Self-healing non-asphalt-based waterproof coating and preparation method thereof

Abstract

The invention relates to the technical field of waterproof coatings, in particular to a self-healing non-asphalt-based waterproof coating and a preparation method thereof. The waterproof coating disclosed by the invention is prepared from the following raw materials in parts by weight: 25 to 40 parts of aromatic hydrocarbon oil, 3 to 6 parts of butadiene styrene rubber-graft-4, 4 '-dithio-diphenylamine, 5 to 10 parts of petroleum resin, 4 to 8 parts of emulsifier, 30 to 50 parts of water, 0.4 to 2 parts of other auxiliaries, 8 to 20 parts of powder and 2 to 5 parts of butadiene styrene rubber emulsion. According to the waterproof coating disclosed by the invention, the key modified component butadiene styrene rubber-graft-4, 4 '-dithio diphenylamine is introduced, so that the coating is endowed with an excellent self-healing function. The specific raw materials are matched, so that a better synergistic effect is formed among the raw materials, and the overall performance such as low-temperature flexibility and bonding strength of the waterproof coating is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of waterproof coating, in particular to a self-repairing non-asphalt-based waterproof coating and a preparation method thereof. BACKGROUND

[0002] The waterproof coatings on the market are mainly divided into two categories: oil-based waterproof coatings and water-based waterproof coatings. The oil-based waterproof coatings include: (1) solvent type: such as polyurethane, polyurea, epoxy resin, etc., which are diluted by solvents and then brushed, and react with water, oxygen or two components to solidify. This type of coating releases a large amount of harmful gas during the solidification process, which not only harms the health of the construction personnel, but also pollutes the air environment. (2) Hot melt type: mainly hot melt modified asphalt waterproof coating, which needs to be heated and melted before brushing and solidified after the temperature drops. During the construction process, it will produce irritating odor and smoke, which is harmful to health after being inhaled, and is prone to scalding accidents. The water-based waterproof coatings include: (1) Emulsified asphalt system: the adhesion and waterproof performance are improved by water emulsification of asphalt and addition of modifiers. However, due to the water sensitivity of asphalt, the adhesion performance of this system is poor when it is exposed to water, and the adhesion effect on the wet base surface is not good. At the same time, the compatibility and stability of the modifier with asphalt are generally poor, and the adhesion performance with asphalt waterproofing membrane is poor, which is prone to water channeling. (2) Acrylic emulsion system: the performance and construction performance are improved by adding modifiers to the acrylic emulsion. However, this system is prone to cracking, efflorescence and other problems after construction.

[0003] Although the water-based waterproof coating solves the problem of construction pollution to some extent, most of the existing waterproof coatings have the following defects: the emulsified asphalt system has poor adhesion performance when exposed to water, poor adhesion effect on the wet base surface, poor adhesion performance with asphalt waterproofing membrane, and is prone to water channeling. The acrylic emulsion waterproof coating is prone to cracking and efflorescence after construction. Most of the waterproof coatings cannot self-repair after physical damage, and need to be re-constructed to restore the waterproof function. SUMMARY

[0004] The present application provides a self-repairing non-asphalt-based waterproof coating and a preparation method thereof, which solves the problems of poor adhesion performance when exposed to water, water channeling, and lack of self-repairing function of the existing waterproof coatings.

[0005] According to the first aspect of the present application, the present application provides a self-repairing non-asphalt-based waterproof coating, which comprises the following raw materials by weight: aromatic hydrocarbon oil 25-40 parts, butyl rubber-graft-4,4'-dithiodianiline 3-6 parts, petroleum resin 5-10 parts, emulsifier 4-8 parts, water 30-50 parts, other additives 0.4-2 parts, powder 8-20 parts, and butyl rubber emulsion 2-5 parts.

