Epoxy-modified polyurethane waterproof coating, preparation method and waterproof product

Abstract

The present application provides an epoxy-modified polyurethane waterproof coating, a preparation method and a waterproof product. The epoxy-modified polyurethane waterproof coating comprises raw materials: 186 parts by weight of a polyurethane prepolymer; and based on 186 parts by weight of the polyurethane prepolymer: 80 to 150 parts by weight of an epoxy plasticizer; 18 to 34 parts by weight of an epoxy group-terminated modified resin, wherein one epoxy group-terminated modified resin molecule in the epoxy group-terminated modified resin comprises at least one hydroxyl group; 70 to 100 parts by weight of an active diluent; 23 to 75 parts by weight of a latent curing agent; and 201 to 355 parts by weight of an additive. The coating of the present application has a very low VOC content after curing, and can simultaneously improve the adhesion and water immersion resistance of the coating film. The coating film still has an excellent adhesion strength retention rate after long-term soaking in water.

Description

Technical Field

[0001] This application belongs to the technical field of waterproof coatings, and specifically relates to an epoxy-modified polyurethane waterproof coating, a preparation method, and a waterproof product. Background Art

[0002] Polyurethane waterproof coating is one of the important components of the application of polyurethane synthetic materials. Due to the characteristics of the polyurethane coating film having elasticity, good extensibility, good adhesion, small volume shrinkage, no joints in the coating film waterproof layer, strong adaptability to the expansion and contraction deformation of the base layer cracks, convenient construction and maintenance, and easy construction on the surface of any complex base layer, it can be used for waterproofing and plugging of different parts of buildings, so it has become one of the main materials for building waterproofing. One-component polyurethane waterproof coating has small metering error during construction, low requirements for the quality of construction operators, low viscosity, easy construction, long pot life, stable performance, convenient use, and wide application range. Therefore, in recent years, the usage amount of one-component polyurethane waterproof coating has been increasing, and it has been more and more affirmed by users. One-component polyurethane waterproof coating has become the development direction of polyurethane waterproof coating.

[0003] At present, most of the polyurethane waterproof coatings on the market are solvent-based, especially one-component polyurethane waterproof coatings. However, solvent-based one-component polyurethane waterproof coatings have high VOC content, and the bonding strength decreases significantly under long-term immersion in water, and the coating film will have water leakage, resulting in the failure of the waterproof layer. Summary of the Invention

[0004] This application provides an epoxy-modified polyurethane waterproof coating, a preparation method, and a waterproof product, aiming to reduce the VOC content of polyurethane waterproof coating and improve its bonding strength retention rate under immersion in water.

[0005] In the first aspect of this application, an epoxy-modified polyurethane waterproof coating is provided, which includes the following parts by weight of raw materials: polyurethane prepolymer, 186 parts by weight; and based on 186 parts by weight of polyurethane prepolymer: epoxy plasticizer, 80 - 150 parts by weight; epoxy group-terminated modified resin, 18 - 34 parts by weight; one epoxy group-terminated modified resin molecule in the epoxy group-terminated modified resin includes at least one hydroxyl group; active diluent, 70 - 100 parts by weight; latent curing agent, 23 - 75 parts by weight; additive, 200 - 355 parts by weight.

[0006] In a feasible embodiment of the first aspect of this application, at least one epoxy group-terminated modified resin molecule in the epoxy group-terminated modified resin further includes at least one acrylic chain segment, or it can also be an acrylate chain segment.

[0007] In a feasible embodiment of the first aspect of the present application, at least one epoxy group-terminated modified resin molecule in the epoxy group-terminated modified resin includes at least three epoxy group end groups.

[0008] In a feasible embodiment of the first aspect of the present application, the number average molecular weight of the epoxy group-terminated modified resin is 600 to 1800.

[0009] In a feasible embodiment of the first aspect of the present application, the epoxy equivalent of the epoxy group-terminated modified resin is 175 g / mol to 360 g / mol.

[0010] In a feasible embodiment of the first aspect of the present application, the epoxy group-terminated modified resin includes the following

[0011] structure shown in Formula 1:

[0012]

[0013] In Formula 1, n is an integer from 1 to 25, preferably an integer from 1 to 5, and X is an integer from 1 to 3.

[0014] In a feasible embodiment of the first aspect of the present application, the viscosity of the epoxy-modified polyurethane waterproof coating is 10000 mPa·s to 20000 mPa·s.

[0015] In a feasible embodiment of the first aspect of the present application, the epoxy-modified polyurethane waterproof coating satisfies at least one of the following conditions:

[0016] a. The epoxy plasticizer includes one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, and epoxy sunflower oil;

[0017] b. The latent curing agent includes one or more of aldehyde imine curing agents, ketone imine curing agents, and oxazolidine curing agents;

[0018] c. The reactive diluent includes one or more of allyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, butyl glycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, and tert-carbonic acid glycidyl ester; and / or;

[0019] The polyurethane prepolymer is prepared by reacting a polyether diol, a polyether triol, and a polyisocyanate; optionally, it includes 100 parts by weight of the polyether diol; and based on 100 parts by weight of the polyether diol: 30 to 80 parts by weight of the polyether triol; 14 to 20 parts by weight of the polyisocyanate.

