Single-component solvent-free epoxy modified polyurethane waterproof coating, preparation method thereof and waterproof product

Abstract

The invention discloses a single-component solvent-free epoxy modified polyurethane waterproof coating as well as a preparation method and a waterproof product thereof. The coating comprises the following raw material components in parts by weight: 100 parts of polyether glycol; 30 to 80 parts by weight of polyether triol; 80-120 parts by weight of an epoxy vegetable oil plasticizer; 200 to 350 parts by weight of pigment and filler; 14 to 20 parts by weight of diisocyanate; 9-17 parts by weight of a modified epoxy resin A comprising an epoxy-terminated group and an epoxy alkyl acrylate monomer derivative chain segment; 2 to 11 parts by weight of hydroxyl oxazolidine, and the hydroxyl oxazolidine is an oxazolidine compound containing an active hydroxyl group; 70 to 100 parts by weight of a reactive diluent; 1-3 parts by weight of a defoaming agent; 0.1-0.5 part by weight of a dispersant; 12-41 parts by weight of a latent curing agent; and 0.4 to 1.8 parts by weight of a catalyst. The coating can effectively solve the problem that the bonding strength retention rate is poor after a traditional polyurethane waterproof coating is soaked in water, and the product performance is excellent.

Description

Technical Field

[0001] The present application belongs to the technical field of polyurethane coatings, and in particular relates to a one-component solvent-free epoxy-modified polyurethane waterproof coating, a preparation method thereof, and a waterproof product. Background Art

[0002] Polyurethane waterproof coating is one of the important directions of polyurethane synthetic material application. Because the polyurethane coating film is elastic, has good extensibility, good adhesion, small volume shrinkage, and the coating waterproof layer has no joints, it has strong adaptability to the deformation of the base crack expansion and contraction, and is easy to construct and maintain. It is easy to construct on any complex base surface, and can be used for waterproofing and plugging leaks in different parts of the building, so it has become one of the main materials for building waterproofing.

[0003] There is no measurement error during the construction of single-component polyurethane waterproof coatings, and the quality requirements for construction personnel are not high. The viscosity is low, the construction is easy, and the trial period is long, the performance is stable, the use is convenient, and the application is wide. Therefore, single-component polyurethane waterproof coatings are increasingly recognized by users, and the usage is increasing. Single-component polyurethane waterproof coatings have become the development direction of polyurethane waterproof coatings. However, most of the polyurethane waterproof coatings on the market are solvent-based. The coatings on the market often need to reduce the viscosity of the coating by adding various organic solvents or adding a large amount of low-viscosity plasticizers to achieve the effect of convenient construction. However, the use of organic solvents in the coating and its subsequent volatilization inevitably cause VOC emissions and environmental pollution, and are not good for the physical and mental health of on-site construction workers. At the same time, the addition of a large amount of plasticizers will reduce the strength of the coating, and in the later use process, with the migration of plasticizers and the volatilization of solvents, the coating film will shrink, deform, and harden. In the case of long-term immersion in water, it is easy to bulge, fall off, peel off, etc., resulting in water leakage of the coating film and even failure of the waterproof layer. In addition, the coating is easily affected by the ambient temperature and humidity, and it is difficult to construct at low temperatures. As the country's environmental protection requirements continue to increase, the control of VOC content is becoming more and more stringent. In the future, polyurethane waterproof coatings will gradually develop towards high performance and high environmental protection. Therefore, the preparation of a polyurethane waterproof coating with excellent performance, good construction performance and high environmental protection has become a technical problem that needs to be solved urgently. Summary of the invention

[0004] The embodiment of the present application provides a one-component solvent-free epoxy modified polyurethane waterproof coating, which can improve the curing speed and adhesion performance of the coating. The coating film has excellent adhesion performance and is resistant to water immersion and bulging, and has good construction performance.

[0005] In the first aspect, the present application provides a one-component solvent-free epoxy-modified polyurethane waterproof coating, including the following raw material components in parts by weight: polyether diol, 100 parts by weight; polyether triol, 30 to 80 parts by weight; epoxy vegetable oil plasticizer, 80 to 120 parts by weight; diisocyanate, 14 to 20 parts by weight; modified epoxy resin A, 9 to 17 parts by weight; modified epoxy resin A includes terminal epoxy groups and epoxy alkyl acrylate monomer derived segments; hydroxy oxazolidine, 2 to 11 parts by weight; hydroxy oxazolidine is an oxazolidine compound containing one active hydroxyl group; active diluent, 70 to 100 parts by weight; latent curing agent, 12 to 41 parts by weight; pigments and fillers, 200 to 350 parts by weight; defoamer, 1 to 3 parts by weight; dispersant, 0.1 to 0.5 parts by weight; catalyst, 0.4 to 1.8 parts by weight.

[0006] According to an embodiment of the first aspect of the present application, the polyether diol is selected from DL-2000D or DL-1000D or a combination thereof.

[0007] According to an embodiment of the first aspect of the present application, the polyether triol is selected from EP330N or MN1000 or a combination thereof.

[0008] According to an embodiment of the first aspect of the present application, the epoxidized vegetable oil plasticizer is selected from epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized rice bran oil, epoxidized sunflower oil or a combination thereof.

[0009] According to an embodiment of the first aspect of the present application, the filler is selected from nano calcium carbonate, talc, heavy calcium, kaolin, silica powder or a combination thereof.

[0010] According to an embodiment of the first aspect of the present application, the pigment is selected from carbon black, titanium dioxide, iron oxide red or a combination thereof.

[0011] According to an embodiment of the first aspect of the present application, the active diluent is selected from propenyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, butyl glycidyl ether, polypropylene glycol glycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol glycidyl ether, tert-butyl carbonate glycidyl ether or a combination thereof.

[0012] According to an embodiment of the first aspect of the present application, the diisocyanate is selected from aromatic diisocyanate, aliphatic diisocyanate or a combination thereof.

[0013] According to an embodiment of the first aspect of the present application, the diisocyanate is selected from toluene diisocyanate, diphenylmethane-4,4′-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate or a combination thereof.

[0014] According to an embodiment of the first aspect of the present application, the epoxy equivalent of the modified epoxy resin A is 170 g / mol to 200 g / mol.

[0015] According to an embodiment of the first aspect of the present application, the modified epoxy resin A comprises a structure represented by the following formula (1):

[0016]

[0017] In formula (1), n ​​is an integer of 1 to 25, and R1 is a group having the following structural formula:

[0018]

[0019] In formula (2), X is an integer of 1 to 3, R2 is a C3 or C7 alkylene oxide, R3 is H or a methyl group, and R4 is H. It indicates the position where R1 is connected to the molecular chain skeleton of modified epoxy resin A.

[0020] According to an embodiment of the first aspect of the present application, the hydroxyoxazolidine includes the structure shown below:

[0021]

[0022] In formula (3), R is selected from H, C1-C5 alkyl, and phenyl, and n is an integer of 1-3.

