Polyurethane waterproof coating composition, polyurethane waterproof coating and preparation method and application thereof

Abstract

The present application relates to the technical field of paint, and discloses a composition for polyurethane waterproof paint, polyurethane waterproof paint and a preparation method and application thereof.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 prepolymer is prepared by a method including the following steps: in the presence of a polymerization catalyst, bisphenol A type epoxy resin, polyaspartic acid ester, diisocyanate B and isocyanate trimer are subjected to contact reaction to obtain the prepolymer;the molar ratio of the bisphenol A type 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.The paint provided by the present application has high modulus, and has higher tensile strength, hardness and waterproof performance.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a polyurethane waterproof coating composition, a polyurethane waterproof coating, its preparation method, and its application. Background Technology

[0002] Polyurethane waterproof coatings are an important component of polyurethane synthetic materials applications. Due to the elasticity, good extensibility, good adhesion, low volume shrinkage, seamless waterproof layer, strong adaptability to deformation caused by cracks in the substrate, convenient construction and maintenance, and ease of application on any complex substrate surface, polyurethane coatings are widely used for waterproofing and leak sealing in various parts of buildings, becoming one of the main materials for building waterproofing.

[0003] Single-component polyurethane waterproof coatings eliminate measurement errors during application, require less skilled operators, have lower viscosity, are easy to apply, and offer a long service life, stable performance, ease of use, and wide applicability. As a result, their usage has been increasing in recent years, and they have gained greater recognition from users. Single-component polyurethane waterproof coatings have become the future direction of polyurethane waterproof coatings.

[0004] However, in some special scenarios with high requirements for waterproofing performance, such as large bridges, airport runways, industrial plants, underground garages, and sports venues, the existing ordinary polyurethane waterproof coatings have a low modulus, making it difficult to meet the waterproofing needs under long-term high load and high stress environments. When subjected to external forces, the existing polyurethane waterproof coating is prone to large deformation, which can lead to cracking, damage, and leakage, ultimately affecting the waterproofing effect and service life of the coating.

[0005] Therefore, developing high-modulus polyurethane waterproof coatings to improve their resistance to deformation, enhance their waterproof performance and durability is of great practical significance.

[0006] Currently, common methods to improve the modulus of waterproof coatings include using high-reinforcing fillers (such as nano-calcium carbonate, fumed silica, quartz powder, etc.), adjusting crosslinking density, and introducing rigid chain segments into the molecule (such as aromatic isocyanates, small molecule alcohols or amine chain extenders). However, these methods have limited modulus improvement and still have problems such as insufficient modulus improvement, poor adhesion to cement-based surfaces, and often 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; 51-2 parts chemical root inhibitor B; 46-15 parts defoamer B-0304. While this solution can improve the modulus to some extent, it lacks sufficient adhesion strength to cementitious surfaces, exhibits poor deformation resistance, and has a low retention rate of adhesion strength after immersion in water, resulting in poor water resistance. Summary of the Invention

[0008] The purpose of this invention is to solve the problems of low modulus, poor deformation resistance, poor waterproof performance and poor durability of existing polyurethane waterproof coatings.

[0009] To achieve the above objectives, a first aspect of the present invention provides a composition for a polyurethane waterproof coating, the composition comprising a main agent and an auxiliary agent; the main agent is polymerized from raw material components including a polyol, diisocyanate A, bisphenol A epoxy acrylate, and a prepolymer; the polyol is selected from polyether polyols and / or polyester polyols.

[0010] Relative to 100 parts by weight of the polyol, the content of diisocyanate A is 20-28 parts by weight, the content of 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 additives is 210-420 parts by weight.

[0011] The prepolymer is prepared by a method comprising the following steps:

[0012] In the presence of a polymerization catalyst, bisphenol A type epoxy resin, polyaspartic acid ester, diisocyanate B, and isocyanate trimer are subjected to a contact reaction to obtain the prepolymer; the molar ratio of the bisphenol A type 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.