[0020] In a feasible embodiment of the first aspect of the present application, the epoxy-modified polyurethane waterproof coating satisfies at least one of the following conditions:

[0021] d. The number-average molecular weight of the polyether diol is 1000 - 3000. Optionally, the polyether diol includes one or a combination of DL-2000D and DL-1000D;

[0022] e. The number-average molecular weight of the polyether triol is 1000 - 6000. Optionally, the polyether triol includes one or a combination of EP330N and MN1000;

[0023] f. The weight ratio of the polyether diol to the polyether triol is 1:(0.55 - 0.75);

[0024] g. The polyisocyanate includes one or a combination of aromatic diisocyanates and aliphatic diisocyanates;

[0025] Optionally, the polyisocyanate includes one or several of toluene diisocyanate, diphenylmethane - 4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate;

[0026] h. The additive includes one or several of pigments and fillers, defoamers, dispersants, and catalysts;

[0027] Optionally, the pigments and fillers include one or more of nano calcium carbonate, talc powder, heavy calcium, kaolin, silica powder, carbon black, titanium dioxide, and iron oxide red powder;

[0028] Optionally, the defoamer includes one or a combination of silicone-based and polyether-based defoamers;

[0029] Optionally, the dispersant includes one or a combination of anionic wetting dispersants and polymeric hyperdispersants;

[0030] Optionally, the catalyst includes one or several of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate, and zinc neodecanoate;

[0031] Optionally, the additive includes: 180 - 350 parts by weight of pigments and fillers; 1 - 3 parts by weight of defoamer; 0.1 - 0.5 parts by weight of dispersant; 0.3 - 1.5 parts by weight of catalyst.

[0032] The second aspect of the present application provides a preparation method of the epoxy-modified polyurethane waterproof coating provided in the first aspect of the present application, including:

[0033] Mix a predetermined weight portion of a polyurethane prepolymer, an epoxy plasticizer, and an additive under first environmental conditions to obtain a first reactant;

[0034] Mix the first reactant and an epoxy group-terminated modified resin under second environmental conditions to obtain a second reactant;

[0035] Mix the second reactant, a latent curing agent, and an active diluent under third environmental conditions to obtain an epoxy-modified polyurethane waterproof coating.

[0036] In a feasible embodiment of the second aspect of the present application, the preparation method satisfies at least one of the following conditions:

[0037] i. In the step of mixing a predetermined weight portion of a polyether diol, a polyether triol, an epoxy plasticizer, a polyisocyanate, and an additive under first environmental conditions to obtain a first reactant, the first environmental conditions include mixing the polyether diol, the polyether triol, the epoxy plasticizer, an antifoaming agent, a dispersant, a pigment filler, stirring and heating to 100°C to 110°C, dehydrating for 2 h to 3 h under a vacuum condition of -0.08 MPa to -0.1 MPa, cooling to 70°C to 80°C, adding a diisocyanate under stirring, and then heating to 75°C to 85°C and reacting for 2 h to 3 h to obtain the first reactant;

[0038] j. In the step of mixing the first reactant and an epoxy group-terminated modified resin under second environmental conditions to obtain a second reactant, the second environmental conditions include cooling the first reactant to 70°C to 80°C, adding the epoxy group-terminated modified resin and a catalyst under stirring, and reacting for 2 h to 3 h to obtain the second reactant;

[0039] k. In the step of mixing the second reactant, a latent curing agent, and an active diluent under third environmental conditions to obtain an epoxy-modified polyurethane waterproof coating, the third environmental conditions include cooling the second reactant to below 50°C, adding the latent curing agent and the active diluent, and reacting for 0.5 h to 1 h; filling with nitrogen for protection and discharging to obtain the epoxy-modified polyurethane waterproof coating;

[0040] l. In the step of mixing the first reactant and an epoxy group-terminated modified resin under second environmental conditions to obtain a second reactant, the epoxy group-terminated modified resin is obtained by a free radical polymerization reaction including bisphenol A epoxy resin and glycidyl methacrylate or 3,4-epoxyhexyl methacrylate.

[0041] The third aspect of the present application provides a waterproof product, including: a waterproof coating and a substrate covering the waterproof coating, and the waterproof coating is formed by the epoxy-modified polyurethane waterproof coating provided in the first aspect of the present application.

[0042] In the coating of the present application, the hydroxyl groups in the epoxy - terminated modified resin react with the polyurethane prepolymer to form an epoxy - terminated polyurethane prepolymer. The epoxy - terminated polyurethane prepolymer, the epoxy - terminated modified resin, the epoxy plasticizer, and the reactive diluent also jointly carry out a cross - linking curing reaction with the amino groups after the hydrolysis of the latent curing agent. There are many cross - linking sites and the curing speed is fast, so that the VOC content of the coating after curing in the present application is very low, which can reduce the shrinkage, deformation, and hardening of the coating film caused by the volatilization of organic solvents in the later stage, improve the adhesion of the coating film, and at the same time reduce the problems of coating film blistering and hollowing under the condition of soaking in water, so that the coating film still has an excellent adhesion strength retention rate after long - term soaking in water. Detailed Embodiments

[0043] In order to make the invention purpose, technical solution, and beneficial technical effects of the present application clearer, the present application will be further described in detail below with reference to the embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application and not for limiting the present application.

