Bio-based water repellent coating and method of making the same

Abstract

The application provides a kind of bio-based waterproof coating and its preparation method.The coating includes the first component and the second component with weight ratio of 1:(1.0-1.5), the first component includes organic fungicide 0.3 parts by weight;Bio-based polyacrylate emulsion 60-294 parts based on 0.3 parts of organic fungicide;First additive 0.3-30 parts based on 0.3 parts of organic fungicide;The second component includes:inorganic fungicide 0.6 parts;Portland cement 18-60 parts based on 0.6 parts of inorganic fungicide;Second additive 24-212 parts based on 0.6 parts of inorganic fungicide;Wherein, the weight ratio of bio-based polyacrylate emulsion and Portland cement is 1:(0.3-0.8).The coating of the application takes bio-based polyacrylate as the main material, which is environmentally friendly, and has chemical bonding effect and physical filling effect between the bio-based polyacrylate and Portland cement, and then matches organic fungicide and inorganic fungicide, so that the obtained coating layer not only has good mechanical properties and waterproof and impermeable properties, but also has excellent mildew resistance and antibacterial effect.

Description

Technical Field

[0001] This application belongs to the field of waterproof coating technology, specifically relating to a bio-based waterproof coating and its preparation method. Background Technology

[0002] JS waterproof coating, also known as polymer cement waterproof coating, is a two-component water-based building waterproof coating that combines the flexibility of polymer emulsion with the rigidity of cement. It has good high temperature resistance, strong adhesion, crack resistance, freeze resistance and low temperature flexibility. It is easy to apply, safe to use and simple to operate. It has become a popular waterproof material in recent years and is widely used in waterproofing applications for walls, floors, kitchens and bathrooms, water storage tanks and basements.

[0003] However, JS waterproof coatings are polymer-based waterproof materials, with most of their components derived from non-renewable petrochemical resources, which is detrimental to environmental protection and sustainable development. Furthermore, the petrochemical-based emulsions they use result in poor adhesion strength and water resistance. Although there are reports that introducing bio-based materials into waterproof materials could address environmental issues to some extent, the resulting coatings exhibit poor anti-mildew and antibacterial properties, and their mechanical properties are also unsatisfactory. Summary of the Invention

[0004] This application provides a bio-based waterproof coating and its preparation method, which can at least improve one of the above-mentioned technical problems.

[0005] The first aspect of this application provides a bio-based waterproof coating, comprising a first component and a second component:

[0006] The first component comprises the following components in parts by weight: 0.3 parts of organic bactericide; 60 to 294 parts of bio-based polyacrylate emulsion based on 0.3 parts of organic bactericide; and 0.3 to 30 parts of a first adjuvant based on 0.3 parts of organic bactericide.

[0007] The second component comprises the following components in parts by weight: 0.6 parts of inorganic bactericide; 18 to 60 parts of silicate cement based on 0.6 parts of inorganic bactericide; 24 to 212 parts of second additive based on 0.6 parts of inorganic bactericide; the weight ratio of the first component to the second component is 1:(1.0 to 1.5).

[0008] The weight ratio of bio-based polyacrylate emulsion to silicate cement is 1:(0.3-0.8).

[0009] When in use, the first component is mixed and dispersed with the second component to obtain a coating.

[0010] In a feasible embodiment of the first aspect of this application, the weight ratio of the bio-based polyacrylate emulsion, the organic bactericide, and the inorganic bactericide is 1:(0.002-0.005):(0.003-0.012).

[0011] In a feasible embodiment of the first aspect of this application, the first additive includes one or more of a dispersant, an antifoaming agent, and water; the second additive includes a filler, a water-reducing agent, or a combination thereof.

[0012] In a feasible embodiment of the first aspect of this application, the first component comprises, by weight parts: 0.3 parts of an organic bactericide; 92 to 98 parts of a bio-based polyacrylate emulsion based on 0.3 parts of the organic bactericide; 0.12 to 1.5 parts of a dispersant based on 0.3 parts of the organic bactericide; 0.12 to 1.5 parts of an antifoamer based on 0.3 parts of the organic bactericide; and 0.6 to 24 parts of water based on 0.3 parts of the organic bactericide.

[0013] The second component includes: 0.6 parts of inorganic bactericide; 30-50 parts of silicate cement based on 0.6 parts of inorganic bactericide; 24-84 parts of filler based on 0.6 parts of inorganic bactericide; and 0.12-6 parts of water-reducing agent based on 0.6 parts of inorganic bactericide. The weight ratio of the first component to the second component is 1:(1.0-1.5).

[0014] In a feasible embodiment of the first aspect of this application, the bio-based carbon content of the bio-based polyacrylate emulsion is 20% to 45%.

[0015] In a feasible embodiment of the first aspect of this application, the solid content of the bio-based polyacrylate emulsion is 50% to 60%.

[0016] In a feasible embodiment of the first aspect of this application, the bio-based waterproof coating satisfies at least one of the following conditions:

[0017] a. Organic fungicides include one or a combination of isothiazolinone and 2,2-dibromopropionamide;

[0018] b. Inorganic bactericides include one or a combination of silver-loaded phosphates, silver-loaded silicates, and silver-loaded borates;

[0019] c. The dispersant includes one or a combination of polyphosphates, polycarboxylate salts, and triethylhexylphosphonic acid;

[0020] d. Defoamers include one or a combination of silicone-based defoamers and mineral oil-based defoamers;

[0021] e. Silicate cement includes one or a combination of P.W32.5 white silicate cement, P.W42.5 white silicate cement, P.W32.5 gray silicate cement and P.W42.5 gray silicate cement;

[0022] f. The filler includes one or a combination of 200-400 mesh heavy calcium carbonate, talc powder and quartz powder;

[0023] g. Water-reducing agents include one or a combination of polycarboxylate-based water-reducing agents, melamine-based water-reducing agents, and melamine-based water-reducing agents.

[0024] A second aspect of this application provides a method for preparing a bio-based waterproof coating, comprising:

[0025] Preparation of the first component: Take 0.3 parts by weight of organic bactericide; 60-294 parts by weight of bio-based polyacrylate emulsion based on 0.3 parts by weight of organic bactericide; 0.3-30 parts by weight of the first adjuvant based on 0.3 parts by weight of organic bactericide; mix and stir to obtain the first component;

[0026] Preparation of the second component: Take 0.6 parts by weight of inorganic bactericide; 18-60 parts by weight of silicate cement based on 0.6 parts by weight of inorganic bactericide; 24-212 parts by weight of second additive based on 0.6 parts by weight of inorganic bactericide; mix them to obtain the second component;

[0027] The weight ratio of the first component to the second component is 1:(1.0 to 1.5).