[0013] A second aspect of the present invention provides a method for preparing a polyurethane waterproof coating, the method being carried out using the composition described in the first aspect, comprising: mixing and reacting a mixture containing the polyurethane waterproof coating composition to obtain the polyurethane waterproof coating.

[0014] A third aspect of the present invention provides a polyurethane waterproof coating prepared by the method described in the second aspect.

[0015] The fourth aspect of the present invention provides the application of the waterproof coating described in the third aspect in the field of building waterproofing.

[0016] This invention, through careful design and optimization of the proportions of each raw material, enables the raw materials to support each other and achieve synergistic effects, thereby giving the polyurethane waterproof coating excellent performance in different performance indicators.

[0017] The technical solution provided by this invention has at least the following advantages over the prior art:

[0018] The self-made prepolymer provided by this invention has high reactivity and can synergistically interact with the raw materials of the polyurethane composition to give the coating higher mechanical properties, thereby significantly improving the modulus of the coating. The resulting polyurethane waterproof coating has higher tensile strength, hardness and waterproof performance.

[0019] The polyurethane waterproof coating provided by this invention can improve the adhesion performance to cement-based surfaces without the use of a primer, and in particular, it can greatly improve the retention rate of adhesion strength after soaking in water. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges 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 endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] As previously described, a first aspect of the present invention provides a composition for a polyurethane waterproof coating, the composition comprising a main agent and an auxiliary agent; the main agent is polymerized from raw material components including a polyol, diisocyanate A, bisphenol A epoxy acrylate, and a prepolymer; the polyol is selected from polyether polyols and / or polyester polyols.

[0022] Relative to 100 parts by weight of the polyol, the content of diisocyanate A is 20-28 parts by weight, the content of 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 additives is 210-420 parts by weight.

[0023] The prepolymer is prepared by a method comprising the following steps:

[0024] In the presence of a polymerization catalyst, bisphenol A type epoxy resin, polyaspartic acid ester, diisocyanate B, and isocyanate trimer are subjected to a contact reaction to obtain the prepolymer; the molar ratio of the bisphenol A type 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.

[0025] Preferably, the polyol is a combination of polyether polyol and polyester polyol in a mass ratio of 1:0.1-0.3.

[0026] More preferably, the polyether polyol has a functionality of 2-4 and a number-average molecular weight of 1500-2000.

[0027] More preferably, the number-average molecular weight of the polyester polyol is 800-2000, and the hydroxyl value is 55-115 mgKOH / g.

[0028] Preferably, relative to 100 parts by weight of the polyol, the content of diisocyanate A is 25-28 parts by weight, the content of 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 additives is 210-420 parts by weight. The inventors have found that, under this preferred embodiment, the synergistic effect between the raw material components is better, which can significantly improve the tensile strength of the polyurethane waterproof coating.

[0029] In a preferred embodiment, during the preparation of the prepolymer, the molar ratio of the bisphenol A epoxy resin, the polyaspartic ester, the diisocyanate B, and the isocyanate trimer is 1:0.8-1.2:0.6-0.8:0.1-0.3. The inventors have found that, under this preferred embodiment, the obtained prepolymer exhibits a distinctly rigid structure, which significantly improves the modulus of the coating and imparts higher mechanical properties to the coating.

[0030] Preferably, the bisphenol A epoxy acrylate has a functionality of 2-3 and a viscosity of 20,000-50,000 mPa·s at 23°C.

[0031] Preferably, the bisphenol A type epoxy resin has an epoxy equivalent of 180-200 g / mol and a viscosity of 7000-18000 mPa·s at 25°C.

[0032] In a preferred embodiment, 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, phenylmethylene diisocyanate, and tetramethyl isophthalimethylene diisocyanate.

[0033] It should be noted that the "A" and "B" in diisocyanate A and diisocyanate B in this invention are only used to distinguish diisocyanates in different application scenarios, and "A" and "B" themselves do not have any limiting meaning; this invention will not be elaborated further here, and those skilled in the art should not understand it as a limitation of this invention.

