Waterproof coating as well as preparation method and application thereof

Abstract

The invention discloses a waterproof coating as well as a preparation method and application thereof, and the waterproof coating comprises the following raw material components in parts by weight: 20-75 parts of diisocyanate; 100 parts to 500 parts of bio-based polyhydric alcohol; 100 to 300 parts of a plasticizer; 15 to 60 parts of a latent curing agent; the diisocyanate and the bio-based polyol are used for reaction to generate an isocyanate group-terminated polyurethane prepolymer, the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the bio-based polyol is 1.5: 1-2.5: 1, and after the diisocyanate and the bio-based polyol are used for reaction to generate the isocyanate group-terminated polyurethane prepolymer, the isocyanate group-terminated polyurethane prepolymer is added into the bio-based polyol, so that the isocyanate group-terminated polyurethane prepolymer is formed. The molar ratio of the residual amount of the isocyanate groups to reactive hydrogen after hydrolysis of the latent curing agent is 1: 1-1: 2. Compared with an existing waterproof coating, the waterproof coating has more excellent water resistance, acid and alkali resistance and thermal aging resistance, and meanwhile the use amount of petrochemical products is reduced.

Description

Technical Field

[0001] This application belongs to the technical field of waterproof coatings, and particularly relates to a waterproof coating, a preparation method thereof, and an application thereof. Background Art

[0002] Polyurethane waterproof coating is a prepolymer containing isocyanate groups formed by the addition polymerization reaction of isocyanates, polyethers, etc., and is made into a waterproof coating through mixing and processing with catalysts, auxiliaries, fillers, etc. Polyurethane waterproof coating is a reaction-curing type coating, which has the characteristics of high strength, large elongation, and good water resistance.

[0003] The composite waterproof technology represented by coatings and membranes has become a common technology in the field of building / road and bridge waterproofing. However, after the traditional solvent-based polyurethane waterproof coating is combined with the asphalt waterproof membrane, the residual unevaporated solvent will cause the waterproof membrane to swell, reducing the physical properties of the asphalt membrane. At the same time, the migration of plasticizers in the polyurethane coating will lead to poor adhesion between the coating and the asphalt membrane, easy detachment, and affect the waterproof effect. Summary of the Invention

[0004] The embodiments of this application provide a waterproof coating, a preparation method thereof, and an application thereof, which have more excellent water resistance, acid and alkali resistance, and heat aging resistance compared with the existing waterproof coatings. At the same time, the usage amount of petrochemical products is reduced.

[0005] In the first aspect, a waterproof coating is provided, which includes the following raw material components in parts by weight: diisocyanate, 20 parts to 75 parts; bio-based polyol, 100 parts to 500 parts; plasticizer, 100 parts to 300 parts; latent curing agent, 15 parts to 60 parts. The diisocyanate and the bio-based polyol are used to react to form an isocyanate group-terminated polyurethane prepolymer. Among them, the molar ratio of the isocyanate groups in the diisocyanate to the hydroxyl groups in the bio-based polyol is 1.5:1 to 2.5:1, and after the diisocyanate and the bio-based polyol react to form the isocyanate group-terminated polyurethane prepolymer, the molar ratio of the remaining amount of the isocyanate groups to the active hydrogen after the hydrolysis of the latent curing agent is 1:1 to 1:2.

[0006] In this application, the waterproof coating uses bio-based polyol to form an isocyanate group-terminated polyurethane prepolymer. At the same time, by controlling the molar ratio of the isocyanate groups to the hydroxyl groups in the bio-based polyol and the molar ratio of the remaining amount of the isocyanate groups to the active hydrogen after the hydrolysis of the latent curing agent, the waterproof coating of this application can not only ensure the adhesion effect between the waterproof coating and the asphalt membrane, but also has excellent water resistance, acid and alkali resistance, and heat aging resistance.

[0007] In the first possible implementation, the bio-based polyol satisfies at least one of the following conditions: (1) the hydroxyl value of the bio-based polyol is 30 mg KOH / g to 120 mg KOH / g; (2) the functionality of the bio-based polyol is 2 to 5; (3) the viscosity of the bio-based polyol at 25 °C is 300 cp to 7000 cp.

[0008] Combined with the above possible implementation, the plasticizer includes a bio-based reactive plasticizer and a common plasticizer. The mass ratio of the bio-based reactive plasticizer to the common plasticizer is 1.5:1 to 14:1. Preferably, the bio-based reactive plasticizer includes one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, and epoxidized linseed oil, and the common plasticizer includes one or more of chlorinated paraffins, citrate esters, phthalates, and trioctyl phosphate.

[0009] By controlling the mass ratio of the bio-based reactive plasticizer and the common plasticizer in the plasticizer, this application not only ensures the construction viscosity of the solvent-free polyurethane waterproof coating, but also solves the problem of plasticizer migration in the waterproof coating, ensuring the bonding effect between the polyurethane waterproof coating and the asphalt roll.