[0028] In a feasible embodiment of the second aspect of this application, the method for preparing the bio-based polyacrylate emulsion includes:

[0029] The raw materials provided include the following weight percentages: 8%–18% first monomer, 50%–70% second monomer, 6%–10% third monomer, 8%–14% fourth monomer and 1%–5% fifth monomer;

[0030] The above raw materials are mixed and reacted to obtain a bio-based polyacrylate emulsion;

[0031] The first monomer includes one or more of methyl methacrylate (MMA), n-butyl methacrylate (BMA), and styrene (St); the second monomer includes one or more of 2-octyl acrylate (2-OA), n-butyl acrylate (BA), and isooctyl acrylate (2-EHA); the third monomer includes one or more of octadecyl methacrylate (SMA), hexadecyl methacrylate (HMA), and dodecyl methacrylate (LMA); the fourth monomer includes one or more of isobornyl methacrylate (IBOMA), tetrahydrofurfuryl acrylate (THFMA), and dimethyl itaconic acid (DMI); and the fifth monomer includes one or more of acrylic acid (AA), methacrylic acid (MAA), and itaconic acid (ITA).

[0032] In a feasible embodiment of the second aspect of this application, the ratio of the fourth monomer to the second monomer is 1:(4 to 9), and optionally 1:(5 to 6.5).

[0033] In a feasible embodiment of the second aspect of this application, the ratio of SMA to LMA in the third monomer is 1:(3 to 16), and optionally 1:(5 to 7).

[0034] In a feasible embodiment of the second aspect of this application, the ratio of the fifth monomer to the second monomer is 1:(14-30), and optionally 1:(15-26).

[0035] In a feasible embodiment of the second aspect of this application, a method for preparing a bio-based polyacrylate emulsion includes:

[0036] Preparation of preemulsion: Emulsifier, water and first monomer, second monomer, third monomer, fourth monomer and fifth monomer are mixed and stirred to obtain preemulsion; the preemulsion is divided into first preemulsion and second preemulsion with a weight ratio of 1:(1.2~1.8);

[0037] The first pre-emulsion and the first initiator are subjected to a first reaction to obtain a first emulsion; the first emulsion, the second pre-emulsion and the second initiator are subjected to a second reaction, the mixture is cooled and a pH adjuster is added to obtain a bio-based polyacrylate emulsion.

[0038] In a feasible embodiment of the second aspect of this application, the method for preparing the bio-based polyacrylate emulsion satisfies at least one of the following conditions:

[0039] h. The temperature of the first reaction is 80–90℃, and the reaction time is 40–60 min;

[0040] i. The temperature of the second reaction is 80–90℃, and the reaction time is 50–70 min;

[0041] j. The amount of water added is 25% to 30% of the total weight of the first, second, third, fourth and fifth monomers;

[0042] k. The emulsifier is anionic or nonionic, and the amount of emulsifier added is 1% to 3% of the total weight of the first monomer, the second monomer, the third monomer, the fourth monomer, and the fifth monomer.

[0043] 1. Both the first and second initiators are persulfate initiators, and their weight ratio is 1:(1.5-4);

[0044] m. Cooling down to 30-50℃;

[0045] n. The pH adjuster is a 10wt% sodium hydroxide aqueous solution, used to adjust the pH of the system to 7.0–9.0.

[0046] The total amount of the first initiator and the second initiator added is 0.3 to 1.0% of the total weight of the first monomer, the second monomer, the third monomer, the fourth monomer, and the fifth monomer.

[0047] Ammonium persulfate initiators include one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0048] The bio-based waterproof coating provided in this application uses polyacrylate emulsion as the main material, which has chemical bonding and physical filling effects with silicate cement. It is not only green and environmentally friendly, but its physical properties also meet the standards of GB / T 23445~2009Ⅱ. Combined with organic and inorganic bactericides, it also has highly efficient and long-lasting anti-mildew and antibacterial properties without affecting other properties of the coating. It overcomes the shortcomings of previous waterproof coatings that could not simultaneously achieve environmental protection, physical properties, waterproof and seepage-proof performance and anti-mildew and antibacterial properties. It is suitable for waterproofing, seepage-proofing, anti-mildew and antibacterial treatment of interior and exterior walls of buildings, basements, water tanks and water towers, etc., and has high application value. Detailed Implementation

[0049] To make the inventive objectives, technical solutions, and beneficial technical effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the embodiments described in this specification are merely illustrative and not intended to limit the scope of this application.

[0050] For simplicity, this paper only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, just as any upper limit can be combined with any other upper limit to form an undefined range. Furthermore, although not explicitly stated, every point or individual value between the endpoints of a range is included within that range. Therefore, each point or individual value can serve as its own lower or upper limit and be combined with any other point or individual value, or with other lower or upper limits, to form an undefined range.

[0051] In the description herein, when a composition is described as containing, comprising, or including a specific component, or when a process is described as containing, comprising, or including a specific process step, it is anticipated that the composition of this application is also primarily composed of or consisting of the said component, and that the process of this application is also primarily composed of or consisting of the said process step.

[0052] Unless otherwise expressly stated, the use of the terms “including,” “contains,” “comprising,” “containing,” and “having” should generally be interpreted as open-ended and non-restrictive.

[0053] In this description, it should be noted that, unless otherwise stated, "above" and "below" include the stated number, and "multiple" in "one or more" means two or more.

[0054] The foregoing description of this invention is not intended to describe every disclosed embodiment or implementation. Instead, the following description provides more specific examples of exemplary embodiments. Throughout the application, guidance is provided through a series of embodiments that can be used in various combinations. The examples listed are merely representative and should not be construed as exhaustive.

[0055] Existing JS waterproof coatings often use polyacrylate emulsions such as ethylene-vinyl acetate emulsion and styrene-acrylic emulsion, all of which are derived from non-renewable petrochemical resources. Overexploitation of petrochemical-based resources increases carbon emissions, which is detrimental to environmental protection. Furthermore, the finite nature of non-renewable resources also restricts sustainable development for humankind.

