Composition for polyurethane waterproof coating, polyurethane waterproof coating as well as preparation method and application of polyurethane waterproof coating

Abstract

The invention relates to the technical field of coatings, and discloses a composition for a polyurethane waterproof coating, the polyurethane waterproof coating as well as a preparation method and application of the polyurethane waterproof coating. The composition contains a main agent and an auxiliary agent, the main agent is formed by polymerizing raw material components including polyol, diisocyanate A, bisphenol A epoxy acrylate and a prepolymer; the prepolymer is prepared by a method comprising the following steps: in the presence of a polymerization catalyst, carrying out contact reaction on bisphenol A epoxy resin, polyaspartic acid ester, diisocyanate B and an isocyanate tripolymer to obtain the prepolymer, the use amount molar ratio of the bisphenol A epoxy resin to the polyaspartic acid ester to the diisocyanate B to the isocyanate tripolymer is 1: (0.6 to 1.5): (0.5 to 1): (0.05 to 0.5). The coating provided by the invention is high in modulus, and has higher tensile strength, hardness and waterproof performance.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a polyurethane waterproof coating composition, a polyurethane waterproof coating, and a preparation method and application thereof. Background Art

[0002] Polyurethane waterproof coatings are a key component of polyurethane synthetic materials. Due to their elasticity, good extensibility, excellent adhesion, minimal shrinkage, seamless waterproofing, strong adaptability to deformation caused by cracks in the base layer, ease of construction and maintenance, and ease of application on any complex base surface, polyurethane coatings are widely used for waterproofing and leak-proofing in various parts of buildings, becoming a key material for building waterproofing.

[0003] There is no measurement error during the construction of single-component polyurethane waterproof coatings, and the quality requirements for construction operators are not high. The viscosity is low and the construction is easy. At the same time, it has a long application period, stable performance, easy use, and a wide range of applications. Therefore, in recent years, the use of single-component polyurethane waterproof coatings has become more and more popular, and it has been increasingly recognized by users. Single-component polyurethane waterproof coatings have become the development direction of polyurethane waterproof coatings.

[0004] However, in some special scenarios with high requirements for waterproof performance, such as large bridges, airport runways, industrial plants, underground garages, sports venues, etc., the existing ordinary polyurethane waterproof coatings have a low modulus and are difficult to meet the waterproofing needs under long-term high load and high stress environments; when subjected to external forces, the existing polyurethane waterproof coatings are prone to large deformation, causing the waterproof layer to crack, break, and cause leakage, which ultimately affects the waterproof effect and service life of the coating.

[0005] Therefore, it is of great practical significance to develop high modulus polyurethane waterproof coatings to improve their ability to resist deformation and enhance their waterproof performance and durability.

[0006] At present, in order to improve the modulus of waterproof coatings, commonly used methods include using high-reinforcement fillers (such as nano-calcium carbonate, fumed silica, quartz powder, etc.), adjusting the cross-linking density, and introducing rigid segments into the molecules (such as aromatic isocyanates, small molecule alcohols or amine chain extenders). However, these methods have limited modulus improvement, and there are still problems such as insufficient modulus improvement, poor adhesion to cement-based surfaces, and the need to be used in conjunction with a primer.

[0007] CN105733432A discloses a high-modulus polyurethane waterproof coating composed of two components, A and B. Its composition and content, calculated by weight, are as follows: Component A: 0-33 parts toluene diisocyanate; 35-82 parts diphenylmethane diisocyanate; 115-137 parts polyether polyol; 15-30 parts dioctyl phthalate; Component B: 65-79 parts polyether triol; 29-35 parts 3,3'-dichloro-4,4'-diaminodiphenylmethane; 10-35 parts chlorinated paraffin; 55-100 parts filler; 1-2 parts catalyst; 1-2 parts chemical root inhibitor B5; and 6-15 parts defoamer B-0304. Although this solution can improve the modulus to a certain extent, it suffers from insufficient bonding strength to cement-based surfaces, poor deformation resistance, low bonding strength retention after soaking in water, and poor water resistance. Summary of the Invention

[0008] The purpose of the present invention is to solve the problems of low modulus, poor deformation resistance, waterproof performance and durability of the polyurethane waterproof coating in the prior art.