[0023] According to an embodiment of the first aspect of the present application, the hydroxyoxazolidine is selected from 3-hydroxyethyl-1,3-oxazolidine, 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, 2-phenyl-3-hydroxyethyl-1,3-oxazolidine or a combination thereof.

[0024] According to an embodiment of the first aspect of the present application, the defoaming agent is selected from a silicone defoaming agent or a polyether defoaming agent or a combination thereof.

[0025] According to an embodiment of the first aspect of the present application, the defoaming agent is selected from TEGO Antifoam 2290, BYK-051, BYK-052, BYK-065, BYK-141 or a combination thereof.

[0026] According to an embodiment of the first aspect of the present application, the dispersant is an anionic dispersant.

[0027] According to an embodiment of the first aspect of the present application, the dispersant is selected from sodium oleate, sulfate ester salts, and sulfonates.

[0028] According to an embodiment of the first aspect of the present application, the latent curing agent is selected from aldimine, ketimine compound or a combination thereof.

[0029] According to an embodiment of the first aspect of the present application, the catalyst is selected from dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, zinc neodecanoate or a combination thereof.

[0030] In a second aspect, the present application provides a method for preparing a one-component solvent-free epoxy-modified polyurethane waterproof coating, comprising:

[0031] Reacting polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment, filler, and diisocyanate at a first reaction temperature to obtain a -NCO-terminated first reaction product;

[0032] Adding modified epoxy resin A and a catalyst to the first reaction product and maintaining the reaction temperature to obtain a second reaction product having -NCO end-capping at one end and epoxy end-capping at the other end;

[0033] Add hydroxy oxazolidine to the second reaction product and react at a second reaction temperature to obtain a third reaction product having one end capped with an oxazolidine group and the other end capped with an epoxy group;

[0034] A latent curing agent and an active diluent are added to the third reaction product to react at a set temperature to obtain a one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0035] The third aspect of the present application provides a waterproof product, comprising a substrate and a waterproof coating coated on at least one surface of the substrate, wherein the waterproof coating is formed by the above-mentioned one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0036] The one-component solvent-free epoxy-modified polyurethane waterproof coating and its preparation method of the embodiment of the present application, by limiting the raw material components of the ratio, forms a polyurethane prepolymer with one end capped by modified epoxy resin A and the other end capped by oxazolidinyl, which can improve the adhesion performance of the coating through the terminal epoxy group and epoxyalkyl acrylate monomer derived segment in the polyurethane prepolymer segment, so that the coating can maintain good adhesion strength after soaking in water, while improving the curing speed of the coating product to improve construction efficiency. In addition, the present application uses epoxy vegetable oil plasticizers and active diluents that can participate in the curing reaction of the coating system, which fully participate in the cross-linking reaction during the curing process of the coating, and do not seep out or volatilize after curing, thereby reducing pollution to the environment. DETAILED DESCRIPTION

[0037] The features and exemplary embodiments of various aspects of the present application will be described in detail below. In order to make the purpose, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application, rather than to limit the present application. For those skilled in the art, the present application can be implemented without the need for some of these specific details. The following description of the embodiments is only to provide a better understanding of the present application by illustrating the examples of the present application.

[0038] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the statement "include..." do not exclude the presence of other identical elements in the process, method, article or device including the elements.

[0039] In order to solve the problems of the prior art, the present application provides a one-component solvent-free epoxy-modified polyurethane waterproof coating and a preparation method and waterproof product thereof. The one-component solvent-free epoxy-modified polyurethane waterproof coating provided by the present application is first introduced below.

[0040] The embodiment of the present application provides a one-component solvent-free epoxy modified polyurethane waterproof coating, including the following raw material components in parts by weight: polyether diol, 100 parts by weight; polyether triol, 30 to 80 parts by weight; epoxy vegetable oil plasticizer, 80 to 120 parts by weight; diisocyanate, 14 to 20 parts by weight; modified epoxy resin A, 9 to 17 parts by weight; modified epoxy resin A includes terminal epoxy groups and epoxy alkyl acrylate monomer derived chain segments; hydroxy oxazolidine, 2 to 11 parts by weight, hydroxy oxazolidine is an oxazolidine compound containing one active hydroxyl group; active diluent, 70 to 100 parts by weight; latent curing agent, 12 to 41 parts by weight; pigments and fillers, 200 to 350 parts by weight; defoamer, 1 to 3 parts by weight; dispersant, 0.1 to 0.5 parts by weight; catalyst, 0.4 to 1.8 parts by weight.

[0041] The one-component solvent-free epoxy-modified polyurethane waterproof coating of the embodiment of the present application is a polyurethane prepolymer prepared from a polyether polyol and a diisocyanate. The polyurethane prepolymer is reacted with a modified epoxy resin A and a hydroxyl oxazolidine in a specified ratio to obtain a polyurethane prepolymer with one end capped with a modified epoxy resin A (i.e., one end is capped with a terminal epoxy group of the modified epoxy resin A) and the other end is capped with an oxazolidinyl group, thereby improving the adhesion performance of the coating product and increasing the curing speed of the coating to improve the construction efficiency. After the coating is applied, the terminal oxazolidinyl group and the latent curing agent undergo a hydrolysis reaction to release primary amino groups and hydroxyl groups to react rapidly with the epoxy groups in the coating system, thereby making the coating cross-linked and cured from the inside to the outside surface to form a coating faster, greatly improving the construction efficiency of the coating, and the coating film formed by the coating is bubble-free, thereby solving the problem of blistering of the coating film caused by the slow curing speed of the terminal -NCO of traditional polyurethane coatings and the susceptibility to the influence of environmental temperature and humidity.

[0042] The one-component solvent-free epoxy modified polyurethane waterproof coating of the embodiment of the present application introduces modified epoxy resin A and hydroxyoxazolidine to utilize the high bonding strength of multiple epoxy groups contained in the modified epoxy resin A to the base layer, thereby further improving the adhesion and water resistance of the coating film formed by the coating, so that the coating film of the coating can also have a high bonding strength retention rate after being soaked in water.

[0043] In addition, the one-component solvent-free epoxy-modified polyurethane waterproof coating of the embodiment of the present application can realize self-crosslinking after the functional groups at both ends of the polyurethane prepolymer are hydrolyzed, and the epoxy vegetable oil plasticizer and the active diluent fully participate in the self-crosslinking curing of the coating system during the curing process. After curing, there is no shrinkage of the coating film caused by the volatilization and migration of free components such as organic solvents and plasticizers, that is, no interfacial stress is caused, and the adhesion performance of the coating film is prevented from decreasing. The present invention is an environmentally friendly one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0044] In some embodiments of the present application, the polyether diol is selected from DL-2000D or DL-1000D or a combination thereof.

[0045] In some embodiments of the present application, the polyether triol is selected from EP330N or MNI000. For example, the amount of the polyether triol can be 32, 35, 38, 40, 45, 52, 56, 60, 64, 68, 70, 72, 75 parts by weight. The polyether diol and the polyether triol can be purchased from at least Shandong Bluestar Dongda Co., Ltd.

