 100 or 450; the thickener is a mixture of ASE-60 and RM-2020 NPR at a mass ratio of 65:35; and the preservative is Acticide MBS.

7. A method for preparing the waterproof and decorative integrated coating according to claim 1, characterized in that, Includes the following steps: a) Add the specified amounts of ethylene glycol, dispersant, 2 / 3 of the specified amount of water, and half of the specified amount of defoamer to the reactor, and stir to mix evenly; b) Then add the specified amounts of pigment, heavy calcium carbonate, flake kaolin, silica powder, modified graphene oxide and nano silica, stir and mix evenly, add the resulting mixture to the grinder, use zirconium dioxide as the grinding media ball to grind the mixture, after grinding, separate the resulting grinding liquid from the zirconium dioxide, use the remaining 1 / 3 of the specified amount of deionized water to clean the grinder, stir and mix the cleaning liquid and grinding liquid evenly; c) Then add the specified amounts of silicone emulsion and acrylic emulsion, and stir to mix evenly; then add the specified amounts of film-forming aid, ultraviolet absorber, light stabilizer, heat stabilizer, water repellent, leveling agent and the remaining defoamer, and stir to mix evenly; then add the specified amounts of preservative and thickener, and stir to mix evenly to obtain a waterproof and decorative integrated coating.

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