[0009] To achieve the above-mentioned object, the first aspect of the present invention provides a polyurethane waterproof coating composition, which comprises a main agent and an auxiliary agent; the main agent is prepared by polymerizing raw material components including polyol, diisocyanate A, bisphenol A epoxy acrylate, and prepolymer; the polyol is selected from polyether polyol and / or polyester polyol; Relative to 100 parts by weight of the polyol, the content of the diisocyanate A is 20-28 parts by weight, the content of the bisphenol A epoxy acrylate is 2-8 parts by weight, the content of the prepolymer is 1-10 parts by weight, and the content of the auxiliary agent is 210-420 parts by weight; The prepolymer is prepared by a method comprising the following steps: In the presence of a polymerization catalyst, bisphenol A epoxy resin, polyaspartic acid ester, diisocyanate B and isocyanate trimer are contact-reacted to obtain the prepolymer; the molar ratio of the bisphenol A epoxy resin, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.6-1.5:0.5-1:0.05-0.5.

[0010] The second aspect of the present invention provides a method for preparing a polyurethane waterproof coating, which is carried out using the composition described in the first aspect, comprising: mixing a mixture containing the composition for the polyurethane waterproof coating to obtain the polyurethane waterproof coating.

[0011] The third aspect of the present invention provides a polyurethane waterproof coating prepared by the method described in the second aspect.

[0012] The fourth aspect of the present invention provides application of the waterproof coating described in the third aspect in the field of building waterproofing.

[0013] The present invention achieves synergy between the raw materials by carefully designing and optimizing the ratio of the raw materials so that the raw materials support each other, thus giving the polyurethane waterproof coating excellent effects in different performance indicators.

[0014] The technical solution provided by the present invention has at least the following beneficial effects compared with the prior art: The self-made prepolymer provided by the present invention has high reactivity and can synergize with the various raw materials of the polyurethane composition to give the coating higher mechanical properties, thereby significantly improving the modulus of the coating. The obtained polyurethane waterproof coating has higher tensile strength, hardness and waterproof performance.

[0015] The polyurethane waterproof coating provided by the present invention can improve the bonding performance to the cement-based surface without using a primer, and in particular can greatly improve the bonding strength retention rate after soaking in water. DETAILED DESCRIPTION

[0016] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0017] As mentioned above, the first aspect of the present invention provides a polyurethane waterproof coating composition, which contains a main agent and an auxiliary agent; the main agent is polymerized from raw material components including polyol, diisocyanate A, bisphenol A epoxy acrylate, and prepolymer; the polyol is selected from polyether polyol and / or polyester polyol; Relative to 100 parts by weight of the polyol, the content of the diisocyanate A is 20-28 parts by weight, the content of the bisphenol A epoxy acrylate is 2-8 parts by weight, the content of the prepolymer is 1-10 parts by weight, and the content of the auxiliary agent is 210-420 parts by weight; The prepolymer is prepared by a method comprising the following steps: In the presence of a polymerization catalyst, bisphenol A epoxy resin, polyaspartic acid ester, diisocyanate B and isocyanate trimer are contact-reacted to obtain the prepolymer; the molar ratio of the bisphenol A epoxy resin, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.6-1.5:0.5-1:0.05-0.5.

[0018] Preferably, the polyol is a combination of polyether polyol and polyester polyol with a mass ratio of 1:0.1-0.3.

[0019] More preferably, the polyether polyol has a functionality of 2-4 and a number average molecular weight of 1500-2000.

[0020] Further preferably, the polyester polyol has a number average molecular weight of 800-2000 and a hydroxyl value of 55-115 mgKOH / g.

[0021] Preferably, the content of the diisocyanate A is 25-28 parts by weight, the content of the bisphenol A epoxy acrylate is 3-6 parts by weight, the content of the prepolymer is 3-6 parts by weight, and the content of the auxiliary is 210-420 parts by weight, relative to 100 parts by weight of the polyol. The inventor has found that in this preferred embodiment, the interaction between the raw material components is better, and the tensile strength of the polyurethane waterproof coating can be significantly improved.

[0022] Preferably, in the step of preparing the prepolymer, the molar ratio of the bisphenol A epoxy resin, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.8-1.2:0.6-0.8:0.1-0.3. The inventor has found that in this preferred embodiment, the obtained prepolymer has a rigid structure, which can significantly improve the modulus of the coating and impart higher mechanical properties to the coating.

