Mosquito repellent group modified polyacrylate emulsion, exterior wall waterproof coating and preparation method

Abstract

The present invention discloses a mosquito repellent group modified polyacrylate emulsion, an exterior wall waterproof coating and a preparation method. The mosquito repellent group modified polyacrylate emulsion provided by the present invention is made of raw materials comprising the following parts by weight: 45 to 60 parts of soft monomers, 5 to 20 parts of hard monomers, 0 to 1.5 parts of functional monomers, and 25 to 40 parts of mosquito repellent group monomers. The present invention also provides an exterior wall waterproof coating, comprising a liquid component and a powder component, wherein the liquid component comprises the mosquito repellent group modified polyacrylate emulsion. The exterior wall waterproof coating prepared by the present invention through the preferred combination of a composite mosquito repellent synergist with a polymer emulsion, aluminate cement, and a pigment filler has excellent waterproof and decorative effects, weather resistance, and a good mosquito repellent rate.

Description

Technical Field

[0001] The invention relates to a waterproof coating, in particular to a mosquito repellent group modified polyacrylate emulsion, an exterior wall waterproof coating and a preparation method thereof. Background Art

[0002] In buildings, the exterior wall of a building is a very important component and plays a very important role; it can not only effectively isolate the internal environment of the building from the harsh external environment, but also play the role of sunshade, waterproofing, and thermal insulation. In recent years, with the continuous development of social economy, people have put forward higher and higher requirements for the artistry, aesthetics, and decoration of the exterior walls of buildings. According to the requirements of GB 55030-2022 "General Specifications for Buildings and Municipal Engineering", the waterproofing of the exterior walls of buildings should be designed as a whole according to the category of the engineering waterproofing use environment in the area where the project is located, and the wall waterproofing layer should be set according to the engineering waterproofing level. At present, the commonly used waterproof design scheme for the exterior wall is usually to use non-exposed waterproof coatings. After the construction is completed, the waterproof coating needs to be protected to avoid aging and cracking of the waterproof coating, which affects the waterproof effect. The waterproof layer does not play a decorative role and increase the aesthetics. In addition, the waterproof layer and the external decorative protective layer are prone to bonding and compatibility problems, which affect the safety of the building's exterior wall. In addition, since most parts of my country have heavy rain in the summer, the humid environment easily breeds mosquitoes, which can spread infectious diseases such as dengue fever, malaria, meningitis, and Zika, endangering our physical health and life safety. Therefore, mosquito repellent work is particularly important. Summary of the invention

[0003] In view of this, the present invention proposes a mosquito repellent group modified polyacrylate emulsion, an exterior wall waterproof coating and a preparation method.

[0004] The mosquito repellent group modified polyacrylate emulsion provided by the present invention is prepared from the following raw materials in parts by weight: 45 to 60 parts of soft monomer, 5 to 20 parts of hard monomer, 0 to 1.5 parts of functional monomer, and 25 to 40 parts of mosquito repellent group monomer;

[0005] The soft monomer has a relatively low glass transition temperature, usually -20°C to -70°C, measured by differential scanning calorimetry according to Part 2 of GB / T19466.2-2004; the soft monomer is selected from at least one of butyl acrylate (BA), isooctyl acrylate (2-EHA), ethyl acrylate (EA), n-octyl acrylate (OA), and isooctyl methacrylate (2-EHMA);

[0006] The hard monomer has a relatively high glass transition temperature, usually greater than 0°C, as measured by differential scanning calorimetry according to Part 2 of GB / T19466.2-2004; the hard monomer is selected from at least one of methyl acrylate (MA), methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (BMA), styrene SM, and vinyl acetate;

[0007] The functional monomer is selected from at least one of acrylic acid (AA), methacrylic acid (MAA), and acrylonitrile (AN);

[0008] The mosquito repellent group monomer is selected from at least one of d-propargylthrin, d-allethrin, d-tetrafluorothrin, and carbamate. After copolymerization with soft monomers, hard monomers, and functional monomers, an acrylate copolymer emulsion with functional groups can be obtained, which can significantly improve the cohesion and bonding strength of the coating film.

[0009] Preferably, the mosquito repellent group modified polyacrylate emulsion is made of raw materials including the following parts by weight: 45-55 parts of soft monomers, 6-16 parts of hard monomers, 0.05-1.0 parts of functional monomers, and 30-40 parts of mosquito repellent group monomers.

[0010] The solid content of the mosquito repellent group modified polyacrylate emulsion is 45-60%; the glass transition temperature is -10°C to 0°C, the weight content of the mosquito repellent group monomer is 25-40%, for example, 30-40%; the weight content of the soft monomer is 45-60%, for example, 45-55%; the weight content of the hard monomer is 5-20%, for example, 6-16%; the weight content of the functional monomer is 0.0-1.5%, for example, 0.05-1.0%; the weight content of each monomer is based on the weight of the monomer composition. In a specific embodiment of the present invention, the monomer composition is composed of soft monomers, hard monomers, mosquito repellent group monomers and optional functional monomers. The term "mosquito repellent group monomer modification" refers to the introduction of mosquito repellent groups into the polymer chain of polyacrylate, that is, the mosquito repellent group monomer can be added in the process of synthesizing polyacrylate to achieve this purpose.