[0010] Combined with the above possible implementation, the plasticizer includes a bio-based reactive plasticizer. The raw material components may further include 0.1 part to 0.5 part of a catalyst. The mass ratio of the catalyst to the bio-based polyol is 1:200 to 1:5000. The catalyst is used to catalyze the cross-linking reaction of the isocyanate group-terminated polyurethane prepolymer, the latent curing agent, and the bio-based reactive plasticizer. Preferably, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, and bismuth isooctanoate.

[0011] Combined with the above possible implementation, the raw material components may further include 0.1 part to 0.5 part of a latent curing agent hydrolysis promoter. The mass ratio of the latent curing agent hydrolysis promoter to the latent curing agent is 1:30 to 1:450.

[0012] Combined with the above possible implementation, the diisocyanate includes one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate; and / or, the latent curing agent includes one or more of aldehyde imine-based latent curing agents, ketone imine-based latent curing agents, and oxazolidine-based latent curing agents.

[0013] Combined with the above possible implementation, the raw material components may further include additives. By weight, the additives include: filler, 100 parts to 500 parts; pigment, 5 parts to 10 parts; dispersant, 0.5 part to 1 part; defoaming agent, 1 part to 3 parts.

[0014] Combined with the above possible implementation manners, the filler includes one or more of nano calcium carbonate, talcum powder, fumed silica, barium sulfate, heavy calcium carbonate, light calcium carbonate and kaolin. Preferably, the particle size of the filler is 800 mesh to 3000 mesh; and / or, the pigment includes one or more of carbon black, iron oxide red, titanium dioxide, iron oxide yellow and composite emerald green; and / or, the dispersant includes non-ionic dispersants and / or anionic dispersants; and / or, the defoamer includes silicone defoamers and / or mineral oil defoamers.

[0015] In a second aspect, a preparation method of a waterproof coating includes: stirring and mixing 100 parts to 500 parts of a bio-based polyol and 100 parts to 300 parts of a plasticizer for dehydration to obtain a first mixture; adding 20 parts to 75 parts of a diisocyanate to the first mixture for reaction to obtain a second mixture; adding 15 parts to 60 parts of a latent curing agent to the second mixture for mixing reaction to obtain the waterproof coating.

[0016] In a first possible implementation manner, in the step of stirring and mixing 100 parts to 500 parts of a bio-based polyol and 100 parts to 300 parts of a plasticizer for dehydration to obtain a first mixture, the bio-based polyol and the additive are stirred and heated to 102°C to 108°C, and then dehydrated for 2h to 4h; and / or, in the step of stirring and mixing 100 parts to 500 parts of a bio-based polyol and 100 parts to 300 parts of a plasticizer for dehydration to obtain a first mixture, an additive can also be added before mixing; and / or, in the step of adding 20 parts to 75 parts of a diisocyanate to the first mixture for reaction to obtain a second mixture, the first mixture is cooled to 75°C to 80°C, the diisocyanate is added, and then the temperature is adjusted to 78°C to 82°C for reaction for 2h to 4h.

[0017] Combined with the above possible implementation manners, the step of adding 15 parts to 60 parts of a latent curing agent to the second mixture for mixing reaction to obtain the waterproof coating includes: controlling the temperature of the second mixture to 73°C to 77°C, adding a catalyst, reacting for 0.5h to 2h to obtain a third mixture; controlling the temperature of the third mixture at 73°C to 77°C, adding the latent curing agent, and continuing to react for 0.5 to 2h to obtain a fourth mixture; controlling the temperature of the fourth mixture to 65°C to 70°C, adding a latent curing agent hydrolysis promoter, reacting for 20min to 50min to obtain a fifth mixture; controlling the temperature of the fifth mixture to 63°C to 67°C, performing vacuum defoaming for 10min to 20min, and discharging under the protection of a protective gas to obtain the waterproof coating.

[0018] In a third aspect, a composite waterproof layer includes a bituminous waterproofing membrane and a waterproof coating layer formed by the waterproof coating of the first aspect and / or a waterproof coating layer formed by the waterproof coating prepared by the preparation method of the second aspect. Description of the Drawings

[0019] To more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the accompanying drawings required for the embodiments of the present application. Obviously, the accompanying drawings described below are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can be obtained based on these drawings.

[0020] Figure 1 It is a schematic diagram of the curing principle of a waterproof coating using an aldehyde imine-based latent curing agent according to an embodiment of the present application.

[0021] Figure 2 It is a schematic diagram of the curing principle of a waterproof coating using a ketone imine-based latent curing agent according to an embodiment of the present application.

[0022] Figure 3 It is a schematic diagram of the curing principle of a waterproof coating using an oxazolidine-based latent curing agent according to an embodiment of the present application.

[0023] Figure 4 It is a schematic diagram of the curing principle of a waterproof coating using an oxazolidine-based latent curing agent according to another embodiment of the present application. Detailed Embodiments

[0024] The following will describe in detail the features and exemplary embodiments of various aspects of the present application. To make the objectives, technical solutions, and advantages of the present application clearer and more understandable, the present application will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application, rather than limiting the present application. For those skilled in the art, the present application can be implemented without some of these specific details. The following description of the embodiments is only to provide a better understanding of the present application by showing examples of the present application.