[0023] Preferably, the bisphenol A epoxy acrylate has a functionality of 2-3 and a viscosity of 20000-50000 mpa.s at 23℃.

[0024] Preferably, the bisphenol A epoxy resin has an epoxy equivalent weight of 180-200 g / mol and a viscosity of 7000-18000 mpa.s at 25℃.

[0025] Preferably, the diisocyanate A and diisocyanate B are each independently selected from at least one of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl m-xylylene diisocyanate.

[0026] It should be noted that the "A" and "B" in the diisocyanate A and diisocyanate B in the present application are only used to distinguish the diisocyanates in different use scenarios, and the "A" and "B" themselves do not have any limiting meaning; the present application does not repeat here, and those skilled in the art should not understand it as a limitation of the present application.

[0027] Preferably, the polymerization catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, triethylamine, dimethylethanolamine, N,N-dimethylbenzylamine, bismuth isooctoate.

[0028] Preferably, the isocyanate trimer is at least one of toluene diisocyanate trimer, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer.

[0029] Preferably, the operation of the contact reaction comprises: SI-1, contacting a bisphenol A type epoxy resin and a polyaspartic ester for the first time; obtaining a first material; SI-2, contacting a diisocyanate B with the first material for the second time, obtaining a second material; SI-3, contacting a polymerization catalyst with the second material for the third time, obtaining a third material; SI-4, contacting an isocyanate trimer with the third material for the fourth time; obtaining the prepolymer.

[0030] Preferably, the conditions of the second contact comprise: a temperature of 85-95℃, and a time of 3-4h.

[0031] Preferably, the conditions of the third contact comprise: a temperature of 70-82℃, and a time of 0.5-1h.

[0032] Preferably, the conditions of the fourth contact comprise: a temperature of 60-68℃, and a time of 0.5-1h.

[0033] Preferably, the conditions of the first contact comprise: a temperature of 50-60℃, and a time of 5-15min.

[0034] Preferably, the first contact reaction, the second contact reaction, the third contact reaction and the fourth contact reaction are all carried out under stirring conditions, and the stirring speed is 150-250rpm.

[0035] It should be noted that in the present application, the amount of the polymerization catalyst is not particularly required, and can meet the expected reaction, preferably, the amount of the catalyst is 0.005-0.01wt% of the total system mass.

[0036] It should be noted that in the present application, in the step of preparing the prepolymer, a conventional post-treatment step is also included, for example, in order to remove unreacted small molecular compounds, a person skilled in the art can add a solvent during the synthesis of the prepolymer according to the needs, reduce the viscosity of the system material reaction, and perform vacuum stirring treatment on the product after the completion of the contact reaction. The present application does not repeat here, and a person skilled in the art should not understand it as a limitation of the present application.

[0037] Preferably, relative to 100 parts by weight of the polyol, the auxiliary agent contains 80-150 parts by weight of a plasticizer, 1-3 parts by weight of a defoamer, 0.1-0.5 parts by weight of a dispersant, 110-185 parts by weight of a filler, 25-60 parts by weight of a solvent, 0.5-1 parts by weight of a hydrolysis accelerator, 0.3-1.2 parts by weight of a urethanization catalyst, and 5-12 parts by weight of a latent curing agent.

[0038] Preferably, the urethanization catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, triethylamine, dimethylethanolamine, N,N-dimethylbenzylamine, and bismuth isooctanoate.

[0039] Preferably, the defoamer is selected from at least one of silicone defoamers, polyether defoamers, and organic fatty acid defoamers; the plasticizer is selected from at least one of phthalates, trioctyl phosphate, acetyl citrate, citrate, and chlorinated paraffin plasticizers.

[0040] Preferably, the dispersant is selected from at least one of anionic dispersants, cationic dispersants, nonionic dispersants, and polymer dispersants; the latent curing agent is selected from at least one of aldimines, ketimines, and oxazolidines; and the hydrolysis accelerator is selected from at least one of benzoic acid, salicylic acid, acetic acid, p-toluenesulfonic acid, and citric acid.

[0041] Preferably, the filler is selected from at least one of silica, nano-alumina, glass fiber, carbon fiber, talc, and nano-calcium carbonate; the solvent is selected from at least one of trimethylbenzene, tetramethylbenzene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether acetate.

