One-component solvent-free epoxy-modified polyurethane waterproof coating, its preparation method and waterproof product

Abstract

The present application discloses a one-component solvent-free epoxy-modified polyurethane waterproof coating, its preparation method and a waterproof product. The coating 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; pigments and fillers, 200 - 350 parts by weight; diisocyanate, 14 - 20 parts by weight; modified epoxy resin A, including a terminal epoxy group and an epoxyalkyl acrylate monomer-derived chain segment, 9 - 17 parts by weight; hydroxyoxazoline, 2 - 11 parts by weight, and the hydroxyoxazoline is an oxazoline compound containing one active hydroxyl group; active diluent, 70 - 100 parts by weight; defoamer, 1 - 3 parts by weight; dispersant, 0.1 - 0.5 parts by weight; latent curing agent, 12 - 41 parts by weight; catalyst, 0.4 - 1.8 parts by weight. The above coating can effectively improve the problem of poor adhesion strength retention rate of traditional polyurethane waterproof coatings after being soaked in water, and the product has excellent performance.

Description

Technical Field

[0001] This application belongs to the technical field of polyurethane coatings, and particularly relates to a one-component solvent-free epoxy-modified polyurethane waterproof coating, its preparation method and waterproof product. Background Art

[0002] Polyurethane waterproof coating is one of the important application directions of polyurethane synthetic materials. Since the polyurethane coating film has elasticity, good extensibility, good adhesiveness, small volume shrinkage, no joints in the coating film waterproof layer, strong adaptability to the expansion and contraction deformation of the base layer cracks, and is convenient for construction and maintenance. It is easy to construct on the surface of any complex base structure and other characteristics, and can be used for waterproof plugging of different parts of buildings, so it has become one of the main materials for building waterproofing.

[0003] When constructing one-component polyurethane waterproof coating, there is no metering error, the quality requirements for construction workers are not high, the viscosity is low, the construction is easy, and at the same time, it has a long trial period, stable performance, convenient use and wide application range. Therefore, one-component polyurethane waterproof coating is increasingly affirmed by users and the usage amount is increasing. One-component polyurethane waterproof coating has become the development direction of polyurethane waterproof coating. 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 by 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 their subsequent volatilization inevitably cause the emission of VOC and environmental pollution, and are not conducive to 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 performance of the coating, and during the later use process, with the migration of plasticizers and the volatilization of solvents, it will cause the coating film to shrink, deform and harden, and it is easy to appear phenomena such as bulging, peeling and peeling under long-term immersion in water, resulting in water seepage through the coating film and even the failure of the waterproof layer. And the coating is easily affected by the environmental temperature and humidity and is difficult to construct at low temperatures. With the continuous improvement of national environmental protection requirements, the control of VOC content is becoming more and more strict, and polyurethane waterproof coatings will also gradually develop towards high performance and high environmental protection in the future. Therefore, preparing 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 at present. Summary of the Invention

[0004] The embodiment of this 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 of the coating has excellent adhesion performance, is resistant to water immersion, has no bulging, and has good construction performance.

[0005] In a first aspect, the present application provides a one-component solvent-free epoxy-modified polyurethane waterproof coating, comprising 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 - 20 parts by weight; modified epoxy resin A, 9 - 17 parts by weight; the modified epoxy resin A includes terminal epoxy groups and an epoxy alkyl acrylate monomer-derived chain segment; hydroxyoxazolidine, 2 - 11 parts by weight; the hydroxyoxazolidine is an oxazolidine compound containing one active hydroxyl group; active diluent, 70 - 100 parts by weight; latent curing agent, 12 - 41 parts by weight; pigments and fillers, 200 - 350 parts by weight; defoaming agent, 1 - 3 parts by weight; dispersant, 0.1 - 0.5 parts by weight; catalyst, 0.4 - 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 epoxy vegetable oil plasticizer is selected from epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, epoxy 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, talcum powder, 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 red powder or a combination thereof.

[0011] According to an embodiment of the first aspect of the present application, the active diluent is selected from allyl 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-carbonic acid glycidyl ester or a combination thereof.

[0012] According to an embodiment of the first aspect of the present application, the diisocyanate is selected from aromatic diisocyanates, aliphatic diisocyanates 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, tetramethylxylylene 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 includes the structure shown in the following formula (1):

[0016]

[0017] In formula (1), n is an integer from 1 to 25, and R 1 is a group including the following structural formula:

[0018]

[0019] In formula (2), X is an integer from 1 to 3, and R 2 is an epoxyalkyl group of C3 or C7, R 3 is H or methyl, R 4 is H, represents the position where R 1 is connected to the molecular chain backbone of the modified epoxy resin A.