[0025] For simplicity, the present application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form a range not explicitly recorded; and any lower limit can be combined with other lower limits to form a range not explicitly recorded, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recorded. In addition, although not explicitly recorded, each point or single value between the range endpoints is included in this range. Thus, each point or single value can be used as its own lower limit or upper limit and combined with any other point or single value or combined with other lower limits or upper limits to form a range not explicitly recorded.

[0026] The above-mentioned summary of the invention of the present application does not intend to describe every disclosed embodiment or every implementation mode in the present application. The following description more specifically exemplifies exemplary embodiments. Throughout the application, guidance is provided through a series of embodiments, which can be used in various combinations. In each instance, the enumeration is only as a representative group and should not be construed as exhaustive. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "a plurality of" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0027] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0028] Polyurethane waterproof coating is a prepolymer containing isocyanate groups formed by the addition polymerization reaction of isocyanate, polyether, etc., and is made into a waterproof coating through mixing and processing with catalysts, auxiliaries, fillers, etc. Polyurethane waterproof coating is a reaction-curing type coating, which has the characteristics of high strength, large elongation rate, good water resistance, etc. The commonly used raw materials of polyurethane waterproof coating are petrochemical products. Due to the fluctuation of crude oil prices and the continuous deepening of the concept of social green environmental protection, the development speed of bio-based materials industries such as bio-based polyols and bio-based plasticizers will be further accelerated, and the development trend of its industry will continue to be good.

[0029] The composite waterproof process represented by coatings and membranes has become a common process in the field of building / road and bridge waterproofing. However, after the traditional solvent-based polyurethane waterproof coating is combined with the asphalt waterproof membrane, the residual unevaporated solvent will cause the waterproof membrane to swell, reducing the physical properties of the asphalt membrane. At the same time, the migration of plasticizers in the polyurethane coating will lead to poor adhesion between the coating and the asphalt membrane, making it easy to fall off and affecting the waterproof effect. At the same time, the new waterproof regulations require that the water immersion adhesion strength retention rate of polyurethane waterproof coating reaches 80%. It is very difficult for the existing polyurethane waterproof coatings to meet the requirements on the cement-based surface without primer.

[0030] In view of the above technical problems, the embodiments of the present application provide a waterproof coating, which has more excellent water resistance, acid and alkali resistance, and heat aging resistance than the existing waterproof coatings. At the same time, the usage amount of petrochemical products is reduced.

[0031] First, the waterproof coating provided by the embodiments of the present application will be introduced below.

[0032] According to the present application, the waterproof coating comprises the following raw material components in parts by weight: diisocyanate, 20 to 75 parts; bio-based polyol, 100 to 500 parts; plasticizer, 100 to 300 parts; latent curing agent, 15 to 60 parts; diisocyanate and bio-based polyol are used to react to form an isocyanate group-terminated polyurethane prepolymer, wherein the molar ratio of the isocyanate group (-NCO) in the diisocyanate to the hydroxyl group (-OH) in the bio-based polyol is 1.5:1 to 2.5:1, for example, The molar ratio of the isocyanate group (-NCO) to the active hydrogen (α-H) after the hydrolysis of the latent curing agent is 1:1 to 1:2, for example, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, or any combination of the above values.

[0033] The inventors have found that by using bio-based polyols to generate isocyanate group-terminated polyurethane prepolymers, and at the same time controlling the molar ratio of isocyanate groups to hydroxyl groups in the bio-based polyols and the molar ratio of the residual amount of isocyanate groups to the active hydrogen after hydrolysis of the latent curing agent, the waterproof coating of the present application can not only ensure the bonding effect between the waterproof coating and the asphalt roll, but also improve the water-immersion bonding strength retention rate of the polyurethane waterproof coating, which can ensure that the water-immersion bonding strength retention rate is higher than 80%, and has excellent water resistance, acid and alkali resistance, and heat aging resistance.

[0034] In some specific embodiments, the bio-based polyol satisfies at least one of the following conditions: (1) the hydroxyl value of the bio-based polyol is 30 mg KOH / g to 120 mg KOH / g, for example, 30 mg KOH / g, 40 mg KOH / g, 50 mg KOH / g, 60 mg KOH / g, 70 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 120 mg KOH / g, or any combination range of the above values; (2) the functionality of the bio-based polyol is 2 to 5, for example, 2, 3, 4, 5; (3) the viscosity of the bio-based polyol at 25° C. is 300 cp to 7000 cp, for example, 300 cp, 500 cp, 800 cp, 1000 cp, 2000 cp, 3000 cp, 4000 cp, 5000 cp, 6000 cp, 7000 cp, or any combination range of the above values.

[0035] In some specific embodiments, the plasticizer includes a bio-based reactive plasticizer and a common plasticizer. The mass ratio of the bio-based reactive plasticizer to the common plasticizer is 1.5:1 to 14:1. For example, it can be 1.5:1, 2:1, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, or any combination range of the above values. Preferably, the bio-based reactive plasticizer includes one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, and epoxidized linseed oil, and the common plasticizer includes one or more of chlorinated paraffin, citrate ester, phthalic acid, and tributyl phosphate.