[0006] The self-healing non-asphalt-based waterproof coating of the present application introduces butadiene-styrene rubber-graft-4,4'-dithiodiamine with special chemical structure and function, which can realize self-healing function. The introduction of dithiodiamine group is the key to realize self-healing function. Sulfur atom has high reactivity and can repair the damaged part through chemical bond breaking and reformation after being damaged by external force (such as nail rod puncture). This dynamic chemical bonding mechanism enables the material to automatically repair defects at the micro level, thereby restoring its waterproof performance. In addition to the chemical bonding mechanism, the rubber matrix of butadiene-styrene rubber-graft-4,4'-dithiodiamine also has a certain elasticity. This elasticity enables the material to fill cracks or holes through physical means after being damaged by external force, further enhancing the repair effect. The elasticity and flexibility of rubber enable the material to adapt to the deformation and stress changes of the base surface at the macro level, reducing the damage of the waterproof layer caused by the deformation of the base surface. In addition, butadiene-styrene rubber-graft-4,4'-dithiodiamine is compounded with specific raw materials with aromatic oil, butadiene-styrene rubber emulsion and powder components in waterproof coating, so that better synergy between raw materials is formed, improving the overall performance of waterproof coating (such as low temperature flexibility and bonding strength). Aromatic oil has good solubility and permeability, which can improve the flowability and wettability of the coating to the base surface. This helps the coating to better cover the base surface and reduce defects caused by uneven construction. High content of aromatic oil can also provide certain flexibility and enhance the crack resistance of the material. Butadiene-styrene rubber emulsion further enhances the flexibility and elasticity of the material, and cooperates with butadiene-styrene rubber-graft-4,4'-dithiodiamine to improve the overall performance of the material. The presence of butadiene-styrene rubber emulsion can also improve the construction performance of the coating, so that it can maintain good adhesion under different humidity conditions. Powder can improve the mechanical strength and durability of the material, and fill the small pores inside the material, reducing the channels for water penetration. The presence of powder can also enhance the thermal stability and chemical stability of the material, further improving its performance in complex environments.

[0007] Butadiene-styrene rubber-graft-4,4'-dithiodiamine refers to a graft product of butadiene-styrene rubber, whose molecular structure is that 4,4'-dithiodiamine structural units are grafted on the chain of butadiene-styrene rubber through chemical bonds.

[0008] Further, in the butadiene-styrene rubber-graft-4,4'-dithiodiamine, the weight ratio of graft (4,4'-dithiodiamine) to main chain (butadiene-styrene rubber) is (0.5-1):10.

[0009] By controlling the ratio of graft and main chain, the chemical structure and performance of styrene-butadiene rubber-graft-4,4'-dithiodianiline can be accurately adjusted, so as to further optimize the self-healing performance of the material, so that it can repair defects more efficiently after being damaged. At the same time, the above grafting ratio can improve the mechanical strength of the material while ensuring its flexibility, so that the waterproof coating can maintain good performance under different construction conditions.

[0010] Preferably, in the styrene-butadiene rubber-graft-4,4'-dithiodianiline, the weight ratio of graft and main chain is (0.8-0.9):10.

[0011] Further, the other auxiliary agents include pH adjuster 0.2-1 parts, thickening agent 0.1-0.5 parts, and defoaming agent 0.1-0.5 parts.

[0012] By adjusting the pH value of the coating, the stability and construction performance of the coating can be optimized. For example, a suitable acidic environment helps to improve the stability and emulsification effect of the emulsifier, thereby improving the uniformity and adhesion of the coating. The thickening agent can increase the viscosity of the coating, improve its construction performance and coating effect, prevent the coating from flowing or dripping during construction, and ensure the uniformity of the coating. The defoaming agent can effectively reduce the air bubbles generated during the stirring and construction of the coating, avoid defects caused by air bubbles, and improve the quality and waterproof performance of the waterproof layer. By limiting the amount of each auxiliary agent within a reasonable range, the performance of each raw material can be better synergized, further improving the overall performance of the waterproof coating.

[0013] Preferably, the pH adjuster is one or more of glacial acetic acid, sodium hydrogen phosphate, and dilute hydrochloric acid; the thickening agent is one of BASF CO 40, Dow ASE60, and sodium carboxymethyl cellulose CMC; and the defoaming agent is one or more of Dow AFE1410, Zhonglian B313, Zhonglian 314, and Zhonglian 315.