[0011] The invention also provides a method for preparing the mosquito repellent group modified polyacrylate emulsion.

[0012] The preparation method of the mosquito repellent group modified polyacrylate emulsion provided by the present invention comprises the following steps:

[0013] (1) adding water into a pre-emulsification device, adding an emulsifier sodium dodecylbenzene sulfonate or sodium secondary alkyl sulfate, stirring, and then adding a soft monomer, a hard monomer, a functional monomer, and a mosquito repellent group monomer, respectively, and stirring to prepare a pre-emulsion A;

[0014] (2) adding water and an emulsifier into a reaction kettle, wherein the emulsifier is sodium alkyl sulfonate or sodium secondary alkyl sulfate, and heating the kettle to 80 to 90° C. to obtain a reaction kettle bottom material liquid B;

[0015] (3) adding water and a catalyst into a catalytic cylinder, stirring and dissolving, and obtaining an initiator aqueous solution C; wherein the catalyst is selected from any one of the following combinations: ammonium persulfate and sodium bisulfite, cumene hydroperoxide and ferrous chloride, potassium persulfate and ferrous chloride;

[0016] (4) dissolving the initiator aqueous solution C in water and stirring to dissolve, thereby obtaining an initial initiator solution D;

[0017] (5) 3% to 10% of the total mass of the pre-emulsion A is added to the bottom liquid B of the reactor; then the initial initiator solution D is added to the reactor, and the reaction is carried out for 20 to 30 minutes, and the reaction temperature is controlled at 80 to 90° C.; the remaining pre-emulsion A and the remaining initiator aqueous solution C are simultaneously added dropwise to the reactor, and the addition time is 3.0 to 5.0 hours, and the temperature is controlled at 80 to 90° C.; the temperature is kept for 0.5 to 1.5 hours; after the temperature is kept, the temperature is lowered to 30 to 50° C., and the solid content is adjusted to 45% to 60% with clean water to obtain the mosquito repellent group modified polyacrylate emulsion.

[0018] Optionally, in step (1), 15 to 25 parts of water are added; 0.5 to 2.0 parts of emulsifier sodium dodecylbenzene sulfonate or sodium secondary alkyl sulfate are added; 45 to 55 parts of soft monomer, 6 to 16 parts of hard monomer, 0.05 to 1.0 parts of functional monomer, and 30 to 40 parts of mosquito repellent group monomer are added.

[0019] Optionally, in step (2), 35 to 50 parts of water and 0.05 to 0.5 parts of an emulsifier, sodium alkyl sulfonate or sodium secondary alkyl sulfate, are added to the reaction kettle.

[0020] Optionally, in step (3), 1 to 5 parts of water, 0.03 to 0.10 parts of ammonium persulfate, cumene hydroperoxide or potassium persulfate, and 0.03 to 0.10 parts of sodium bisulfite or ferrous chloride are added to the catalytic cylinder.

[0021] Optionally, the water in steps (1) to (4) is deionized water.

[0022] The invention also provides an exterior wall waterproof coating.

[0023] The exterior wall waterproof coating provided by the present invention comprises a liquid component and a powder component, wherein the liquid component comprises the following raw materials in parts by weight: 75-90 parts of the mosquito repellent group modified polyacrylate emulsion, 0.2-0.50 parts of preservatives, 1.0-8.0 parts of water, 0.1-1.0 parts of wetting dispersants, 0.2-0.50 parts of defoamers, 0.5-1.0 parts of thickeners, 0.5-5 parts of color pastes, 2.0-8.0 parts of composite mosquito repellent synergists, and 0.5-2.0 parts of magnesium aluminum silicate;

[0024] The powder component includes the following raw materials in parts by weight: 30-60 parts of aluminate cement, 10-30 parts of graded sand, 0.2-0.50 parts of water reducing agent, and 25-40 parts of pigments and fillers;

[0025] The mass ratio of the liquid component to the powder component is 1:(1.5-2.5).

[0026] Optionally, the preservative is selected from at least one of isothiazolinone (also known as kasson), phenylisothiazolinone, and 2,2-dibromopropionamide; for example, it can be a commercially available kasson preservative. The preservative prevents microorganisms from degrading the liquid material of the waterproof coating, and can solve a series of problems of the waterproof coating caused by bacterial infection, such as mildew, deterioration, fermentation, odor, and demulsification.

[0027] Optionally, the water is municipal tap water;

[0028] Optionally, the wetting and dispersing agent includes but is not limited to one or a mixture of inorganic dispersants or organic dispersants, the inorganic dispersants include but are not limited to sodium tripolyphosphate, sodium hexametaphosphate, polycarboxylates, and the organic dispersants include but are not limited to triethylhexyl phosphate; the main functions of the wetting and dispersing agent are to wetting and disperse powders such as cement, pigments and fillers, to enhance the compatibility of the polymer emulsion with the powder and the mosquito repellent enhancer, to prevent the powder from settling during the construction process, and to adjust the surface tension of the system so that the coating can be smoothly spread on the base layer without causing shrinkage holes or pinholes, thereby improving the uniformity of the coating.

[0029] Optionally, the defoaming agent includes but is not limited to one or more of mineral oils, silicones, and high molecular polymers; the defoaming agent can eliminate or reduce bubbles in the coating during production and construction, which is beneficial to improving the density of the coating and the appearance of the coating.