[0044] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recorded; and any lower limit can be combined with other lower limits to form a range not explicitly recorded, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recorded. In addition, although not explicitly recorded, each point or single value between the range endpoints is included in this range. Thus, each point or single value can be used as its own lower limit or upper limit and combined with any other point or single value or combined with other lower limits or upper limits to form a range not explicitly recorded.

[0045] In the description herein, when a composition is described as containing, comprising, or including a specific component, or when a process is described as containing, comprising, or including a specific process step, it is contemplated that the composition of the present application also consists essentially of or consists of the said components, and the process of the present application also consists essentially of or consists of the said process steps.

[0046] Unless otherwise clearly stated, the use of the terms "including", "comprising", "containing", "having" should generally be interpreted as open - ended and non - restrictive.

[0047] In the description herein, it should be noted that unless otherwise stated, "above" and "below" include the number itself, and the meaning of "one or more" in "one or more" is two or more.

[0048] The above - mentioned summary of the invention of this application does not intend to describe every disclosed embodiment or every implementation mode in this application. The following description more specifically exemplifies exemplary embodiments. Throughout the application, guidance is provided through a series of embodiments, which can be used in various combinations. In each instance, the enumeration is only as a representative group and should not be construed as exhaustive.

[0049] The inventors found that by adding various organic solvents or by adding a large amount of low - viscosity plasticizers and other means, the viscosity of the coating can be reduced to achieve the effect of convenient construction. However, the addition of a large amount of ordinary plasticizers and organic solvents will reduce the strength performance of the coating, and in the later use process, with the migration and volatilization of the plasticizer and solvent, it will cause the coating film to shrink, deform, and harden, and it is easy to appear phenomena such as bulging, peeling, and stripping under the condition of long - term immersion in water, resulting in the waterproof layer losing its waterproof function due to water seepage in the coating film. Moreover, 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.

[0050] In view of this, through a large number of experimental studies and demonstrations, the inventors provide an epoxy - modified polyurethane waterproof coating, a preparation method, and a waterproof product in this application, aiming to reduce the VOC content of the polyurethane waterproof coating and improve its adhesion strength retention rate under immersion conditions.

[0051] In an embodiment of the first aspect of this application, an epoxy - modified polyurethane waterproof coating is provided, which includes the following parts by weight of raw materials: polyurethane prepolymer, 186 parts by weight; and based on 186 parts by weight of the polyurethane prepolymer: epoxy plasticizer, 80 - 150 parts by weight; epoxy - terminated modified resin, 18 - 34 parts by weight; one epoxy - terminated modified resin molecule in the epoxy - terminated modified resin includes at least one hydroxyl group; active diluent, 70 - 100 parts by weight; latent curing agent, 23 - 75 parts by weight; additive, 201 - 355 parts by weight.

[0052] In the coating of this application, the hydroxyl group in the epoxy - terminated modified resin reacts with the polyurethane prepolymer to form an epoxy - terminated polyurethane prepolymer. The epoxy - terminated polyurethane prepolymer, the epoxy - terminated modified resin, the epoxy plasticizer, and the active diluent also jointly carry out a cross - linking and curing reaction with the amino group after the hydrolysis of the latent curing agent. There are many cross - linking sites and the curing speed is fast, so that the VOC content of the coating of this application is very low after curing, and it can reduce the shrinkage, deformation, and hardening of the coating film caused by the volatilization of organic solvents in the later stage, improve the adhesion of the coating film. At the same time, it can reduce the problems of coating film blistering and hollowing under the condition of soaking in water, so that the coating film still has excellent adhesion strength retention rate after long - term soaking in water.

[0053] The inventors also found that introducing acrylic linkages, or alternatively acrylate linkages, into the epoxy group-terminated modified resin can improve the foaming problem of the coating film formed by the polyurethane coating and further enhance the adhesion strength of the coating film after long-term immersion in water. In some embodiments, at least one epoxy group-terminated modified resin molecule in the epoxy group-terminated modified resin further includes at least one acrylic linkage, or alternatively an acrylate linkage. The large number of polar groups contained in acrylic molecules, such as hydroxyl groups and carboxyl groups, have good affinity with the base surface and can interact with the polar groups on the surface of the base to form intermolecular forces, forming a uniform and dense coating film, enhancing the adhesion and density of the coating film, and preventing the penetration of moisture; moreover, the epoxy resin modified with acrylic acid can make the polymer molecular chains in the cured coating longer, denser, and have stronger intermolecular cohesion, so as to enhance the water resistance, adhesion strength, and toughness of the adhesive layer.

[0054] In some embodiments, at least one epoxy group-terminated modified resin molecule in the epoxy group-terminated modified resin includes at least three epoxy group end groups. The modified resin terminated with multiple epoxy groups can provide multiple crosslinking sites, accelerate the crosslinking and curing speed, and better improve the problem of slow curing speed of the isocyanate group (full English name, NCO) at the end of the polyurethane molecular chain in traditional polyurethane coatings and the foaming problem of the coating film caused by being extremely susceptible to environmental temperature and humidity. At the same time, it can make the solvent volatilize less after the coating system is cured, and a solvent-free environmentally friendly high-performance polyurethane waterproof coating can be obtained.