[0014] Further, the aromatic hydrocarbon content in the aromatic hydrocarbon oil is not less than 70%. Aromatic hydrocarbon oil with high aromatic hydrocarbon content can provide good solubility and permeability, enhance the wettability of the coating to the base surface, and improve the adhesion and waterproof performance of the coating.

[0015] Further, the petroleum resin is C9 petroleum resin, and the color number is required to be 3-5. C9 petroleum resin has good compatibility and adhesion, which can enhance the adhesion strength and durability of the coating, and the specific color number requirement helps to ensure the stability of product quality.

[0016] The solid content of the styrene-butadiene rubber emulsion is 50-70%. Styrene-butadiene rubber emulsion with high solid content can improve the flexibility and elasticity of the coating, further enhance the waterproof performance, and reduce coating defects caused by insufficient emulsion content.

[0017] Further, the powder is one or both of barium sulfate and talcum powder. As inorganic solid powder, barium sulfate and talcum powder can improve the mechanical strength and wear resistance of the coating, while filling the tiny pores inside the material, reducing the channels for water penetration, and further improving the waterproof performance. In addition, the presence of these powders can improve the rheological properties of the coating, making it easier to apply and disperse during construction, improving construction efficiency.

[0018] Further, the emulsifier is a cationic emulsifier. Cationic emulsifiers can better interact with other ingredients in the coating, improve emulsification, and ensure uniformity and stability of the coating.

[0019] Preferably, the emulsifier is selected from one or more of amide emulsifier X42, dodecyl ammonium chloride, and imidazoline amide. The charge characteristics of these cationic emulsifiers can enhance the adhesion of the coating to the substrate, especially on wet or charged substrates, further improving waterproof performance.

[0020] According to the second aspect of the present application, the present application also provides a preparation method of the self-healing non-asphalt-based waterproof coating described above, comprising the following steps: stirring the aromatic oil to a first temperature, then adding styrene-butadiene rubber-graft-4,4'-dithiodiamine, stirring to a second temperature, then adding petroleum resin, stirring to a third temperature, to obtain a mixed solution; grinding the obtained mixed solution to obtain a modified compound; mixing the pH adjuster and the emulsifier in the other auxiliaries in part of the water to obtain an emulsion; recirculating emulsification of the modified compound and the emulsion to obtain an emulsified modified material; mixing the styrene-butadiene rubber emulsion, the powder, the thickening agent and the defoaming agent in the other auxiliaries, and the remaining water, and mixing with the emulsified modified material.

[0021] The preparation method of the self-healing non-asphalt-based waterproof coating of the present application comprises the steps of mixing, grinding, and emulsifying raw materials such as aromatic oil, styrene-butadiene rubber-graft-4,4'-dithiodiamine, and petroleum resin. Through specific mixing and grinding process, the uniformity and stability of the coating can be ensured by ensuring the uniform dispersion of each raw material component. Through the recirculating emulsification process, the emulsification effect can be further optimized to ensure good flowability and coating performance of the coating during construction. The preparation method is simple and easy to operate, and the synergistic effect between the steps can effectively improve the production efficiency and reduce the production cost.

[0022] Further, the preparation method of the styrene-butadiene rubber-graft-4,4'-dithiodiamine is as follows: Step S1: Dissolve styrene-butadiene rubber in a solvent, add formic acid, control the temperature at 30-40℃, add hydrogen peroxide, stir for 8-10h, then add anhydrous alcohol to precipitate the styrene-butadiene rubber epoxidation product; Step S2: Wash and dry the styrene-butadiene rubber epoxidation product to obtain epoxy styrene-butadiene rubber; Step S3: Dissolve the epoxy styrene-butadiene rubber and 4,4'-dithiodianiline in cyclohexane, reflux at 70-90℃ under nitrogen for 5-8h, then add anhydrous alcohol to obtain styrene-butadiene rubber-graft-4,4'-dithiodianiline.