[0034] Preferably, the polymerization catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, triethylamine, dimethylethanolamine, N,N-dimethylbenzylamine, and bismuth isooctanoate.

[0035] Preferably, the isocyanate trimer is at least one of toluene diisocyanate trimer, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer.

[0036] Preferably, the operation of performing the contact reaction includes:

[0037] SI-1, bisphenol A type epoxy resin and polyaspartic acid ester are subjected to a first contact to obtain a first material;

[0038] SI-2, Diisocyanate B is brought into a second contact with the first material to obtain the second material;

[0039] SI-3: The polymerization catalyst is brought into a third contact with the second material to obtain a third material;

[0040] SI-4, the isocyanate trimer is brought into a fourth contact with the third material to obtain the prepolymer.

[0041] Preferably, the conditions for the second contact include: a temperature of 85-95°C and a time of 3-4 hours.

[0042] Preferably, the conditions for the third contact include: a temperature of 70-82°C and a time of 0.5-1 hour.

[0043] Preferably, the conditions for the fourth contact include: a temperature of 60-68°C and a time of 0.5-1 hour.

[0044] In a preferred embodiment, the conditions for the first contact include: a temperature of 50-60°C and a time of 5-15 minutes.

[0045] 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 150-250 rpm.

[0046] It should be noted that in this invention, there are no special requirements for the amount of the polymerization catalyst, as long as it can satisfy the reaction to proceed as expected. Preferably, the amount of the catalyst is 0.005-0.01 wt% of the total mass of the reaction system.

[0047] It should be noted that in this invention, the prepolymer preparation step also includes conventional post-processing steps. For example, to remove unreacted small molecule compounds, those skilled in the art can add a solvent during prepolymer synthesis to reduce the viscosity of the reacting materials, and perform vacuum stirring on the product after the contact reaction is complete, as needed. These details will not be elaborated upon here, and should not be construed as limiting the invention.

[0048] In a preferred embodiment, relative to 100 parts by weight of the polyol, the additive contains 80-150 parts by weight of plasticizer, 1-3 parts by weight of defoamer, 0.1-0.5 parts by weight of dispersant, 110-185 parts by weight of filler, 25-60 parts by weight of solvent, 0.5-1 parts by weight of hydrolysis accelerator, 0.3-1.2 parts by weight of urethane catalyst, and 5-12 parts by weight of latent curing agent.

[0049] Preferably, the esterification catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, triethylamine, dimethylethanolamine, N,N-dimethylbenzylamine, and bismuth isooctanoate.

[0050] 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, acetylic acid ester, citrate, and chlorinated paraffin plasticizers.

[0051] Preferably, the dispersant is selected from at least one of anionic dispersants, cationic dispersants, nonionic dispersants, and polymeric dispersants; the latent curing agent is selected from at least one of aldehyde imines, 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.

[0052] 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 thylene, tetramethylbenzene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether acetate.

[0053] As previously stated, a second aspect of the present invention provides a method for preparing a polyurethane waterproof coating, the method being carried out using the composition described in the first aspect, comprising: mixing and reacting a mixture containing the polyurethane waterproof coating composition to obtain the polyurethane waterproof coating.

[0054] According to a specific preferred embodiment, the operation of the mixing reaction includes:

[0055] (1) The polyol, plasticizer, defoamer, dispersant and filler are mixed in the first mixture to obtain material I;

[0056] (2) The diisocyanate, a portion of the amine esterification catalyst, a first portion of the solvent, and the material I and the second mixture in reverse order are mixed to obtain material II;

[0057] (3) The prepolymer, bisphenol A epoxy acrylate, the second solvent and the material II are mixed in a third mixture to obtain material III;

[0058] (4) Mix the latent curing agent, the solvent in the third part, and the material III in a fourth mixture to obtain material IV;

[0059] (5) The hydrolysis accelerator, the remaining urethane catalyst, the remaining solvent and the material IV are subjected to a fifth reaction to obtain the polyurethane waterproof coating.

