Cement-based capillary crystalline waterproof coating

Abstract

The invention discloses a cement-based capillary crystalline waterproof coating, and relates to the technical field of waterproof coatings. The waterproof coating comprises powder and emulsion, is suitable for water-saturated concrete surfaces, and provides a lasting waterproof effect. The powder penetrates into the concrete through water reaction to form insoluble crystals, and pores and cracks are sealed. The hydrophilic property of the powder ensures the continuous reaction with water, and long-term protection is realized. The powder is composed of a plurality of components, a continuous-phase barrier structure is formed through different particle size combinations, and the lasting waterproof and anti-permeability effects are ensured. The slurry combines the characteristics of organic silicon and epoxy resin, forms a compact three-dimensional interpenetrating network structure, improves the self-waterproof performance of concrete, has two waterproof structures, improves the overall waterproof quality, forms a high-strength film layer with biomass ash, enhances the elasticity of an external flexible waterproof layer, and provides reliable and lasting protection for concrete.

Description

Technical Field

[0001] The invention relates to the technical field of waterproof coatings, and in particular to a cement-based penetrating crystalline waterproof coating. Background Art

[0002] With the widespread application of concrete in the engineering field, the durability of its structure has received increasing attention. Among them, water penetration is considered to be the key factor leading to concrete deterioration and reduced durability. Therefore, waterproofing of concrete has become an effective strategy to delay the repair cycle and improve structural durability.

[0003] In the current field of waterproof coatings, there are many types of products, which can be mainly divided into two categories: flexible waterproof coatings and rigid waterproof coatings. After long-term practical verification at home and abroad, traditional flexible waterproof coatings such as coils and coatings, although they have good flexibility and durability, have weak adhesion to the base concrete, especially when the base is damp or there is water seepage, they cannot be effectively applied, so they are not suitable for waterproofing of back water surfaces and damp base surfaces. At the same time, rigid cement-based waterproof coatings are widely used due to their unique properties. However, most of the rigid cement-based waterproof coatings commonly used in the market are surface sealing waterproofing agents, and their waterproofing effect is limited to the surface and cannot automatically penetrate deep into the structure, resulting in the inability to maintain the waterproofing effect for a long time. Over time, these materials will undergo a continuous performance degradation process. Once the waterproof layer is damaged, its waterproof ability will be immediately lost, and it is easy to cause defects such as concrete alkali-aggregate reaction. Based on an in-depth analysis of the causes of cracking of concrete structures, engineering application characteristics, and waterproof performance, the development of a new type of waterproof coating with micro-crack self-healing ability and penetrating crystallization characteristics-cement-based penetrating crystallization waterproof coating has become an inevitable trend in the development of the industry. Summary of the invention

[0004] The purpose of the present invention is to provide a cement-based penetrating crystalline waterproof coating to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a cement-based permeable crystalline waterproof coating, comprising powder and slurry, wherein the powder comprises, by weight: 40-70 parts of cement, 10-24 parts of modified mica powder, 2-6 parts of phenolic fiber, 5-11 parts of brucite fiber, 4-8 parts of calcium sulfoaluminate with a particle size of 10-20 nm, 6-14 parts of calcium sulfoaluminate with a particle size of 1-15 μm, 6-14 parts of porous basalt, and 1-5 parts of a water reducer; The slurry comprises, by weight: 20-30 parts of acrylic modified epoxy resin emulsion, 40-50 parts of vinyl silicone oil, 8-15 parts of biomass ash, and 0.01-0.03 parts of initiator.

[0006] Furthermore, the cement is 600# Portland cement.

[0007] Furthermore, the particle size of the modified mica powder is 50-80 nm.

[0008] Furthermore, the particle size of the biomass ash is 0.5~5mm.

[0009] Furthermore, the porous basalt has a particle size of 2-5 μm and an apparent density of 2450-2650 kg / m 3 .

[0010] Furthermore, the length of the phenolic fiber is 0.3-0.5 mm.

[0011] Furthermore, the length of the brucite fiber is 0.5 mm-1.0 mm.