[0023] The preparation method of the styrene-butadiene rubber-graft-4,4'-dithiodianiline of the present application includes the steps of dissolving in a solvent (such as n-hexane), adding formic acid and hydrogen peroxide, washing and drying, and reacting with 4,4'-dithiodianiline. Through the synergistic effect between these steps, the styrene-butadiene rubber-graft-4,4'-dithiodianiline can be accurately synthesized, ensuring that its chemical structure and performance meet the requirements, thereby providing protection for the self-healing function of the coating. Through strict washing and drying steps, impurities can be removed to obtain high-purity modified rubber, further improving the quality and performance of the coating.

[0024] Further, in step S1, the weight ratio of styrene-butadiene rubber, formic acid and hydrogen peroxide is 10: (1-1.5): (0.4-0.5); the amount of solvent used is 4-10 times the mass of styrene-butadiene rubber; the amount of anhydrous alcohol used is 6-15 times the mass of styrene-butadiene rubber.

[0025] By accurately controlling the amount and proportion of each raw material in step S1, the reaction conditions can be optimized, and the reaction efficiency and product quality can be improved.

[0026] Further, in step S1, the solvent is n-hexane.

[0027] Further, in step S3, the weight ratio of epoxy styrene-butadiene rubber and 4,4'-dithiodianiline is 1: (0.1-0.3); the amount of cyclohexane used is 4-10 times the mass of epoxy styrene-butadiene rubber; the amount of anhydrous alcohol used is 6-15 times the mass of epoxy styrene-butadiene rubber.

[0028] By accurately controlling the amount and proportion of each raw material in step S3, the reaction conditions can be optimized, and the reaction efficiency and product quality can be improved.

[0029] Further, the first temperature is 120-140℃; the second temperature is 160-180℃, the mixing time after adding the styrene-butadiene rubber-graft-4,4'-dithiodianiline is 10-15 min; the third temperature is 170-190℃, the mixing time after adding the petroleum resin is 20-40 min; The addition of styrene-butadiene rubber-graft-4,4'-dithiodianiline in the first temperature (120-140℃) range can ensure its full mixing with aromatic oil, while avoiding the occurrence of chemical structure damage or side reactions due to excessive temperature. The setting of this temperature range helps to maintain the activity of the modified rubber, providing a good basis for subsequent reactions. At the second temperature (160-180℃), styrene-butadiene rubber-graft-4,4'-dithiodianiline can be fully dissolved and uniformly mixed with aromatic oil. The mixing time is 10-15 min, which can ensure uniformity of mixing and avoid material degradation or performance decline due to excessive mixing time. After adding the petroleum resin, the third temperature (170-190℃) range can ensure the full fusion of the petroleum resin with the modified rubber. The mixing time is 20-40 min, which can make the petroleum resin uniformly dispersed in the system, while avoiding uneven coating performance due to insufficient mixing.

[0030] Further, the self-grinding time is 0.5-1.5 h.

[0031] By self-grinding the mixed rubber within this time range, it can ensure that each raw material component (such as aromatic oil, styrene-butadiene rubber-graft-4,4'-dithiodianiline and petroleum resin, etc.) is fully mixed and dispersed at the micro level, thereby forming a uniform and stable modified rubber. This uniformity is a key factor to achieve excellent performance of the coating (such as good adhesion, waterproofness and self-healing function). If the grinding time is too short (less than 0.5 h), it may lead to uneven dispersion of raw materials, affecting the performance of the coating; while the grinding time is too long (more than 1.5 h), it may cause unnecessary energy consumption and performance decline of the material.

[0032] Further, the temperature of the circulating emulsification is 40-50℃, and the time is 20-40 min.