[0036] In the above specific embodiments, by controlling the mass ratio of the bio-based reactive plasticizer and the common plasticizer in the plasticizer, the present application not only ensures the construction viscosity of the solvent-free polyurethane waterproof coating, but also solves the problem of plasticizer migration in the waterproof coating, ensuring the bonding effect between the polyurethane waterproof coating and the asphalt coil. Thus, it solves the problem that the existing solvent-free polyurethane waterproof coating generally adds small molecule plasticizers to control the product viscosity to ensure the construction performance, but the small molecule plasticizers have a high price and poor plasticizing effect, resulting in low product performance, and only by further increasing the cost can the product performance be controlled.

[0037] In some specific embodiments, the plasticizer includes a bio-based reactive plasticizer, and the raw material components may further include 0.1 part to 0.5 part of a catalyst. For example, it can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, or any combination range of the above values. The mass ratio of the catalyst to the bio-based polyol is 1:200 to 1:5000. For example, it can be 1:200, 1:500, 1:800, 1:1000, 1:2000, 1:3000, 1:4000, 1:5000, or any combination range of the above values. The catalyst is used to catalyze the cross-linking reaction of the isocyanate group-terminated polyurethane prepolymer, the latent curing agent, and the bio-based reactive plasticizer. Preferably, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctoate, and bismuth isooctoate.

[0038] In some specific embodiments, the raw material components may further include 0.1 part to 0.5 part of a latent curing agent hydrolysis promoter. For example, it can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, or any combination range of the above values. The mass ratio of the latent curing agent hydrolysis promoter to the latent curing agent is 1:30 to 1:450. For example, it can be 1:30, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, or any combination range of the above values.

[0039] In some specific embodiments, the diisocyanate includes one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate; and / or, the latent curing agent includes one or more of aldehyde imine-based latent curing agents, ketone imine-based latent curing agents, and oxazolidine-based latent curing agents.

[0040] In some specific embodiments, the raw material components may further include additives. By weight, the additives include: filler, 100 parts to 500 parts; pigment, 5 parts to 10 parts; dispersant, 0.5 parts to 1 part; defoamer, 1 part to 3 parts.

[0041] In some specific embodiments, the filler includes one or more of nano calcium carbonate, talcum powder, fumed silica, barium sulfate, heavy calcium carbonate (heavy calcium), light calcium carbonate (light calcium), and kaolin. Preferably, the particle size of the filler is 800 mesh to 3000 mesh. For example, it can be 800 mesh, 1000 mesh, 1500 mesh, 2000 mesh, 2500 mesh, 3000 mesh, or any combination range of the above values; and / or, the pigment includes one or more of carbon black, iron oxide red, titanium dioxide, iron oxide yellow, and composite emerald green; and / or, the dispersant includes non-ionic dispersants and / or anionic dispersants; and / or, the defoamer includes silicone-based defoamers and / or mineral oil-based defoamers.

[0042] Second, a preparation method of a waterproof coating, including: stirring and mixing 100 parts to 500 parts of bio-based polyol and 100 parts to 300 parts of plasticizer for dehydration to obtain a first mixture; adding 20 parts to 75 parts of diisocyanate to the first mixture for reaction to obtain a second mixture, wherein the diisocyanate reacts with the bio-based polyol to form an isocyanate group-terminated polyurethane prepolymer; adding 15 parts to 60 parts of latent curing agent to the second mixture for mixing reaction to obtain a waterproof coating. The specific mechanism is as Figures 1 to 4 shown. In the figure, the chemical formula where R is located represents a bio-based reactive plasticizer containing an epoxy group, the chemical formula where R1 is located represents an isocyanate group-terminated polyurethane prepolymer obtained by reacting a bio-based polyol and an isocyanate, and R2, R3, and R4 are each selected from any one of C1-C6 alkyl groups, C6-C 10 aryl groups, and C3-C6 cycloalkyl groups. The isocyanate group-terminated polyurethane prepolymer, bio-based reactive plasticizer, and latent curing agent crosslink in the presence of water to obtain polyurethane and volatile organic compounds (VOCs). Specifically, after the waterproof coating of the present application is constructed, the water vapor in the air reacts with the latent curing agent, the latent curing agent hydrolyzes, the aldehyde or ketone substance as a blocking agent volatilizes, and the substance containing active hydrogen acts as a chain extender and participates in the chain extension reaction between the NCO group and the epoxy group, so that the coating cures into a film.