[0020] According to an embodiment of the first aspect of the present application, the hydroxyoxazoline includes the following structure:

[0021]

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

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

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

[0025] According to an embodiment of the first aspect of the present application, the defoamer 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 aldehyde imines, ketimine compounds, or combinations thereof.

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

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

[0031] 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.

[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 capped with -NCO at one end and an epoxy group at the other end.

[0033] Adding hydroxyoxazolidine to the second reaction product and reacting at a second reaction temperature to obtain a third reaction product capped with an oxazolidinyl group at one end and an epoxy group at the other end.

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

[0035] A third aspect of the present application provides a waterproof article, including a substrate and a waterproof coating coated on at least one surface of the substrate, and the waterproof coating is formed from 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 according to the embodiments of the present application, by limiting the raw material components in a specific ratio, form a polyurethane prepolymer capped with modified epoxy resin A at one end and an oxazolidinyl group at the other end. It can improve the adhesion performance of the coating through the terminal epoxy groups in the polyurethane prepolymer chain segments and the epoxyalkyl acrylate monomer-derived chain segments, enabling the coating to maintain good adhesion strength after soaking in water, while increasing the curing speed of the coating product to improve the construction efficiency. In addition, the present application uses an epoxy vegetable oil plasticizer and an active diluent that can participate in the curing reaction of the coating system. They fully participate in the cross-linking reaction during the coating curing process and do not exude or volatilize after curing, reducing environmental pollution. Detailed Embodiments

[0037] The features and exemplary embodiments of various aspects of the present application will be described in detail below. In order to make the objectives, technical solutions, and advantages of the present application clearer and more understandable, 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 limiting the present application. For those skilled in the art, the present application can be implemented without some of these specific details. The following description of the embodiments is only to provide a better understanding of the present application by showing examples of the present application.

[0038] It should be noted that, in this document, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "comprising..." does not exclude the presence of additional identical elements in the process, method, article or device comprising the element.

[0039] To solve the problems of the prior art, the embodiments of the present application provide a one-component solvent-free epoxy-modified polyurethane waterproof coating, its preparation method, and a waterproof product. First, the one-component solvent-free epoxy-modified polyurethane waterproof coating provided by the embodiments of the present application will be introduced below.

[0040] The embodiments of the present application provide a one-component solvent-free epoxy-modified polyurethane waterproof coating, which comprises 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, and the modified epoxy resin A comprises a terminal epoxy group and an epoxyalkyl acrylate monomer-derived chain segment; hydroxyoxazoline, 2 to 11 parts by weight, and the hydroxyoxazoline is an oxazoline 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; defoaming agent, 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 prepared from a polyurethane prepolymer made from a polyether polyol and a diisocyanate. Through the reaction of the polyurethane prepolymer with modified epoxy resin A and hydroxyoxazolidine in a defined ratio combination, a polyurethane prepolymer with one end capped by modified epoxy resin A (i.e., one end capped by the terminal epoxy group of modified epoxy resin A) and the other end capped by an oxazolidine group is prepared, which improves the adhesion performance of the coating product and increases the curing speed of the coating to improve the construction efficiency. After the coating is applied, the terminal oxazolidine 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, making the coating crosslink and cure from the inside to the outside surface to form a coating faster, greatly improving the construction efficiency of the coating. The coating film formed by the coating has no bubbles, solving the problem of slow curing speed of traditional polyurethane coatings through terminal -NCO and the problem of coating film blistering caused by being extremely susceptible to 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 characteristic that the multiple epoxy groups contained in the modified epoxy resin A itself have a high adhesion strength to the substrate, further improving the adhesion and water immersion resistance of the coating film formed by the coating, so that the coating film can also have a high adhesion strength retention rate after being soaked in water.