[0056] Chinese patent application CN 106433328 A discloses a moisture-resistant, high-strength, environmentally friendly polymer cement waterproof coating, which uses plant-based synthetic ester plasticizer instead of DOP plasticizer to ensure the environmental friendliness of the JS waterproof coating. However, the main emulsion component in its liquid component is a petrochemical-based VAE emulsion, and the environmental friendliness of the raw materials needs to be improved. Moreover, JS waterproof coatings prepared from VAE emulsions generally have poor water resistance.

[0057] Chinese patent application CN 106699064 A discloses an economical and environmentally friendly polymer cement waterproof coating that uses polished brick waste and quartz sand tailings as fillers, which is relatively in line with economic, environmental protection and resource recycling. However, its emulsion uses non-renewable fossil-based styrene-acrylic emulsion, which is not conducive to environmental protection. At the same time, the JS waterproof coating prepared with styrene-acrylic emulsion has slightly poor adhesion strength and usually requires primer treatment before construction.

[0058] Bio-based JS waterproof coating is a type of coating made primarily from bio-based raw materials, which are renewable and environmentally friendly. Bio-based waterproof coatings can alleviate the resource crisis to some extent, hence the increasing demand for bio-based materials in this field.

[0059] Chinese patent application CN 115141503 A discloses a bio-based polymer cement waterproof coating, whose JS waterproof coating includes a liquid component and a powder component. The liquid component consists of a bio-based acrylic emulsion, a defoamer, a dispersant, a stabilizer, a preservative, and water. The powder component includes cement, heavy calcium carbonate, quartz powder, and a water-reducing agent. Although the bio-based acrylic emulsion is derived from renewable resources and is environmentally friendly, it is easily contaminated by bacteria and microorganisms due to the large number of polar groups in its emulsion, resulting in poor anti-mildew and antibacterial effects and generally poor physical properties of the coating.

[0060] In addition, JS waterproof coatings use water as a dispersion medium and are rich in nutrients for microbial growth. When the ambient temperature and humidity are suitable, microorganisms will multiply and grow rapidly, which can easily cause problems such as a decline in the performance of the waterproof coating or even spoilage and deterioration in a short period of time.

[0061] In view of this, the inventors, after extensive experimental research and demonstration, have provided a bio-based waterproof coating and its preparation method in this application. This bio-based waterproof coating uses polyacrylate emulsion as the main material, which has chemical bonding and physical filling effects with silicate cement. It is not only environmentally friendly but also meets the physical properties of GB / T 23445~2009Ⅱ standards. Combined with a combination of organic and inorganic bactericides, it also possesses highly efficient and long-lasting antifungal and antibacterial properties without affecting other properties of the coating. This overcomes the shortcomings of previous waterproof coatings, which could not simultaneously achieve environmental friendliness, physical properties, waterproofing and seepage prevention, and antifungal and antibacterial properties. It is suitable for waterproofing, seepage prevention, antifungal and antibacterial treatment of building interior and exterior walls, basements, water tanks, water towers, and other similar applications, and has high application value.

[0062] The first aspect of this application provides a bio-based waterproof coating, comprising a first component and a second component:

[0063] The first component comprises the following components in parts by weight: 0.3 parts of organic bactericide; 60 to 294 parts of bio-based polyacrylate emulsion based on 0.3 parts of organic bactericide; and 0.3 to 30 parts of a first adjuvant based on 0.3 parts of organic bactericide.

[0064] The second component comprises the following components in parts by weight: 0.6 parts of inorganic bactericide; 18 to 60 parts of silicate cement based on 0.6 parts of inorganic bactericide; 24 to 212 parts of second additive based on 0.6 parts of inorganic bactericide; the weight ratio of the first component to the second component is 1:(1.0 to 1.5).

[0065] The weight ratio of bio-based polyacrylate emulsion to silicate cement is 1:(0.3-0.8).

[0066] In use, the first component is mixed and dispersed with the second component to obtain a coating.

[0067] For example, the weight parts of the bio-based polyacrylate emulsion can be 60, 70, 80, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110, 120, 130, 140, 160, 180, 200, 220, 240, 260, 280, 290, 294, or any value within the range of 60 to 294. The weight parts of the first adjuvant can be 0.3, 0.4, 0.5, 1.0, 2.0, 3.0, 3.5, 3.7, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 10, 12, 15, 20, 25, 30, or any value within the range of 0.3 to 30. The weight parts of silicate cement can be 18, 25, 30, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, or any value within the range of 18 to 60. The weight parts of the second additive can be 24, 30, 50, 70, 90, 110, 130, 150, 170, 190, 210, 212, or any value within the range of 24 to 212.

[0068] For example, the weight ratio of bio-based polyacrylate emulsion to silicate cement can be any value within the range of 1:0.3, 1:0.4, 1:0.45, 1:0.46, 1:0.47, 1:0.48, 1:0.48, 1:0.50, 1:0.55, 1:0.60, 1:0.65, 1:0.7, 1:0.8, or 1:(0.3 to 0.8). The weight ratio of the first component and the second component can be any value within the range of 1:1.0, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or 1:(1.0 to 1.5).

[0069] On the one hand, the waterproof coating provided in this application uses bio-based polyacrylate emulsion as the main material. Its raw materials are derived from renewable resources, making it environmentally friendly. It also contains a large number of -COOR groups (R can be alkyl groups). These groups form a three-dimensional network structure during film formation, with strong molecular bonds, resulting in a large molecular structure that is not easily degraded. Simultaneously, it exhibits both physical filling and chemical bonding effects with the inorganic gel material of silicate cement. Physical filling refers to the polyacrylate emulsion coating the surface of cement particles and their hydration products as the cement hydration reaction proceeds, mechanically filling each other after film formation. Chemical bonding refers to the ester groups in the polyacrylate emulsion undergoing a reverse hydrolysis reaction, generating CH3COO... - With Ca in cement 2+ A reaction occurs, and new chemical bonds are formed. The synergistic effect of physical filling and chemical bonding between bio-based polyacrylate and silicate cement effectively improves the coating's cohesion, strength, water resistance, and weather resistance.