[0012] Furthermore, the preparation method of the coating is: (1) The coupling agent and water are mixed in a mass ratio of 1:2~3, stirred at 100rpm for 10min, and then biomass ash and emulsifier are added. The mass ratio of biomass ash, coupling agent and emulsifier is 8~15:3~5:0.1. After stirring at 1000rpm for 10~20min, vinyl silicone oil is added, and emulsifier and water are added until the mass ratio of vinyl silicone oil, emulsifier and water is 20~25:1~3:40~50. After stirring at 1000rpm for 20min, a silicone emulsion is obtained; (2) Stirring the silicone emulsion, acrylic modified epoxy resin emulsion and initiator at 65-80° C. for 15-50 minutes to obtain a slurry; (3) Calcium sulfoaluminate with a particle size of 10-20 nm and porous basalt are mixed and ground for 20 minutes, and then modified mica powder, phenolic fiber, brucite fiber, calcium sulfoaluminate with a particle size of 1-15 μm, and 1-5 parts of a water reducer are added to cement in sequence and stirred evenly to obtain a powder; (4) Mix the powder and slurry in a mass ratio of 5:2 to obtain the coating, which can then be used for construction.

[0013] Furthermore, the molecular weight of the vinyl silicone oil in step (1) is between 300-10000, and the double bond content is between 8-12%.

[0014] Furthermore, the coupling agent in step (1) is at least one of vinyltrimethoxysilane, methacryloxymethyltrimethoxysilane and 3-butenetriethoxysilane.

[0015] Furthermore, the biomass ash in step (1) is primary biomass ash residue, which comes from biomass combustion.

[0016] Furthermore, the emulsifier in step (1) includes any one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan monooleate and sorbitan monostearate.

[0017] Furthermore, the acrylic modified epoxy resin emulsion in step (1) is model T-08, produced by the first branch of Jushi Group, and has a Tg between 10 and 25°C.

[0018] Furthermore, the initiator in step (2) is ammonium persulfate.

[0019] Furthermore, the preparation method of the modified mica powder in step (3) is as follows: weigh 10-15g of mica powder and put it into 300-500mL of ethanol, stir and disperse it at 200rpm for 40-50min, put it into a water bath heated to 70-85°C, add 20-30mL of silane coupling agent solution, continue to stir and react for 50-110min, filter the solution, wash off the ethanol on the surface, and dry it for 100-150min; the silane coupling agent solution is: add 8-10g of silane coupling agent KH-540 and 2-7g of epoxypropyltrimethoxysilane to 108-135g of deionized water and 70-80g of ethanol, mix well, and stir at 400rpm for 30-45min.

[0020] Furthermore, the water reducing agent in step (3) is a polycarboxylic acid water reducing agent.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) The present invention relates to a two-phase waterproof coating, comprising a powder and an emulsion, which is suitable for use on a concrete surface that has been pre-saturated with water, and is intended to provide a comprehensive and lasting waterproof effect. The powder, with the aid of water as a transmission medium, penetrates deep into the concrete matrix and reacts with the moisture, hydration products and unhydrated cement particles in the concrete. This interaction stimulates a catalytic crystallization reaction, starting from the surface of the concrete and advancing inward to form insoluble crystals, thereby permanently sealing the pores, capillaries, cracks and microcracks in the concrete. In addition, the powder has a certain hydrophilic property and can detect the presence of new moisture. This continuous detection and reaction capability ensures the continuity of the crystallization process, and as the water molecules diffuse deeper, a permanent seal and long-term protective effect are achieved.

[0022] (2) The powder used in the present invention is composed of cement and mica powder, phenolic fiber powder, brucite fiber, calcium sulfoaluminate, and porous basalt with different nanoparticle sizes. It can diffuse freely into the capillary channels of concrete and will not block those channels with too small pore sizes. By utilizing the large specific surface area and pore adsorption characteristics of porous basalt, some small-sized calcium sulfoaluminate is adsorbed on the surface of porous basalt, so that the coating has a certain activity. Under the condition that the base layer contains water, the active material can be automatically released and brought into the deeper part of the base layer with water, and gradually further polymerize to form stable crystals to block the water channel and realize the function of automatically making up for the defects. As time goes by, the waterproof performance gradually increases, and finally achieves the best waterproof effect. By adopting a combination of different particle sizes, this study can form an irregular barrier structure of a continuous phase, which has a limiting effect on the generated insoluble crystals and prevents them from escaping from the pores of concrete, thereby ensuring a long-lasting waterproof and anti-seepage effect.