[0060] Preferably, the conditions for the first mixing include: a temperature of 100-110℃, a vacuum of -0.08 to -0.1MPa, a time of 2-3h, and a stirring speed of 300-350rpm; the conditions for the second mixing include: a temperature of 70-85℃, a time of 3-4h, and a stirring speed of 250-300rpm.

[0061] Preferably, the conditions for the third mixing include: a temperature of 70-85℃, a time of 0.5-1h, and a stirring speed of 250-300rpm.

[0062] Preferably, the conditions for the fourth mixing include: a temperature of 70-85℃, a time of 0.5-1h, and a stirring speed of 250-300rpm; the conditions for the fifth mixing include: a temperature of 50-60℃, a time of 0.5-1h, and a stirring speed of 250-300rpm.

[0063] It should be noted that in the above method for preparing polyurethane waterproof coatings, there are no particular requirements for the amounts of the partial catalyst and the remaining catalyst. The total amount of the esterification catalyst relative to 100 parts by weight of the polyol is sufficient to be 0.3-1.2 parts by weight. Those skilled in the art can adjust the amount added in batches according to actual needs. Similarly, this invention does not have particular requirements for the amounts of the first, second, third, and fourth solvents mentioned above. The total amount of the solvent relative to 100 parts by weight of the polyol is sufficient to be 25-60 parts by weight. Those skilled in the art can adjust the amount added in batches according to actual needs. Further details are omitted here, and those skilled in the art should not interpret this as a limitation of the invention.

[0064] As previously stated, a third aspect of the present invention provides a polyurethane waterproof coating prepared by the method described in the second aspect.

[0065] As previously stated, the fourth aspect of this invention provides the application of the waterproof coating described in the third aspect in the field of building waterproofing.

[0066] The present invention will be described in detail below through examples.

[0067] Unless otherwise specified, all reagents and raw materials used in the following examples are commercially available products, and all reagents are analytical grade products.

[0068] raw material

[0069] Polymerization catalyst: dibutyltin dibutylsilicate;

[0070] Bisphenol A type epoxy resin I: viscosity at 25℃ is 11000-15000 mpa.s, epoxy equivalent is 184-194 g / eq, model (grade) is E51, purchased from Jinan Baorui Resin Chemical Co., Ltd.

[0071] Bisphenol A type epoxy resin II: viscosity at 25℃ is 15000-25000 mpa.s, epoxy equivalent is 210-240 g / eq, model (grade) is E44, purchased from Jinan Baorui Resin Chemical Co., Ltd.

[0072] Polyaspartic acid ester: Model (brand name) F520, purchased from Shenzhen Feiyang Junyan Co., Ltd.;

[0073] Diisocyanate B: Toluene diisocyanate, model (brand name) TDI-80, purchased from Wanhua Chemical Group Co., Ltd.

[0074] Isocyanate trimer: TDI trimer, model (grade) HT-100, purchased from Wanhua Chemical Group Co., Ltd.;

[0075] The polyether polyol was DL-2000D, with a functionality of 2 and a number-average molecular weight of 2000, and was purchased from Wanhua Chemical Group Co., Ltd.

[0076] The polyester polyol was PTMG1000, with a functionality of 2, a number-average molecular weight of 1000, and a hydroxyl value of 112 mgKOH / g; it was purchased from Guangzhou Haoyi New Material Technology Co., Ltd.