[0033] The activity of the emulsifier can be fully utilized in the temperature range of 40-50℃, while avoiding the instability of the emulsion system or the degradation of chemical components caused by excessive temperature. The emulsification time of 20-40min ensures the sufficient mixing and uniform emulsification between the modified sizing material and the emulsion, making the microstructure of the coating more delicate and uniform. This precise temperature and time control not only improves the emulsification effect of the coating, enhances its adhesion and waterproof performance on the base surface, but also ensures the good flowability and coating performance of the coating during the construction process. In addition, by optimizing the emulsification process, the self-healing function of the coating can be further improved, which can more effectively repair defects after being damaged by external force, prolong the service life of the waterproof layer, and improve the efficiency and economy of the production process.

[0034] Further, the part of water used in the emulsion accounts for 60-80% of the total mass of water.

[0035] By reasonably allocating the amount of water in the emulsion, the stability of the emulsification process and the uniformity of the emulsion can be ensured. Specifically, the water amount ratio of 60-80% can not only provide sufficient flowability to fully disperse the emulsifier and other ingredients, but also avoid the instability or stratification of the emulsion caused by excessive water. This optimization of water amount ratio helps to improve the compatibility and emulsification efficiency between the emulsion and the modified sizing material, so as to form a more uniform and stable emulsified modified material in the subsequent steps.

[0036] The beneficial effects of the present application are: The self-healing non-asphalt-based waterproof coating provided by the present application introduces butadiene-styrene rubber-graft-4,4'-dithiodiamine as a key modified component, which gives the coating excellent self-healing function. This self-healing function enables the coating to automatically repair defects and restore waterproof performance after being pierced by a nail rod or other physical damage, thereby significantly prolonging the service life of the waterproof layer and reducing maintenance costs. In addition, this coating abandons the heating construction method of traditional hot melt asphalt waterproof coating, avoiding the oil fume pollution and the risk of scalding during construction, reducing the emission of harmful gases, and being more environmentally friendly and safe.

[0037] The self-healing non-asphalt-based waterproof coating of the present application is optimized in terms of formulation and process, overcoming many shortcomings of existing waterproof coatings. For example, it solves the problem of weak adhesion between emulsified asphalt waterproof coating and asphalt waterproof membrane, reduces the risk of water leakage, and overcomes the insufficient water resistance of emulsified asphalt. Compared with acrylic waterproof coating, the coating is less prone to cracking and efflorescence, has better construction performance, is more suitable for different humidity substrates, and further improves construction efficiency. In addition, by precisely controlling the amount ratio of each raw material and the temperature, time and other parameters during the preparation process, the high quality and high performance of the coating are ensured. The present application provides a new type of environmentally friendly, safe, high-performance and self-repairing waterproof coating with wide application prospects, providing a reliable and efficient solution for building waterproof engineering.

[0038] The preparation method of the self-healing non-asphalt-based waterproof coating of the present application is simple, easy to operate, can effectively improve production efficiency, and reduce production cost. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme in the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0040] The sources of raw materials used in the following examples and comparative examples are as follows: Aromatic hydrocarbon oil I: waterproof special aromatic hydrocarbon oil from Shandong Furunda Chemical Co., Ltd.; Styrene-butadiene rubber: SBR1502 from Shandong Qilu Petrochemical; Petroleum resin: C9 petroleum resin from Henghe Material Technology Co., Ltd.; Emulsifier: hexadecyl trimethyl ammonium chloride, supplier: Shandong Deyitai New Material Co., Ltd.; pH value regulator: sodium hydrogen phosphate: Shanxi Chenming Biological Technology Co., Ltd.; Thickening agent: BASF CO 40; Defoamer: Dow AFE1410; Inorganic solid powder: talc powder BHS-818S from Quanzhou Xufeng Powder Raw Material Co., Ltd.; Styrene-butadiene rubber emulsion: 65% content styrene-butadiene emulsion from Shandong Haifang Technology Co., Ltd.

[0041] Example 1 The present embodiment provides a self-healing non-asphalt-based waterproof coating, which is composed of the following components in Table 1 by weight.