[0030] Optionally, the thickener is a functional thickener, including but not limited to one or more of cellulose thickener, inorganic thickener, polyurethane thickener, acrylic thickener and alkali swelling thickener; it can effectively improve the viscosity of the waterproof coating, prevent the coating from settling, and prevent the coating from sagging during facade construction. In addition, by matching thickeners with different shear effects (such as high shear, low shear, and medium shear thickeners) and coordinating with different construction tools, a coating with a decorative effect of different textures can be obtained. For example, using Samsung Chemical's B50K cellulose ether with a low shear viscosity thickener Dow ASE60 can obtain a three-dimensional coating with a roughening effect; for example, using Dow's medium shear thickener TT935 with high shear thickeners RM-2020 and RM-8W can obtain a coating with good leveling properties.

[0031] The color paste mainly plays a role in color adjustment in the coating system. Adding different color pastes can obtain waterproof coatings of different colors. Optionally, the color paste is selected from at least one of commercially available water-based yellow color paste, phthalocyanine green, royal blue paste, red paste, and black paste; for example, the water-based color paste of Guangzhou Panyu Cody Color Co., Ltd. and Zhejiang Namei New Materials Co., Ltd.

[0032] Optionally, the composite mosquito repellent synergist comprises DEET, piperonyl butoxide and component A; the mass ratio thereof is: DEET: piperonyl butoxide: component A = 1: (0.5-1.0): (0.5-2.0); component A includes but is not limited to one or more of eucalyptol, linalool, geraniol, peppermint oil, garlic essential oil and thymol; DEET can work by blocking the 1-octen-3-ol of the insect olfactory receptors, and DEET does not affect the insect's ability to smell carbon dioxide, but can effectively make the insect lose the sense of the special smell of humans or animals. When mixed with other mosquito repellent ingredients, especially carbamates, the mosquito repellent effect can be enhanced; piperonyl butoxide is a broad-spectrum mosquito repellent synergist that can increase the activity of pyrethrins, various pyrethroids, rotenone and carbamate insecticides. Eucalyptus oil can release substances such as citronellal and eucalyptol, which emit a cool and refreshing smell, but it is an irritating smell for mosquitoes, which can achieve the purpose of repelling mosquitoes; linalool belongs to the chain terpene alcohol class, and has two isomers, α- and β-; it is a colorless liquid with the aroma of lily of the valley, and can also play a role in repelling mosquitoes and flies. Geraniol is a chemical organic substance, with Chinese aliases such as 3,7-dimethyl-2,6-octadien-1-ol and geranium alcohol. It contains volatile components of acyclic monoterpenoid compounds, has a mild, sweet rose scent, and tastes bitter; the smell of peppermint oil can quickly confuse the mosquito's sense of smell, making it unable to perceive the smell of the human body, thereby achieving the effect of repelling mosquitoes. In addition, peppermint contains essential oils and volatile compounds, such as menthol and menthone, which have mosquito repellent effects and can stimulate and anesthetize the sensory nerves of mosquitoes, keeping them away. Garlic essential oil is a multi-component mixture composed of allicin (C6H 10 OS2), allicin (C6H 10 O2S) and various sulfide compounds composed of allyl and methyl groups, including more than 40 sulfide compounds; allicin can volatilize into the air, inhibiting the ability of mosquitoes to sense carbon dioxide, making up for the shortcoming of DEET that cannot inhibit mosquitoes from sensing carbon dioxide. Thymol is an extract of plants such as thyme, with a pungent smell; by combining the mosquito repellent group with the composite mosquito repellent enhancer, it is possible to bypass the mosquito's resistance to pyrethroids, prevent mosquitoes from detoxifying, ensure mosquitoes escape or die, and make the resulting waterproof coating have a better mosquito repellent effect.

[0033] The magnesium aluminum silicate is used as a stabilizer for waterproof coatings, and its outstanding advantage is that it can stabilize emulsions. It has a certain thickening ability, reduces the possibility of emulsions becoming thinner or being destroyed, and can protect the storage stability of the composite mosquito repellent synergist and other components in the liquid. Magnesium aluminum silicate can stabilize various mineral oils, vegetable oils and emulsions containing anionic or non-ionic surfactants. It can also provide spreading, increase viscosity and film-forming properties.

[0034] Optionally, the strength grade of the aluminate cement is at least one of CA50, CA60, CA70, and CA80. Cement, as an inorganic gelling material, is a modifier of organic polymers. The carboxyl-COOH in the polymer emulsion can undergo a cross-linking reaction with the hydration reactants of the aluminate cement to form a large number of cross-linked bodies, such as aluminum carbonate, calcium carbonate, etc., thereby forming a special "cement / polymer" interface chemical bond bonding structure, and improving the cohesion, strength, water resistance and durability of the polymer coating through interface enhancement. Its main characteristics include high early strength, high temperature resistance and corrosion resistance. The aluminate cement hydration process generates aluminum hydroxide gel, which forms a protective film on the surface of the particles, and does not generate free calcium hydroxide by-products, thereby avoiding the by-products of the hydration reaction when using silicate cement, which causes the coating to be alkali-white (calcium hydroxide migrates to the surface of the coating under the action of water and capillaries, forming a phenomenon of whitening of the coating), affecting the appearance of the waterproof coating as an exterior wall decorative material.