[0070] On the other hand, waterproof coatings use water as a dispersant, making them prone to microbial growth. Bio-based emulsions also contain polar groups, which can further increase the coating's susceptibility to bacterial and microbial contamination. Adding a single bactericide is insufficient to achieve highly effective and long-lasting antifungal and antibacterial effects. While single organic bactericides can quickly disrupt the cell structure of existing microorganisms and inhibit bacterial formation, they are easily soluble and have poor antibacterial durability. Therefore, the bactericide in this application contains both organic and inorganic bactericides. Inorganic bactericides offer better durability in antifungal and antibacterial effects, better heat resistance, a broader antibacterial spectrum, longer duration of action, and are less prone to dissolution. When combined with organic bactericides in a specific ratio, the synergistic effect effectively reduces the risk of performance degradation or even spoilage of waterproof coatings caused by bacterial and other microbial infections.

[0071] In some embodiments, the weight ratio of the bio-based polyacrylate emulsion, the organic bactericide, and the inorganic bactericide is 1:(0.002-0.005):(0.003-0.012), optionally 1:(0.003-0.004):(0.006-0.009).

[0072] Not intended to be limited by any theory or explanation, the inventors, through extensive experimental research and demonstration, discovered that by further controlling the weight ratio of bio-based polyacrylate emulsion, organic bactericide and inorganic bactericide within the above range, this application can obtain a bio-based waterproof coating with more ideal comprehensive performance, especially with a mildew resistance level of 0 and an antibacterial rate of up to 99.99%.

[0073] In some embodiments, the bio-based polyacrylate emulsion has a bio-based carbon content of 20% to 45%. Exemplarily, the bio-based carbon content of the bio-based polyacrylate emulsion can be any value within the range of 20%, 25%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 45%, or 20% to 45%. In this invention, the bio-based carbon content of the bio-based polyacrylate emulsion is determined using radiocarbon (C). 14 The bio-based carbon content was determined by analytical method to be bio-based carbon (C). 14 ) accounts for a portion of total organic carbon (C 14 +C 12 The percentage is based on ASTM D6866.

[0074] Not intended to be limited by any theory or explanation, waterproof coatings made primarily from bio-based polyacrylate emulsions within the aforementioned bio-based carbon content range can balance environmental protection, cost, and physical properties. When the bio-based carbon content is too low, it is difficult to pass environmental certification; when the content is too high, it can easily lead to excessively high coating costs and may also affect the coating's mechanical properties.

[0075] In some embodiments, the solid content of the bio-based polyacrylate emulsion is 50% to 60%. For example, the solid content of the bio-based polyacrylate emulsion can be any value within the range of 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, or 50% to 60%.

[0076] Not intended to be limited by any theory or explanation, this application allows for control of the amount of bio-based polyacrylate in bio-based waterproof coatings by further controlling the solid content of the bio-based polyacrylate emulsion, thus influencing the selection of other components and their proportions. The bio-based polyacrylate emulsion with the solid content within the aforementioned range of this application can better synergize with the various components of this application, resulting in more ideal coating performance.

[0077] In some embodiments, the first component, by weight, comprises: 0.3 parts of an organic bactericide; 92-98 parts of a bio-based polyacrylate emulsion based on 0.3 parts of the organic bactericide; and 2-5 parts of a first adjuvant based on 0.3 parts of the organic bactericide. The second component comprises: 0.6 parts of an inorganic bactericide; 30-50 parts of silicate cement based on 0.6 parts of the inorganic bactericide; and 40-60 parts of a second adjuvant based on 0.6 parts of the inorganic bactericide. The weight ratio of the first component to the second component is 1:(1.0-1.5).

[0078] In some embodiments, the first additive includes a dispersant, an antifoaming agent, and one or a combination thereof in water; the second additive includes a filler, a water-reducing agent, or a combination thereof.

[0079] In some embodiments, the first component comprises, by weight parts: 0.3 parts of an organic bactericide; 92 to 98 parts of a bio-based polyacrylate emulsion based on 0.3 parts of the organic bactericide; 0.12 to 1.5 parts of a dispersant based on 0.3 parts of the organic bactericide; 0.12 to 1.5 parts of an antifoamer based on 0.3 parts of the organic bactericide; and 0.6 to 24 parts of water based on 0.3 parts of the organic bactericide.

[0080] The second component comprises: 0.6 parts of inorganic bactericide; 30-50 parts of silicate cement based on 0.6 parts of inorganic bactericide; 24-84 parts of filler based on 0.6 parts of inorganic bactericide; and 0.12-6 parts of water-reducing agent based on 0.6 parts of inorganic bactericide. The weight ratio of the first component to the second component is 1:(1.0-1.5).

[0081] In some embodiments, the first component comprises, by weight: 0.3 parts of an organic bactericide; 92-98 parts of a bio-based polyacrylate emulsion based on 0.3 parts of the organic bactericide; 0.2-0.5 parts of a dispersant based on 0.3 parts of the organic bactericide; 0.2-0.5 parts of an antifoamer based on 0.3 parts of the organic bactericide; and 0.8-5 parts of water based on 0.3 parts of the organic bactericide.

[0082] The second component comprises: 0.6 parts of inorganic bactericide; 20-45 parts of silicate cement based on 0.6 parts of inorganic bactericide; 50-80 parts of filler based on 0.6 parts of inorganic bactericide; and 0.2-0.3 parts of water-reducing agent based on 0.6 parts of inorganic bactericide. The weight ratio of the first component to the second component is 1:(1.0-1.5).

[0083] Not intended to be limited by any theory or explanation, dispersants, on the one hand, ensure the full dispersion of powder particles such as cement and fillers, and improve the suspension of solid particles in liquid materials, thereby ensuring the stability of the slurry during construction; on the other hand, by reducing the interfacial tension of the system, they enable the liquid material and powder surface to make full contact, thereby ensuring the uniformity of the coating after construction.

[0084] Defoamer is used because bubbles inevitably form during the production or application of JS waterproof coatings. These bubbles can cause stress concentration, leading to micro-cracks and loss of waterproofing. The defoamer in this application has excellent defoaming and foam-suppressing effects, effectively eliminating existing bubbles in the system while inhibiting the formation of new bubbles, thus ensuring the density of the coating.