[0042] The butadiene styrene rubber-graft-4,4'-dithiodianiline used in this embodiment is a modified rubber synthesized in the laboratory, which is obtained by reacting butadiene styrene rubber after epoxidation modification with 4,4'-dithiodianiline; the specific preparation method is as follows: 100g butadiene styrene rubber is dissolved in 500g n-hexane, 11g formic acid is added, the temperature is controlled at 30-40°C by water bath, 4.5g hydrogen peroxide is slowly dropped, after stirring for 9h, 200g anhydrous alcohol is added to precipitate the butadiene styrene rubber epoxidation product, the solid powder is repeatedly washed with 800g anhydrous alcohol to remove formic acid and hydrogen peroxide, and then dried to obtain pure epoxy butadiene styrene rubber; 100g epoxy butadiene styrene rubber and 21g 4,4'-dithiodianiline are dissolved in 500g cyclohexane, and refluxed for 6.5h under nitrogen atmosphere and oil bath at 80°C, then 300g anhydrous alcohol is added to obtain butadiene styrene rubber-graft-4,4'-dithiodianiline, and the butadiene styrene rubber graft modification is completed. The weight ratio of the graft to the main chain in butadiene styrene rubber-graft-4,4'-dithiodianiline is 0.865:10.

[0043] This embodiment also provides a preparation method of the self-healing non-asphalt-based waterproof coating, which comprises the following steps: Step (1): butadiene styrene rubber-graft-4,4'-dithiodianiline powder is slowly added into the reaction kettle after aromatic oil is stirred and heated to 130°C, and then heated to 170°C and stirred for 12min.

[0044] Step (2): petroleum resin is added into the reaction kettle, heated to 180°C and stirred for 30min.

[0045] Step (3): the glue in step (2) is self-ground by colloid mill for 1h to obtain modified glue.

[0046] Step (4): pH regulator and emulsifier are added into 70% deionized water required by the formula mass, and then fully mixed and heated to 30-40°C to adjust the pH value to 2-3, so as to obtain an emulsion.

[0047] Step (5): the modified glue prepared in step (3) and the emulsion prepared in step (4) are circulated and emulsified by colloid mill for 30min, and the emulsification temperature is controlled at 40-50°C, so as to obtain emulsified modified material.

[0048] Step (6): 65% butadiene emulsion, inorganic solid powder, thickening agent and defoaming agent are added into the remaining deionized water and fully stirred and dispersed to obtain a mixture.

[0049] Step (7): the mixture prepared in step (6) and the emulsified modified material prepared in step (5) are fully mixed.

[0050] Example 2-12 Each of the following Examples 2-12 independently provides a self-healing non-asphalt-based waterproofing coating, which is composed of the components in the following Table 1 by weight parts. The self-healing non-asphalt-based waterproofing coating of these examples is prepared in the same manner as Example 1.

[0051] Table 1

[0052] Comparative Example 1 This comparative example provides a self-healing non-asphalt-based waterproofing coating DS1, which differs from Example 2 in that equal mass of styrene-butadiene-styrene copolymer is used instead of styrene-butadiene rubber-graft-4,4'-dithiodianiline. The rest is the same as Example 2.

[0053] The self-healing non-asphalt-based waterproofing coating is prepared in the same manner as Example 2.

[0054] Comparative Example 2 This comparative example provides a self-healing non-asphalt-based waterproofing coating DS2, which differs from Example 2 in that equal mass of styrene-butadiene rubber is used instead of styrene-butadiene rubber-graft-4,4'-dithiodianiline. The rest is the same as Example 2.

[0055] The self-healing non-asphalt-based waterproofing coating is prepared in the same manner as Example 2.

[0056] Comparative Example 3 This comparative example provides a self-healing non-asphalt-based waterproofing coating DS3, which differs from Example 2 in that equal mass of acrylic emulsion is used instead of styrene-butadiene rubber emulsion. The rest is the same as Example 2.

[0057] The self-healing non-asphalt-based waterproofing coating is prepared in the same manner as Example 2.

[0058] Comparative Example 4 This comparative example provides a self-healing non-asphalt-based waterproofing coating DS4, which differs from Example 2 in that equal grafting ratio of styrene-butadiene rubber and 4,4'-dithiodianiline is used instead of styrene-butadiene rubber-graft-4,4'-dithiodianiline. The rest is the same as Example 2.