[0043] In some specific embodiments, in the step of obtaining the first mixture by stirring and mixing 100 parts to 500 parts of bio-based polyol and 100 parts to 300 parts of plasticizer and dehydrating, the bio-based polyol and the additive are stirred and heated to 102°C to 108°C. For example, it can be 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, or any combination range of the above values. Then, dehydration is carried out for 2h to 4h. For example, it can be 2h, 2.5h, 3h, 3.5h, 4h, or any combination range of the above values; and / or, in the step of obtaining the first mixture by stirring and mixing 100 parts to 500 parts of bio-based polyol and 100 parts to 300 parts of plasticizer and dehydrating, an additive can also be added before mixing; and / or, in the step of adding 20 parts to 75 parts of diisocyanate to the first mixture to react to obtain the second mixture, after the first mixture is cooled to 75°C to 80°C, for example, it can be 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, or any combination range of the above values, diisocyanate is added and then the temperature is adjusted to 78°C to 82°C. For example, it can be 78°C, 79°C, 80°C, 81°C, 82°C, or any combination range of the above values, and the reaction is carried out for 2h to 4h. For example, it can be 2h, 2.5h, 3h, 3.5h, 4h, or any combination range of the above values.

[0044] In some specific embodiments, the steps of adding 15 to 60 parts of a latent curing agent to the second mixture and mixing and reacting to obtain a waterproof coating include: controlling the temperature of the second mixture to 73°C to 77°C. For example, it can be 73°C, 74°C, 75°C, 76°C, 77°C, or any combination range of the above values. Adding a catalyst and reacting for 0.5 h to 2 h to obtain a third mixture. For example, it can be reacting for 0.5 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, or any combination range of the above values; controlling the temperature of the third mixture at 73°C to 77°C. For example, it can be 73°C, 74°C, 75°C, 76°C, 77°C, or any combination range of the above values. Adding a latent curing agent and continuing to react for 0.5 h to 2 h. For example, it can be reacting for 0.5 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, or any combination range of the above values to obtain a fourth mixture; controlling the temperature of the fourth mixture to 65°C to 70°C. For example, it can be 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, or any combination range of the above values. Adding a latent curing agent hydrolysis promoter and reacting for 20 min to 50 min. For example, it can be 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, or any combination range of the above values to obtain a fifth mixture; controlling the temperature of the fifth mixture to 63°C to 67°C. For example, it can be 63°C, 64°C, 65°C, 66°C, 67°C, or any combination range of the above values. Performing vacuum degassing for 10 to 20 min. For example, it can be 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, or any combination range of the above values, and discharging the material under the protection of an inert gas to obtain a waterproof coating.

[0045] In a third aspect, a composite waterproof layer includes a waterproof coating layer formed by an asphalt waterproofing membrane and the waterproof coating of the first aspect and / or a waterproof coating layer formed by the waterproof coating prepared by the preparation method of the second aspect. The composite waterproof layer of the present application effectively solves the problem that the residual solvent swells the asphalt roll, and ensures the physical properties of the composite waterproof layer.

[0046] In addition, the term "and / or" in this article is merely a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this article generally represents an "or" relationship between the associated objects before and after.

[0047] It should be understood that in the embodiments of the present application, "B corresponding to A" means that B is associated with A, and B can be determined according to A. However, it should also be understood that determining B according to A does not mean determining B only according to A, and B can also be determined according to A and / or other information.

[0048] Embodiment

[0049] The following embodiments more specifically describe the content disclosed in the present application, and these embodiments are only for illustrative purposes.

[0050] Because various modifications and changes within the scope of the disclosure of the present application are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on mass, and all raw materials used in the embodiments are commercially available or prepared by conventional methods and can be used directly without further treatment, and all instruments used in the embodiments are commercially available.

[0051] In the subsequent embodiments, the sources and models of some raw materials are as follows: Bio-based polyol: ECOPROL H2700, etc. Polyether diol: DL-2000D, Shandong Bluestar Dongda Co., Ltd.; trifunctional polyether polyol: EP330N, Shandong Bluestar Dongda Co., Ltd. Filler, 800-mesh heavy calcium carbonate, 1250-mesh talc powder. Pigment: carbon black, composite emerald green. Ordinary plasticizer: 52# chlorinated paraffin, tributyl acetylcitrate. Bio-based reactive plasticizer: epoxidized soybean oil. Catalyst: dibutyltin dilaurate (T12 organotin catalyst). Dispersant: Disuper S18, purchased from Guangzhou Core New Materials Technology Co., Ltd. Defoamer: BYK-052N. Latent curing agent: latent curing agent YRLH-1106 (containing 2 active hydrogen functional groups, molecular weight of 250), Guangzhou Yourun Synthetic Materials Co., Ltd. Latent curing agent hydrolysis promoter: promoter B, Shandong Zhihuapu New Materials Co., Ltd.