[0035] Optionally, the graded sand is white quartz sand with a gradation of 80 to 200 meshes. Quartz sand as aggregate can form a good skeleton structure, and a good gradation can improve the pore structure of the repair coating, increase the density of the mortar, and be beneficial to the growth of the strength of the waterproof coating.

[0036] Optionally, the water reducer includes but is not limited to one or more of a high-efficiency polycarboxylate water reducer and a melamine water reducer; it has a high water reduction rate and high plasticity, can effectively disperse solid particles, and has excellent rheological properties, reduces water bleeding, and improves the early strength and ultimate strength of the product.

[0037] Optionally, the pigment filler is selected from one or more of 400 mesh heavy calcium, wollastonite powder, titanium dioxide, calcined kaolin, and mica powder to improve the workability of the coating, increase its density, impermeability, weather resistance, mechanical properties, and play an active filling and reinforcing role.

[0038] Further optionally, the wetting and dispersing agent is selected from one or more of Rohm and Haas dispersant OROTAN 1618, BYK-190 dispersant, San Nopco SN5040 dispersant, Ryan universal wetting agent EMULSOGEN LCN407, and Dow nonionic surfactant wetting agent EH-9;

[0039] Further optionally, the defoamer is selected from one or more of Kemira 6660 defoamer, Japan's NOPCO NXZ defoamer, BASF's 2410 defoamer, and Germany's BYK024 defoamer.

[0040] The invention also provides a method for preparing the exterior wall waterproof coating.

[0041] The preparation method of the exterior wall waterproof coating comprises:

[0042] (1) A liquid material production method comprising the following steps:

[0043] S1, weighing mosquito repellent group modified polyacrylate emulsion and putting it into a stirring tank, stirring;

[0044] S2. Weigh the preservative and water, mix them in advance, and put them into a stirring tank while stirring, and keep stirring;

[0045] S3, weigh the wetting dispersant, defoamer and thickener, put them into the dispersion kettle while stirring, and keep stirring;

[0046] S4, adding color paste, composite mosquito repellent, and magnesium aluminum silicate in sequence, and stirring;

[0047] S5, filter through a filter, and pack the material for later use;

[0048] (2) A powder production method comprising the following steps:

[0049] Weigh the raw materials according to the proportion, put them into the dispersion kettle, stir and disperse them evenly, and then pack them for use;

[0050] (3) According to the ratio of liquid material to powder material, the dispersed material is stirred to form a uniform slurry, thereby obtaining an exterior wall waterproof coating.

[0051] Beneficial effects:

[0052] The mosquito repellent group modified polyacrylate emulsion provided by the present invention has good compatibility with cement and composite mosquito repellent, and is the main film-forming substance of the coating. The polymer emulsion particles can cover the surface of cement particles and cement hydration products, or fill in the cracks of cement particles and hydration products to form a polymer network structure. The polymer emulsion improves the dry shrinkage and rigidity of cement, can improve the flexibility of waterproof coatings, the impermeability of cement mortar, freeze-thaw resistance, impermeability, etc. The polymer emulsion has good weather resistance and color retention, excellent adhesion and stain resistance, can effectively resist the photo-oxidative degradation of ultraviolet rays to the coating film, and the coating made from it has good durability and water resistance. After the introduction of monomers containing pyrethroid groups and carbamate groups, the groups with mosquito repellent effects are chemically bonded to the acrylic polymer chain, thus having the intrinsic mosquito repellent function. The mosquito repellent groups are released into the air when the temperature is high in summer. When the mosquito repellent active ingredients in the air reach a certain concentration, the closure of voltage-gated sodium channels in the mosquito nerve cells can be delayed, resulting in repeated and prolonged nerve discharges, causing the mosquitoes to lose motor coordination, and the nerves to become excited, resulting in paralysis due to spasms, and in severe cases, poisoning and death, or fleeing in panic. The mosquito repellent groups have the effects of repelling, paralyzing, knocking down and killing mosquitoes.

[0053] The waterproof coating provided by the present invention is an environmentally friendly water-based coating, and its physical properties meet the requirements of T / CECS 10108-2020 polymer cement waterproof decorative coatings. It also has a mosquito repellent function, can be used for waterproofing exterior walls and roofs of buildings, and has an exterior wall decorative effect. DETAILED DESCRIPTION

[0054] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0055] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0056] Example 1: Preparation of mosquito repellent group modified polyacrylate emulsion

[0057] The preparation method of mosquito repellent group modified polyacrylate emulsion comprises the following steps:

[0058] (1) Preparation of pre-emulsion A:

[0059] Put 15 parts of deionized water into the pre-emulsification device (Laizhou Longjun Machinery Co., Ltd.), add 0.5 parts of emulsifier such as sodium dodecylbenzene sulfonate while stirring, stir for 10 minutes, add 45 parts of soft monomer (butyl acrylate BA), 6 parts of hard monomer (methyl acrylate MA), 0.05 parts of functional monomer (acrylic acid AA), 30 parts of mosquito repellent group monomer (d-propylthrin), stir thoroughly for 30 minutes and set aside.