[0023] (3) The present invention relates to an innovative polymer composite emulsion technology, which cleverly combines the characteristics of silicone emulsion and epoxy resin emulsion to achieve a synergistic and complementary effect between the two. Through the application of this composite emulsion, the film-forming speed of the emulsion can be significantly accelerated, thereby quickly forming a dense three-dimensional interpenetrating network structure. This structure can not only effectively improve the self-waterproofing performance of the concrete structure, but also form a waterproof layer on the material itself, achieving the unique advantage of one material having two waterproof structures at the same time. Such a design greatly improves the overall waterproof quality, and the composite emulsion also has the function of self-locking water, effectively preventing the problem that the active crystalline chemical substances cannot penetrate and modify the base concrete due to the lack of water channels in the absence of watering maintenance. In addition, the present invention also specifically adds biomass ash to the formula of the composite emulsion, which can actively participate in the reaction process of the emulsion and accumulate to form a high-strength film layer during the film-forming process. This high-strength film layer further enhances the elasticity of the external flexible waterproof layer, thereby providing more reliable and lasting protection for the concrete structure. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0025] Example 1 (1) Vinyl trimethoxysilane and water were mixed in a mass ratio of 1:2, stirred at 100 rpm for 10 min, and then 8 parts by weight of biomass ash with a particle size of 0.5 mm and polyoxyethylene sorbitan monooleate were added. The mass ratio of biomass ash, coupling agent, and polyoxyethylene sorbitan monooleate was 8:3:0.1. After stirring at 1000 rpm for 10 min, 40 parts by weight of vinyl silicone oil was added, and polyoxyethylene sorbitan monooleate and water were supplemented until the mass ratio of vinyl silicone oil, polyoxyethylene sorbitan monooleate, and water was 20:1:40. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the organosilicon emulsion, 20 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.01 parts by weight of ammonium persulfate at 65° C. for 15 minutes to obtain a slurry; (3) Weigh 10 g of mica powder and put it into 300 mL of ethanol. After stirring and dispersing at 200 rpm for 40 min, put it into a water bath heated to 70°C, add 20 mL of silane coupling agent solution, continue stirring and reacting for 50 min, filter the solution, wash off the ethanol on the surface, dry it for 100 min, and grind it to a particle size of 50 nm to obtain modified mica powder; the silane coupling agent solution is: add 8 g of silane coupling agent KH-540 and 2 g of epoxypropyltrimethoxysilane to 108 g of deionized water and 70 g of ethanol, mix well, and stir at 400 rpm for 30 min; (4) 4 parts by weight of calcium sulphoaluminate with a particle size of 10 nm and 6 parts by weight of calcium sulphoaluminate with a particle size of 2 μm and an apparent density of 2450 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 10 parts by weight of modified mica powder, 2 parts by weight of phenolic fiber with a length of 0.3 mm, 5 parts by weight of brucite fiber with a length of 0.5 mm, 6 parts by weight of calcium sulfoaluminate with a particle size of 1 μm, and 1 part by weight of a water reducer are sequentially added into 40 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0026] Example 2 (1) Methacryloxymethyltrimethoxysilane and water were mixed in a mass ratio of 1:2, stirred at 100 rpm for 10 minutes, and then 9.4 parts by weight of biomass ash with a particle size of 1.4 mm and an emulsifier were added. The mass ratio of biomass ash, methacryloxymethyltrimethoxysilane and emulsifier was 9.4:3:0.1. After stirring at 1000 rpm for 10 minutes, 42 parts by weight of vinyl silicone oil were added, and the emulsifier and water were supplemented to a mass ratio of vinyl silicone oil, emulsifier and water of 21:1:40. After stirring at 1000 rpm for 20 minutes, a silicone emulsion was obtained; the emulsifier was composed of sodium dodecylbenzene sulfonate and fatty alcohol polyoxyethylene ether in a mass ratio of 1:1; (2) stirring the organosilicon emulsion, 22 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.01 parts by weight of ammonium persulfate at 65° C. for 15 minutes to obtain a slurry; (3) Weigh 10 g of mica powder and put it into 300 mL of ethanol. After stirring and dispersing at 200 rpm for 40 min, put it into a water bath heated to 70°C, add 20 mL of silane coupling agent solution, continue stirring and reacting for 50 min, filter the solution, wash off the ethanol on the surface, dry it for 100 min, and grind it to a particle size of 56 nm to obtain modified mica powder; the silane coupling agent solution is: add 8 g of silane coupling agent KH-540 and 2 g of epoxypropyltrimethoxysilane to 108 g of deionized water and 70 g of ethanol, mix well, and stir at 400 rpm for 30 min; (4) 4.8 parts by weight of calcium sulfoaluminate with a particle size of 12 nm and 7.6 parts by weight of calcium sulfoaluminate with a particle size of 2.6 μm and an apparent density of 2490 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 12.8 parts by weight of modified mica powder, 2.8 parts by weight of phenolic fiber with a length of 0.3 mm, 6.2 parts by weight of brucite fiber with a length of 0.6 mm, 7.6 parts by weight of calcium sulfoaluminate with a particle size of 3.8 μm, and 1 part by weight of a water reducer are sequentially added into 46 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0027] Example 3 (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:2.5, stirred at 100 rpm for 10 min, and then 10.8 parts by weight of biomass ash with a particle size of 2.3 mm and sodium dodecylbenzene sulfonate were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and sodium dodecylbenzene sulfonate was 10.8:4:0.1. After stirring at 1000 rpm for 15 min, 44 parts by weight of vinyl silicone oil was added, and sodium dodecylbenzene sulfonate and water were supplemented until the mass ratio of vinyl silicone oil, sodium dodecylbenzene sulfonate and water was 22:2:45. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring an organic silicone emulsion, 24 parts by weight of an acrylic acid-modified epoxy resin emulsion, and 0.02 parts by weight of ammonium persulfate at 72° C. for 30 minutes to obtain a slurry; (3) Weigh 12 g of mica powder and put it into 400 mL of ethanol. After stirring and dispersing at 200 rpm for 45 minutes, put it into a water bath heated to 77°C, add 25 mL of silane coupling agent solution, continue stirring and reacting for 80 minutes, filter the solution, wash off the ethanol on the surface, dry it for 125 minutes, and grind it to a particle size of 62 nm to obtain modified mica powder; the silane coupling agent solution is: 9 g of silane coupling agent KH-540 and 4 g of epoxypropyltrimethoxysilane are added to 121 g of deionized water and 75 g of ethanol, mix well, and stir at 400 rpm for 38 minutes; (4) 5.6 parts by weight of calcium sulfoaluminate with a particle size of 14 nm and 9.2 parts by weight of calcium sulfoaluminate with a particle size of 3.2 μm and an apparent density of 2530 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 15.6 parts by weight of modified mica powder, 3.6 parts by weight of phenolic fiber with a length of 0.4 mm, 7.4 parts by weight of brucite fiber with a length of 0.7 mm, 9.2 parts by weight of calcium sulfoaluminate with a particle size of 6.6 μm, and 3 parts by weight of a water reducer are sequentially added into 52 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0028] Example 4 (1) Vinyl trimethoxysilane and water were mixed in a mass ratio of 1:2.5, stirred at 100 rpm for 10 min, and then 12.2 parts by weight of biomass ash with a particle size of 3.2 mm and sorbitan monostearate were added. The mass ratio of biomass ash, vinyl trimethoxysilane and sorbitan monostearate was 12.2:4:0.1. After stirring at 1000 rpm for 15 min, 46 parts by weight of vinyl silicone oil were added, and emulsifier and water were added until the mass ratio of vinyl silicone oil, sorbitan monostearate and water was 23:2:45. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the organosilicon emulsion, 26 parts by weight of acrylic modified epoxy resin emulsion, and 0.02 parts by weight of ammonium persulfate at 74° C. for 32 minutes to obtain a slurry; (3) Weigh 12 g of mica powder and put it into 400 mL of ethanol. After stirring and dispersing at 200 rpm for 45 minutes, put it into a water bath heated to 77°C, add 25 mL of silane coupling agent solution, continue stirring and reacting for 80 minutes, filter the solution, wash off the ethanol on the surface, dry it for 125 minutes, and grind it to a particle size of 68 nm to obtain modified mica powder; the silane coupling agent solution is: 9 g of silane coupling agent KH-540 and 4 g of epoxypropyltrimethoxysilane are added to 122 g of deionized water and 75 g of ethanol, mix well, and stir at 400 rpm for 38 minutes; (4) 6.4 parts by weight of calcium sulfoaluminate with a particle size of 16 nm and 10.8 parts by weight of calcium sulfoaluminate with a particle size of 3.8 μm and an apparent density of 2570 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 18.4 parts by weight of modified mica powder, 4.4 parts by weight of phenolic fiber with a length of 0.4 mm, 8.6 parts by weight of brucite fiber with a length of 0.8 mm, 10.8 parts by weight of calcium sulfoaluminate with a particle size of 9.4 μm, and 3 parts by weight of a water reducer are sequentially added into 58 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0029] Example 5 (1) Methacryloxymethyltrimethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 13.6 parts by weight of biomass ash with a particle size of 4.1 mm and sodium dodecyl sulfate were added. The mass ratio of biomass ash, methacryloxymethyltrimethoxysilane and sodium dodecyl sulfate was 13.6:5:0.1. After stirring at 1000 rpm for 20 min, 48 parts by weight of vinyl silicone oil was added, and sodium dodecyl sulfate and water were supplemented until the mass ratio of vinyl silicone oil, sodium dodecyl sulfate and water was 24:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring an organic silicone emulsion, 28 parts by weight of an acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 74 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 7.2 parts by weight of calcium sulphoaluminate with a particle size of 18 nm and 12.4 parts by weight of calcium sulphoaluminate with a particle size of 4.4 μm and an apparent density of 2610 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 21.2 parts by weight of modified mica powder, 5.2 parts by weight of phenolic fiber with a length of 0.5 mm, 9.8 parts by weight of brucite fiber with a length of 0.9 mm, 10.8 parts by weight of calcium sulfoaluminate with a particle size of 12.2 μm, and 5 parts by weight of a water reducer are sequentially added into 64 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0030] Example 6 (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 15 parts by weight of biomass ash with a particle size of 5 mm and fatty alcohol polyoxyethylene ether were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and fatty alcohol polyoxyethylene ether was 15:5:0.1. After stirring at 1000 rpm for 20 min, 50 parts by weight of vinyl silicone oil was added, and fatty alcohol polyoxyethylene ether and water were supplemented until the mass ratio of vinyl silicone oil, fatty alcohol polyoxyethylene ether and water was 25:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 80 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 8 parts by weight of calcium sulfoaluminate with a particle size of 20 nm, 14 parts by weight of calcium sulfoaluminate with a particle size of 5 μm and an apparent density of 2650 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 24 parts by weight of modified mica powder, 6 parts by weight of phenolic fiber with a length of 0.5 mm, 11 parts by weight of brucite fiber with a length of 1.0 mm, 14 parts by weight of calcium sulfoaluminate with a particle size of 15 μm, and 5 parts by weight of a water reducer are sequentially added into 70 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0031] Comparative Example 1 (Mica powder is not modified) (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 15 parts by weight of biomass ash with a particle size of 5 mm and fatty alcohol polyoxyethylene ether were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and fatty alcohol polyoxyethylene ether was 15:5:0.1. After stirring at 1000 rpm for 20 min, 50 parts by weight of vinyl silicone oil was added, and fatty alcohol polyoxyethylene ether and water were supplemented until the mass ratio of vinyl silicone oil, fatty alcohol polyoxyethylene ether and water was 25:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) 8 parts by weight of calcium sulfoaluminate with a particle size of 20 nm, 14 parts by weight of calcium sulfoaluminate with a particle size of 5 μm and an apparent density of 2650 kg / m 3 The porous basalt was mixed and ground for 20 minutes, and then added with 24 parts by weight of mica powder, 6 parts by weight of phenolic fiber with a length of 0.5 mm, 11 parts by weight of brucite fiber with a length of 1.0 mm, 14 parts by weight of calcium sulfoaluminate with a particle size of 15 μm, and 5 parts by weight of a water reducer in 70 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (4) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0032] Comparative Example 2 (powders are uniformly small in particle size) (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 