[0046] In the embodiments of the present application, a combination of polyether diol and polyether triol is used, so that the one-component solvent-free epoxy modified polyurethane waterproof coating can not only react with diisocyanate to polymerize the molecular chains formed by the coating in the length direction, but also can form a network structure by connecting with each other through the extra alcohol hydroxyl groups of the polyether triol on the side chains of the molecular chains, thereby improving the overall connection strength and tensile properties of the coating.

[0047] In some embodiments of the present application, the epoxidized vegetable oil plasticizer is selected from epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized rice bran oil, epoxidized sunflower oil or a combination thereof. Exemplarily, the amount of the epoxidized vegetable oil plasticizer can be 81, 85, 88, 90, 96, 100, 108, 112, 116, 118 parts by weight.

[0048] In the embodiments of the present application, the epoxy group contained in the epoxy vegetable oil plasticizer can effectively improve the bonding performance and bonding rate of the coating, so that the coating can be quickly bonded to the base surface.

[0049] In some embodiments of the present application, the active diluent is selected from propenyl glycidyl ether, phenyl glycidyl ether, ethylene glycol bisglycidyl ether, resorcinol bisglycidyl ether, butyl glycidyl ether, polypropylene glycol glycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol glycidyl ether, tert-butyl carbonate glycidyl ether or a combination thereof.

[0050] In the embodiments of the present application, the amount of the active diluent may be 72, 75, 80, 83, 86, 90, 94, 95, 96, or 98 parts by weight.

[0051] In the embodiments of the present application, the glycidyl ether groups contained in the active diluent all contain epoxy groups, and the epoxy groups in the active diluent and the epoxidized vegetable oil plasticizer participate in the crosslinking reaction of the system together. The epoxidized vegetable oil plasticizer and the active diluent both participate in the curing process of the coating, are non-volatile, and reduce environmental pollution.

[0052] In some embodiments, the diisocyanate is selected from aromatic diisocyanate, aliphatic diisocyanate or a combination thereof. Exemplarily, the diisocyanate may be 15, 16, 17, 18 parts by weight.

[0053] In some embodiments of the present application, the diisocyanate is selected from toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate or a combination thereof.

[0054] In the embodiments of the present application, pigments and fillers can be added to the coating alone or together. For example, the amount of the pigments and fillers added together can be 220, 232, 240, 248, 256, 260, 265, 267, 270, 273, 277, 280, 284, 288, 290, 293, 297, 300, 314, 317, 320, 344, 348 parts by weight.

[0055] In some embodiments of the present application, the pigment is selected from carbon black, titanium dioxide, iron oxide red or a combination thereof. The pigment can give the coating a color suitable for the object being coated.

[0056] In some embodiments, the filler is selected from nano calcium carbonate, talc, heavy calcium, kaolin, silica powder or a combination thereof. Adding fillers to the coating can appropriately improve the strength and stability of the coating.

[0057] In some embodiments of the present application, the amount of modified epoxy resin A may be 10, 12, 14, or 16 parts by weight.

[0058] In some embodiments of the present application, the epoxy equivalent of the modified epoxy resin A is 170g / mol to 200g / mol. The modified epoxy resin A of the present application has a suitable epoxy equivalent range, especially the modified epoxy resin A within the above epoxy equivalent range is not only highly active, fast crosslinking speed, high crosslinking density, can improve the peel strength and bonding performance of the coating, but also can further take into account the heat resistance and mechanical strength of the coating, such as tensile strength, tear strength, etc. Exemplarily, the epoxy equivalent of the modified epoxy resin A is 172g / mol, 175g / mol, 180g / mol, 184g / mol, 185g / mol, 188g / mol, 190g / mol, 192g / mol, 195g / mol, 197g / mol, 199g / mol.

[0059] In addition, the raw material bisphenol A epoxy resin for preparing modified epoxy resin A contains epoxy groups at both ends, a rigid double benzene ring structure in the molecule, and epoxy groups and hydroxyl groups contained in its epoxyalkyl acrylate monomer derived chain segment make the modified epoxy resin A have good activity. Modification with bisphenol A epoxy resin as the carbon chain skeleton can further improve the strength and bonding properties of the coating, such as improving the tensile strength, tear strength and bonding strength of the coating.

[0060] In some embodiments of the present application, the modified epoxy resin A comprises a structure shown in formula (1):

[0061]

[0062] In formula (1), n ​​is an integer of 1 to 25, and R1 is a group having the following structural formula:

[0063]

[0064] In formula (2), X is an integer of 1 to 3, R2 is a C3 or C7 alkylene oxide, R3 is H or a methyl group, and R4 is H. It indicates the position where R1 is connected to the molecular chain skeleton of modified epoxy resin A.

[0065] In an embodiment of the present application, the modified epoxy resin A is prepared by the following steps: using a first solvent to disperse a bisphenol A type epoxy resin to obtain a first dispersion; adding an acrylate epoxy alkyl ester monomer to the first dispersion and reacting to obtain a modified epoxy resin A; wherein the reaction of the bisphenol A type epoxy resin and the acrylate epoxy alkyl ester monomer is as follows:

[0066]

[0067] In the reaction structure (4), n is an integer of 1 to 25, R2 is a C3 or C7 alkylene oxide, R3 is H or methyl; and R1 is a group including the following structure:

[0068]

[0069] In formula (2), X is an integer of 1 to 3, R2 is a C3 or C7 alkylene oxide, R3 is H or a methyl group, and R4 is H. It indicates the position where R1 is connected to the molecular chain skeleton of modified epoxy resin A.

[0070] In some embodiments of the present application, R1 includes a structure shown in any one of formula (2-a) to formula (2-d):

[0071]

[0072]

[0073] In formulas (2-a) to (2-d), X is an integer of 1 to 3, R4 is H, It indicates the position where R1 is connected to the molecular chain skeleton of modified epoxy resin A.

[0074] In some embodiments of the present application, the bisphenol A epoxy resin may be selected from brands such as bisphenol A epoxy resin E44, bisphenol A epoxy resin E51, bisphenol A epoxy resin 128 or a combination thereof.

[0075] In an embodiment of the present application, the first solvent can be a mixed solvent of at least two of n-butanol, ethylene glycol butyl ether, diethylene glycol, ethylene glycol ethyl ether, propylene glycol methyl ether, and N,N-dimethylformamide. Exemplarily, the volume ratio of n-butanol to ethylene glycol butyl ether in the first solvent is 1:(1-2).

[0076] In some embodiments of the present application, the molar ratio of bisphenol A epoxy resin to epoxy alkyl acrylate monomer is 1: (1-3). Exemplarily, the molar ratio of bisphenol A epoxy resin to epoxy alkyl acrylate monomer is 1: 1.1, 1: 1.2, 1: 1.3, 1: 1.4, 1: 1.5, 1: 1.7, 1: 1.8, 1: 2.0, 1: 2.2, 1: 2.3, 1: 2.45, 1: 2.5, 1: 2.7, 1: 2.8.