[0055] The number-average molecular weight of the epoxy group-terminated modified resin also affects the performance of the coating. If the molecular weight is too small, it will have a certain impact on the crosslinking degree or bonding performance. If the molecular weight is too large, its activity will be reduced and it is not suitable for use. In some embodiments, the number-average molecular weight of the epoxy group-terminated modified resin is 600 - 1800. The number-average molecular weight of the epoxy group-terminated modified resin in this application within the above range can make the coating of this application have excellent bonding performance, and the reaction speed is fast, which can greatly improve the construction efficiency.

[0056] In some embodiments, the epoxy equivalent of the epoxy group-terminated modified resin is 175 g / mol - 360 g / mol. The epoxy group-terminated modified resin of this application also has a suitable range of epoxy equivalent. Especially, the performance of the epoxy group-terminated modified resin within the above range is relatively ideal.

[0057] Bisphenol-type epoxy resin contains multiple epoxy groups, a bisphenyl ring rigid structure, and has good activity. Using bisphenol-type epoxy resin as the backbone structure and then modifying it can further improve the strength of the coating, such as adhesion strength, tensile strength, and tear strength. In some embodiments, the epoxy group-terminated modified resin includes the structure shown in Formula 1 below:

[0058]

[0059] In Formula 1, n is an integer from 1 to 25, preferably an integer from 1 to 5, and X is an integer from 1 to 3.

[0060] Furthermore, in some embodiments, the viscosity of the epoxy-modified polyurethane waterproof coating is 10,000 mPa·s to 20,000 mPa·s. The inventors found that although the content of plasticizers and organic solvents can be reduced, for example, by directly not adding plasticizers and organic solvents, this will result in a very high viscosity of the coating, poor workability, great construction difficulty, and after construction, due to the poor leveling property of the coating, it is easy to cause uneven film formation, a decrease in bonding performance, and a more obvious decrease in the bonding performance of the film in the case of soaking in water, and a low strength retention rate. The coating of the present application has a relatively low viscosity, especially within the above range, which not only has high construction efficiency but also has excellent bonding performance.

[0061] In the present application, the epoxy plasticizer, latent curing agent, and active diluent all participate in the crosslinking and curing of the coating system. In some embodiments, the epoxy-modified polyurethane waterproof coating satisfies at least one of the following conditions:

[0062] a. The epoxy plasticizer includes one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, and epoxy sunflower oil;

[0063] b. The latent curing agent includes one or more of aldehyde imine curing agents, ketone imine curing agents, and oxazolidine curing agents;

[0064] c. The active diluent includes one or more of allyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, butyl glycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, and tert-carbonic acid glycidyl ester; and / or;

[0065] The polyurethane prepolymer can be prepared by reacting polyether diol, polyether triol, and polyisocyanate; optionally, it includes 100 parts by weight of polyether diol; and based on 100 parts by weight of polyether diol: 30 to 80 parts by weight of polyether triol; 14 to 20 parts by weight of polyisocyanate.

[0066] The plasticizer selected in this application is a plasticizer with an epoxy group, and the diluent is an active diluent with an epoxy group. Both of them can react with the epoxy group in the epoxy group-terminated modified resin and the amino group released by the hydrolysis of the latent curing agent to undergo ring-opening cross-linking reaction, improving the speed and cross-linking density of the epoxy group ring-opening cross-linking reaction. As a result, the plasticizer and diluent can be fixed in the coating film, enabling the system to be completely solvent-free after curing, improving the construction efficiency, enhancing the adhesion of the coating film and its water immersion resistance, improving the bubble problem of the coating film, and maintaining excellent adhesive strength retention rate after long-term soaking in water.

[0067] In some embodiments, the epoxy-modified polyurethane waterproof coating satisfies at least one of the following conditions:

[0068] d. The number-average molecular weight of the polyether diol is 1000 - 3000. Optionally, the polyether diol includes one or a combination of DL-2000D and DL-1000D;

[0069] e. The number-average molecular weight of the polyether triol is 1000 - 6000. Optionally, the polyether triol includes one or a combination of EP330N and MN1000;

[0070] f. The weight ratio of the polyether diol to the polyether triol is 1:(0.55 - 0.75);

[0071] g. The polyisocyanate includes one or a combination of aromatic diisocyanates and aliphatic diisocyanates;

[0072] Optionally, the polyisocyanate includes one or several of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate;

[0073] h. The additive includes one or several of pigments and fillers, defoamers, dispersants, and catalysts;

[0074] Optionally, the pigments and fillers include one or more of nano calcium carbonate, talc powder, heavy calcium, kaolin, silica powder, carbon black, titanium dioxide, and iron oxide red powder;

[0075] Optionally, the defoamer includes one or a combination of silicone-based and polyether-based defoamers;

[0076] Optionally, the dispersant includes one or a combination of anionic wetting dispersants and polymer-type superdispersants;

[0077] Optionally, the catalyst includes one or several of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate, and zinc neodecanoate;

[0078] Optionally, the additives include: 180 to 350 parts by weight of pigment and filler; 1 to 3 parts by weight of defoamer; 0.1 to 0.5 parts by weight of dispersant; 0.3 to 1.5 parts by weight of catalyst.