[0077] Polyol I: A combination of polyether polyol and polyester polyol in a mass ratio of 1:0.2;

[0078] Bisphenol A epoxy acrylate I: CT-3100A, functionality 2, viscosity at 23℃ 25000-33000 mPa·s;

[0079] Bisphenol A epoxy acrylate II: EBECRYL3701, functionality 4, viscosity at 60°C 7000 mPa·s;

[0080] Diisocyanate A: Diphenylmethane diisocyanate, model (brand name) MDI-50, purchased from Wanhua Chemical Group Co., Ltd.;

[0081] Acrylation catalyst: Dibutyltin dilaurate, model (grade) CT-12, purchased from Nantong Mingtai Chemical Co., Ltd.;

[0082] Isocyanate trimer: TDI trimer, model (grade) HT-100, purchased from Wanhua Chemical Group Co., Ltd.;

[0083] Plasticizer: Chlorinated paraffin, type (brand) 52# chlorinated paraffin, purchased from Jiangxi Dongfang Julong Chemical Co., Ltd.

[0084] Defoamer: Organosilicon defoamer, model (brand) D6800, purchased from Guangdong Shierli New Materials Co., Ltd.

[0085] Dispersant: High molecular weight polymer, model (brand name) S18, purchased from Core Chemical Co., Ltd.;

[0086] Filler: Nano alumina, model (grade) ALUNA-100, purchased from Hubei Huifu Nanomaterials Co., Ltd.; Talc powder, model HT-4, purchased from Qixia Rongguan Talc Powder Co., Ltd.

[0087] Hydrolysis accelerator: Accelerator, model (brand) A-289, purchased from Foshan Juchuang New Material Technology Co., Ltd.;

[0088] Latent curing agent: Aldehyde imide latent curing agent, model (brand) BH-5, purchased from Shandong Zhihuapu New Materials Co., Ltd.

[0089] Preparation Example 1

[0090] This preparation example illustrates the preparation of the prepolymer provided by the present invention using the following method:

[0091] SI-1, Bisphenol A type epoxy resin I and polyaspartic acid ester are brought into first contact to obtain the first material; the conditions of the first contact include: temperature of 50°C, time of 10 min, and stirring speed of 200 rpm.

[0092] SI-2, Diisocyanate B is brought into a second contact with the first material to obtain a second material; the conditions for the second contact include: temperature of 85°C, time of 3 hours, and stirring speed of 250 rpm.

[0093] SI-3. The polymerization catalyst is brought into a third contact with the second material to obtain a third material; the conditions for the third contact include: a temperature of 75°C, a time of 1 hour, and a stirring speed of 250 rpm.

[0094] SI-4. The isocyanate trimer is brought into a fourth contact with the third material, and then vacuum stirred for 1 hour (vacuum degree of 0.1 MPa, stirring speed of 250 rpm) to obtain prepolymer Z1; the conditions for the fourth contact include: temperature of 65°C, time of 1 hour, and stirring speed of 250 rpm.

[0095] The molar ratio of the bisphenol A type epoxy resin I, the polyaspartic acid ester, the diisocyanate B, and the isocyanate trimer is 1:0.8:0.6:0.3;

[0096] The amount of the polymerization catalyst is 0.01 wt% of the total mass of bisphenol A epoxy resin I, the polyaspartic acid ester, the diisocyanate B, and the isocyanate trimer.

[0097] Preparation Example 2

[0098] SI-1, Bisphenol A type epoxy resin I and polyaspartic acid ester are brought into first contact to obtain the first material; the conditions of the first contact include: temperature of 60°C, time of 10 min, and stirring speed of 200 rpm.

[0099] SI-2, Diisocyanate B is brought into a second contact with the first material to obtain a second material; the conditions for the second contact include: temperature of 90°C, time of 4 hours, and stirring speed of 200 rpm.

[0100] SI-3. The polymerization catalyst is brought into a third contact with the second material to obtain a third material; the conditions for the third contact include: a temperature of 80°C, a time of 0.5 h, and a stirring speed of 200 rpm.

[0101] SI-4. The isocyanate trimer is brought into a fourth contact with the third material, and then vacuum stirred for 1 hour (vacuum degree of 0.1 MPa, stirring speed of 200 rpm) to obtain prepolymer Z2; the conditions for the fourth contact include: temperature of 70°C, time of 1 hour, and stirring speed of 200 rpm.