[0052] In the present application has a hydroxyl value of 56 mg KOH / g, a functionality of 2, and a viscosity of 1360 cp at 25°C; ECOPROL H2700 has a hydroxyl value of 42 mg KOH / g, a functionality of 2, and a viscosity of 3100 cp at 25°C; has a hydroxyl value of 37 mg KOH / g, a functionality of 2, and a viscosity of 3860 cp at 25°C; ECOPROL H1000 has a hydroxyl value of 112 mg KOH / g, a functionality of 2, and a viscosity of 500 cp at 25°C; HM-1070 has a hydroxyl value of 81 mg KOH / g, a functionality of 4, and a viscosity of 2250 cp at 25°C; The hydroxyl value of it is 28 mg KOH / g, the functionality is 2, and the viscosity at 25°C is 8600 cp; the hydroxyl value of HM-140 is 110 mg KOH / g, the functionality is 6, and the viscosity at 25°C is 1400 cp. The hydroxyl value of the polyether diol DL-2000D is 56 mg KOH / g, the functionality is 2, and the viscosity at 25°C is 400 cp; the hydroxyl value of the trifunctional polyether polyol EP330N is 35 mg KOH / g, the functionality is 3, and the viscosity at 25°C is 900 cp.

[0053] In this example, the molecular weight of the polyol can be calculated by the following formula: Molecular weight = 56.1×1000×f / (hydroxyl value + acid value), where 56.1 is the molecular weight of KOH and f is the functionality.

[0054] Example 1

[0055] A waterproof coating, comprising the following raw material components in parts by weight: 180 parts of D-2000, 140 parts of ECOPROL H2700, 100 parts of 52# chlorinated paraffin, 200 parts of epoxy soybean oil, 0.8 part of DisuperS18, 2 parts of BYK-052N, 280 parts of 800-mesh heavy calcium, 170 parts of 1250-mesh talc powder, 0.8 part of carbon black, 7 parts of composite emerald green, 45 parts of toluene diisocyanate (TDI), 0.4 part of T12, 35 parts of latent curing agent YRLH-1106, and 0.4 part of accelerator B.

[0056] In this example, the molar ratio of the isocyanate groups in the diisocyanate to the hydroxyl groups in the bio-based polyol is 1.82:1. After the diisocyanate reacts with the bio-based polyol to form an isocyanate group-terminated polyurethane prepolymer, the remaining amount of the isocyanate groups and the molar ratio of the active hydrogen after hydrolysis of the latent curing agent is 1:1.201. The mass ratio of the catalyst to the bio-based polyol is 1:800, and the mass ratio of the latent curing agent hydrolysis accelerator to the latent curing agent is 1:87.5.

[0057] The waterproof coating is prepared by the following method:

[0058] Add the bio-based polyol ECOPROL H2700, plasticizer 52# chlorinated paraffin, and epoxy soybean oil, pigment and filler (a mixture of heavy calcium, talc powder, carbon black and composite emerald green), dispersant DisuperS18, defoamer BYK-052N into the reaction vessel, stir and heat up to 105°C ± 3°C, and carry out dehydration reaction for 2 h under a vacuum of -0.1 MPa to obtain the first mixture.

[0059] After dehydration is completed, cool the first mixture to 75°C - 80°C, add diisocyanate, and then heat it to 80°C ± 2°C and react for 3 hours to obtain the second mixture.

[0060] Control the temperature of the second mixture to 75°C ± 2°C, add a catalyst, and react for 1 hour to obtain the third mixture.

[0061] Control the temperature of the third mixture at 75°C ± 2°C, add a latent curing agent, and continue to react for 1 hour to obtain the fourth mixture.

[0062] Cool the fourth mixture to 65°C - 70°C, add a latent curing agent hydrolysis promoter, and react for 20 minutes to obtain the fifth mixture.

[0063] Cool the fifth mixture to 65°C ± 2°C, carry out vacuum degassing for 10 minutes, and discharge the material under nitrogen protection to obtain the waterproof coating.

[0064] Example 2

[0065] The preparation process of the waterproof coating in Example 2 is the same as that in Example 1, except for the material selection and addition amount. The addition amount of each material is shown in Table 1 and Table 3.

[0066] Example 3

[0067] The preparation process of the waterproof coating in Example 3 is the same as that in Example 1, except for the material selection and addition amount. The addition amount of each material is shown in Table 1 and Table 3.

[0068] Example 4

[0069] The preparation process of the waterproof coating in Example 4 is the same as that in Example 1, except for the material selection and addition amount. The addition amount of each material is shown in Table 1 and Table 3.

[0070] Example 5

[0071] The preparation process of the waterproof coating in Example 5 is the same as that in Example 1, except for the material selection and addition amount. The addition amount of each material is shown in Table 1 and Table 3.

[0072] Example 6

[0073] The preparation process of the waterproof coating in Example 6 is the same as that in Example 1, except for the material selection and addition amount. The addition amount of each material is shown in Table 1 and Table 3.

[0074] Example 7

[0075] The preparation process of the waterproof coating in Example 7 is the same as that in Example 1, except for the material selection and addition amount. The addition amount of each material is shown in Table 1 and Table 3.

[0076] Example 8

[0077] The preparation process of the waterproof coating in Example 8 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0078] Example 9

[0079] The preparation process of the waterproof coating in Example 9 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0080] Example 10

[0081] The preparation process of the waterproof coating in Example 10 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0082] Example 11

[0083] The preparation process of the waterproof coating in Example 11 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0084] Example 12

[0085] The preparation process of the waterproof coating in Example 12 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0086] Example 13

[0087] The preparation process of the waterproof coating in Example 13 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0088] Example 14

[0089] The preparation process of the waterproof coating in Example 14 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 1 and Table 3.