15 parts by weight of biomass ash with a particle size of 5 mm and fatty alcohol polyoxyethylene ether were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and fatty alcohol polyoxyethylene ether was 15:5:0.1. After stirring at 1000 rpm for 20 min, 50 parts by weight of vinyl silicone oil was added, and fatty alcohol polyoxyethylene ether and water were supplemented until the mass ratio of vinyl silicone oil, fatty alcohol polyoxyethylene ether and water was 25:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 80 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 22 parts by weight of calcium sulphoaluminate and 14 parts by weight of aluminate having an apparent density of 2650 kg / m 3 Porous basalt, 24 parts by weight of modified mica powder, 6 parts by weight of phenolic fiber with a length of 0.5 mm, and 11 parts by weight of brucite fiber with a length of 1.0 mm are mixed and ground to an average particle size of 20 nm, and then added with 5 parts by weight of a water reducing agent to 70 parts by weight of 600# Portland cement, and stirred to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0033] Comparative Example 3 (powders are uniformly large in particle size) (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 15 parts by weight of biomass ash with a particle size of 5 mm and fatty alcohol polyoxyethylene ether were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and fatty alcohol polyoxyethylene ether was 15:5:0.1. After stirring at 1000 rpm for 20 min, 50 parts by weight of vinyl silicone oil was added, and fatty alcohol polyoxyethylene ether and water were supplemented until the mass ratio of vinyl silicone oil, fatty alcohol polyoxyethylene ether and water was 25:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 80 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 22 parts by weight of calcium sulphoaluminate and 14 parts by weight of aluminate having an apparent density of 2650 kg / m 3 Porous basalt, 24 parts by weight of modified mica powder, 6 parts by weight of phenolic fiber, and 11 parts by weight of brucite fiber are uniformly mixed to obtain an active material, wherein the average particle size of the active material is 1.0 mm, and then the active material and 5 parts by weight of a water reducer are added to 70 parts by weight of 600# Portland cement, and the mixture is uniformly stirred to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0034] Comparative Example 4 (all using large particle size calcium sulphoaluminate) (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 15 parts by weight of biomass ash with a particle size of 5 mm and fatty alcohol polyoxyethylene ether were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and fatty alcohol polyoxyethylene ether was 15:5:0.1. After stirring at 1000 rpm for 20 min, 50 parts by weight of vinyl silicone oil was added, and fatty alcohol polyoxyethylene ether and water were supplemented until the mass ratio of vinyl silicone oil, fatty alcohol polyoxyethylene ether and water was 25:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 80 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 14 parts by weight of a 5 μm particle size, an apparent density of 2650 kg / m 3 Porous basalt, 24 parts by weight of modified mica powder, 6 parts by weight of phenolic fiber with a length of 0.5 mm, 11 parts by weight of brucite fiber with a length of 1.0 mm, 22 parts by weight of calcium sulfoaluminate with a particle size of 15 μm, and 5 parts by weight of a water reducing agent are sequentially added into 70 parts by weight of 600# Portland cement, and stirred to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0035] Comparative Example 5 (using small particle size calcium sulphoaluminate throughout) (1) 3-Butenetriethoxysilane and water were mixed in a mass ratio of 1:3, stirred at 100 rpm for 10 min, and then 15 parts by weight of biomass ash with a particle size of 5 mm and fatty alcohol polyoxyethylene ether were added. The mass ratio of biomass ash, 3-Butenetriethoxysilane and fatty alcohol polyoxyethylene ether was 15:5:0.1. After stirring at 1000 rpm for 20 min, 50 parts by weight of vinyl silicone oil was added, and fatty alcohol polyoxyethylene ether and water were supplemented until the mass ratio of vinyl silicone oil, fatty alcohol polyoxyethylene ether and water was 25:3:50. After stirring at 1000 rpm for 20 min, a silicone emulsion was obtained; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 80 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 22 parts by weight of calcium sulfoaluminate with a particle size of 20 nm and 14 parts by weight of calcium sulfoaluminate with a particle size of 5 μm and an apparent density of 2650 kg / m 3 After the porous basalt is mixed and ground for 20 minutes, 24 parts by weight of modified mica powder, 6 parts by weight of phenolic fiber with a length of 0.5 mm, 11 parts by weight of brucite fiber with a length of 1.0 mm, and 5 parts by weight of a water reducer are sequentially added into 70 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0036] Comparative Example 6 (without adding biomass ash) (1) Vinyl silicone oil, fatty alcohol polyoxyethylene ether and water were stirred at a mass ratio of 25:3:50 at 1000 rpm for 20 minutes to obtain a silicone emulsion; (2) stirring the silicone emulsion, 30 parts by weight of acrylic acid-modified epoxy resin emulsion, and 0.03 parts by weight of ammonium persulfate at 80° C. for 50 minutes to obtain a slurry; (3) Weigh 15 g of mica powder and put it into 500 mL of ethanol. After stirring and dispersing at 200 rpm for 50 min, put it into a water bath heated to 85°C, add 30 mL of silane coupling agent solution, continue stirring and reacting for 110 min, filter the solution, wash off the ethanol on the surface, dry it for 150 min, and grind it to a particle size of 80 nm to obtain modified mica powder; the silane coupling agent solution is: add 10 g of silane coupling agent KH-540 and 7 g of epoxypropyltrimethoxysilane to 135 g of deionized water and 80 g of ethanol, mix well, and stir at 400 rpm for 45 min; (4) 8 parts by weight of calcium sulfoaluminate with a particle size of 20 nm, 14 parts by weight of calcium sulfoaluminate with a particle size of 5 μm and an apparent density of 2650 kg / m 3After the porous basalt is mixed and ground for 20 minutes, 24 parts by weight of modified mica powder, 6 parts by weight of phenolic fiber with a length of 0.5 mm, 11 parts by weight of brucite fiber with a length of 1.0 mm, 14 parts by weight of calcium sulfoaluminate with a particle size of 15 μm, and 5 parts by weight of a water reducer are sequentially added into 70 parts by weight of 600# Portland cement, and stirred evenly to obtain a powder; (5) Mix the powder and slurry in a mass ratio of 5:2 to obtain a cement-based penetrating crystalline waterproof coating, which can then be used for construction.