[0102] 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;

[0103] The amount of catalyst used is 0.005 wt% of the total mass of bisphenol A epoxy resin I, the polyaspartic acid ester, the diisocyanate B, and the isocyanate trimer.

[0104] Preparation Example 3

[0105] This preparation example uses a similar process to Preparation Example 1. The difference is that in this preparation example, equimolar amounts of bisphenol A type epoxy resin II are used to replace bisphenol A type epoxy resin I in Preparation Example 1.

[0106] The rest are the same as in Preparation Example 1.

[0107] Prepolymer Z3 was prepared.

[0108] Preparation Example 4

[0109] This preparation example uses a similar process to Preparation Example 1. The difference is that in this preparation example, the molar amount of bisphenol A type epoxy resin I is controlled in the same way as in 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.

[0110] The rest are the same as in Preparation Example 1.

[0111] Prepolymer Z4 was prepared.

[0112] Preparation Example 5

[0113] This preparation example uses a similar process to Preparation Example 1. The difference is that in this preparation example, the molar amount of bisphenol A type epoxy resin I is controlled in the same way as in 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.

[0114] The rest are the same as in Preparation Example 1.

[0115] Prepolymer Z5 was prepared.

[0116] Preparation Example 6

[0117] This preparation example uses a similar process to Preparation Example 1. The difference is that in this preparation example, the molar amount of bisphenol A type epoxy resin I is controlled to be the same as in Preparation Example 1, but polyaspartic acid ester is not added. The specific steps are as follows:

[0118] SI-1. Diisocyanate B and bisphenol A type epoxy resin I are brought into a first contact to obtain a first material; the conditions for the first contact include: temperature of 85°C, time of 3 hours, and stirring speed of 200 rpm.

[0119] SI-2, The polymerization catalyst is brought into a second contact with the first material to obtain a second material; the conditions for the second contact include: a temperature of 75°C, a time of 1 hour, and a stirring speed of 250 rpm.

[0120] SI-3: The isocyanate trimer is brought into a third contact with the second material, and then vacuum stirred for 1 hour (vacuum degree of 0.1 MPa, stirring speed of 250 rpm) to obtain prepolymer DZ1; the conditions of the third contact include: temperature of 65°C, time of 1 hour, and stirring speed of 250 rpm.

[0121] The molar ratio of the bisphenol A type epoxy resin I, the diisocyanate B, and the isocyanate trimer is 1:0.6:0.3;

[0122] The amount of catalyst used is 0.01 wt% of the total mass of bisphenol A type epoxy resin I, diisocyanate B, and isocyanate trimer.

[0123] Preparation Example 7

[0124] This preparation example uses a similar process to Preparation Example 1. The difference is that in this preparation example, the molar amount of bisphenol A type epoxy resin I is controlled to be the same as in Preparation Example 1, but diisocyanate B is not added. The specific steps are as follows:

[0125] SI-1, Bisphenol A type epoxy resin I and polyaspartic acid ester are brought into first contact to obtain the first material; the conditions of the first contact include: temperature of 50°C, time of 10 min, and stirring speed of 200 rpm.

[0126] SI-3. The polymerization catalyst is brought into a second contact with the first material to obtain a second material; the conditions for the second contact include: a temperature of 75°C, a time of 1 hour, and a stirring speed of 250 rpm.

[0127] SI-4. The isocyanate trimer is brought into a third contact with the second material, and then vacuum stirred for 1 hour (vacuum degree of 0.1 MPa, stirring speed of 250 rpm) to obtain prepolymer DZ2; the conditions of the third contact include: temperature of 65°C, time of 1 hour, and stirring speed of 250 rpm.

[0128] The molar ratio of the bisphenol A type epoxy resin I, the polyaspartic acid ester, and the isocyanate trimer is 1:0.8:0.3;

[0129] The amount of catalyst used is 0.01 wt% of the total mass of bisphenol A type epoxy resin I, the polyaspartic acid ester, and the isocyanate trimer.