[0060] (2) Preparation of reactor bottom liquid B

[0061] Add 35 parts of deionized water and 0.05 parts of an emulsifier such as sodium alkyl sulfonate into a reaction kettle (Laizhou Longjun Machinery Co., Ltd.), and heat it to 80°C.

[0062] (3) Preparation of initiator aqueous solution C added dropwise to the catalyst cylinder:

[0063] Add 1 part of deionized water, 0.03 parts of ammonium persulfate, and 0.03 parts of sodium bisulfite into a catalytic cylinder (Laizhou Longjun Machinery Co., Ltd.), stir and fully dissolve for later use.

[0064] (4) Preparation of initial initiator solution D:

[0065] Dissolve 0.3 parts of an initiator, such as the above solution C, in 0.5 parts of deionized water and stir until fully dissolved to obtain an initial initiator solution D.

[0066] (5) Synthesis process

[0067] After the materials are prepared according to the above method, 3% of the total amount of material A is added to the bottom material liquid B of the reactor; after completion, the initial initiator solution D is poured into the reactor, and the reaction is carried out for 20 minutes, and the reaction temperature is controlled at 80°C; after completion, the remaining emulsion A and the initiator aqueous solution C are added dropwise at the same time, and the dropping time is 3.0 hours, and the temperature is controlled at 80°C at the same time; after completion, the heat is kept for 0.5h, and after the heat preservation is completed, the temperature is lowered to 30°C, and the solid content is adjusted to 45% with clean water to obtain a mosquito repellent group modified polyacrylate emulsion.

[0068] The test results of basic parameters of mosquito repellent group modified polyacrylate emulsion are shown in Table 1.

[0069] Table 1 Basic parameter test results of mosquito repellent group modified polyacrylate emulsion prepared in Example 1

[0070]

[0071] Example 2: Preparation of mosquito repellent group modified polyacrylate emulsion

[0072] The preparation method of mosquito repellent group modified polyacrylate emulsion comprises the following steps:

[0073] (1) Preparation of pre-emulsion A:

[0074] Add 20 parts of deionized water into the pre-emulsification device, add 1.0 part of emulsifier such as sodium dodecylbenzene sulfonate while stirring, stir for 10 minutes, add 50 parts of soft monomer (2-ethylhexyl acrylate, ethyl acrylate EA and n-octyl acrylate OA in a mass ratio of 25:15:10), 10 parts of hard monomer (methyl methacrylate MMA, ethyl methacrylate EMA and n-butyl methacrylate BMA in a mass ratio of 2:3:5), 0.08 parts of functional monomer (methacrylate MAA), 35 parts of mosquito repellent group monomer (d-allyl thrin and tetrafluoromethyl thrin in a mass ratio of 20:15), stir thoroughly for 30 minutes and set aside.

[0075] (2) Preparation of reactor bottom liquid B

[0076] Add 40 parts of deionized water and 0.2 parts of an emulsifier such as sodium alkyl sulfonate into the reaction kettle, and raise the temperature to 85°C.

[0077] (3) Preparation of initiator aqueous solution C added dropwise to the catalyst cylinder:

[0078] Add 2 parts of deionized water, 0.05 parts of cumene hydroperoxide, and 0.05 parts of ferrous chloride into a catalytic cylinder, stir until fully dissolved and set aside.

[0079] (4) Preparation of initial initiator solution D:

[0080] Dissolve 0.5 parts of an initiator, such as the above solution C, in 1.0 parts of deionized water and stir until fully dissolved to obtain an initial initiator solution D.

[0081] (5) Synthesis process

[0082] After the materials are prepared as described above, 6% of the total amount of material A is added to the bottom material liquid B of the reactor; after completion, the initial initiator solution D is poured into the reactor, and the reaction is carried out for 25 minutes, and the reaction temperature is controlled at 85°C; after completion, the remaining emulsion A and the initiator aqueous solution C are added dropwise at the same time, and the dropping time is 4.0 hours, and the temperature is controlled at 85°C at the same time; after completion, the temperature is kept warm for 1.0h, and after the insulation is completed, the temperature is lowered to 40°C, and the solid content is adjusted to 50% with clean water to obtain a mosquito repellent group modified polyacrylate emulsion.

[0083] The test results of basic parameters of mosquito repellent group modified polyacrylate emulsion are shown in Table 2.

[0084] Table 2 Basic parameter test results of mosquito repellent group modified polyacrylate emulsion prepared in Example 2

[0085]

[0086] Example 3: Preparation of mosquito repellent group modified polyacrylate emulsion

[0087] The preparation method of mosquito repellent group modified polyacrylate emulsion comprises the following steps:

[0088] (1) Preparation of pre-emulsion A:

[0089] Add 25 parts of deionized water into the pre-emulsification device, add 2.0 parts of emulsifier such as secondary alkyl sodium sulfate while stirring, stir for 10 minutes, add 55 parts of soft monomer (2-ethylhexyl methacrylate), 16 parts of hard monomer (styrene SM and vinyl acetate in a mass ratio of 6:10), 1.0 part of functional monomer (acrylonitrile AN), 40 parts of mosquito repellent group monomer (carbamic acid oxime ester, specifically S-methyl-N-[(methylcarbamoyl)-oxy]thioacetamiprate, i.e., methomyl, purchased from Shandong Tiansheng Biotechnology Co., Ltd.), stir thoroughly for 30 minutes and set aside.