[0059] The self-healing non-asphalt-based waterproofing coating is prepared in the same manner as Example 2.

[0060] Comparative Example 5 This comparative example provides a self-healing non-asphalt-based waterproofing coating DS5, which differs from Example 2 in that the amount of styrene-butadiene rubber-graft-4,4'-dithiodianiline is 2 parts. The rest is the same as Example 2.

[0061] The preparation method of the self-healing non-asphalt-based waterproof coating is the same as that of Example 2.

[0062] Test Case The same process was used to perform performance tests on the self-healing non-asphalt-based waterproof coatings obtained in the embodiment and the comparative example. The results are shown in Table 2.

[0063] Test standard for low temperature flexibility and bonding strength: JC / T408-2005.

[0064] Self-healing test standard: refer to JC / T2678-2022.

[0065] Table 2

[0066] It can be seen from the experimental data in Table 2 that the self-healing non-asphalt-based waterproof coating of the present invention performs excellently in low-temperature flexibility (no breakage at -15°C), bonding strength, and self-healing properties (no water seepage).

[0067] In Comparative Examples 1, 2, and 3, due to the lack of key modifying ingredients (such as styrene-butadiene rubber-graft-4,4'-disulfide diphenylamine) or the use of other alternative ingredients, their self-healing performance is significantly poor, and some water seepage occurs, which further demonstrates the importance of key modifying ingredients in achieving self-healing function.

[0068] Compared to Example 2, Comparative Example 4, which only physically mixed styrene-butadiene rubber with 4,4'-diphenylamine disulfide without forming a grafted structure, exhibited breakage at -15°C, a drop in bond strength to 0.15 MPa, and water seepage. This comparison demonstrates that the grafted styrene-butadiene rubber-graft-4,4'-diphenylamine disulfide structure is key to imparting the coating's excellent low-temperature flexibility, high bond strength, and self-healing properties.

[0069] In Example 2, 4.5 parts of styrene-butadiene rubber-graft-4,4'-diphenylamine disulfide were used. The coating showed no cracking at -15°C, a bond strength of 0.41 MPa, and no water seepage. In Comparative Example 5, the dosage was reduced to 2 parts. While no cracking occurred, the bond strength dropped sharply to 0.12 MPa, and water seepage occurred. These results demonstrate that a sufficient amount of styrene-butadiene rubber-graft-4,4'-diphenylamine disulfide is essential to ensure the coating's adhesion and self-healing properties.

[0070] It should be pointed out finally that the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit the same; and although the present application has been described in detail with reference to the foregoing embodiments, it should be appreciated by those skilled in the art that the technical solutions recorded in the foregoing embodiments can be modified, or some technical features thereof can be replaced equivalently; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A self-healing non-asphalt-based waterproof coating, characterized in that: The method comprises the following raw materials in parts by weight: 25-40 parts of aromatic oil, 3-6 parts of styrene-butadiene rubber-graft-4,4'-disulfide diphenylamine, 5-10 parts of petroleum resin, 4-8 parts of emulsifier, 30-50 parts of water, 0.4-2 parts of other additives, 8-20 parts of powder and 2-5 parts of styrene-butadiene rubber emulsion.

2. The self-healing non-asphalt-based waterproof coating according to claim 1, characterized in that: In the styrene-butadiene rubber-graft-4,4'-disulfide diphenylamine, the weight ratio of the grafted material to the main chain is (0.5-1):

10.

3. The self-healing non-asphalt-based waterproof coating according to claim 1 or 2, characterized in that: The other additives include 0.2-1 parts of pH regulator, 0.1-0.5 parts of thickener, and 0.1-0.5 parts of defoaming agent; Preferably, the pH adjuster is one or more of glacial acetic acid, sodium hydrogen phosphate and dilute hydrochloric acid; the thickener is one of BASF CO 40, Dow ASE60 and sodium carboxymethyl cellulose CMC; the defoaming agent is one or more of Dow AFE1410, Zhonglian B313, Zhonglian 314 and Zhonglian 315.