[0042] As mentioned above, the second aspect of the present invention provides a method for preparing a polyurethane waterproof coating, which is carried out using the composition described in the first aspect, and includes: mixing a mixture containing the composition for the polyurethane waterproof coating to obtain the polyurethane waterproof coating.

[0043] According to a specific preferred embodiment, the operation of performing the mixing reaction comprises: (1) performing a first mixing of polyol, plasticizer, defoamer, dispersant and filler to obtain material I; (2) mixing the diisocyanate, a portion of the urethanization catalyst, the first portion of the solvent, the material I, and the second portion in a reverse direction to obtain a material II; (3) performing a third mixing of the prepolymer, bisphenol A epoxy acrylate, the second portion of the solvent, and the material II to obtain a material III; (4) carrying out fourth mixing of the latent curing agent, the third part of the solvent and the material III to obtain a material IV; (5) carrying out fifth mixing of the hydrolysis promoter, the residual urethane catalyst, the residual solvent and the material IV to obtain the polyurethane waterproof coating.

[0044] Preferably, the conditions of the first mixing include: temperature of 100-110℃, vacuum degree of -0.08 to -0.1 MPa, time of 2-3h, stirring speed of 300-350rpm; the conditions of the second mixing include: temperature of 70-85℃, time of 3-4h, stirring speed of 250-300rpm.

[0045] Preferably, the conditions of the third mixing include: temperature of 70-85℃, time of 0.5-1h, stirring speed of 250-300rpm.

[0046] Preferably, the conditions of the fourth mixing include: temperature of 70-85℃, time of 0.5-1h, stirring speed of 250-300rpm; the conditions of the fifth mixing include: temperature of 50-60℃, time of 0.5-1h, stirring speed of 250-300rpm.

[0047] It should be noted that in the above method for preparing the polyurethane waterproof coating, the amount of the partial catalyst and the residual catalyst is not particularly required, and the total amount of the urethane catalyst is 0.3-1.2 parts by weight with respect to 100 parts by weight of the polyol, which can be adjusted according to actual needs; similarly, the amount of the first part of the solvent, the second part of the solvent, the third part of the solvent and the fourth part of the solvent is not particularly required, and the total amount of the solvent is 25-60 parts by weight with respect to 100 parts by weight of the polyol, which can be adjusted according to actual needs; the present application does not repeat here, and those skilled in the art should not be construed as limiting the present application.

[0048] As described above, the third aspect of the present application provides a polyurethane waterproof coating prepared by the method of the second aspect.

[0049] As described above, the fourth aspect of the present application provides the use of the waterproof coating of the third aspect in the field of building waterproofing.

[0050] The present application will be described in detail below by way of examples.

[0051] In the following examples, the reagents and raw materials involved are commercially available unless otherwise specified, and the reagents are all analytical pure products.