[0037] Performance Testing The cement-based penetrating crystalline waterproof coatings obtained in Examples 1, 2, 3, 4, 5, 6 and Comparative Examples 1, 2, 3, 4, 5, 6 were prepared according to the test materials and mix ratios specified in Part 7 of the national standard GB18445-2012 "Cement-based penetrating crystalline waterproof coatings", and according to the relevant provisions of the national standard GB50081-2016 "Standard for Test Methods for Mechanical Properties of Ordinary Concrete"; according to the test method specified in Part 7 of the national standard GB18445-2012 "Cement-based penetrating crystalline waterproof coatings", the wet base surface bonding strength of the concrete specimens, the coating mixed The secondary anti-seepage pressure of concrete was tested; and under the condition of crystallization destruction of the specimen, the width of the cracks that can be repaired by recrystallization in water was tested; the anti-seepage pressure of the recrystallization of the specimen was tested according to the test method specified in Part 6 of GB23440-2009 "Inorganic Waterproofing and Leakage-proofing Materials"; the penetration height test method refers to JC / T1018-2006 "Water-based Penetrating Inorganic Waterproofing Agents", the smaller the value, the better the waterproofness of the penetrating crystallization; the impermeability test method adopts the Caston tube method, which is impermeable after 20 hours under the action of 1000mm water column. The specific results are shown in Table 1.