[0090] Comparative Example 1

[0091] The preparation process of the waterproof coating in Comparative Example 1 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 2 and Table 3.

[0092] Comparative Example 2

[0093] The preparation process of the waterproof coating in Comparative Example 2 is the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Table 2 and Table 3.

[0094] Comparative Example 3

[0095] The preparation process of the waterproof coating in Comparative Example 3 was the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Tables 2 and 3.

[0096] Comparative Example 4

[0097] The preparation process of the waterproof coating in Comparative Example 4 was the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Tables 2 and 3.

[0098] Comparative Example 5

[0099] The preparation process of the waterproof coating in Comparative Example 5 was the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Tables 2 and 3.

[0100] Comparative Example 6

[0101] The preparation process of the waterproof coating in Comparative Example 6 was the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Tables 2 and 3.

[0102] Comparative Example 7

[0103] The preparation process of the waterproof coating in Comparative Example 7 was the same as that in Example 1, except for the material selection and addition amount. The addition amounts of each material are shown in Tables 2 and 3.

[0104]

[0105]

[0106] Table 2 Raw material batching table of Comparative Examples 1 - 7

[0107]

[0108] Table 3 Parameter table of Examples 1 - 14 and Comparative Examples 1 - 7

[0109]

[0110]

[0111]

[0112] Testing Part

[0113] The elongation at break, tensile strength, tear strength, and VOC content of the waterproof coatings prepared in Examples 1 - 14 and Comparative Examples 1 - 7 were tested using the test methods of GB / T 16777 - 2008, GB / T 19250 - 2013, and GB 55030 - 2022. The test results are shown in Table 4.

[0114] Table 4 Test Results of Waterproof Coatings of Examples 1-14 and Comparative Examples 1-7

[0115]

[0116]

[0117] As shown by the performance data in Table 4, by controlling the molar ratio of isocyanate groups to hydroxyl groups in the bio-based polyol, the molar ratio of the remaining amount of isocyanate groups to the active hydrogen after hydrolysis of the latent curing agent, and the mass ratio of the bio-based reactive plasticizer to the common plasticizer, the waterproof coating obtained by the synergistic action of the above has excellent mechanical strength, and at the same time has good retention rate of bonding strength in water immersion and retention rate of strength in acid, alkali and heat treatment.

[0118] Among them, from the performance data of Example 1 using bio-based polyol, Comparative Example 1 using conventional polyether polyol and Comparative Examples 6-9, by controlling the molar ratio of isocyanate groups to hydroxyl groups in the bio-based polyol, the molar ratio of the remaining amount of isocyanate groups to the active hydrogen after hydrolysis of the latent curing agent, and the mass ratio of the bio-based reactive plasticizer to the common plasticizer, under the synergistic action of the two, the retention rates of strength in acid, alkali and heat treatment of the waterproof coating in Example 1 are significantly higher than those in Comparative Example 1, and the comprehensive performance of the waterproof coating in Example 1 is also significantly higher than that of the waterproof coatings in Comparative Examples 4-7; from the performance data of Example 1, Example 11, Example 12 and Comparative Examples 2-3, by adopting the control of the molar ratio of isocyanate groups to hydroxyl groups in the bio-based polyol, the molar ratio of the remaining amount of isocyanate groups to the active hydrogen after hydrolysis of the latent curing agent, and the mass ratio of the bio-based reactive plasticizer to the common plasticizer, the synergistic action of the three can ensure the bonding strength of the waterproof coating in water immersion while ensuring the mechanical properties of the waterproof coating, and the finished product has a lower viscosity and is easy to construct. For example, only using conventional plasticizers, the retention rate of bonding strength in water immersion obviously does not meet the requirements (Comparative Examples 2 and 3), only using bio-based reactive plasticizers will cause a decrease in the elongation at break of the coating (Example 11); when the mass ratio of the bio-based reactive plasticizer to the conventional curing agent decreases, both the retention rate of bonding strength in water immersion and the mechanical properties are poor (Example 12). In addition, from the performance data of Example 1, Example 13 and Example 14, it can be seen that the comprehensive performance of the waterproof coating can be further improved by the special selection of the hydroxyl value, viscosity and functionality of the bio-based polyol.

[0119] The above is only the specific implementation manner of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should all be covered within the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A waterproof coating, characterized in that It comprises raw material components in the following parts by weight: Diisocyanate, 20 parts to 75 parts; Bio-based polyol, 100 parts to 500 parts; Plasticizer, 100 parts to 300 parts; Latent curing agent, 15 parts to 60 parts; The diisocyanate and the bio-based polyol are used to react to form an isocyanate group-terminated polyurethane prepolymer. Among them, the molar ratio of the isocyanate group in the diisocyanate to the hydroxyl group in the bio-based polyol is 1.5:1 to 2.5:1, and after the diisocyanate and the bio-based polyol react to form the isocyanate group-terminated polyurethane prepolymer, the remaining amount of the isocyanate group and the active hydrogen after hydrolysis of the latent curing agent have a molar ratio of 1:1 to 1:

2.