[0077] In some embodiments of the present application, the epoxyalkyl acrylate monomer is selected from 2,3-epoxypropyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl methacrylate or a combination thereof. The structural formula of 2,3-epoxypropyl acrylate is:

[0078]

[0079] The structural formula of glycidyl methacrylate is:

[0080]

[0081] The structural formula of 3,4-epoxyhexyl methacrylate is:

[0082]

[0083] The structural formula of 3,4-epoxyhexylmethyl methacrylate is:

[0084]

[0085] In the embodiments of the present application, the modified epoxy resin A prepared by the reaction of bisphenol A epoxy resin and epoxyalkyl acrylate monomers contains at least 3 epoxy groups and one hydroxyl group in each molecule of the modified epoxy resin. The multiple epoxy groups contained in the molecular structure work together with the epoxy groups contained in the epoxy vegetable oil plasticizer and the reactive diluent to provide multiple cross-linking sites with other components, accelerate the cross-linking and curing speed of the coating, and better improve the problem that traditional polyurethane coatings are easily affected by the ambient temperature and humidity and difficult to construct, and the problem that the coating film is easy to bulge and fall off when immersed in water. The hydroxyl groups contained in the modified epoxy resin make it easy for the modified epoxy resin to react or form hydrogen bonds with the epoxy, hydroxyl, and isocyanate groups of other components, so that covalent bonds or hydrogen bonds are formed between the coating components, the strength and tensile properties of the coating film are improved, and the adhesive properties of the coating are further prevented from being reduced after being soaked in water.

[0086] In some embodiments, the initiator is selected from dibenzoyl peroxide, t-butyl perbenzoate, benzoyl peroxide, t-amyl peroxy-2-ethylhexyl ester, 1,1-bis(t-amylperoxy)cyclohexane, or a combination thereof.

[0087] Exemplarily, the preparation method of modified epoxy resin A includes:

[0088] S1, putting a calculated amount of dried bisphenol A epoxy resin into a reactor, adding a mixed solvent of n-butanol and ethylene glycol butyl ether into the reactor, stirring until the bisphenol A epoxy resin is completely dissolved, to obtain a first dispersion, and maintaining the temperature of the first dispersion at 45° C. to 50° C.;

[0089] S2, add calculated amounts of glycidyl methacrylate and benzoyl peroxide to the first dispersion in the reactor, control the dripping reaction speed of glycidyl methacrylate, continue to heat and stir the reaction, control the temperature to 90°C to 95°C, react at constant temperature for 6 to 7 hours, then evacuate, and distill under reduced pressure for 0.5 to 1 hour to obtain modified epoxy resin A. Wherein, the bisphenol A type epoxy resin is bisphenol A type epoxy resin E44, the molar ratio of bisphenol A type epoxy resin E44 to glycidyl methacrylate is 1: (1 to 3), the amount of the mixed solvent of n-butanol and ethylene glycol butyl ether is 10wt.% to 15wt.% of the total mass of the reactants of the reaction, and the amount of benzoyl peroxide is 0.3wt.% to 0.5wt.% of the total mass of the reactants of the reaction.

[0090] In some embodiments of the present application, the hydroxyoxazolidine is an oxazolidine compound containing one active hydroxyl group, which satisfies the molecular formula:

[0091]

[0092] In formula (3), R is selected from H, C1-C5 alkyl, and phenyl, and n is an integer of 1-3.

[0093] In some embodiments of the present application, the hydroxyoxazolidine is selected from 3-hydroxyethyl-1,3-oxazolidine, 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, 2-phenyl-3-hydroxyethyl-1,3-oxazolidine or a combination thereof.

[0094] In the embodiments of the present application, hydroxyoxazolidine, as a latent curing agent different from aldimine and ketimine, can release a single-terminal primary amine group by hydrolysis, has relatively low activity, and cannot play a significant chain extension role, which promotes the curing reaction of the coating to a certain extent, and improves the elongation performance of the coating film. The present application uses the hydroxyl group contained in the hydroxyoxazolidine itself and the single-terminal primary amino group and hydroxyl group released by the above-mentioned amount of hydroxyoxazolidine when it is easily hydrolyzed in water as active groups to react with the components in the coating, so that the coating has a suitable degree of crosslinking, and further improves the tensile properties of the coating after curing.

[0095] In some embodiments, the defoaming agent is selected from silicone defoaming agents or polyether defoaming agents or a combination thereof.

[0096] In some embodiments of the present application, the defoaming agent is selected from TEGO Antifoam 2290, BYK-051, BYK-052, BYK-065, BYK-141 or a combination thereof.

[0097] In some embodiments of the present application, the dispersant is an anionic dispersant. The anionic dispersant is selected from sodium oleate (e.g., C 17 H 33 COONa), sulfate ester salt (such as ROSO3Na), sulfonate salt (such as RSO3Na) or a combination thereof. Exemplarily, DisuperS18 can be selected as a dispersant.

[0098] In some embodiments, the latent curing agent is selected from aldimine, ketimine compound or a combination thereof. Exemplarily, the latent curing agent is selected from XY-3767, XY-401, ALT-403 or a combination thereof.

[0099] In some embodiments of the present application, the catalyst is selected from dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, zinc neodecanoate or a combination thereof.

[0100] In the second aspect, the preparation method of the one-component solvent-free epoxy modified polyurethane waterproof coating includes: reacting polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment, filler, and diisocyanate at a first reaction temperature to obtain a first reaction product capped with -NCO; adding modified epoxy resin A and a catalyst to the first reaction product and maintaining the reaction temperature to obtain a second reaction product with -NCO capping at one end and epoxy capping at the other end; adding hydroxy oxazolidine to the second reaction product and reacting at a second reaction temperature to obtain a third reaction product with oxazolidinyl capping at one end and epoxy capping at the other end; adding a latent curing agent and an active diluent to the third reaction product and reacting them at a set temperature to obtain a one-component solvent-free epoxy modified polyurethane waterproof coating.

[0101] The preparation method of the one-component solvent-free epoxy modified polyurethane waterproof coating of the embodiment of the present application comprises the following steps: firstly, a polyether polyol and a diisocyanate are mixed to obtain a polyurethane prepolymer, and then the polyurethane prepolymer is reacted with a modified epoxy resin A and a hydroxyl oxazolidine in a specified ratio to obtain a polyurethane prepolymer having an epoxy end capped at one end and an oxazolidinyl end capped at the other end; after construction, the terminal oxazolidinyl group and the latent curing agent undergo a hydrolysis reaction to release primary amino groups and hydroxyl groups, which react rapidly with the epoxy groups in the coating system, so that the coating forming the coating film has a faster internal and external cross-linking and curing speed, greatly improving the coating construction efficiency, and the coating film has no blistering, thereby solving the problem of slow curing speed of the traditional polyurethane coating through the terminal -NCO and the blistering of the coating film caused by being easily affected by the ambient temperature.