[0052] Raw materials Polymerization catalyst: dibutyltin dilaurate; Bisphenol A epoxy resin I: viscosity at 25℃ of 11000-15000 mpa.s, epoxy equivalent weight of 184-194 g / eq, model (brand) of E51, purchased from Jinan Baorui Resin Chemical Co., Ltd.; Bisphenol A epoxy resin II: viscosity at 25℃ of 15000-25000 mpa.s, epoxy equivalent weight of 210-240 g / eq, model (brand) of E44, purchased from Jinan Baorui Resin Chemical Co., Ltd.; Polyaspartic ester: model (brand) of F520, purchased from Shenzhen Feiyangjun Research Co., Ltd.; Diisocyanate B: toluene diisocyanate, model (brand) of TDI-80, purchased from Wanhua Chemical Group Co., Ltd.; Isocyanate trimer: TDI trimer, model (brand) of HT-100, purchased from Wanhua Chemical Group Co., Ltd.; Polyether polyol is DL-2000D, functionality of 2, number average molecular weight of 2000, purchased from Wanhua Chemical Group Co., Ltd.; Polyester polyol is PTMG1000, functionality of 2, number average molecular weight of 1000, hydroxyl value of 112 mgKOH / g; purchased from Guangzhou Haoyi New Material Technology Co., Ltd.; Polyol I: combination of polyether polyol and polyester polyol in a mass ratio of 1:0.2; Bisphenol A epoxy acrylate I: CT-3100A, functionality of 2, viscosity at 23℃ of 25000-33000 mpa.s; Bisphenol A epoxy acrylate II: EBECRYL3701, functionality of 4, viscosity at 60℃ of 7000 mpa.s; Diisocyanate A: diphenylmethane diisocyanate, model (brand) of MDI-50, purchased from Wanhua Chemical Group Co., Ltd.; Urethane catalyst: dibutyltin dilaurate, model (brand) of CT-12, purchased from Nantong Menty Chemical Co., Ltd.; Isocyanate trimer: TDI trimer, model (brand) of HT-100, purchased from Wanhua Chemical Group Co., Ltd.; Plasticizer: chlorinated paraffin, model (brand) of 52# chlorinated paraffin, purchased from Jiangxi Dongfang Julong Chemical Co., Ltd.; Defoaming agent: silicone defoaming agent, model (brand) of D6800, purchased from Guangdong Shierli New Material Co., Ltd.; Dispersant: high molecular polymer, model (brand) S18, purchased from Core Chemical Co., Ltd. Filler: nano-aluminum oxide, model (brand) ALUNA-100, purchased from Hubei Hui Fu Nano Materials Co., Ltd.; talc powder, model HT-4, purchased from Qixia Rongguan Talc Powder Co., Ltd. Hydrolysis accelerator: accelerator, model (brand) A-289, purchased from Foshan Jinyuan New Material Technology Co., Ltd. Latent curing agent: aldehyde imine latent curing agent, model (brand) BH-5, purchased from Shandong Zhihua Puxin Material Co., Ltd.

[0053] Preparation Example 1 This preparation example is used to illustrate the preparation of the prepolymer provided by the application as follows: SI-1, the bisphenol A type epoxy resin I and the polyaspartic acid ester are first contacted; the first material is obtained; the conditions of the first contact include: the temperature is 50℃, the time is 10min, and the stirring speed is 200rpm; SI-2, the diisocyanate B is second contacted with the first material to obtain the second material; the conditions of the second contact include: the temperature is 85℃, the time is 3h, and the stirring speed is 250rpm; SI-3, the polymerization catalyst is third contacted with the second material to obtain the third material; the conditions of the third contact include: the temperature is 75℃, the time is 1h, and the stirring speed is 250rpm; SI-4, the isocyanate trimer is fourth contacted with the third material, and then vacuum stirring is carried out for 1h (the vacuum degree is 0.1MPa, and the stirring speed is 250rpm) to obtain the prepolymer Z1; the conditions of the fourth contact include: the temperature is 65℃, the time is 1h, and the stirring speed is 250rpm; The molar ratio of the use amount of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.8:0.6:0.3; The use amount of the polymerization catalyst is 0.01wt% of the total use amount of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer.

[0054] Preparation Example 2 SI-1, the bisphenol A type epoxy resin I and the polyaspartic acid ester are first contacted; the first material is obtained; the conditions of the first contact include: the temperature is 60℃, the time is 10min, and the stirring speed is 200rpm; SI-2, second contact the diisocyanate B with the first material to obtain a second material; the conditions of the second contact include: temperature is 90℃, time is 4h, stirring speed is 200rpm; SI-3, third contact the polymerization catalyst with the second material to obtain a third material; the conditions of the third contact include: temperature is 80℃, time is 0.5h, stirring speed is 200rpm; SI-4, fourth contact the isocyanate trimer with the third material, then vacuum stirring for 1h (vacuum degree is 0.1MPa, stirring speed is 200rpm) to obtain the prepolymer Z2; the conditions of the fourth contact include: temperature is 70℃, time is 1h, stirring speed is 200rpm; The molar ratio of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:1.2:0.8:0.1; The amount of the catalyst is 0.005wt% of the total amount of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer.

[0055] Preparation Example 3 The preparation example adopts the similar process with the preparation example 1, except that in the preparation example, the equal molar bisphenol A type epoxy resin II is used to replace the bisphenol A type epoxy resin I in the preparation example 1.

[0056] The rest is the same with the preparation example 1.

[0057] The prepolymer Z3 is prepared.

[0058] Preparation Example 4 The preparation example adopts the similar process with the preparation example 1, except that in the preparation example, the molar amount of the bisphenol A type epoxy resin I is controlled to be the same with the preparation example 1, but the molar ratio of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:1.5:0.6:0.3.