[0038] Table 1 Wet base bonding strength / MPa, 28d Secondary impermeability pressure of coated concrete / MPa, 56d Recrystallization impermeability pressure (with coating) / MPa, 7d Repair crack width / mm Penetration height / mm Waterproof Example 1 1.05 0.91 0.40 0.49 17 impermeable Example 2 1.49 1.23 0.55 0.55 15 impermeable Example 3 1.77 1.59 0.69 0.77 14 impermeable Example 4 2.15 2.07 1.15 0.87 13 impermeable Example 5 1.98 1.88 1.00 0.80 15 impermeable Example 6 1.83 1.79 0.73 0.65 17 impermeable Comparative Example 1 1.65 1.54 0.37 0.52 17 impermeable Comparative Example 2 1.72 1.33 0.48 0.73 15 impermeable Comparative Example 3 1.55 1.21 0.40 0.48 22 impermeable Comparative Example 4 1.80 1.69 0.61 0.57 20 impermeable Comparative Example 5 1.75 1.58 0.69 0.50 18 impermeable Comparative Example 6 1.60 1.49 0.70 0.61 25 impermeable It can be seen from Table 1 that the waterproof coating prepared by the present invention has good waterproof and self-repairing properties, excellent comprehensive performance, and significant advantages in the safety and durability of building materials.