[0090] (2) Preparation of reactor bottom liquid B

[0091] Add 50 parts of deionized water and 0.5 parts of an emulsifier such as sodium secondary alkyl sulfate into the reaction kettle, and raise the temperature to 90°C.

[0092] (3) Preparation of initiator aqueous solution C added dropwise to the catalyst cylinder:

[0093] Add 5 parts of deionized water, 0.10 parts of potassium persulfate and 0.10 parts of ferrous chloride into the catalytic cylinder, stir and fully dissolve them for later use.

[0094] (4) Preparation of initial initiator solution D:

[0095] Dissolve 0.8 parts of an initiator, such as the above solution C, in 1.5 parts of deionized water and stir until fully dissolved to obtain an initial initiator solution D.

[0096] (5) Synthesis process

[0097] After the materials are prepared according to the above method, 10% of the total amount of material A is added to the bottom material liquid B of the reactor; after completion, the initial initiator solution D is poured into the reactor, and the reaction is carried out for 30 minutes, and the reaction temperature is controlled at 90°C; after completion, the remaining emulsion A and the initiator aqueous solution C are added dropwise at the same time, and the dropping time is 5.0 hours, and the temperature is controlled at 90°C at the same time; after completion, the heat is kept for 1.5 hours, and after the heat preservation is completed, the temperature is lowered to 50°C, and the solid content is adjusted to 60% with clean water to obtain a mosquito repellent group modified polyacrylate emulsion.

[0098] The test results of basic parameters of mosquito repellent group modified polyacrylate emulsion are shown in Table 3.

[0099] Table 3 Basic parameter test results of mosquito repellent group modified polyacrylate emulsion prepared in Example 3

[0100]

[0101] Example 4: Preparation of exterior wall waterproof coating

[0102] Exterior wall waterproof coating is a two-component product, and the production process of each component is as follows:

[0103] (1) Liquid material production process:

[0104] S1. According to Table 4, weigh the mosquito repellent group-modified polyacrylate emulsion prepared in Example 1 above and put it into a stirring kettle, start stirring, and the speed is 300r / min to 500r / min;

[0105] S2. Weigh the preservative and clean water according to Table 4, mix them in advance, and gradually put them into the stirring tank while stirring, and keep stirring;

[0106] S3. Weigh the wetting dispersant, defoamer and thickener according to Table 4 and gradually add them into the dispersion kettle while stirring, and keep stirring;

[0107] S4, add color paste, composite mosquito repellent, and magnesium aluminum silicate in sequence, adjust the stirring speed to 800-1000r / min, and stir for 5-20 minutes;

[0108] S5. Filter the material with a 100-mesh filter and package it for later use;

[0109] (2) Powder production process:

[0110] After weighing various raw materials in proportion according to Table 4, transport them to the dispersion kettle through the pipeline or feeding port, stir and disperse them evenly, and then package them for use.

[0111] (3) According to the ratio of liquid material to powder material shown in Table 4, the dispersed material is stirred to form a uniform slurry to obtain an exterior wall waterproof coating.

[0112] Table 4 Example 4 Raw material types and proportions for preparing exterior wall waterproof coating

[0113]

[0114]

[0115] The exterior wall waterproof coating prepared in this embodiment is an environmentally friendly water-based coating, and its physical properties meet the requirements of T / CECS10108-2020 polymer cement waterproof decorative coating, and has a long-lasting waterproof effect and an exterior wall decorative effect. It also has an excellent mosquito repellent function and is particularly suitable for use on building roofs and exterior walls. The performance test results of the exterior wall waterproof coating prepared in this embodiment are shown in Table 5 below:

[0116] Table 5 Performance test results of the exterior wall waterproof coating prepared in Example 4

[0117]

[0118]

[0119] The repellency rate test is to evaluate the effectiveness of mosquito repellent products by calculating the probability of being bitten by mosquitoes.

[0120] Repellent rate test method: within a certain period of time (1 hour), in a certain space painted with the waterproof coating of the present invention (a room with an area of ​​about 10 square meters and open doors and windows can be selected, and there are a large number of mosquitoes in the surrounding environment of the room, or a certain number of mosquitoes are manually released outside the room during the test). 10 mosquitoes fly into the test area, and only one of them bites the tester, then the repellent rate of the mosquito repellent product is 90%.

[0121] Example 5: Preparation of exterior wall waterproof coating

[0122] Exterior wall waterproof coating is a two-component product, and the production process of each component is as follows:

[0123] (1) Liquid material production process:

[0124] S1. According to Table 6, weigh the mosquito repellent group-modified polyacrylate emulsion prepared in Example 2 above and put it into a stirring kettle, start stirring, and the speed is 300r / min to 500r / min;

[0125] S2. Weigh the preservative and clean water according to Table 6, mix them in advance, and gradually put them into the stirring tank while stirring, and keep stirring;

[0126] S3. Weigh the wetting dispersant, defoamer and thickener according to Table 6 and gradually add them into the dispersion kettle while stirring, and keep stirring;

[0127] S4, add color paste, composite mosquito repellent, and magnesium aluminum silicate in sequence, adjust the stirring speed to 800-1000r / min, and stir for 5-20 minutes;

[0128] S5. Filter the material with a 100-mesh filter and package it for later use;

[0129] (2) Powder production process:

[0130] After weighing various raw materials in proportion according to Table 6, transport them to the dispersion kettle through pipelines or feeding ports, stir and disperse them evenly, and then package them for use.