[0059] The rest is the same with the preparation example 1.

[0060] The prepolymer Z4 is prepared.

[0061] Preparation Example 5 The preparation example adopts the similar process with the preparation example 1, except that in the preparation example, the molar amount of the bisphenol A type epoxy resin I is controlled to be the same with the preparation example 1, but the molar ratio of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.8:1:0.3.

[0062] The rest are the same as in Preparation Example 1.

[0063] The prepolymer Z5 was prepared.

[0064] Preparation Example 6 This preparation example is carried out using a process similar to that of Preparation Example 1, except that in this preparation example, the molar amount of bisphenol A epoxy resin I is controlled to be the same as that of Preparation Example 1, but polyaspartic acid ester is not added. The specific steps are as follows: SI-1. Contacting diisocyanate B with bisphenol A epoxy resin I to obtain a first material; the conditions for the first contacting include: temperature of 85° C., time of 3 hours, and stirring speed of 200 rpm; SI-2, contacting the polymerization catalyst with the first material for a second time to obtain a second material; the conditions of the second contact include: temperature of 75° C., time of 1 hour, and stirring speed of 250 rpm; SI-3. The isocyanate trimer was contacted with the second material for a third time, followed by vacuum stirring for 1 hour (vacuum degree of 0.1 MPa, stirring speed of 250 rpm) to obtain prepolymer DZ1. The conditions of the third contacting included: temperature of 65° C., time of 1 hour, and stirring speed of 250 rpm. The molar ratio of the bisphenol A epoxy resin I, the diisocyanate B and the isocyanate trimer is 1:0.6:0.3; The amount of the catalyst used is 0.01 wt % of the total amount of the bisphenol A epoxy resin I, the diisocyanate B and the isocyanate trimer.

[0065] Preparation Example 7 This preparation example is carried out using a process similar to that of Preparation Example 1, except that in this preparation example, the molar amount of bisphenol A epoxy resin I is controlled to be the same as that of Preparation Example 1, but diisocyanate B is not added. The specific steps are as follows: SI-1. A bisphenol A epoxy resin I and polyaspartic acid ester are first contacted to obtain a first material; the conditions of the first contact include: temperature of 50° C., time of 10 minutes, and stirring speed of 200 rpm; SI-3, contacting the polymerization catalyst with the first material for a second time to obtain a second material; the conditions of the second contact include: temperature of 75° C., time of 1 hour, and stirring speed of 250 rpm; SI-4. The isocyanate trimer was contacted with the second material for a third time, followed by vacuum stirring for 1 hour (vacuum degree of 0.1 MPa, stirring speed of 250 rpm) to obtain prepolymer DZ2; the conditions of the third contacting included: temperature of 65° C., time of 1 hour, and stirring speed of 250 rpm; The molar ratio of the bisphenol A epoxy resin I, the polyaspartic acid ester and the isocyanate trimer is 1:0.8:0.3; The amount of the catalyst used is 0.01 wt % of the total amount of the bisphenol A epoxy resin I, the polyaspartic acid ester and the isocyanate trimer.

[0066] Example 1 This example is used to illustrate that the polyurethane waterproof coating provided by the present invention is prepared according to the formula in Table 1 and the following method: (1) performing a first mixing of polyol, plasticizer, defoamer, dispersant and filler to obtain material I; (2) mixing the diisocyanate, a portion of the urethanization catalyst (50 wt% of the total amount), the first portion of the solvent (25 wt% of the total amount), the material I, and the second portion in a reverse direction to obtain a material II; (3) performing a third mixing of the prepolymer, bisphenol A epoxy acrylate, the second portion of the solvent (25 wt% of the total amount) and the material II to obtain a material III; (4) performing a fourth mixing of the latent curing agent, the third portion of the solvent (25 wt% of the total amount) and the material III to obtain a material IV; (5) The hydrolysis accelerator, the remaining urethanization catalyst, the remaining solvent and the material IV are subjected to a fifth reaction to obtain the polyurethane waterproof coating.