[0102] In some embodiments of the present application, reacting polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment, filler and diisocyanate at a first reaction temperature includes: mixing polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment and filler, stirring and heating to 100°C to 110°C, and dehydrating under vacuum conditions of -0.08MPa to -0.1MPa for 2 hours to 3 hours to obtain a first mixture; cooling the first mixture to 70°C to 80°C, adding diisocyanate while stirring, and heating to 75°C to 85°C, reacting for 2 hours to 3 hours to prepare a -NCO-terminated first reaction product.

[0103] In some embodiments of the present application, a modified epoxy resin A catalyst is added to the first reaction product and the reaction temperature is maintained, including: cooling the temperature of the first reaction product to 70°C to 80°C, adding the modified epoxy resin A and the catalyst to the first reaction product, reacting for 2 hours to 3 hours, and preparing a second reaction product with -NCO end-capping at one end and epoxy end-capping at the other end.

[0104] In some embodiments of the present application, adding hydroxyoxazolidine to the second reaction product includes: maintaining the temperature of the second reaction product at 70°C to 80°C, adding hydroxyoxazolidine to the second reaction product, and reacting for 2 hours to 3 hours to prepare a third reaction product having an oxazolidinyl end capped at one end and an epoxy end capped at the other end.

[0105] In the embodiments of the present application, a polyurethane prepolymer having an -NCO end-capped end is first generated by reacting a polyether diol, a polyether triol and a diisocyanate, and then the -NCO end-capped polyurethane prepolymer is further reacted with an epoxy resin modified with an acrylate epoxyalkyl ester monomer (i.e., modified epoxy resin A) and hydroxyoxazolidine to generate a polyurethane prepolymer having one end capped by the modified epoxy resin A and the other end capped by an oxazolidinyl group.

[0106] In some embodiments, adding a latent curing agent and a reactive diluent to the third reaction product comprises: cooling the third reaction product to ≤50°C, adding a latent curing agent and a reactive diluent, and reacting for 0.5 to 1 hour to obtain a one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0107] In the embodiments of the present application, the oxazolidinyl group and latent curing agent of the polyurethane prepolymer undergo hydrolysis reaction in a humid environment to release primary amino groups and hydroxyl groups, which react rapidly with the epoxy groups in the coating system, thereby quickly bonding to the moist base surface to form a coating film, thereby improving the construction efficiency of the coating.

[0108] In some embodiments of the present application, the method for preparing the one-component solvent-free epoxy-modified polyurethane waterproof coating further includes: nitrogen filling protection on the one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0109] In a third aspect, an embodiment of the present application provides a waterproof product, comprising a substrate and a waterproof coating covering at least one surface of the substrate, wherein the waterproof coating is formed by the above-mentioned one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0110] In some embodiments of the present application, the waterproof product is a waterproof roll material, the corresponding substrate is PET or polyester, and the waterproof coating covers at least one side of the two side surfaces in the thickness direction of the substrate to form a single-layer or double-layer or multi-layer waterproof coating.

[0111] Test Section

[0112] The following are the models and / or available sources of some raw material components used in the examples or comparative examples: Bisphenol A epoxy resin, model: Bisphenol A epoxy resin E44, purchased from Baling Petrochemical. DL-2000D (functionality is 2, number average molecular weight is 2000); EP330N (functionality is 3, number average molecular weight is 5000), both purchased from Shandong Bluestar Dongda Co., Ltd. Dispersant, model DisuperS18, purchased from Core Chemical. Defoamer, model: BYK-141, purchased from BYK Chemical. Hydroxyoxazolidine, 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, purchased from Zibo Changrong New Materials Technology Co., Ltd. Epoxidized soybean oil plasticizer, model: Plasticizer ESO, purchased from Jinan Youshengyuan Chemical Co., Ltd. Allyl alcohol glycidyl ether, purchased from Shandong Yuanjin New Materials Co., Ltd. Aldimine type latent curing agent, model: XY-401, was purchased from Suzhou Xiangyuan New Materials Co., Ltd. Other raw material components not mentioned can be obtained through commercial channels.

[0113] Preparation of modified epoxy resin A

[0114] Preparation Example 1

[0115] The modified epoxy resin A1 is prepared by the following steps:

[0116] S1, putting a calculated amount of dried bisphenol A epoxy resin E44 into a reactor, adding a mixed solvent of n-butanol and ethylene glycol butyl ether into the reactor, stirring until the bisphenol A epoxy resin is completely dissolved, to obtain a first dispersion, and keeping the temperature of the first dispersion at 50° C.;

[0117] S2, add the calculated amount of glycidyl methacrylate and benzoyl peroxide to the first dispersion in the reactor, control the dripping reaction speed of glycidyl methacrylate, continue to heat and stir the reaction, control the temperature to 90°C to 95°C, react at a constant temperature for 6 hours, then evacuate, and distill under reduced pressure for 1 hour to obtain a modified epoxy resin A1, which includes terminal epoxy groups and epoxyalkyl methacrylate monomer derived segments, and its epoxy equivalent is 183g / mol. Wherein, the bisphenol A type epoxy resin is bisphenol A type epoxy resin E44, the molar ratio of bisphenol A type epoxy resin E44 to glycidyl methacrylate is 1:2, the amount of the mixed solvent of n-butanol and ethylene glycol butyl ether is 15wt.% of the total mass of the reactants of the reaction, and the amount of benzoyl peroxide is 0.3wt.% of the total mass of the reactants of the reaction.

[0118] Preparation Example 2

[0119] The preparation steps of the modified epoxy resin A2 are different from those of Preparation Example 1 in that the molar ratio of bisphenol A epoxy resin E44 to glycidyl methacrylate is 1:1.6, and the epoxy equivalent of the modified epoxy resin A2 is 188 g / mol.

[0120] Preparation Example 3

[0121] The preparation steps of the modified epoxy resin A3 are different from those of Preparation Example 1 in that the molar ratio of bisphenol A epoxy resin E44 to glycidyl methacrylate is 1:2.7, and the epoxy equivalent of the modified epoxy resin A2 is 177 g / mol.

[0122] Preparation Example 4

[0123] The preparation steps of the modified epoxy resin A4 are different from those of Preparation Example 1 in that the molar ratio of bisphenol A epoxy resin E44 to 3,4-epoxycyclohexylmethyl methacrylate is 1:1.8, and the epoxy equivalent of the modified epoxy resin A4 is 211 g / mol.

[0124] Example 1

[0125] A one-component solvent-free epoxy modified polyurethane waterproof coating comprises, by weight: 100 parts by weight of polyether diol DL-2000D; 68 parts by weight of polyether triol EP330N; 110 parts by weight of epoxy soybean oil plasticizer; 208 parts by weight of pigments and fillers, including 80 parts by weight of talc and 128 parts by weight of heavy calcium powder; 16 parts by weight of toluene diisocyanate; 9 parts by weight of modified epoxy resin A1; 8 parts by weight of 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine; 87 parts by weight of allyl alcohol glycidyl ether, an active diluent; 1.8 parts by weight of a defoamer; 0.3 parts by weight of a dispersant; 18 parts by weight of an aldimine type latent curing agent; and 0.5 parts by weight of a catalyst, stannous octoate.