[0043] In addition, for the one-component solvent-free epoxy-modified polyurethane waterproof coating of the embodiment of the present application, the functional groups at both ends of the polyurethane prepolymer can achieve self-crosslinking through hydrolysis reaction. At the same time, the epoxy vegetable oil plasticizer and the reactive diluent fully participate in the self-crosslinking curing of the coating system during the curing process. After curing, there is no volatilization and migration of these free components such as organic solvents and plasticizers, which will not cause shrinkage of the coating film, that is, it will not cause interfacial stress and prevent the adhesion performance of the coating film 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 MN1000. Exemplarily, the dosage 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 adopted, 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 form a network structure by connecting the extra hydroxyl groups of the polyether triol on the side chains of the molecular chains, thereby enhancing the overall connection strength and tensile properties of the coating.

[0047] In some embodiments of the present application, the epoxy vegetable oil plasticizer is selected from epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, epoxy sunflower oil or a combination thereof. Exemplarily, the dosage of the epoxy 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 groups contained in the epoxy vegetable oil plasticizer can effectively improve the adhesion performance and adhesion rate of the coating, enabling the coating to quickly adhere to the substrate surface.

[0049] In some embodiments of the present application, the reactive diluent is selected from allyl 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-carbonic acid glycidyl ester or a combination thereof.

[0050] In the embodiments of the present application, the dosage of the reactive diluent can be 72, 75, 80, 83, 86, 90, 94, 95, 96, 98 parts by weight.

[0051] In the embodiments of the present application, the glycidyl ether groups contained in the reactive diluent all contain epoxy groups, and the epoxy groups in the reactive diluent and the epoxy vegetable oil plasticizer participate in the system cross-linking reaction together. Both the epoxy vegetable oil plasticizer and the reactive diluent participate in the curing process of the coating, do not volatilize, and reduce environmental pollution.

[0052] In some embodiments, the diisocyanate is selected from aromatic diisocyanates, aliphatic diisocyanates or a combination thereof. Exemplarily, the diisocyanate can 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, tetramethylxylylene diisocyanate or a combination thereof.

[0054] In the embodiments of the present application, the pigment and the filler can be added to the coating alone or jointly. Exemplarily, the amount of their joint addition 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 powder or a combination thereof. The pigment can endow the coating with a color suitable for the object to be coated.

[0056] In some embodiments, the filler is selected from nano calcium carbonate, talcum powder, heavy calcium carbonate, kaolin, silica powder or a combination thereof. Adding a filler 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 can be 10, 12, 14, 16 parts by weight.

[0058] In some embodiments of the present application, the epoxy equivalent of the modified epoxy resin A is 170 g / mol to 200 g / mol. The modified epoxy resin A of the present application has a suitable epoxy equivalent range. In particular, the modified epoxy resin A within the above epoxy equivalent range not only has high activity, fast crosslinking speed and high crosslinking density, which can improve the peel strength and adhesion 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 172 g / mol, 175 g / mol, 180 g / mol, 184 g / mol, 185 g / mol, 188 g / mol, 190 g / mol, 192 g / mol, 195 g / mol, 197 g / mol, 199 g / mol.

[0059] In addition, the raw material bisphenol A epoxy resin for preparing the modified epoxy resin A contains epoxy groups at both ends, a rigid bisphenyl ring structure in the molecule, and the epoxy groups and hydroxyl groups contained in the epoxy alkyl acrylate monomer-derived chain segment make the modified epoxy resin A have good reactivity. Modifying with bisphenol A epoxy resin as the carbon chain skeleton can further improve the strength and adhesion performance of the coating, such as improving the tensile strength, tear strength and adhesion strength of the coating.

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

[0061]

[0062] In formula (1), n is an integer from 1 to 25, R 1is a group including the following structural formula:

[0063]

[0064] In formula (2), X is an integer from 1 to 3, and R 2 is an epoxyalkyl group of C3 or C7, and R 3 is H or methyl, and R 4 is H, represents the position where R 1 is connected to the molecular chain backbone of modified epoxy resin A.

[0065] In the examples of the present application, modified epoxy resin A is prepared through the following steps: dispersing bisphenol A type epoxy resin with a first solvent to obtain a first dispersion; adding an acrylic epoxyalkyl ester monomer to the first dispersion and reacting to obtain modified epoxy resin A; wherein, the reaction of bisphenol A type epoxy resin and acrylic epoxyalkyl ester monomer is as follows:

[0066]

[0067] In the reaction structural formula (4), n is an integer from 1 to 25, and R 2 is an epoxyalkyl group of C3 or C7, and R 3 is H or methyl; R 1 is a group including the following structural formula:

[0068]

[0069] In formula (2), X is an integer from 1 to 3, and R 2 is an epoxyalkyl group of C3 or C7, and R 3 is H or methyl, and R 4 is H, represents the position where R 1 is connected to the molecular chain backbone of modified epoxy resin A.