[0130] Example 1

[0131] This embodiment illustrates the preparation of the polyurethane waterproof coating provided by the present invention according to the formulation in Table 1 and the following method:

[0132] (1) The polyol, plasticizer, defoamer, dispersant and filler are mixed in the first mixture to obtain material I;

[0133] (2) The diisocyanate, a portion of the amine esterification catalyst (50 wt% of the total amount), the first portion of the solvent (25 wt% of the total amount), and the material I and the reverse second mixture are mixed to obtain material II;

[0134] (3) The prepolymer, bisphenol A epoxy acrylate, the second part of the solvent (25 wt% of the total amount) and the material II are mixed in a third mixture to obtain material III;

[0135] (4) Mix the latent curing agent, the third part of the solvent (25 wt% of the total amount) and the material III in a fourth mixture to obtain material IV;

[0136] (5) The hydrolysis accelerator, the remaining urethane catalyst, the remaining solvent and the material IV are subjected to a fifth reaction to obtain the polyurethane waterproof coating.

[0137] The conditions for the first mixing are: temperature 110℃, vacuum degree -0.1MPa, time 2h, and stirring speed 300rpm; the conditions for the second mixing are: temperature 75℃, time 4h, and stirring speed 250rpm; the conditions for the third mixing are: temperature 75℃, time 1h, and stirring speed 250rpm; the conditions for the fourth mixing are: temperature 75℃, time 0.5h, and stirring speed 250rpm; and the conditions for the fifth mixing are: temperature 55℃, time 0.5h, and stirring speed 250rpm.

[0138] Unless otherwise specified, the remaining examples follow a similar process to Example 1, except that the formulations used in each example are different, as detailed in Table 1 (Note: Parameters not listed in Table 1 are the same as those in Example 1).

[0139] Table 1

[0140]

[0141] Example 6

[0142] This embodiment follows a similar process to that of Example 1. The difference is that this embodiment uses an equal mass of polyether polyol (same as Example 1) to replace the polyester polyol in Example 1 (that is, polyester polyol is not used in this embodiment).

[0143] Everything else is the same as in Example 1.

[0144] Polyurethane waterproof coating S6 was prepared.

[0145] Example 7

[0146] This embodiment follows a similar process to Example 1, except that the prepolymer Z3 obtained in Preparation Example 3 is used to replace Z1 in Example 1.

[0147] Everything else is the same as in Example 1.

[0148] Polyurethane waterproof coating S7 was prepared.

[0149] Example 8

[0150] This embodiment follows a similar process to Example 1, except that the prepolymer Z4 obtained in Preparation Example 4 is used to replace Z1 in Example 1.

[0151] Everything else is the same as in Example 1.

[0152] Polyurethane waterproof coating S8 was prepared.

[0153] Example 9

[0154] This embodiment follows a similar process to Example 1, except that the prepolymer Z5 obtained in Preparation Example 5 is used to replace Z1 in Example 1.

[0155] Everything else is the same as in Example 1.

[0156] Polyurethane waterproof coating S9 was prepared.

[0157] Comparative Example 1

[0158] This comparative example was carried out using a similar process to Example 1. The difference is that this comparative example used an equivalent mass of prepolymer DZ1 obtained in Preparation Example 6 to replace Z1 in Example 1.

[0159] Everything else is the same as in Example 1.

[0160] Polyurethane waterproof coating DS1 was prepared.

[0161] Comparative Example 2

[0162] This comparative example was carried out using a similar process to Example 1, except that the prepolymer DZ2 obtained in Preparation Example 7 was used to replace Z1 in Example 1.

[0163] Everything else is the same as in Example 1.

[0164] Polyurethane waterproof coating DS2 was prepared.

[0165] Comparative Example 3

[0166] This comparative example follows a similar process to Example 1, except that the prepolymer Z1 from Example 1 is not added in this comparative example.

[0167] Everything else is the same as in Example 1.