[0079] The polyether diol has few crosslinking sites, which easily results in low strength of the coating, such as tensile strength; although the polyether triol has many crosslinking sites, it easily leads to high elongation rate and high elongation at break of the coating. In this application, the crosslinking density between the raw materials in the coating can be controlled by controlling the combination and ratio of the polyether diol and the polyether triol, so that the coating film can simultaneously have excellent mechanical strength and water immersion adhesion performance.

[0080] In the implementation manner of the second aspect of this application, a preparation method of the epoxy-modified polyurethane waterproof coating provided in the first aspect of this application is provided, including:

[0081] Mixing a predetermined weight portion of polyether diol, polyether triol, epoxy plasticizer, polyisocyanate and additives under the first environmental conditions to obtain a first reactant;

[0082] Mixing the first reactant and the epoxy group-terminated modified resin under the second environmental conditions to obtain a second reactant;

[0083] Mixing the second reactant with a latent curing agent and an active diluent under the third environmental conditions to obtain the epoxy-modified polyurethane waterproof coating.

[0084] Specifically, in the step of mixing a predetermined weight portion of polyurethane prepolymer, epoxy plasticizer and additives under the first environmental conditions to obtain a first reactant, it may include mixing polyether diol, polyether triol, epoxy plasticizer, defoamer, dispersant, pigment and filler, stirring and heating to 100°C to 110°C, dehydrating for 2 h to 3 h under a vacuum condition of -0.08 MPa to -0.1 MPa, cooling to 70°C to 80°C, adding diisocyanate under stirring, and then heating to 75°C to 85°C and reacting for 2 h to 3 h to obtain the first reactant.

[0085] Specifically, in the step of mixing the first reactant and the epoxy group-terminated modified resin under the second environmental conditions to obtain a second reactant, it may include cooling the first reactant to 70°C to 80°C, adding the epoxy group-terminated modified resin and catalyst under stirring, and reacting for 2 h to 3 h to obtain the second reactant.

[0086] Specifically, in the step of mixing the second reactant, the latent curing agent, and the reactive diluent under the third environmental conditions to obtain the epoxy-modified polyurethane waterproof coating, it may include cooling the second reactant to below 50°C, adding the latent curing agent and the reactive diluent, and reacting for 0.5 h to 1 h; protecting with nitrogen, discharging, to obtain the epoxy-modified polyurethane waterproof coating.

[0087] In addition, in some embodiments, in the step of mixing the first reactant and the epoxy group-terminated modified resin under the second environmental conditions to obtain the second reactant, the epoxy group-terminated modified resin is obtained by a free radical polymerization reaction including bisphenol A epoxy resin and glycidyl methacrylate or 3,4-epoxyhexyl methacrylate.

[0088] Specifically, the preparation of the epoxy group-terminated modified resin may include: putting the calculated amount of dried bisphenol A epoxy resin E44 into a reactor, adding a mixed solvent of n-butanol and ethylene glycol monobutyl ether (volume ratio 1:1), starting stirring until the epoxy resin is completely dissolved, and controlling the material temperature at 85°C; then dropping the calculated amount of glycidyl methacrylate and benzoyl peroxide into the reactor, controlling a certain dropping reaction rate, continuing to heat up and stir the reaction, controlling the temperature at 90°C to 95°C, reacting at a constant temperature for 6 h to 7 h, and then evacuating and performing vacuum distillation for 0.5 h to 1 h to obtain the epoxy group-terminated modified resin (which may include the structure shown in Formula 1 above). Among them, the molar ratio of bisphenol A epoxy resin E44 to glycidyl methacrylate = 1:(1 to 3), the amount of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 10% to 15% of the total mass of the reactants, and benzoyl peroxide is 0.3% to 0.5% of the total mass of the reactants.

[0089] Among them, bisphenol A epoxy resin E44 may include the structure shown in Formula 2 below. Glycidyl methacrylate may include the structure shown in Formula 3 below.

[0090]

[0091] In Formula 2 and Formula 3, n may be an integer from 1 to 25, preferably an integer from 1 to 5, and X may be an integer from 1 to 3.

[0092] In an embodiment of the third aspect of the present application, a waterproof product is provided, including: a waterproof coating and a substrate covering the waterproof coating, and the waterproof coating is formed by the epoxy-modified polyurethane waterproof coating provided in the first aspect of the present application above.

[0093] Embodiment

[0094] The following examples describe more specifically the content disclosed in the present application. These examples are for illustrative purposes only, as various modifications and variations within the scope of the present application are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all commercially available.

[0095] The raw material sources used in this example and the comparative example include: DL-2000D (functionality of 2, number average molecular weight of 2000), Bluestar Dongda EP330N (functionality of 3, number average molecular weight of 5000), purchased from Shandong Bluestar Dongda Co., Ltd.

[0096] The aldehyde imine curing agent XY-401, purchased from Suzhou Xiangyuan New Materials Co., Ltd.

[0097] Bisphenol A epoxy resin E44, purchased from Baling Petrochemical Company.

[0098] Epoxidized soybean oil, model: plasticizer ESO, purchased from Jinan Youshengyuan Chemical Co., Ltd.