[0067] The first mixing conditions include: temperature of 110°C, vacuum degree of -0.1MPa, time of 2h, and stirring speed of 300rpm; the second mixing conditions include: temperature of 75°C, time of 4h, and stirring speed of 250Rpm; the third mixing conditions include: temperature of 75°C, time of 1h, and stirring speed of 250Rpm; the fourth mixing conditions include: temperature of 75°C, time of 0.5-h, and stirring speed of 250rpm; the fifth mixing conditions include: temperature of 55°C, time of 0.5h, and stirring speed of 250rpm.

[0068] Unless otherwise specified, the remaining examples were carried out using a process similar to that of Example 1, except that the formulations used in each example were different. For details, see Table 1 (Note: the parameters not listed in Table 1 are the same as the corresponding parameters in Example 1).

[0069] Table 1

[0070] Example 6 This example is carried out using a process similar to that of Example 1, except that this example uses polyether polyol (same as in Example 1) of equal mass to replace the polyester polyol in Example 1 (ie, polyester polyol is not used in this example).

[0071] The rest are the same as in Example 1.

[0072] The polyurethane waterproof coating S6 was prepared.

[0073] Example 7 This example was carried out using a process similar to that of Example 1, except that the prepolymer Z3 obtained in Preparation Example 3 of equal quality was used to replace Z1 in Example 1.

[0074] The rest are the same as in Example 1.

[0075] The polyurethane waterproof coating S7 was prepared.

[0076] Example 8 This example was carried out using a process similar to that of Example 1, except that the prepolymer Z4 obtained in Preparation Example 4 of equal quality was used to replace Z1 in Example 1.

[0077] The rest are the same as in Example 1.

[0078] The polyurethane waterproof coating S8 was prepared.

[0079] Example 9 This example was carried out using a process similar to that of Example 1, except that the prepolymer Z5 obtained in Preparation Example 5 of equal quality was used to replace Z1 in Example 1.

[0080] The rest are the same as in Example 1.

[0081] The polyurethane waterproof coating S9 was prepared.

[0082] Comparative Example 1 This comparative example was carried out using a process similar to that of Example 1, except that the prepolymer DZ1 obtained in Preparation Example 6 of equal mass was used to replace Z1 in Example 1.

[0083] The rest are the same as in Example 1.

[0084] The polyurethane waterproof coating DS1 was prepared.

[0085] Comparative Example 2 This comparative example was carried out using a process similar to that of Example 1, except that the prepolymer DZ2 obtained in Preparation Example 7 of equal mass was used to replace Z1 in Example 1.

[0086] The rest are the same as in Example 1.

[0087] The polyurethane waterproof coating DS2 was prepared.

[0088] Comparative Example 3 This comparative example was carried out using a process similar to that of Example 1, except that the prepolymer Z1 in Example 1 was not added in this comparative example.

[0089] The rest are the same as in Example 1.

[0090] The polyurethane waterproof coating DS3 was prepared.

[0091] Comparative Example 4 This comparative example was carried out using a process similar to that of Example 1, except that the bisphenol A epoxy acrylate I in Example 1 was not added in this comparative example.

[0092] The rest are the same as in Example 1.

[0093] The polyurethane waterproof coating DS4 was prepared.

[0094] Test Case The elastic modulus of the polyurethane waterproof coating obtained in the above example was tested with reference to HG / T 3321-2012; Water-immersion bond strength retention was determined by preparing specimens according to the method specified in GB / T 16777-2008, 7.1 (Method A). Initial bond strength was measured by curing the specimens for 7 days under standard test conditions (23±2°C, 50±10% relative humidity). The specimens were completely immersed in water, removed at the prescribed time, and then tested for bond strength after 12 hours under standard test conditions.

[0095] Strength retention = (bond strength / initial bond strength) × 100%. Other performance indicators were tested in accordance with the GB / T19250-2013 standard. Specific test items and results are shown in Table 2.

[0096] Table 2

[0097] From the results in Table 2, it can be seen that the various properties of the present invention are better than those of the comparative example, the elastic modulus is significantly higher than that of the comparative example, and the bonding performance is good. The bonding strength retention rate after soaking in water for 14 days is maintained at more than 80%, and the water resistance is better, which can comprehensively improve the durability of the waterproof coating.