[0131] (3) According to the ratio of liquid material to powder material shown in Table 6, the dispersed material is stirred to form a uniform slurry to obtain an exterior wall waterproof coating.

[0132] Table 6 Example 5 Preparation of raw material ratio of exterior wall waterproof coating

[0133]

[0134]

[0135]

[0136] The exterior wall waterproof coating prepared in this embodiment is an environmentally friendly water-based coating, and its physical properties meet the requirements of T / CECS10108-2020 polymer cement waterproof decorative coating, has a long-lasting waterproof effect, and has an exterior wall decorative effect, and has an excellent mosquito repellent function, and is particularly suitable for use on building roofs and exterior walls. The performance test results are shown in Table 7 below.

[0137] Table 7 Performance test of preparing exterior wall waterproof coating in Example 5

[0138]

[0139] Table 8 shows the raw materials and proportions for preparing the exterior wall waterproof coatings in Examples 6 to 8, as well as the raw materials and proportions for Comparative Examples 1 and 2.

[0140] Table 8 Raw material ratios for preparing exterior wall waterproof coatings in Examples 6 to 8, Comparative Example 1 and Comparative Example 2

[0141]

[0142]

[0143]

[0144] Table 9 shows the performance test results of the exterior wall waterproof coatings prepared in Examples 6 to 8, and the performance test results of the exterior wall waterproof coatings prepared in Comparative Examples 1 and 2.

[0145] Table 9 Performance test results of exterior wall waterproof coatings prepared in Examples 6 to 8, Comparative Examples 1 and 2

[0146]

[0147] As can be seen from Table 9, the liquid material composed of the modified polyacrylate emulsion with mosquito repellent group and the composite mosquito repellent, and the waterproof coating composed of the powder mainly composed of aluminate cement, has excellent resistance to artificial weathering aging, and will not have the situation that affects the decorative effect of the coating film, such as efflorescence and salinization. With different colors of color paste, an exterior wall coating with excellent decorative effect can be obtained, and the coating film has excellent waterproof function and good mosquito repellent effect. On the contrary, in the comparative example that does not use this technical solution, the waterproof coating film basically has no mosquito repellent function, and the decorative effect is greatly reduced when the coating film efflorescence and salinization occur.

[0148] The above specific implementations do not constitute a limitation on the protection scope of the present invention. It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and substitutions may occur depending on design requirements and other factors. Any modification, equivalent substitution and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. Mosquito repellent group modified polyacrylate emulsion, characterized in that: It is made of the following raw materials in parts by weight: 45-60 parts of soft monomer, 5-20 parts of hard monomer, 0-1.5 parts of functional monomer, and 25-40 parts of mosquito repellent group monomer; The soft monomer is selected from at least one of butyl acrylate, isooctyl acrylate, ethyl acrylate, n-octyl acrylate, and isooctyl methacrylate; The hard monomer is at least one selected from methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, styrene, and vinyl acetate; The functional monomer is selected from at least one of acrylic acid, methacrylic acid and acrylonitrile; The mosquito repellent group monomer is selected from at least one of d-propargylthrin, d-allethrin, tetrafluthrin, and carbamate oxime ester.

2. The mosquito repellent group-modified polyacrylate emulsion according to claim 1, characterized in that: The mosquito repellent group modified polyacrylate emulsion is prepared from the following raw materials in parts by weight: 45-55 parts of soft monomers, 6-16 parts of hard monomers, 0.05-1.0 parts of functional monomers, and 30-40 parts of mosquito repellent group monomers.

3. The method for preparing the mosquito repellent group modified polyacrylate emulsion according to claim 1 or 2, comprising the following steps: (1) adding water into a pre-emulsification device, adding an emulsifier sodium dodecylbenzene sulfonate or sodium secondary alkyl sulfate, stirring, and then adding a soft monomer, a hard monomer, a functional monomer, and a mosquito repellent group monomer, respectively, and stirring to prepare a pre-emulsion A; (2) adding water and an emulsifier into a reaction kettle, wherein the emulsifier is sodium alkyl sulfonate or sodium secondary alkyl sulfate, and heating the kettle to 80 to 90° C. to obtain a reaction kettle bottom material liquid B; (3) adding water and a catalyst into a catalytic cylinder, stirring and dissolving, and obtaining an initiator aqueous solution C; wherein the catalyst is selected from any one of the following combinations: ammonium persulfate and sodium bisulfite, cumene hydroperoxide and ferrous chloride, potassium persulfate and ferrous chloride; (4) dissolving a portion of the initiator aqueous solution C in water and stirring to dissolve, thereby obtaining an initial initiator solution D; (5) 3% to 10% of the total mass of the pre-emulsion A is added to the bottom material liquid B of the reactor; then the initial initiator solution D is added to the reactor, and the reaction is carried out for 20 to 30 minutes, and the reaction temperature is controlled at 80 to 90° C.; the remaining pre-emulsion A and the remaining initiator aqueous solution C are simultaneously added dropwise to the reactor, and the dropping time is 3.0 to 5.0 hours, and the temperature is controlled at 80 to 90° C.; the temperature is kept for 0.5 to 1.5 hours; after the temperature is kept, the temperature is lowered to 30 to 50° C., and the solid content is adjusted to 45% to 60% with clean water to obtain the mosquito repellent group modified polyacrylate emulsion.