[0099] Other raw materials not specifically mentioned are all ordinary commercially available products.

[0100] Preparation Example 1

[0101] The preparation method of the epoxy group-terminated modified resin in this preparation example includes:

[0102] Put the dried bisphenol A epoxy resin E44 into the reactor, add a mixed solvent of n-butanol and ethylene glycol monobutyl ether with a volume ratio of 1:1, start stirring until the epoxy resin is completely dissolved, and control the material temperature at 85°C; then dropwise add glycidyl methacrylate and benzoyl peroxide into the reactor, control the dropping reaction rate, continue to heat and stir the reaction, control the temperature at 95°C, keep the temperature constant for 6 hours, and then evacuate and carry out vacuum distillation for 0.5 hours to obtain the epoxy group-terminated modified resin (the structural general formula is as shown in Formula 1 above, the number average molecular weight is 740, and the epoxy equivalent is 185 g / mol).

[0103] Among them, the molar ratio of bisphenol A epoxy resin E44 to glycidyl methacrylate = 1:2, the amount of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 12% of the total mass of the reactants, and benzoyl peroxide is 0.4% of the total mass of the reactants. Bisphenol A epoxy resin E44 has the structure shown in Formula 2 above, and glycidyl methacrylate has the structure shown in Formula 3 above.

[0104] Preparation Example 2

[0105] Compared with Preparation Example 1, the main difference of this Preparation Example is that there are only 2 epoxy end groups in one molecule of the epoxy group-terminated modified resin. After using α-methylacrylic acid instead of glycidyl methacrylate, it reacts with bisphenol A epoxy resin E44.

[0106] The preparation method of the epoxy group-terminated modified resin in this Preparation Example includes:

[0107] Put the dried bisphenol A epoxy resin E44 into the reactor, add a mixed solvent of n-butanol and ethylene glycol monobutyl ether with a volume ratio of 1:1, start stirring until the epoxy resin is completely dissolved, and control the material temperature at 85°C; then dropwise add α-methylacrylic acid and benzoyl peroxide into the reactor, control the dropping reaction rate, continue to heat up and stir the reaction, control the temperature at 95°C, keep the temperature constant for 6h, then evacuate and distill under reduced pressure for 0.5h to obtain the epoxy group-terminated modified resin (number average molecular weight is 620, epoxy equivalent is 310 g / mol).

[0108] Among them, the molar ratio of bisphenol A epoxy resin E44:α-methylacrylic acid = 1:2, the dosage of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 12% of the total mass of the reactants, and benzoyl peroxide is 0.4% of the total mass of the reactants. Bisphenol A epoxy resin E44 has the structure shown in Formula 2 above.

[0109] Preparation Example 3

[0110] Compared with Preparation Example 1, the main difference of this Preparation Example is that the number average molecular weight of the epoxy group-terminated modified resin is larger and the epoxy equivalent is smaller, and the number average molecular weight is 2000 - 3000.

[0111] The preparation method of the epoxy group-terminated modified resin in this Preparation Example includes:

[0112] Put the dried bisphenol A epoxy resin E44 into the reactor, add a mixed solvent of n-butanol and ethylene glycol monobutyl ether with a volume ratio of 1:1, start stirring until the epoxy resin is completely dissolved, and control the material temperature at 85°C; then dropwise add glycidyl methacrylate and benzoyl peroxide into the reactor, control the dropping reaction rate, continue to heat up and stir the reaction, control the temperature at 95°C, keep the temperature constant for 6h, then evacuate and distill under reduced pressure for 0.5h to obtain the epoxy group-terminated modified resin (number average molecular weight is 2150, epoxy equivalent is 154 g / mol).

[0113] Among them, the molar ratio of bisphenol A epoxy resin E44:glycidyl methacrylate = 1:12, the dosage of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 12% of the total mass of the reactants, and benzoyl peroxide is 0.4% of the total mass of the reactants. Bisphenol A epoxy resin E44 has the structure shown in Formula 2 above, and glycidyl methacrylate has the structure shown in Formula 3 above.

[0114] Example 1

[0115] In this example, a solvent-free epoxy-modified one-component polyurethane waterproof coating comprises the following raw materials in parts by weight: DL-2000D, 100 parts by weight; EP330N, 55 parts by weight; epoxy soybean oil, 124 parts by weight; talcum powder, 70 parts by weight; heavy calcium carbonate, 135 parts by weight; dispersant sodium octyl sulfate, 0.3 parts by weight; defoamer polydimethylsiloxane, 1.8 parts by weight; toluene diisocyanate, 16 parts by weight; epoxy group-terminated modified resin (the above Preparation Example 1), 22 parts by weight; aldehyde imine curing agent XY-401, 25 parts by weight; allyl glycidyl ether, 86 parts by weight; stannous octoate, 0.6 parts by weight.

[0116] The preparation method of the solvent-free epoxy-modified one-component polyurethane waterproof coating in this example comprises the following steps:

[0117] S01, Mix polyether diol DL-2000D, polyether triol EP330N, epoxy soybean oil, defoamer polydimethylsiloxane, dispersant sodium octyl sulfate, pigment and filler talcum powder and heavy calcium carbonate, stir and heat up to 105°C, dehydrate under a vacuum condition of -0.09 MPa for 2.5 h, cool down to 75°C, add toluene diisocyanate under stirring, then heat up to 80°C and react for 2.5 h to obtain a first reactant.