[0126] A method for preparing a one-component solvent-free epoxy-modified polyurethane waterproof coating comprises:

[0127] S1. Mix polyether diol DL-2000D, polyether triol EP330N, epoxy vegetable oil plasticizer, defoamer, dispersant, and pigment filler, stir and heat to 105° C., and dehydrate under -0.09 MPa vacuum condition for 3 hours to obtain a first mixture; cool the first mixture to 75° C., add toluene diisocyanate under stirring, then heat to 85° C., react for 3 hours to prepare a -NCO terminated first reaction product;

[0128] S2, cooling the temperature of the first reaction product to 80° C., adding modified epoxy resin A1 and a catalyst to the first reaction product and maintaining the reaction temperature, reacting for 2 hours to prepare a second reaction product having a -NCO end capping at one end and an epoxy end capping at the other end;

[0129] S3, maintaining the temperature of the second reaction product at 80° C., adding hydroxy oxazolidine to the second reaction product, reacting at a temperature of 70° C. to 80° C., reacting for 2 hours, to obtain a third reaction product having one end capped with an oxazolidine group and the other end capped with an epoxy group;

[0130] S4. Cool the third reaction product to 45°C, add a latent curing agent and a reactive diluent to the third reaction product, react at 40°C to 45°C, react for 0.5 hours, then fill with nitrogen and discharge the product to obtain a one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0131] Example 2

[0132] A one-component solvent-free epoxy-modified polyurethane waterproof coating comprises, by weight: 100 parts by weight of polyether diol DL-2000D; 68 parts by weight of polyether triol EP330N; 85 parts by weight of epoxy soybean oil plasticizer; 208 parts by weight of pigments and fillers, including 80 parts by weight of talc and 128 parts by weight of heavy calcium powder; 16 parts by weight of toluene diisocyanate; 9 parts by weight of modified epoxy resin A1; 8 parts by weight of 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine; 87 parts by weight of active diluent, allyl alcohol glycidyl ether; 1.8 parts by weight of defoamer; 0.3 parts by weight of dispersant; 18 parts by weight of aldimine type latent curing agent; and 0.5 parts by weight of catalyst, stannous octoate. The preparation method of the one-component solvent-free epoxy-modified polyurethane waterproof coating of this embodiment is the same as that of embodiment 1.

[0133] Example 3

[0134] A one-component solvent-free epoxy-modified polyurethane waterproof coating comprises, by weight: 100 parts by weight of polyether diol DL-2000D; 68 parts by weight of polyether triol EP330N; 110 parts by weight of epoxy soybean oil plasticizer; 208 parts by weight of pigments and fillers, including 80 parts by weight of silicon micropowder and 128 parts by weight of heavy calcium powder; 20 parts by weight of toluene diisocyanate; 9 parts by weight of modified epoxy resin A1; 8 parts by weight of 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine; 87 parts by weight of active diluent, allyl alcohol glycidyl ether; 1.8 parts by weight of defoamer; 0.3 parts by weight of dispersant; 18 parts by weight of aldimine type latent curing agent; and 0.5 parts by weight of catalyst, stannous octoate. The preparation method of the one-component solvent-free epoxy-modified polyurethane waterproof coating of this embodiment is the same as that of embodiment 1.

[0135] Example 4

[0136] A one-component solvent-free epoxy-modified polyurethane waterproof coating comprises, by weight: 100 parts by weight of polyether diol DL-2000D; 68 parts by weight of polyether triol EP330N; 110 parts by weight of epoxy soybean oil plasticizer; 208 parts by weight of pigments and fillers, including 80 parts by weight of talc and 128 parts by weight of heavy calcium powder; 16 parts by weight of toluene diisocyanate; 9 parts by weight of modified epoxy resin A1; 2 parts by weight of 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine; 87 parts by weight of active diluent, allyl alcohol glycidyl ether; 1.8 parts by weight of defoamer; 0.3 parts by weight of dispersant; 18 parts by weight of aldimine type latent curing agent; and 0.5 parts by weight of catalyst, stannous octoate. The preparation method of the one-component solvent-free epoxy-modified polyurethane waterproof coating of this embodiment is the same as that of embodiment 1.

[0137] Example 5

[0138] A one-component solvent-free epoxy modified polyurethane waterproof coating comprises, by weight: 100 parts by weight of polyether diol DL-2000D; 68 parts by weight of polyether triol EP330N; 110 parts by weight of epoxy soybean oil plasticizer; 208 parts by weight of pigments and fillers, including 80 parts by weight of talc and 128 parts by weight of heavy calcium powder; 16 parts by weight of toluene diisocyanate; 12 parts by weight of modified epoxy resin A1; 8 parts by weight of 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine; 87 parts by weight of active diluent, allyl alcohol glycidyl ether; 1.8 parts by weight of defoamer; 0.3 parts by weight of dispersant; 18 parts by weight of aldimine type latent curing agent; and 0.5 parts by weight of catalyst, stannous octoate. The preparation method of the one-component solvent-free epoxy modified polyurethane waterproof coating of this embodiment is the same as that of embodiment 1.

[0139] Example 6

[0140] A one-component solvent-free epoxy modified polyurethane waterproof coating comprises, by weight: polyether diol DL-2000D, 100 weight parts; polyether triol EP330N, 68 weight parts; epoxy soybean oil plasticizer, 110 weight parts; pigments and fillers, 208 weight parts, including 80 weight parts of talc and 128 weight parts of heavy calcium powder; toluene diisocyanate, 16 weight parts; modified epoxy resin A1, 15 weight parts; 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, 8 weight parts; active diluent, allyl alcohol glycidyl ether, 87 weight parts; defoamer, 1.8 weight parts; dispersant, 0.3 weight parts; aldimine type latent curing agent, 18 weight parts; catalyst, stannous octoate, 0.5 weight parts. The preparation method of the one-component solvent-free epoxy modified polyurethane waterproof coating of this embodiment is the same as that of embodiment 1.

[0141] Example 7

[0142] The one-component solvent-free epoxy-modified polyurethane waterproof coating of this embodiment is different from that of Embodiment 1 in that the modified epoxy resin A is A2.

[0143] Example 8

[0144] The one-component solvent-free epoxy-modified polyurethane waterproof coating of this embodiment is different from that of Embodiment 1 in that the modified epoxy resin A is A3.

[0145] Example 9

[0146] The one-component solvent-free epoxy-modified polyurethane waterproof coating of this embodiment is different from that of Embodiment 1 in that the modified epoxy resin A is A4.