[0039] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A cement-based penetrating crystalline waterproof coating, comprising powder and slurry, characterized in that: The powder comprises, by weight: 40-70 parts of cement, 10-24 parts of modified mica powder, 2-6 parts of phenolic fiber, 5-11 parts of brucite fiber, 4-8 parts of calcium sulfoaluminate with a particle size of 10-20 nm, 6-14 parts of calcium sulfoaluminate with a particle size of 1-15 μm, 6-14 parts of porous basalt, and 1-5 parts of a water reducing agent; The slurry comprises, by weight: 20-30 parts of acrylic modified epoxy resin emulsion, 40-50 parts of vinyl silicone oil, 8-15 parts of biomass ash, and 0.01-0.03 parts of initiator.

2. A cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The cement is 600# Portland cement.

3. A cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The modified mica powder has a particle size of 50-80 nm.

4. The cement-based penetrating crystalline waterproof coating according to claim 1, characterized in that: The particle size of the biomass ash is 0.5-5 mm.

5. The cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The particle size of the porous basalt is 2-5 μm.

6. The cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The length of the phenolic fiber is 0.3-0.5 mm.

7. The cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The length of the brucite fiber is 0.5 mm-1.0 mm.

8. The cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The preparation method of the coating is: (1) Biomass ash, emulsifier, coupling agent and water are mixed in a mass ratio of 8-15:0.2:3-5:16-30, stirred at 1000 rpm for 10-20 min, vinyl silicone oil is added, emulsifier and water are added until the mass ratio of vinyl silicone oil, emulsifier and water is 20-25:1-3:40-50, stirred at 1000 rpm for 20 min, and a silicone emulsion is obtained; (2) Stirring the silicone emulsion, acrylic modified epoxy resin emulsion and initiator at 65-80° C. for 15-50 minutes to obtain a slurry; (3) Calcium sulfoaluminate with a particle size of 10-20 nm and porous basalt are mixed and ground for 20 minutes, and then modified mica powder, phenolic fiber, brucite fiber, calcium sulfoaluminate with a particle size of 1-15 μm, and 1-5 parts of a water reducer are added to cement in sequence and stirred evenly to obtain a powder; (4) Mix the powder and slurry in a mass ratio of 5:2 to obtain the coating, which can then be used for construction.

9. The cement-based penetrating crystallization waterproof coating according to claim 8, characterized in that: The molecular weight of the vinyl silicone oil in step (1) is between 300 and 10,000, and the double bond content is between 8 and 12%.

10. The cement-based penetrating crystallization waterproof coating according to claim 1, characterized in that: The cement-based penetrating crystallization waterproof coating is suitable for a concrete surface that is pre-saturated with water.