[0085] Silicate cement, selected as the inorganic gelling material in this application, exhibits both physical filling and chemical bonding effects with the bio-based polyacrylate emulsion. As mentioned above regarding the role of the bio-based polyacrylate emulsion, the synergistic effect of physical filling and chemical bonding between silicate cement and the bio-based polyacrylate emulsion effectively improves the cohesion, strength, water resistance, and acid and alkali resistance of the polymer coating.

[0086] The filler selected in this application can play the role of active filling and reinforcement, while effectively improving the workability of the coating, and enhancing its density, impermeability and mechanical properties.

[0087] Water-reducing agents have excellent water reduction rate and plasticity retention. The water-reducing agent selected in this application ensures that the powder particles are fully mixed and dispersed in the liquid, which can effectively improve the fluidity of the mixture, facilitate construction operations, and at the same time improve the strength and tensile properties of the coating.

[0088] Therefore, this application can obtain a bio-based JS waterproof coating with excellent mechanical properties, waterproof and impermeable properties, and efficient and long-lasting antifungal and antibacterial properties by further controlling each component and its ratio.

[0089] In some embodiments, the organic bactericide includes one or a combination of isothiazolinone, 2,2-dibromopropionamide.

[0090] In some embodiments, the inorganic bactericide includes one or a combination of silver-loaded phosphate, silver-loaded silicate, and silver-loaded borate.

[0091] Not intended to be limited to any particular theory or explanation, the aforementioned types of inorganic bactericides, especially phosphate-loaded, silicate-loaded, and borate-loaded silver, are silver-based inorganic antibacterial agents that load nano-sized silver ions with strong antibacterial capabilities onto various inorganic carriers. The nano-silver ions can be continuously released from the carrier and adsorbed onto the negatively charged bacterial cell membrane via Coulomb forces, while simultaneously binding to proteins within the bacteria. This inhibits enzyme synthesis and the replication of genetic material, achieving a long-lasting antibacterial effect.

[0092] In some embodiments, the dispersant includes one or a combination of polyphosphate, polycarboxylate, and triethylhexylphosphonic acid.

[0093] In some embodiments, the defoamer includes one or a combination of silicone-based defoamers and mineral oil-based defoamers.

[0094] In some embodiments, the silicate cement includes one or a combination of P.W32.5 white silicate cement, P.W42.5 white silicate cement, P.W32.5 gray silicate cement, and P.W42.5 gray silicate cement.

[0095] In some embodiments, the filler includes one or a combination of 200-400 mesh heavy calcium carbonate, talc powder and quartz powder.

[0096] Not intended to be limited by any theory or explanation, this application uses heavy calcium carbonate to act as an active filler and reinforcement, while effectively improving the workability of the coating and enhancing its density, impermeability, and mechanical properties.

[0097] In some embodiments, the water-reducing agent includes one or more of polycarboxylate-based water-reducing agents, melamine-based water-reducing agents, and melamine-based water-reducing agents.

[0098] A second aspect of this application provides a method for preparing a bio-based waterproof coating, comprising:

[0099] Preparation of the first component: Take 0.3 parts by weight of organic bactericide; 60-294 parts by weight of bio-based polyacrylate emulsion based on 0.3 parts by weight of organic bactericide; 0.3-30 parts by weight of the first adjuvant based on 0.3 parts by weight of organic bactericide; mix and stir to obtain the first component;

[0100] Preparation of the second component: Take 0.6 parts by weight of inorganic bactericide; 18-60 parts by weight of silicate cement based on 0.6 parts by weight of inorganic bactericide; 24-212 parts by weight of second additive based on 0.6 parts by weight of inorganic bactericide; mix them to obtain the second component;

[0101] The weight ratio of the first component to the second component is 1:(1.0 to 1.5).

[0102] In some embodiments, the method for preparing the bio-based polyacrylate emulsion includes:

[0103] The raw materials provided include the following weight percentages: 8%–18% first monomer, 50%–70% second monomer, 6%–10% third monomer, 8%–14% fourth monomer and 1%–5% fifth monomer;

[0104] The above raw materials are mixed and subjected to a free radical-initiated emulsion polymerization reaction to obtain a bio-based polyacrylate emulsion.

[0105] The first monomer includes one or more of methyl methacrylate (MMA), n-butyl methacrylate (BMA), and styrene (St); the second monomer includes one or more of 2-octyl acrylate (2-OA), n-butyl acrylate (BA), and isooctyl acrylate (2-EHA); the third monomer includes one or more of octadecyl methacrylate (SMA), hexadecyl methacrylate (HMA), and dodecyl methacrylate (LMA); the fourth monomer includes one or more of isobornyl methacrylate (IBOMA), tetrahydrofurfuryl acrylate (THFMA), and dimethyl itaconic acid (DMI); and the fifth monomer includes one or more of acrylic acid (AA), methacrylic acid (MAA), and itaconic acid (ITA).

[0106] In some embodiments, the ratio of the fourth monomer to the second monomer is 1:(4 to 9). For example, the ratio of the fourth monomer to the second monomer can be any value within the range of 1:4.0, 1:4.5, 1:5.0, 1:5.1, 1:5.5, 1:6.0, 1:6.3, 1:6.4, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.1, 1:8.5, 1:9.0 or 1:(4 to 9), and 1:(5 to 6.5) can be selected.

[0107] In some embodiments, the ratio of SMA to LMA in the third monomer is 1:(3 to 16). For example, the ratio of SMA to LMA in the third monomer can be any value within the range of 1:3.0, 1:3.7, 1:3.8, 1:4.0, 1:5.0, 1:6.0, 1:7.0, 1:8.0, 1:9.0, 1:10.0, 1:11.0, 1:12.0, 1:13.0, 1:14.0, 1:15.0, 1:16.0 or 1:(3 to 16), and 1:(5 to 7) can be selected.

[0108] In some embodiments, the ratio of the fifth monomer to the second monomer is 1:(14 to 30). For example, the ratio of the fifth monomer to the second monomer can be any value within the range of 1:14, 1:15, 1:16, 1:17, 1:18, 1:20, 1:22, 1:24, 1:26, 1:28, 1:30 or 1:(14 to 30), and 1:(15 to 26) can be selected.