[0147] Comparative Example 1

[0148] A one-component solvent-free epoxy-modified polyurethane waterproof coating is different from Example 1 in that the epoxy soybean oil plasticizer in the raw material components is replaced by an equal weight portion of chlorinated paraffin.

[0149] Comparative Example 2

[0150] A one-component solvent-free epoxy-modified polyurethane waterproof coating, which differs from Example 1 in that the raw material components do not contain modified epoxy resin A1.

[0151] Comparative Example 3

[0152] A one-component solvent-free epoxy-modified polyurethane waterproof coating is different from Example 1 in that the raw material components do not contain 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine.

[0153] Comparative Example 4

[0154] A one-component solvent-free epoxy-modified polyurethane waterproof coating is different from Example 1 in that the raw material components do not contain modified epoxy resin A1 and 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine.

[0155] Performance Testing

[0156] The one-component solvent-free epoxy-modified polyurethane waterproof coatings prepared in Examples 1-9 and Comparative Examples 1-4 were subjected to the following performance tests:

[0157] (1) Coating film performance

[0158] The coating film performance is tested in accordance with JC / T2435-2018 and GB / T19250-2013, and the thick coating blistering test is tested in accordance with Section 7.14 of JC / T2435-2018;

[0159] (2) Water-immersion bonding performance of coatings

[0160] The test method for the strength retention rate of water-immersion bonding is as follows: prepare the test piece according to the method specified in GB / T 16777-20087.1 (Method A), and test the initial bonding strength of the test piece under standard test conditions (23±2℃, relative humidity 50±10%) for 7 days. Soak the test piece completely in water, take it out at a predetermined time, and test the bonding strength after placing it under standard test conditions for 12 hours; calculate the strength retention rate according to the following formula:

[0161] Strength retention rate = (bonding strength / initial bonding strength)*100%.

[0162] The performance test results of the above projects are shown in Table 1 below:

[0163]

[0164] By comparing the raw material component ratios of the one-component solvent-free epoxy-modified polyurethane waterproof coatings of Examples 1-9 and Comparative Examples 1-4 and the performance test data of Table 1, it can be concluded that:

[0165] The one-component solvent-free epoxy modified polyurethane waterproof coatings of Examples 1-4 have no bubbles under three different temperature and humidity conditions, and the coatings are all cohesively damaged after being immersed in water for 7, 15, and 30 days, and the bonding strength retention rate reaches 80% to 94%, indicating that the one-component solvent-free epoxy modified polyurethane thick waterproof coatings of Examples 1-4 have excellent thick coating blistering and water-immersion bonding properties, which are significantly better than the one-component solvent-free epoxy modified polyurethane waterproof coatings of Comparative Examples 1-4. The bonding properties, thick coating blistering properties, and water-immersion bonding properties of the one-component solvent-free epoxy modified polyurethane waterproof coating of Example 1 are significantly different from the bonding properties, thick coating blistering properties, and water-immersion bonding properties of the one-component solvent-free epoxy modified polyurethane waterproof coatings of Comparative Examples 2-4.

[0166] The single-component solvent-free epoxy modified polyurethane waterproof coating of Comparative Example 4 has the lowest bonding strength, and a small amount of bubbles are generated after coating at 40°C and 60% relative humidity, and the bonding strength retention rate after soaking in water for 7 days is the most serious compared with the bonding strength retention rate after soaking in water for 7 days of Comparative Examples 1-3, which indicates that the lack of the joint use of modified epoxy resin A and 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine has a significant impact on the bonding performance, thick coating blistering performance and soaking bonding performance of the coating. Comparative Example 1 uses ordinary plasticizers to reduce the bonding performance and soaking bonding performance of the coating to a certain extent, and the curing and drying time is long, which indicates that the free plasticizer can significantly affect the bonding performance and drying time of the coating, but has no significant effect on the thick coating blistering performance. The coating of Comparative Example 2 lacks modified epoxy resin Al, which also leads to an increase in the curing time of the coating, reduces the bonding performance and thick coating blistering of the coating, and significantly reduces the soaking bonding performance of the coating. The curing time of the coating in Comparative Example 3 lacking 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine is increased, and the bonding strength, water-immersion bonding performance and thick coating blistering of the coating are reduced.

[0167] The test results of Example 1, Example 5 and Example 6 show that with the increase in the amount of modified epoxy resin A1 in the coating, the curing and drying time of the one-component solvent-free epoxy modified polyurethane waterproof coating is significantly shortened; the tensile strength and bonding properties are improved, and no blistering occurs at three temperatures and humidities, respectively, indicating that the thick coating blistering properties of the coatings of Examples 1, 5 and 6 are good; the water-immersion adhesion is good, and the bonding strength retention rate is still as high as 83% or more after immersion in water for 30 days, but the elongation at break of the coating film is reduced. Overall, the performance of the one-component solvent-free epoxy modified polyurethane waterproof coating is improved overall.

[0168] The test results of Example 1 and Example 9 show that the coating contains 3,4-epoxycyclohexylmethyl methacrylate, and the coating can also shorten the curing time, improve the bonding strength and the retention rate of the bonding strength after soaking in water, and improve the thickness blistering performance. And as the epoxy group in the coating increases, the epoxy equivalent of the modified epoxy resin A decreases, the curing time of the coating is further shortened, and the bonding performance and the retention rate of the bonding strength after soaking in water are also improved.

[0169] The test results of Examples 1, 7 and 8 show that as the amount of glycidyl methacrylate increases, the epoxyalkyl acrylate monomer-derived chain segments in the modified epoxy resin A also increase, but the epoxy equivalent of the modified epoxy resin A decreases, which shortens the curing time of the coating and increases the adhesion performance and water-immersion bonding strength retention rate.

[0170] The VOC content of the coatings prepared in Examples 1-9 is 3 g / L to 5 g / L, which is significantly lower than the VOC content of 6 g / L to 12 g / L of the coatings prepared in Comparative Examples 1-4, indicating that the one-component solvent-free epoxy modified polyurethane coating of the embodiments of the present application can effectively reduce the VOC content of the coating.

[0171] The above is only a specific implementation method of the present application. Those skilled in the art can clearly understand that for the convenience and simplicity of description, the specific working process described above can refer to the corresponding process in the aforementioned method embodiment, and will not be repeated here. It should be understood that the protection scope of the present application is not limited to this. Any technician familiar with the technical field can easily think of various equivalent modifications or replacements within the technical scope disclosed in the present application, and these modifications or replacements should be included in the protection scope of the present application.

Claims

1. A one-component solvent-free epoxy-modified polyurethane waterproof coating, characterized in that: The invention comprises the following raw material components in parts by weight: Polyether diol, 100 parts by weight; Polyether triol, 30-80 parts by weight; Epoxy vegetable oil plasticizer, 80-120 parts by weight; Diisocyanate, 14 to 20 parts by weight; Modified epoxy resin A, 9 to 17 parts by weight; the modified epoxy resin A comprises terminal epoxy groups and epoxyalkyl acrylate monomer derived segments; 2 to 11 parts by weight of hydroxyoxazolidine, wherein the hydroxyoxazolidine is an oxazolidine compound containing one active hydroxyl group; Reactive diluent, 70-100 parts by weight; Latent curing agent, 12 to 41 parts by weight; Pigments and fillers, 200-350 parts by weight; Defoaming agent, 1 to 3 parts by weight; Dispersant, 0.1-0.5 parts by weight; Catalyst, 0.4 to 1.8 parts by weight.