[0168] Polyurethane waterproof coating DS3 was prepared.

[0169] Comparative Example 4

[0170] This comparative example follows a similar process to Example 1, except that bisphenol A epoxy acrylate I, which was used in Example 1, is not added in this comparative example.

[0171] Everything else is the same as in Example 1.

[0172] Polyurethane waterproof coating DS4 was prepared.

[0173] Test case

[0174] The elastic modulus of the polyurethane waterproof coating obtained in the above examples was tested in accordance with HG / T 3321-2012;

[0175] The strength retention rate of water-immersion bonding was determined by preparing specimens according to the method specified in GB / T 16777-2008 7.1 (Method A). The initial bond strength of the specimens was tested after curing for 7 days under standard test conditions (23±2℃, relative humidity 50±10%). Alternatively, the specimens could be completely immersed in water, removed after a predetermined time, and left to stand under standard test conditions for 12 hours before testing the bond strength.

[0176] Strength retention rate = (bond strength / initial bond strength) × 100%. Other indicators were tested according to standard GB / T19250-2013. Specific test items and results are shown in Table 2.

[0177] Table 2

[0178]

[0179] As can be seen from the results in Table 2, the performance of the present invention is superior to that of the comparative example. The elastic modulus is significantly higher than that of the comparative example. At the same time, the adhesion performance is good, and the adhesion strength retention rate is maintained at more than 80% after soaking in water for 14 days. The water resistance is better, which can comprehensively improve the durability of the waterproof coating.

[0180] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition for a polyurethane waterproof coating, 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 diisocyanate A is 20-28 parts by weight, the content of 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 additives 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 type epoxy resin, polyaspartic acid ester, diisocyanate B, and isocyanate trimer are subjected to a contact reaction to obtain the prepolymer; the molar ratio of the bisphenol A type 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. The operation of performing the contact reaction includes: SI-1, bisphenol A type epoxy resin and polyaspartic acid ester are subjected to a first contact to obtain a first material; SI-2, Diisocyanate B is brought into a second contact with the first material to obtain the second material; SI-3: The polymerization catalyst is brought into a third contact with the second material to obtain a third material; SI-4, the isocyanate trimer is brought into a fourth contact with the third material.

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 functionality of the polyether polyol is 2-4 and the number average molecular weight is 1500-2000; And / or, the number average molecular weight of the polyester polyol is 800-2000, and the hydroxyl value is 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 diisocyanate A is 25-28 parts by weight, the content of 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 additives is 210-420 parts by weight.

4. The composition according to any one of claims 1-3, 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 1-3, characterized in that, The bisphenol A epoxy acrylate has a functionality of 2 and a viscosity of 20,000-50,000 mPa·s at 23°C. And / or, the bisphenol A type 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 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, phenylmethylene diisocyanate and tetramethyl isophthalimethylene diisocyanate; And / or, the polymerization catalyst is selected from at least one of 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 1-3, characterized in that, The conditions for the second contact include: a temperature of 85-95℃ and a time of 3-4 hours; And / or, the conditions for the third contact include: a temperature of 70-82°C and a time of 0.5-1 h; And / or, the conditions for the fourth contact include: a temperature of 60-68°C and a time of 0.5-1h.

7. The composition according to any one of claims 1-3, characterized in that, Relative to 100 parts by weight of the polyol, the additive contains 80-150 parts by weight of plasticizer, 1-3 parts by weight of defoamer, 0.1-0.5 parts by weight of dispersant, 110-185 parts by weight of filler, 25-60 parts by weight of solvent, 0.5-1 parts by weight of hydrolysis accelerator, 0.3-1.2 parts by weight of urethane catalyst, and 5-12 parts by weight of latent curing agent; And / or, the esterification catalyst is selected from at least one of 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 according to any one of claims 1-7, comprising: mixing and reacting a mixture containing the polyurethane waterproof coating composition to obtain the polyurethane waterproof coating.

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

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

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