[0098] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A polyurethane waterproof coating composition, characterized in that: The composition contains a main agent and an auxiliary agent; the main agent is polymerized from raw material components including polyol, diisocyanate A, bisphenol A epoxy acrylate, and prepolymer; the polyol is selected from polyether polyol and / or polyester polyol; Relative to 100 parts by weight of the polyol, the content of the diisocyanate A is 20-28 parts by weight, the content of the bisphenol A epoxy acrylate is 2-8 parts by weight, the content of the prepolymer is 1-10 parts by weight, and the content of the auxiliary agent is 210-420 parts by weight; The prepolymer is prepared by a method comprising the following steps: In the presence of a polymerization catalyst, bisphenol A epoxy resin, polyaspartic acid ester, diisocyanate B and isocyanate trimer are contact-reacted to obtain the prepolymer; the molar ratio of the bisphenol A epoxy resin, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.6-1.5:0.5-1:0.05-0.

5.

2. The composition according to claim 1, characterized in that The polyol is a combination of polyether polyol and polyester polyol in a mass ratio of 1:0.1-0.3; and / or, the polyether polyol has a functionality of 2-4 and a number average molecular weight of 1500-2000; And / or, the polyester polyol has a number average molecular weight of 800-2000 and a hydroxyl value of 55-115 mgKOH / g.

3. The composition according to claim 1, characterized in that Relative to 100 parts by weight of the polyol, the content of the diisocyanate A is 25-28 parts by weight, the content of the bisphenol A epoxy acrylate is 3-6 parts by weight, the content of the prepolymer is 3-6 parts by weight, and the content of the auxiliary agent is 210-420 parts by weight.

4. The composition according to any one of claims 1 to 3, characterized in that In the step of preparing the prepolymer, the molar ratio of the bisphenol A epoxy resin, the polyaspartic acid ester, the diisocyanate B and the isocyanate trimer is 1:0.8-1.2:0.6-0.8:0.1-0.

3.

5. The composition according to any one of claims 1 to 3, characterized in that The bisphenol A epoxy acrylate has a functionality of 2-3 and a viscosity of 20,000-50,000 mPa.s at 23°C; And / or, the bisphenol A epoxy resin has an epoxy equivalent of 180-200 g / mol and a viscosity of 7000-18000 mPa.s at 25°C; and / or, the diisocyanate A and the diisocyanate B are each independently selected from at least one of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate; And / or, the polymerization catalyst is at least one selected from dibutyltin dilaurate, stannous octoate, triethylamine, dimethylethanolamine, N,N-dimethylbenzylamine, and bismuth isooctanoate; And / or, the isocyanate trimer is at least one of toluene diisocyanate trimer, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer.

6. The composition according to any one of claims 1 to 3, characterized in that The operation of carrying out the contact reaction includes: SI-1, bringing bisphenol A epoxy resin and polyaspartic acid ester into first contact to obtain a first material; SI-2, contacting diisocyanate B with the first material for a second time to obtain a second material; SI-3, contacting the polymerization catalyst with the second material for a third time to obtain a third material; SI-4, contacting the isocyanate trimer with the third material for the fourth time to obtain the prepolymer; And / or, the second contacting conditions include: temperature of 85-95° C., time of 3-4 h; And / or, the conditions of the third contact include: temperature of 70-82° C., time of 0.5-1 h; And / or, the conditions for the fourth contact include: temperature of 60-68° C., and time of 0.5-1 h.

7. The composition according to any one of claims 1 to 3, characterized in that Relative to 100 parts by weight of the polyol, the auxiliary agent contains 80-150 parts by weight of a plasticizer, 1-3 parts by weight of a defoamer, 0.1-0.5 parts by weight of a dispersant, 110-185 parts by weight of a filler, 25-60 parts by weight of a solvent, 0.5-1 parts by weight of a hydrolysis accelerator, 0.3-1.2 parts by weight of a urethanization catalyst, and 5-12 parts by weight of a latent curing agent; And / or, the urethanization catalyst is at least one selected from dibutyltin dilaurate, stannous octoate, triethylamine, dimethylethanolamine, N,N-dimethylbenzylamine, and bismuth isooctanoate.

8. A method for preparing a polyurethane waterproof coating, characterized in that: The method is carried out using the composition described in any one of claims 1 to 7, and comprises: mixing and reacting a mixture containing the composition for polyurethane waterproof coating to obtain the polyurethane waterproof coating.

9. The polyurethane waterproof coating prepared by the method according to claim 8.

10. Use of the waterproof coating according to claim 9 in the field of building waterproofing.

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