4. The method for preparing the mosquito repellent group modified polyacrylate emulsion according to claim 3, characterized in that: In the step (1), 15 to 25 parts of water are added; 0.5 to 2.0 parts of emulsifier sodium dodecylbenzene sulfonate or sodium secondary alkyl sulfate are added; 45 to 55 parts of soft monomers, 6 to 16 parts of hard monomers, 0.05 to 1.0 parts of functional monomers, and 30 to 40 parts of mosquito repellent group monomers are added.

5. The method for preparing the mosquito repellent group modified polyacrylate emulsion according to claim 3, characterized in that: In the step (2), 35 to 50 parts of water and 0.05 to 0.5 parts of an emulsifier, sodium alkyl sulfonate or sodium secondary alkyl sulfate, are added to the reaction kettle.

6. The method for preparing the mosquito repellent group modified polyacrylate emulsion according to claim 3, characterized in that: In the step (3), 1 to 5 parts of water, 0.03 to 0.10 parts of ammonium persulfate, cumene hydroperoxide or potassium persulfate and 0.03 to 0.10 parts of sodium bisulfite or ferrous chloride are added into the catalytic cylinder.

7. An exterior wall waterproof coating, comprising a liquid component and a powder component, characterized in that: The liquid component comprises the following raw materials in parts by weight: 75-90 parts of the mosquito repellent group modified polyacrylate emulsion according to claim 1 or 2, 0.2-0.50 parts of preservatives, 1.0-8.0 parts of water, 0.1-1.0 parts of wetting and dispersing agents, 0.2-0.50 parts of defoaming agents, 0.5-1.0 parts of thickeners, 0.5-5 parts of color pastes, 2.0-8.0 parts of composite mosquito repellent synergists, and 0.5-2.0 parts of magnesium aluminum silicate; The powder component includes the following raw materials in parts by weight: 30-60 parts of aluminate cement, 10-30 parts of graded sand, 0.2-0.50 parts of water reducing agent, and 25-40 parts of pigments and fillers; The mass ratio of the liquid component to the powder component is 1:(1.5-2.5).

8. The exterior wall waterproof coating according to claim 7, characterized in that: The preservative is selected from at least one of isothiazolinones and 2,2-dibromopropionamide; The water is municipal tap water; The wetting dispersant is one or a mixture of inorganic dispersants or organic dispersants, the inorganic dispersant is one or more selected from sodium tripolyphosphate, sodium hexametaphosphate, and polycarboxylates, and the organic dispersant is triethylhexyl phosphoric acid; The defoaming agent is selected from one or more of mineral oils, silicones, and high molecular polymers; The thickener is a functional thickener, selected from one or more of a cellulose thickener, an inorganic thickener, a polyurethane thickener, an acrylic thickener and an alkali swelling thickener; The color paste is selected from at least one of water-based yellow color paste, phthalocyanine green, royal blue paste, red paste, and black paste; The composite mosquito repellent synergist comprises DEET, piperonyl butoxide and component A; the mass ratio thereof is: DEET: piperonyl butoxide: component A=1:(0.5-1.0):(0.5-2.0); component A is selected from one or more of eucalyptol, linalool, geraniol, peppermint oil, garlic essential oil and thymol; The strength grade of the aluminate cement is at least one of CA50, CA60, CA70 and CA80; The graded sand is white quartz sand with a grade of 80 to 200 meshes; The water reducer is selected from one or more of a high-efficiency polycarboxylate water reducer and a melamine water reducer; The pigment filler is selected from one or more of 400 mesh heavy calcium, wollastonite powder, titanium dioxide, calcined kaolin, and mica powder.

9. The exterior wall waterproof coating according to claim 7 or 8, characterized in that: The wetting and dispersing agent is selected from one or more of Rohm and Haas dispersant OROTAN 1618, BYK-190 dispersant, San Nopco SN5040 dispersant, Ryan universal wetting agent EMULSOGEN LCN407, and American Dow nonionic surfactant wetting agent EH-9; The defoamer is selected from one or more of Kemira 6660 defoamer, Japan's NOPCO NXZ defoamer, BASF's 2410 defoamer, and Germany's BYK024 defoamer.

10. The method for preparing the exterior wall waterproof coating according to any one of claims 7 to 9, comprising: (1) A liquid material production method comprising the following steps: S1, weighing mosquito repellent group modified polyacrylate emulsion and putting it into a stirring tank, stirring; S2. Weigh the preservative and water, mix them in advance, and put them into a stirring kettle while stirring; keep stirring; S3, weigh the wetting dispersant, defoamer and thickener, put them into the dispersion kettle while stirring, and keep stirring; S4, adding color paste, composite mosquito repellent, and magnesium aluminum silicate in sequence, and stirring; S5, filter through a filter, and pack the material for later use; (2) A powder production method comprising the following steps: Weigh the raw materials according to the proportion, put them into the dispersion kettle, stir and disperse them evenly, and then pack them for use; (3) According to the ratio of liquid material to powder material, stir and disperse into a uniform slurry to obtain an exterior wall waterproof coating.

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