[0118] S02, Cool the first reactant down to 75°C, add the epoxy group-terminated modified resin and stannous octoate under stirring and react for 2.5 h to obtain a second reactant.

[0119] S03, Cool the second reactant down to 45°C, add the aldehyde imine curing agent and allyl glycidyl ether, react for 0.5 h; protect with nitrogen, discharge to obtain the solvent-free epoxy-modified one-component polyurethane waterproof coating.

[0120] Example 2

[0121] In this example, a solvent-free epoxy-modified one-component polyurethane waterproof coating comprises the following raw materials in parts by weight: DL-2000D, 100 parts by weight; EP330N, 75 parts by weight; epoxy soybean oil, 130 parts by weight; talcum powder, 70 parts by weight; heavy calcium carbonate, 140 parts by weight; dispersant sodium octyl sulfate, 0.3 parts by weight; defoamer polydimethylsiloxane, 1.8 parts by weight; toluene diisocyanate, 17 parts by weight; epoxy group-terminated modified resin (the same as in Example 1), 22 parts by weight; aldehyde imine curing agent XY-401, 25 parts by weight; allyl glycidyl ether, 85 parts by weight; stannous octoate, 0.6 parts by weight.

[0122] The preparation process of the solvent-free epoxy-modified one-component polyurethane waterproof coating described in this example, and the preparation process of the epoxy group-terminated modified resin are basically the same as those in Example 1, and will not be elaborated here.

[0123] Example 3

[0124] A solvent-free epoxy-modified one-component polyurethane waterproof coating in this example includes the following raw materials in parts by weight: DL-2000D, 100 parts by weight; EP330N, 75 parts by weight; epoxy soybean oil, 130 parts by weight; talcum powder, 70 parts by weight; heavy calcium, 140 parts by weight; dispersant sodium octyl sulfate, 0.3 parts by weight; defoaming agent polydimethylsiloxane, 1.8 parts by weight; toluene diisocyanate, 20 parts by weight; epoxy group-terminated modified resin (the same as in Example 1), 33 parts by weight; aldehyde imine curing agent XY-401, 22 parts by weight; allyl glycidyl ether, 85 parts by weight; stannous octoate, 0.6 parts by weight.

[0125] The preparation process of the solvent-free epoxy-modified one-component polyurethane waterproof coating described in this example, and the preparation process of the epoxy group-terminated modified resin are basically the same as those in Example 1, and will not be elaborated here.

[0126] Example 4

[0127] Compared with Example 1, the difference in this example is that the epoxy group-terminated modified resin does not contain acrylic groups, and its structural formula is as shown in Formula 2 above.

[0128] Example 5

[0129] Compared with Example 1, the difference in this example is that the epoxy group-terminated modified resin used is as shown in Preparation Example 2 above.

[0130] Example 6

[0131] Compared with Example 1, the difference in this example is that the epoxy group-terminated modified resin used is as shown in Preparation Example 3 above.

[0132] Comparative Example 1

[0133] The polyurethane waterproof coating in this comparative example is similar in composition and preparation process to Example 1. The difference is that the epoxy group-terminated modified resin in Example 1 is removed and replaced with an equal mass part of aldehyde imine latent curing agent XY-401.

[0134] Comparative Example 2

[0135] The polyurethane waterproof coating in this comparative example is similar in composition and preparation process to Example 1. The difference is that the epoxy soybean oil in Example 1 is removed and replaced with an equal mass part of 52# chlorinated paraffin (purchased from Jiangxi Dongfang Julong Chemical Co., Ltd.).

[0136] Comparative Example 3

[0137] The composition and preparation process of the polyurethane waterproof coating in this comparative example are similar to those of Example 1, except that the allyl glycidyl ether (purchased from Nanjing Kuncheng Chemical Co., Ltd.) in Example 1 is removed and replaced with an equal mass portion of trimethylol solvent (purchased from Jiangsu Hualun Chemical Co., Ltd.).

[0138] Comparative Example 4

[0139] The composition and preparation process of the polyurethane waterproof coating in this comparative example are similar to those of Example 1, except that the allyl glycidyl ether (purchased from Nanjing Kuncheng Chemical Co., Ltd.) in Example 1 is removed and replaced by an equal amount of epoxy-terminated modified resin agent (Preparation Example 1).

[0140] Performance test section

[0141] The performance of the polyurethane waterproof coatings prepared in each embodiment and comparative example was tested, and the test results are shown in Table 1.

[0142] Test method:

[0143] The surface drying time, actual drying time, tensile strength, elongation at break, tear strength, bonding strength, volatile organic compound content, water impermeability, etc. are carried out in accordance with GB / T19250-2013.

[0144] The thick coating blistering test is carried out according to 7.14 of JC / T2435-2018.

[0145] The viscosity test is carried out using NDJ-1 rotational viscometer. For specific testing methods, refer to the instruction manual of NDJ-1 rotational viscometer.