2. The one-component solvent-free epoxy-modified polyurethane waterproof coating according to claim 1, characterized in that: Meet at least one of the following requirements: The polyether diol is selected from DL-2000D or DL-1000D or a combination thereof; The polyether triol is selected from EP330N or MN1000 or a combination thereof; The epoxidized vegetable oil plasticizer is selected from epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized rice bran oil, epoxidized sunflower oil or a combination thereof; The filler is selected from nano calcium carbonate, talc, heavy calcium, kaolin, silica powder or a combination thereof; The pigment is selected from carbon black, titanium dioxide, iron oxide red powder or a combination thereof; The diisocyanate is selected from aromatic diisocyanate, aliphatic diisocyanate or a combination thereof; The epoxy equivalent of the modified epoxy resin A is 170 g / mol to 200 g / mol; The hydroxyoxazolidine includes the structure shown below: In formula (3), R is selected from H, C1-C5 alkyl, phenyl, and n is an integer of 1-3; The active diluent is selected from the group consisting of propenyl glycidyl ether, phenyl glycidyl ether, ethylene glycol bisglycidyl ether, resorcinol bisglycidyl ether, butyl glycidyl ether, polypropylene glycol glycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol glycidyl ether, tert-butyl carbonate glycidyl ether or a combination thereof; The defoamer is selected from silicone defoamer or polyether defoamer or a combination thereof; The dispersant is an anionic dispersant; The latent curing agent is selected from aldimine, ketimine compound or a combination thereof; The catalyst is selected from dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, zinc neodecanoate or a combination thereof.

3. The one-component solvent-free epoxy-modified polyurethane waterproof coating according to claim 2, characterized in that: The diisocyanate is selected from toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate or a combination thereof; The hydroxyoxazolidine is selected from 3-hydroxyethyl-1,3-oxazolidine, 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, 2-phenyl-3-hydroxyethyl-1,3-oxazolidine or a combination thereof; The defoamer is selected from TEGO Antifoam 2290, BYK-051, BYK-052, BYK-065, BYK-141 or a combination thereof; The anionic dispersant is selected from sodium oleate, sulfate ester salt, sulfonate salt or a combination thereof; The latent curing agent is selected from XY-3767, XY-401, ALT-403 or a combination thereof.

4. The one-component solvent-free epoxy-modified polyurethane waterproof coating according to any one of claims 1 to 3, characterized in that: Meet at least one of the following requirements: The modified epoxy resin A comprises a structure shown in the following formula (1): In formula (1), n ​​is an integer of 1 to 25, and R1 is a group having the following structural formula:

5. The one-component solvent-free epoxy-modified polyurethane waterproof coating according to claim 4, characterized in that: The modified epoxy resin A is prepared by the following preparation method: Dispersing bisphenol A epoxy resin using a first solvent to obtain a first dispersion; Adding epoxy alkyl acrylate monomer and initiator to the first dispersion to react, to obtain modified epoxy resin A; wherein the reaction structure of the bisphenol A type epoxy resin and epoxy alkyl acrylate monomer is as follows: In the reaction structure (4), n is an integer of 1 to 25, R2 is a C3 or C7 alkylene oxide, R3 is H or a methyl group, and R1 is a group including the following structure:

6. The one-component solvent-free epoxy-modified polyurethane waterproof coating according to claim 5, characterized in that: At least one of the following requirements must be met: The epoxyalkyl acrylate monomer is selected from 2,3-epoxypropyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl methacrylate or a combination thereof; The molar ratio of the bisphenol A epoxy resin to the epoxy alkyl acrylate monomer is 1:(1-3); The initiator is selected from dibenzoyl peroxide, tert-butyl perbenzoate, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl ester, 1,1-bis(tert-amylperoxy)cyclohexane or a combination thereof.

7. A method for preparing a one-component solvent-free epoxy-modified polyurethane waterproof coating according to any one of claims 1 to 6, characterized in that: include: Reacting polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment, filler, and diisocyanate at a first reaction temperature to obtain a -NCO-terminated first reaction product; Adding modified epoxy resin A and a catalyst to the first reaction product and maintaining the reaction temperature to obtain a second reaction product having one end capped with -NCO and the other end capped with epoxy; Add hydroxy oxazolidine to the second reaction product and react at a second reaction temperature to obtain a third reaction product having one end capped with an oxazolidine group and the other end capped with an epoxy group; A latent curing agent and a reactive diluent are added to the third reaction product to react at a set temperature to obtain a one-component solvent-free epoxy-modified polyurethane waterproof coating.

8. The preparation method according to claim 7, characterized in that: The step of reacting polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment, filler and diisocyanate at the first reaction temperature comprises: The polyether diol, polyether triol, epoxy vegetable oil plasticizer, defoamer, dispersant, pigment and filler are mixed, heated to 100° C. to 110° C. with stirring, and dehydrated under a vacuum condition of -0.08 MPa to -0.1 MPa to obtain a first mixture; The first mixture is cooled to 70° C. to 80° C., diisocyanate is added under stirring, and the temperature is raised to 75° C. to 85° C. to react, thereby preparing a first reaction product terminated with -NCO.

9. The preparation method according to claim 7, characterized in that: At least one of the following requirements must be met: The step of adding a modified epoxy resin A catalyst to the first reaction product and maintaining the reaction temperature comprises: The temperature of the first reaction product is lowered to 70° C. to 80° C., and a modified epoxy resin A and a catalyst are added to the first reaction product to react, so as to prepare a second reaction product having a -NCO end capping at one end and an epoxy end capping at the other end; The adding of hydroxyoxazolidine to the second reaction product comprises: The temperature of the second reaction product is maintained at 70° C. to 80° C., and hydroxyoxazolidine is added to the second reaction product to react, so as to prepare a third reaction product having an oxazolidine end-capped end and an epoxy end-capped end; The step of adding a latent curing agent and a reactive diluent to the third reaction product comprises: The third reaction product is cooled to ≤50°C, and a latent curing agent and a reactive diluent are added to react for 0.5 to 1 hour to obtain a one-component solvent-free epoxy modified polyurethane waterproof coating; The method also includes: nitrogen filling protection on the one-component solvent-free epoxy modified polyurethane waterproof coating.

10. A waterproof product, characterized in that: It comprises a substrate and a waterproof coating coated on at least one surface of the substrate, wherein the waterproof coating is formed by the one-component solvent-free epoxy-modified polyurethane waterproof coating according to any one of claims 1-6.

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