[0109] The first monomer can be a hard monomer with a high glass transition temperature, providing physical properties such as strength, hardness, and abrasion resistance. The second monomer can be a bio-based soft monomer with a low glass transition temperature, providing physical properties such as flexibility and low-temperature bending properties. The third monomer can be a commercially available acrylate monomer derived from natural renewable resources such as furfural, rosin, and oils. It has a long carbon chain hydrophobic structure, providing excellent water resistance and waterproofing. This third monomer can also be a bio-based long-chain monomer. The fourth monomer can be other bio-based monomers, with all or part of its monomer composition derived from renewable biomass. The fifth monomer can be a functional monomer. Due to the introduction of carboxyl functional groups, it can effectively improve the cohesiveness of the polymer emulsion, increase the viscosity and mechanical stability of the emulsion, and simultaneously improve the wettability of fillers and the adhesion strength to the substrate.

[0110] This application defines bio-based monomers as monomers in which some raw materials are derived from traceable biological sources (i.e., biological ferments or plant extracts). The use of bio-based materials can effectively promote the utilization of renewable resources, reduce the consumption of petrochemical raw materials to lower carbon emissions, thereby reducing environmental pollution and promoting sustainable human development.

[0111] In some embodiments, the method for preparing a bio-based polyacrylate emulsion includes:

[0112] Provide a pre-emulsion: Mix and stir the emulsifier, water, and the first, second, third, fourth, and fifth monomers to obtain a pre-emulsion; divide the pre-emulsion into a first pre-emulsion and a second pre-emulsion with a weight ratio of 1:(1.2~1.8);

[0113] Provide initiator: The initiator is divided into a first initiator and a second initiator with a weight ratio of 1:(1.5~4);

[0114] The first preemulsion and the first initiator are subjected to a first reaction to obtain a first emulsion; the first emulsion, the second preemulsion and the second initiator are subjected to a second reaction, the temperature is lowered and a pH adjuster is added to obtain a bio-based polyacrylate emulsion.

[0115] This application employs a two-step synthesis process, dividing the pre-emulsion into two parts. The first part reacts with an initiator, and the second part reacts with the remaining pre-emulsion and initiator. Compared to a one-step synthesis process, while simpler, the one-step method makes it difficult to control the polymerization reaction. Furthermore, because all materials are added at once, the subsequent polymerization reaction becomes difficult, the reaction rate decreases significantly, and the polymerization stability is poor. The two-step synthesis process used in this application makes the polymerization reaction more stable and easier to control, and the resulting polymer emulsion also exhibits better storage stability.

[0116] In some embodiments, the method for preparing the bio-based polyacrylate emulsion satisfies at least one of the following conditions:

[0117] h. The temperature of the first reaction is 80–90℃, and the reaction time is 40–60 min;

[0118] i. The temperature of the second reaction is 80–90℃, and the reaction time is 50–70 min;

[0119] j. The amount of water added is 25% to 30% of the total weight of the first, second, third, fourth and fifth monomers;

[0120] k. The emulsifier is anionic or nonionic, and the amount of emulsifier added is 1% to 3% of the total weight of the first monomer, the second monomer, the third monomer, the fourth monomer, and the fifth monomer.

[0121] 1. Both the first and second initiators are persulfate initiators, and their weight ratio is 1:(1.5-4);

[0122] m. Cooling down to 30-50℃;

[0123] n. The pH adjuster is a 10wt% sodium hydroxide aqueous solution, used to adjust the pH of the system to 7.0–9.0.

[0124] In some embodiments, the total amount of the first initiator and the second initiator added is 0.3 to 1.0% of the total weight of the first monomer, the second monomer, the third monomer, the fourth monomer, and the fifth monomer.

[0125] In some embodiments, the ammonium persulfate initiator includes one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0126] Example

[0127] The following embodiments describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on weight, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.

[0128] Example 1

[0129] Preparation of bio-based polyacrylate emulsions:

[0130] (1) Add 250 parts deionized water, 15 parts CO-436, and 12 parts SDS to a pre-emulsification vessel and stir for 10 min. Then add 160 parts MMA, 633 parts 2-OA, 60 parts LMA, 10 parts SMA, 100 parts IBOMA, and 37 parts MAA and stir for 35 min to obtain a stable pre-emulsion. Record 2 / 5 of the weight of the pre-emulsion as solution A (first pre-emulsion) and 3 / 5 of the weight of the pre-emulsion as solution B (second pre-emulsion).

[0131] (2) Add 380 parts of deionized water to the reactor, heat to 85°C, add solution A, 2 parts of APS (first initiator) and 3 parts of deionized water in an initiator aqueous solution, react for 45 min to obtain seed emulsion (first emulsion);

[0132] (3) Add component B, 3 parts of APS (second initiator) and 70 parts of deionized water to the reaction vessel containing seed emulsion. Component B is added within 2 hours and the initiator solution is added within 2 hours. After both are added, the temperature is controlled at 85℃ and kept warm for 60 minutes.

[0133] (4) After the heat preservation is completed, the temperature of the reaction solution is lowered to 40℃, and 10% NaOH aqueous solution is added dropwise until the pH of the system is ≈8, thus obtaining bio-based polyacrylate emulsion I with bio-based carbon content ≈38% and solid content = 55%.

[0134] Preparation of bio-based waterproof coatings:

[0135] (1) Preparation of liquid material (first component): 96 parts of bio-based polyacrylate emulsion were added to a stirred tank and stirred at 400 r / min. 3.2 parts of water, 0.3 parts of wetting and dispersing agent, 0.3 parts of organic bactericide, and 0.2 parts of defoamer were added to a dispersion tank under stirring, and the stirring speed was maintained at 800 r / min for 10 min. The mixture was filtered through a 100-mesh filter, discharged, and packaged to obtain powder.

[0136] (2) Preparation of powder (second component): Weigh 45 parts of silicate cement, 54.2 parts of heavy calcium carbonate, 0.2 parts of water-reducing agent and 0.6 parts of inorganic bactericide and put them into the powder mixer in sequence. Start the machine and mix for 10 minutes. After mixing, stop the machine, discharge and package the powder.

[0137] (3) Mix the liquid and powder materials at a weight ratio of 1:1.4 and disperse them evenly with a mixer to obtain the bio-based waterproof coating.

[0138] Example 2

[0139] The preparation steps of Example 1 were repeated, except that 2-OA was adjusted to 613 parts and IBOMA was adjusted to 120 parts, while the remaining components and their addition amounts remained unchanged, to prepare bio-based polyacrylate emulsion II.