[0070] In some examples of the present application, R 1 includes the structure shown in any one of formulas (2-a) to (2-d):

[0071]

[0072]

[0073] In formulas (2-a) to (2-d), X is an integer from 1 to 3, and R 4 are all H, represents the position where R 1 is connected to the molecular chain backbone of modified epoxy resin A.

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

[0075] In the embodiments of the present application, the first solvent may be a mixed solvent of at least two of n-butanol, ethylene glycol monobutyl ether, diethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and N,N-dimethylformamide. Exemplarily, the volume ratio of n-butanol to ethylene glycol monobutyl ether in the first solvent is 1:(1 - 2).

[0076] In some embodiments of the present application, the molar ratio of the bisphenol A epoxy resin to the acrylic epoxyalkyl ester monomer is 1:(1 - 3). Exemplarily, the molar ratio of the bisphenol A epoxy resin to the acrylic epoxyalkyl ester 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 acrylic epoxyalkyl ester monomer is selected from 2,3-epoxypropyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexyl acrylate, or a combination thereof. Among them, 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-epoxycyclohexyl acrylate is:

[0082]

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

[0084]

[0085] In the embodiments of the present application, the modified epoxy resin A prepared by reacting bisphenol A epoxy resin with 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 act together with the epoxy groups contained in the epoxy vegetable oil plasticizer and the active diluent, which can 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 environmental temperature and humidity and are difficult to construct, as well as the problem that the coating film is easily bulged and peeled off when immersed in water. The hydroxyl groups contained in the modified epoxy resin make the modified epoxy resin easily react with the epoxy groups, hydroxyl groups, and isocyanate groups of other components or form hydrogen bonds, so that covalent bonds or hydrogen bond connections are formed between the coating components, improving the strength and tensile properties of the coating film, and further preventing the adhesion performance of the coating from decreasing after being soaked in water.

[0086] In some embodiments, the initiator is selected from benzoyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, 1,1-bis(tert-amylperoxy)cyclohexane, or a combination thereof.

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

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

[0089] S2. Add the calculated amount of glycidyl methacrylate and benzoyl peroxide to the first dispersion liquid in the reactor, control the dropping reaction rate of glycidyl methacrylate, continue to heat up and stir the reaction, control the temperature at 90°C to 95°C, carry out the constant temperature reaction for 6 hours to 7 hours, and then evacuate and carry out vacuum distillation for 0.5 hours to 1 hour to obtain the modified epoxy resin A. Among them, the bisphenol A epoxy resin is bisphenol A epoxy resin E44, the molar ratio of bisphenol A epoxy resin E44 to glycidyl methacrylate is 1:(1 to 3), the dosage of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 10 wt.% to 15 wt.% of the total mass of the reactants in this reaction, and the dosage of benzoyl peroxide is 0.3 wt.% to 0.5 wt.% of the total mass of the reactants in this reaction.

[0090] In some embodiments of the present application, the hydroxyoxazoline is an oxazoline compound containing one active hydroxyl group, and its satisfied molecular formula is:

[0091]

[0092] In formula (3), R is selected from H, an alkyl group having 1 to 5 carbon atoms, or phenyl, and n is an integer from 1 to 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, as a latent curing agent different from aldehyde imine type and ketone imine type, hydroxyoxazolidine can hydrolyze to release a terminal primary amine group, with relatively low activity and no obvious chain extension effect. To a certain extent, it can promote the curing reaction of the coating and improve the elongation performance of the coating film. In the present application, the three functional groups of the hydroxyl group contained in the hydroxyoxazolidine itself, the terminal primary amino group and the hydroxyl group that are easily hydrolyzed and released when the above-mentioned amount of hydroxyoxazolidine encounters water are respectively used as active groups to react with the components in the coating, so that the coating has a suitable crosslinking degree and further improves the tensile performance after the coating is cured.

[0095] In some embodiments, the defoamer is selected from silicone defoamers, polyether defoamers, or a combination thereof.

[0096] In some embodiments of the present application, the defoamer 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 (such as C 17 H 33 COONa), sulfate esters (such as ROSO 3 Na), sulfonates (such as RSO 3 Na), or a combination thereof. Exemplarily, Disuper S18 can be selected as the dispersant.