2. The waterproof coating according to claim 1, wherein The bio-based polyol meets at least one of the following conditions: (1) The hydroxyl value of the bio-based polyol is 30 mg KOH / g to 120 mg KOH / g; (2) The functionality of the bio-based polyol is 2 to 5; (3) The viscosity of the bio-based polyol at 25 °C is 300 cp to 7000 cp.

3. The waterproof coating according to claim 1, wherein The plasticizer includes a bio-based reactive plasticizer and a common plasticizer. The mass ratio of the bio-based reactive plasticizer to the common plasticizer is 1.5:1 to 14:

1. Preferably, the bio-based reactive plasticizer includes one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, and epoxidized linseed oil, and the common plasticizer includes one or more of chlorinated paraffin, citrate, phthalate, and trioctyl phosphate.

4. The waterproof coating according to claim 1, wherein The plasticizer includes a bio-based reactive plasticizer. The raw material components further include 0.1 part to 0.5 part of a catalyst. The mass ratio of the catalyst to the bio-based polyol is 1:200 to 1:5000. The catalyst is used to catalyze the crosslinking reaction of the isocyanate group-terminated polyurethane prepolymer, the latent curing agent, and the bio-based reactive plasticizer. Preferably, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, and bismuth isooctanoate.

5. The waterproof coating according to claim 1, characterized in that, The raw material components further include 0.1 part to 0.5 part of a latent curing agent hydrolysis promoter. The mass ratio of the latent curing agent hydrolysis promoter to the latent curing agent is 1:30 to 1:

450.

6. The waterproof coating according to claim 1, wherein The diisocyanate includes one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate; and / or, the latent curing agent includes one or more of aldehyde imine-based latent curing agents, ketone imine-based latent curing agents, and oxazolidine-based latent curing agents.

7. The waterproof coating according to any one of claims 1 to 5, characterized in that, The raw material components further include additives. In parts by weight, the additives include: Filler, 100 parts to 500 parts; Pigment, 5 parts to 10 parts; Dispersant, 0.5 part to 1 part; Defoamer, 1 part to 3 parts.

8. The waterproof coating according to claim 7, characterized in that, The filler includes one or more of nano calcium carbonate, talc powder, fumed silica, barium sulfate, heavy calcium carbonate, light calcium carbonate, and kaolin. Preferably, the particle size of the filler is 800 mesh to 3000 mesh; and / or, the pigment includes one or more of carbon black, iron oxide red, titanium dioxide, iron oxide yellow, and composite emerald green; And / or, the dispersant includes a nonionic dispersant and / or an anionic dispersant; And / or, the defoamer includes a silicone defoamer and / or a mineral oil defoamer.

9. A preparation method of a waterproof coating, characterized in that, Comprising: Mix 100 to 500 parts of bio-based polyol and 100 to 300 parts of plasticizer by stirring and dehydrate to obtain a first mixture; Add 20 to 75 parts of diisocyanate to the first mixture and react to obtain a second mixture; Add 15 to 60 parts of latent curing agent to the second mixture and mix and react to obtain the waterproof coating.

10. The preparation method according to claim 9, characterized in that, In the step of mixing 100 to 500 parts of bio-based polyol and 100 to 300 parts of plasticizer by stirring and dehydrating to obtain a first mixture, the bio-based polyol and the additive are stirred and heated to 102°C to 108°C, and then dehydrated for 2 to 4 hours; And / or, in the step of mixing 100 to 500 parts of bio-based polyol and 100 to 300 parts of plasticizer by stirring and dehydrating to obtain a first mixture, the additive is added before mixing; And / or, in the step of adding 20 to 75 parts of diisocyanate to the first mixture and reacting to obtain a second mixture, the first mixture is cooled to 75°C to 80°C, diisocyanate is added, and then the temperature is adjusted to 78°C to 82°C and reacted for 2 to 4 hours.

11. The preparation method according to claim 9, characterized in that, The step of adding 15 to 60 parts of latent curing agent to the second mixture and mixing and reacting to obtain the waterproof coating includes: Control the temperature of the second mixture to 73°C to 77°C, add a catalyst, and react for 0.5 to 2 hours to obtain a third mixture; Control the temperature of the third mixture at 73°C to 77°C, add a latent curing agent, and continue to react for 0.5 to 2 hours to obtain a fourth mixture; Control the temperature of the fourth mixture to 65°C to 70°C, add a latent curing agent hydrolysis promoter, and react for 20 to 50 minutes to obtain a fifth mixture; Control the temperature of the fifth mixture to 63°C to 67°C, carry out vacuum degassing for 10 to 20 minutes, and discharge under the protection of a protective gas to obtain the waterproof coating.

12. A composite waterproof layer, characterized in that, Comprising an asphalt waterproofing membrane and a waterproof coating layer formed by the waterproof coating according to any one of claims 1-8 and / or a waterproof coating layer formed by the waterproof coating prepared by the preparation method according to any one of claims 9-11.

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