[0140] Example 3

[0141] The preparation steps of Example 1 were repeated, except that 2-OA was adjusted to 653 parts and IBOMA was adjusted to 80 parts, while the remaining components and their addition amounts remained unchanged, to prepare bio-based polyacrylate emulsion III.

[0142] Example 4

[0143] The preparation steps of Example 1 were repeated, except that IBOMA was replaced with THFMA, while the remaining components and their amounts remained unchanged, to prepare bio-based polyacrylate emulsion IV.

[0144] Example 5

[0145] The preparation steps of Example 1 were repeated, except that IBOMA was replaced with DMI, while the remaining components and their amounts remained unchanged, to prepare bio-based polyacrylate emulsion V.

[0146] Example 6

[0147] The preparation steps of Example 1 were repeated, except that LMA was adjusted to 55 parts and SMA to 15 parts, while the remaining components and their addition amounts remained unchanged, to prepare bio-based polyacrylate emulsion VI.

[0148] Example 7

[0149] The preparation steps of Example 1 were repeated, except that LMA was adjusted to 65 parts and SMA to 5 parts, while the remaining components and their addition amounts remained unchanged, to prepare bio-based polyacrylate emulsion VII.

[0150] Example 8

[0151] The preparation steps of Example 1 were repeated, except that MAA was adjusted to 25 parts and 2-OA was adjusted to 645 parts, while the remaining components and their addition amounts remained unchanged, to prepare bio-based polyacrylate emulsion VIII.

[0152] Example 9

[0153] The preparation steps of Example 1 were repeated, except that MAA was adjusted to 45 parts and 2-OA was adjusted to 625 parts, while the remaining components and their addition amounts remained unchanged, to prepare bio-based polyacrylate emulsion IX.

[0154] Examples 10-13

[0155] The preparation steps of Example 1 were repeated, except that the content of each component in the liquid and powder materials was as detailed in Table 3.

[0156] Comparative Example 1

[0157] The preparation steps of Example 1 were repeated, except that the coating did not contain bio-based polyacrylate emulsion, but instead contained an equal amount of petroleum-based polyacrylate emulsion RS-300SL, manufactured by Badifu, with a solid content of 55%.

[0158] Comparative Examples 2-3

[0159] The preparation steps of Example 1 were repeated, except that the types, contents, and weight ratios of each component in the liquid and powder materials were detailed in Table 3.

[0160] Comparative Example 4

[0161] The preparation steps of Example 1 were repeated, except that the weight ratio of bio-based polyacrylate emulsion to silicate cement was not in the range of 1:(0.3-0.8).

[0162] Mechanical property testing

[0163] The physical and mechanical properties of the waterproof coatings in each embodiment and comparative example were tested in accordance with GB / T23445~2009Ⅱ.

[0164] Antibacterial and antifungal performance test

[0165] The antibacterial and antifungal properties of the waterproof coatings in each embodiment and comparative example were tested in accordance with HG / T3950~2007 "Antibacterial Coatings".

[0166] The raw materials used in each embodiment and comparative example were purchased from commercially available products, as shown in Tables 1-2.

[0167] The composition of the waterproof coatings in each embodiment and comparative example is shown in Table 3.

[0168] The test results of the physical and mechanical properties of the waterproof coatings in each embodiment and comparative example are shown in Table 4.

[0169] The test results of the antibacterial and antifungal properties of the waterproof coatings in each embodiment and comparative example are shown in Table 5.

[0170] Table 1 Source of Raw Materials

[0171]

[0172]

[0173] Table 2 Sources of Raw Materials

[0174] raw material type model Manufacturer Organic fungicides Isothiazolinone Kathon Guangdong Dimei Biotechnology Co., Ltd. wetting and dispersing agents Sodium polycarboxylate dispersant SN5040 Japan's Sannopco Defoamer Mineral oil defoamer 2410 BASF Inorganic bactericides Silver-loaded zirconium phosphate JDGQP-003 Jinda Nanotechnology Co., Ltd. Silicate cement Silicate ash cement PO 42.5 Yingde Conch Cement Co., Ltd. filler 200 mesh calcium carbonate / Guangdong Yuanlei Powder Co., Ltd. Water reducing agent Polycarboxylate superplasticizer 2651F BASF

[0175] Table 3 Composition of waterproof coatings in each embodiment and comparative example

[0176]

[0177]

[0178] Table 4. Physical and mechanical properties of the waterproof coatings in each example and comparative example.

[0179]

[0180]

[0181] Table 5. Antibacterial and antifungal properties of the waterproof coatings in each example and comparative example.

[0182]

[0183] As shown in Table 4, the bio-based JS waterproof coating of the present invention has excellent impermeability, impermeability and mechanical properties, and meets the GB / T 23445~2009 Type II standard.

[0184] Compared with Example 1, the environmentally friendly JS waterproof coating prepared using bio-based emulsion exhibits superior overall performance compared to the JS waterproof coating prepared using petroleum-based emulsion. Therefore, the bio-based JS waterproof coating of this invention not only meets the performance requirements for practical use but also effectively promotes the utilization of renewable resources, reduces carbon emissions, and is more environmentally friendly.

[0185] Compared with Example 1, Comparative Example 4 showed a decrease in the content of bio-based polyacrylate emulsion, which weakened the physical filling and chemical bonding between the emulsion and cement. This resulted in a decrease in the mechanical properties, impermeability, and impermeability of the JS waterproof coating, and even cracking of the coating film during the molding process. Therefore, the weight ratio of bio-based polyacrylate emulsion to silicate cement in this application should be controlled within the range of 1:(0.3–0.8).

[0186] As shown in Table 5, compared with Example 1, Comparative Examples 2-3 demonstrate that the combination of organic and inorganic bactericides in this application imparts highly efficient antifungal and antibacterial effects to the bio-based JS waterproof coating. Compared with Example 1, Examples 10-13 show that further rational combinations of organic and inorganic bactericides can achieve even better antibacterial and antifungal effects.