[0098] In some embodiments, the latent curing agent is selected from aldehyde imines, ketone imine compounds, 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 isooctoate, bismuth isooctoate, zinc neodecanoate, or a combination thereof.

[0100] In a second aspect, a preparation method of a 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 capped with -NCO at one end and epoxy group at the other end; adding hydroxyoxazolidine to the second reaction product and reacting at a second reaction temperature to obtain a third reaction product capped with oxazolidinyl group at one end and epoxy group at the other end; adding a latent curing agent and an active diluent to the third reaction product and reacting at a set temperature to obtain the one-component solvent-free epoxy-modified polyurethane waterproof coating.

[0101] In the preparation method of the one-component solvent-free epoxy-modified polyurethane waterproof coating according to the embodiment of the present application, first, polyether polyol and diisocyanate are mixed to obtain a polyurethane prepolymer, and then the polyurethane prepolymer reacts with modified epoxy resin A and hydroxyoxazolidine in a limited ratio to obtain a polyurethane prepolymer capped with epoxy group at one end and oxazolidinyl group at the other end; after construction, the terminal oxazolidinyl group and the latent curing agent undergo a hydrolysis reaction to release primary amino group and hydroxyl group, which react rapidly with the epoxy group in the coating system, making the crosslinking and curing speed of the coating inside and outside the formed film faster, greatly improving the construction efficiency of the coating, and the film has no bubbles, solving the problems of slow curing speed of traditional polyurethane coatings through terminal -NCO and easy formation of film bubbles caused by being extremely affected by environmental 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, filler, stirring and heating to 100°C - 110°C, and dehydrating for 2 - 3 hours under a vacuum condition of -0.08 MPa - -0.1 MPa to obtain a first mixture; cooling the first mixture to 70°C - 80°C, adding diisocyanate under stirring, and heating to 75°C - 85°C, and reacting for 2 - 3 hours to prepare a first reaction product capped with -NCO.

[0103] In some embodiments of the present application, adding modified epoxy resin A catalyst to the first reaction product and maintaining the reaction temperature includes: cooling the temperature of the first reaction product to 70°C - 80°C, adding modified epoxy resin A and a catalyst to the first reaction product, and reacting for 2 - 3 hours to prepare a second reaction product capped with -NCO at one end and epoxy group 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 to 3 hours to obtain a third reaction product with one end capped with an oxazolidinyl group and the other end capped with an epoxy group.

[0105] In the embodiments of the present application, first, a polyurethane prepolymer capped with -NCO at both ends is formed by reacting a polyether diol, a polyether triol, and a diisocyanate. Then, this -NCO-capped polyurethane prepolymer continues to react with an epoxy resin modified with an acrylic epoxyalkyl ester monomer (i.e., modified epoxy resin A) and hydroxyoxazolidine to form a polyurethane prepolymer capped with modified epoxy resin A at one end and an oxazolidinyl group at the other end.

[0106] In some embodiments, adding a latent curing agent and an active diluent to the third reaction product includes: cooling the third reaction product to ≤50°C, adding the latent curing agent and the active 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 of the polyurethane prepolymer and the latent curing agent are more likely to undergo a 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 a wet substrate surface to form a coating film and improving the construction efficiency of the coating.

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

[0109] In a third aspect, the embodiments of the present application provide a waterproof product, including a substrate and at least one waterproof coating covering one side surface of the substrate, and 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 coil, and the corresponding substrate is PET or a polyester tire. The waterproof coating covers at least one 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 part

[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 of 2, number average molecular weight of 2000); EP330N (functionality of 3, number average molecular weight of 5000), both purchased from Shandong Bluestar Dongda Co., Ltd. Dispersant, model Disuper S18, purchased from Core Chemical. Defoamer, model: BYK-141, purchased from BYK-Chemie. Hydroxyoxazolidine, 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, purchased from Zibo Changrong New Material Technology Co., Ltd. Epoxidized soybean oil plasticizer, model: plasticizer ESO, purchased from Jinan Youshengyuan Chemical Co., Ltd. Allyl glycidyl ether, purchased from Shandong Yuanjin New Materials Co., Ltd. Aldimine-type latent curing agent, model: XY-401, 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] Modified epoxy resin A1 is prepared through the following steps:

[0116] S1. Put the calculated amount of dried bisphenol A epoxy resin E44 into a reactor, add a mixed solvent of n-butanol and ethylene glycol monobutyl ether to the reactor, start stirring until the bisphenol A epoxy resin is completely dissolved to obtain a first dispersion, and keep 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 dropping reaction rate of glycidyl methacrylate, continue to heat and stir the reaction, control the temperature at 90 °C - 95 °C, keep the temperature constant for 6 hours, then evacuate and distill under reduced pressure for 1 hour to obtain modified epoxy resin A1. Modified epoxy resin A1 includes terminal epoxy groups and epoxyalkyl methacrylate monomer-derived segments, and its epoxy equivalent is 183 g / mol. Among them, the bisphenol A epoxy resin is bisphenol A epoxy resin E44, the molar ratio of bisphenol A epoxy resin E44 to glycidyl methacrylate is 1:2, the dosage of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 15 wt.% of the total mass of the reactants in this reaction, and the dosage of benzoyl peroxide is 0.3 wt.% of the total mass of the reactants in this reaction.

[0118] Preparation Example 2

[0119] The preparation steps of 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 modified epoxy resin A2 is 188 g / mol.

[0120] Preparation Example 3

[0121] The preparation steps of 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 modified epoxy resin A2 is 177 g / mol.

[0122] Preparation Example 4

[0123] The preparation steps of 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 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 pigment and filler, including 80 parts by weight of talcum powder 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 glycidyl ether; 1.8 parts by weight of defoaming agent; 0.3 parts by weight of dispersant; 18 parts by weight of aldehyde imine type latent curing agent; 0.5 parts by weight of catalyst, stannous octoate.

[0126] The preparation method of the one-component solvent-free epoxy-modified polyurethane waterproof coating comprises:

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

[0128] S2. Cool the temperature of the first reaction product to 80°C, add modified epoxy resin A1 and a catalyst to the first reaction product and maintain the reaction temperature, and react for 2 hours to obtain a second reaction product with one end capped with -NCO and the other end capped with an epoxy group.

[0129] S3. Maintain the temperature of the second reaction product at 80°C, add hydroxyoxazolidine to the second reaction product and react at a temperature of 70°C - 80°C for 2 hours to obtain a third reaction product with one end capped with an oxazolidinyl 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 an active diluent to the third reaction product and react at 40°C - 45°C for 0.5 hours, and then discharge the material under a nitrogen atmosphere 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, by weight, includes: polyether diol DL-2000D, 100 parts by weight; polyether triol EP330N, 68 parts by weight; epoxy soybean oil plasticizer, 85 parts by weight; pigment and filler, 208 parts by weight, including 80 parts by weight of talc powder and 128 parts by weight of heavy calcium powder; toluene diisocyanate, 16 parts by weight; modified epoxy resin A1, 9 parts by weight; 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, 8 parts by weight; active diluent, allyl alcohol glycidyl ether, 87 parts by weight; defoaming agent, 1.8 parts by weight; dispersant, 0.3 parts by weight; aldehyde imine type latent curing agent, 18 parts by weight; catalyst, stannous octoate, 0.5 parts by weight. The preparation method of the one-component solvent-free epoxy-modified polyurethane waterproof coating in this example is the same as that in Example 1.

[0133] Example 3

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

[0135] Example 4

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

[0137] Example 5

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

[0139] Example 6

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

[0141] Example 7

[0142] The difference between the one - component solvent - free epoxy - modified polyurethane waterproof coating of this example and that of Example 1 is that the modified epoxy resin A is A2.

[0143] Example 8

[0144] The difference between the one - component solvent - free epoxy - modified polyurethane waterproof coating of this example and that of Example 1 is that the modified epoxy resin A is A3.

[0145] Example 9

[0146] The difference between the one - component solvent - free epoxy - modified polyurethane waterproof coating of this example and that of Example 1 is that the modified epoxy resin A is A4.

[0147] Comparative Example 1

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

[0149] Comparative Example 2

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

[0151] Comparative Example 3

[0152] A one - component solvent - free epoxy - modified polyurethane waterproof coating, the difference from Example 1 is 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, the difference from Example 1 is that the raw material components do not contain the modified epoxy resin A1 and 2 - isopropyl - 3 - hydroxyethyl - 1,3 - oxazolidine.