4. The self-healing non-asphalt-based waterproof coating according to any one of claims 1 to 3, characterized in that: The aromatic content of the aromatic oil is not less than 70%; and / or the petroleum resin is C9 petroleum resin, and the required color number is 3-5; the solid content of the styrene-butadiene rubber emulsion is 50-70%.

5. The self-healing non-asphalt-based waterproof coating according to any one of claims 1 to 4, characterized in that: The powder is one or two of barium sulfate and talc.

6. The self-healing non-asphalt-based waterproof coating according to any one of claims 1 to 5, characterized in that: The emulsifier is a cationic emulsifier; Preferably, the emulsifier is selected from one or more of amide emulsifier X42, dodecyl ammonium chloride and imidazoline amide.

7. The method for preparing the self-healing non-asphalt-based waterproof coating according to any one of claims 1 to 6, characterized in that: The steps include: Stirring the aromatic oil and heating it to a first temperature, then adding styrene-butadiene rubber-graft-4,4'-diphenylamine disulfide, heating it to a second temperature and mixing, then adding petroleum resin and heating it to a third temperature and mixing to obtain a mixed solution; and grinding the obtained mixed solution to obtain a modified rubber compound; Adding the pH regulator and emulsifier among other additives to a portion of water and mixing to obtain an emulsion; emulsifying the modified rubber material and the emulsion in a circular manner to obtain an emulsified modified material; The styrene-butadiene rubber emulsion, powder, thickener and defoamer among other additives and the remaining water are mixed and then mixed with the emulsified modified material.

8. The method for preparing the self-healing non-asphalt-based waterproof coating according to claim 7, characterized in that: The preparation method of the styrene-butadiene rubber-graft-4,4'-dithiodiphenylamine is as follows: Step S1: dissolving styrene-butadiene rubber in a solvent, adding formic acid, controlling the temperature at 30-40° C., adding hydrogen peroxide, stirring and reacting for 8-10 hours, and then adding anhydrous alcohol to obtain a styrene-butadiene rubber epoxidation product precipitate; Step S2: precipitating and washing the epoxidized product of styrene butadiene rubber, and drying the epoxidized styrene butadiene rubber; Step S3: dissolving epoxy styrene butadiene rubber and 4,4'-diphenylamine disulfide in cyclohexane, refluxing in an oil bath at 70-90° C. under nitrogen for 5-8 hours, and adding anhydrous alcohol to obtain styrene butadiene rubber-graft-4,4'-diphenylamine disulfide.

9. The method for preparing the self-healing non-asphalt-based waterproof coating according to claim 8, characterized in that: In step S1, the weight ratio of the styrene-butadiene rubber, formic acid, and hydrogen peroxide is 10:(1-1.5):(0.4-0.5); the amount of the solvent is 4-10 times the mass of the styrene-butadiene rubber; the amount of the anhydrous alcohol is 6-15 times the mass of the styrene-butadiene rubber; And / or, in step S3, the weight ratio of epoxy styrene butadiene rubber to 4,4'-diphenyl disulfide is 1:(0.1-0.3); the amount of cyclohexane used is 4-10 times the mass of the epoxy styrene butadiene rubber; and the amount of anhydrous alcohol used is 6-15 times the mass of the epoxy styrene butadiene rubber.

10. The method for preparing the self-healing non-asphalt-based waterproof coating according to claim 8 or 9, characterized in that: The first temperature is 120-140° C.; the second temperature is 160-180° C., and the mixing time after adding the styrene-butadiene rubber-graft-4,4'-dithiodiphenylamine is 10-15 minutes; the third temperature is 170-190° C., and the mixing time after adding the petroleum resin is 20-40 minutes; And / or, the self-grinding time is 0.5-1.5h; And / or, the temperature of the cyclic emulsification is 40-50°C and the time is 20-40 minutes; And / or, the portion of water used in the emulsion accounts for 60-80% of the total mass of water.

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