Claims

1. A bio-based water repellent coating, characterized in that, The bio-based waterproof coating comprises a first component and a second component in a weight ratio of 1:(1.0-1.5), by weight parts: The first component comprises: 0.3 parts of an organic bactericide; 60 to 294 parts of a bio-based polyacrylate emulsion based on 0.3 parts of the organic bactericide; and 0.3 to 30 parts of a first adjuvant based on 0.3 parts of the organic bactericide. The second component comprises: 0.6 parts of inorganic bactericide; 18 to 60 parts of silicate cement based on 0.6 parts of inorganic bactericide; and 24 to 212 parts of a second additive based on 0.6 parts of inorganic bactericide. The weight ratio of the bio-based polyacrylate emulsion, the organic bactericide, and the inorganic bactericide is 1:(0.003-0.004):(0.006-0.009). The weight ratio of the bio-based polyacrylate emulsion to the silicate cement is 1:(0.3-0.8); The preparation method of the bio-based polyacrylate emulsion includes: The raw materials provided include the following weight percentages: 8%–18% first monomer, 50%–70% second monomer, 6%–10% third monomer, 8%–14% fourth monomer and 1%–5% fifth monomer; The above raw materials are mixed and subjected to a free radical-initiated emulsion polymerization reaction to obtain a bio-based polyacrylate emulsion. The first monomer includes one or more of methyl methacrylate, n-butyl methacrylate, and styrene; the second monomer includes one or more of 2-octyl acrylate, n-butyl acrylate, and isooctyl acrylate; the third monomer includes one or more of octadecyl methacrylate, hexadecyl methacrylate, and dodecyl methacrylate; the fourth monomer includes one or more of isobornyl methacrylate, tetrahydrofurfuryl acrylate, and dimethyl itaconic acid (DMI); and the fifth monomer includes one or more of acrylic acid, methacrylic acid, and itaconic acid. The mass ratio of the fifth monomer to the second monomer is 1:(14-24).

2. The bio-based water repellent coating according to claim 1, characterized in that, The bio-based polyacrylate emulsion contains 20% to 45% bio-based carbon; and / or, the bio-based polyacrylate emulsion has a solid content of 50% to 60%.

3. The bio-based water repellent coating of claim 1, wherein, The first additive includes a dispersant, an antifoaming agent, and one or a combination thereof in water; and / or, the second additive includes a filler, a water-reducing agent, or a combination thereof.

4. The bio-based water repellent coating of claim 3, wherein, Based on parts by weight, the first component comprises: 0.3 parts of an organic bactericide; 92-98 parts of a bio-based polyacrylate emulsion based on 0.3 parts of the organic bactericide; 0.12-1.5 parts of a dispersant based on 0.3 parts of the organic bactericide; 0.12-1.5 parts of an antifoamer based on 0.3 parts of the organic bactericide; and 0.6-24 parts of water based on 0.3 parts of the organic bactericide. The second component includes: 0.6 parts of inorganic bactericide; 30-50 parts of silicate cement based on 0.6 parts of inorganic bactericide; 24-84 parts of filler based on 0.6 parts of inorganic bactericide; and 0.12-6 parts of water-reducing agent based on 0.6 parts of inorganic bactericide. The weight ratio of the first component and the second component is 1: (1.0-1.5).

5. The bio-based water repellent coating according to claim 3 or 4, c h a r a c t e r i z e d in that The bio-based waterproof coating at least meets one of the following characteristics: a. The organic bactericide includes one or a combination of isothiazolinone and 2,2-dibromopropionamide; b. The inorganic bactericide includes one or a combination of silver phosphate carrier, silver silicate carrier and silver borate carrier; c. The dispersing agent includes one or a combination of polyphosphate, polycarboxylate and triethylhexyl phosphate; d. The defoaming agent includes one or a combination of silicone defoaming agent and mineral oil defoaming agent; e. The silicate cement includes one or a combination of P.W32.5 white silicate cement, P.W42.5 white silicate cement, P.W32.5 gray silicate cement and P.W42.5 gray silicate cement; f. The filler includes one or a combination of 200-400 mesh heavy calcium carbonate, talcum powder and quartz powder; g. The water reducing agent includes one or a combination of polycarboxylic acid type water reducing agent, melamine type water reducing agent and melamine type water reducing agent.

6. A preparation method of the bio-based waterproof coating according to any one of claims 1-5, comprising: Preparation of the first component: taking 0.3 parts by weight of the organic bactericide; Mixing and stirring 60-294 parts by weight of bio-based polyacrylate emulsion based on 0.3 parts by weight of the organic bactericide, 0.3-30 parts by weight of the first additive based on 0.3 parts by weight of the organic bactericide, to obtain the first component; Preparation of the second component: taking 0.6 parts by weight of the inorganic bactericide; Taking 18-60 parts by weight of silicate cement based on 0.6 parts by weight of the inorganic bactericide; Mixing 24-212 parts by weight of the second additive based on 0.6 parts by weight of the inorganic bactericide, to obtain the second component; The weight ratio of the first component and the second component is 1: (1.0-1.5).

7. The method of producing a bio-based water repellent coating according to claim 6, characterized in that, The preparation method of the bio-based polyacrylate emulsion comprises: Preparation of pre-emulsion: mixing and stirring the emulsifier, water and the first monomer, the second monomer, the third monomer, the fourth monomer and the fifth monomer to obtain the pre-emulsion; dividing the pre-emulsion into a first pre-emulsion and a second pre-emulsion with a weight ratio of 1: (1.2-1.8); The first pre-emulsion and the first initiator are subjected to a first reaction to obtain a first emulsion; the first emulsion, the second pre-emulsion and the second initiator are subjected to a second reaction to obtain the bio-based polyacrylate emulsion.

8. The method of producing a bio-based water repellent coating according to claim 7, characterized in that, The preparation method of the bio-based polyacrylate emulsion at least meets one of the following characteristics: h. The temperature of the first reaction is 80-90°C, and the reaction time is 40-60 min; i. The temperature of the second reaction is 80-90°C, and the reaction time is 50-70 min; j. The amount of water added is 25%-30% of the total weight of the first monomer, the second monomer, the third monomer, the fourth monomer and the fifth monomer. k. The emulsifier is an anionic emulsifier or a nonionic emulsifier, and the amount of the emulsifier added is 1% to 3% of the total weight of the first monomer, the second monomer, the third monomer, the fourth monomer, and the fifth monomer; l. The first initiator and the second initiator are both persulfate initiators, and the weight ratio of the two is 1:(1.5 to 4).

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