[0155] Performance Test

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

[0157] (1) Coating film performance

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

[0159] (2) Coating water immersion adhesion performance

[0160] The test method for the strength retention rate of water immersion adhesion is as follows: Prepare the test specimens according to the method specified in GB / T 16777-2008 7.1 (Method A). Cure the test specimens for 7 days under standard test conditions (23±2°C, relative humidity 50±10%) and then test the initial adhesion strength of the test specimens. Immerse the test specimens completely in water, take them out at the predetermined time, place them for 12 h under standard test conditions, and then test the adhesion strength. Calculate the strength retention rate according to the following formula:

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

[0162] The performance test results of the above items 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 in Table 1, it can be concluded that:

[0165] For the one-component solvent-free epoxy-modified polyurethane waterproof coatings of Examples 1-4, there are no bubbles under three different temperature and humidity conditions, and the coatings show cohesive failure after 7, 15, and 30 days of immersion in water. The adhesion strength retention rate reaches 80% - 94%, indicating that the one-component solvent-free epoxy-modified polyurethane thick waterproof coatings of Examples 1-4 have excellent thick-film foaming properties and water immersion adhesion performance, and are significantly better than the one-component solvent-free epoxy-modified polyurethane waterproof coatings of Comparative Examples 1-4. There are significant differences in the adhesion performance, thick-film foaming performance, and water immersion adhesion performance between the one-component solvent-free epoxy-modified polyurethane waterproof coating of Example 1 and those of Comparative Examples 2-4.

[0166] The single-component solvent-free epoxy-modified polyurethane waterproof coating of Comparative Example 4 had the lowest bonding strength. After coating at 40°C and 60% relative humidity, a small amount of bubbles appeared immediately. After soaking in water for 7 days, the retention rate of the bonding strength decreased most severely compared to that of Comparative Examples 1-3 after soaking in water for 7 days. This indicates that the lack of the combined use of modified epoxy resin A and 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine significantly affects the bonding performance, thick-film foaming performance, and water-soaked bonding performance of the coating. The use of a common plasticizer in Comparative Example 1 caused a certain degree of decline in the bonding performance and water-soaked bonding performance of the coating, and the curing and drying time was relatively long. This indicates that free plasticizer can significantly affect the bonding performance and drying time of the coating, but has no significant effect on the thick-film foaming performance. The coating in Comparative Example 2 lacked modified epoxy resin A1, which also led to an increase in the curing time of the coating, a decrease in the bonding performance and thick-film foaming property of the coating, and a significant reduction in the water-soaked bonding performance of the coating. The coating in Comparative Example 3 lacked 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, resulting in an increase in the curing time of the coating and a decrease in the bonding strength, water-soaked bonding performance, and thick-film foaming property of the coating.

[0167] The test results of Examples 1, 5, and 6 show that as the dosage of modified epoxy resin A1 in the coating increases, the curing and drying time of the single-component solvent-free epoxy-modified polyurethane waterproof coating is significantly shortened; the tensile strength and bonding performance are both improved, and no bubbles appear under three kinds of temperatures and humidity conditions, indicating that the thick-film foaming property of the coatings in Examples 1, 5, and 6 is good; the water-soaked bonding property is good, and the retention rate of the bonding strength is still as high as over 83% after soaking in water for 30 days. However, the elongation at break of the coating film decreases. Generally speaking, the performance of the single-component solvent-free epoxy-modified polyurethane waterproof coating is overall improved.

[0168] The test results of Examples 1 and 9 show that when the coating contains 3,4-epoxycyclohexylmethyl methacrylate, the coating can also shorten the curing time, improve the bonding strength and the retention rate of the water-soaked bonding strength, and improve the thick-film foaming performance. And as the epoxy groups in the coating increase, 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 water-soaked bonding strength are also improved.

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

[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 present application can effectively reduce the VOC content of the coatings.

[0171] As described above, only the specific embodiments of the present application are provided. Those skilled in the art can clearly understand that for the convenience and brevity of description, the specific working processes described above can refer to the corresponding processes in the foregoing method embodiments and will not be repeated here. It should be understood that the protection scope of the present application is not limited thereto. Any person skilled in the art can easily think of various equivalent modifications or substitutions within the technical scope disclosed in the present application, and these modifications or substitutions should be covered within 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, 0.4-1.8 parts by weight; The one-component solvent-free epoxy-modified polyurethane waterproof coating is prepared according to the following method, including: 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.

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 hydroxy oxazolidine 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: 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.

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 formula (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 structural formula: 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.

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: Adding modified epoxy resin A and 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; Adding the 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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