[0146] The test method for the strength retention rate of water-immersion bonding is to prepare the test piece according to the method specified in GB / T 16777-2008 7.1 (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. The test piece is completely immersed in water, taken out at a predetermined time, and the bonding strength is tested after being placed under standard test conditions for 12 hours. Among them, strength retention rate = (bonding strength / initial bonding strength)*100%.

[0147]

[0148]

[0149] From the data analysis in Table 1, it can be seen that in Examples 1 to 6, the content of volatile organic compounds (VOC) in the products is extremely low, and there are no bubbles in thick coatings under different temperatures and humidities. The strength retention rate is high under water immersion conditions, and the effect is significant compared with the comparative examples. Among the comparative examples, the thick coating performance, adhesion performance, water immersion performance and other indicators of Comparative Example 1 decreased most severely, indicating that the epoxy group-terminated modified resin has a significant impact on the adhesion performance, thick coating foaming performance and water immersion adhesion, playing a key role. In Comparative Example 2 and Comparative Example 3, a plasticizer and a solvent without epoxy groups were used respectively, and the adhesion performance and water immersion adhesion decreased to a certain extent. In particular, the impact of chlorinated paraffin was more obvious than that of the solvent, indicating that the plasticizer in the free state can significantly affect the adhesion. In Comparative Example 3, due to the use of mesitylene solvent instead, the content of organic compounds (VOC) is high. In Comparative Example 4, when an equal mass of epoxy group-terminated modified resin agent was used instead, it can be seen that the viscosity increased significantly, which had an obvious impact on the adhesion performance and water immersion adhesion. This may be because the high viscosity of the product affected the wetting effect of the coating on the adhesion interface, resulting in a decrease in adhesion.

[0150] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. An epoxy-modified polyurethane waterproof coating, characterized in that: The ingredients include the following: Polyurethane prepolymer, 186 parts by weight; and all based on 186 parts by weight of polyurethane prepolymer: Epoxy plasticizer, 80-150 parts by weight; Epoxy-terminated modified resin, 18 to 34 parts by weight; one epoxy-terminated modified resin molecule in the epoxy-terminated modified resin includes at least one hydroxyl group; Reactive diluent, 70-100 parts by weight, wherein the reactive diluent is a reactive diluent having an epoxy group; Latent curing agent, 23 to 75 parts by weight; Additives, 200-355 parts by weight; The epoxy-terminated modified resin comprises a structure as shown in Formula 1 below: In Formula 1, n is an integer of 1 to 25, and X is an integer of 1 to 3; The epoxy equivalent of the epoxy-terminated modified resin is 175 g / mol to 360 g / mol; The preparation method of the epoxy modified polyurethane waterproof coating comprises the following steps: Mixing predetermined weight portions of a polyurethane prepolymer, an epoxy plasticizer, and an additive under a first environmental condition to obtain a first reactant; Mixing the first reactant and the epoxy-terminated modified resin under a second environmental condition to obtain a second reactant; The second reactant, the latent curing agent and the active diluent are mixed under a third environmental condition to obtain the epoxy-modified polyurethane waterproof coating.

2. The epoxy-modified polyurethane waterproof coating according to claim 1, characterized in that: n is an integer of 1-5.

3. The epoxy-modified polyurethane waterproof coating according to claim 1, characterized in that: The number average molecular weight of the epoxy-terminated modified resin is 600-1800.

4. The epoxy-modified polyurethane waterproof coating according to claim 1, characterized in that: The viscosity of the epoxy modified polyurethane waterproof coating is 10000mPa·s to 20000mPa·s.

5. The epoxy-modified polyurethane waterproof coating according to claim 1, characterized in that: The epoxy modified polyurethane waterproof coating meets at least one of the following characteristics: a. The epoxy plasticizer comprises one or more of epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized rice bran oil and epoxidized sunflower oil; b. The latent curing agent includes one or more of an aldimine curing agent, a ketimine curing agent and an oxazolidine curing agent; c. The active diluent includes one or more 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 glycidyl ether, and tert-butyl glycidyl ether; and / or; The polyurethane prepolymer is prepared by reacting polyether diol, polyether triol and polyisocyanate.

6. The epoxy-modified polyurethane waterproof coating according to claim 5, characterized in that: The polyurethane prepolymer is prepared from the following components in parts by weight: 100 parts by weight of the polyether diol; 30 to 80 parts by weight of the polyether triol; and 14 to 20 parts by weight of the polyisocyanate, all based on 100 parts by weight of the polyether diol.

7. The epoxy-modified polyurethane waterproof coating according to claim 5, characterized in that: The epoxy modified polyurethane waterproof coating meets at least one of the following characteristics: d. The number average molecular weight of the polyether diol is 1000 to 3000; e. The number average molecular weight of the polyether triol is 1000 to 6000; f. The weight ratio of the polyether diol to the polyether triol is 1:(0.55 to 0.75); g. The polyisocyanate comprises one or a combination of an aromatic diisocyanate and an aliphatic diisocyanate; h. The additives include one or more of pigments, fillers, defoamers, dispersants and catalysts; wherein, The pigments and fillers include one or more of nano calcium carbonate, talc, heavy calcium, kaolin, silica powder, carbon black, titanium dioxide and iron ore red powder; The defoamer comprises one or a combination of silicone and polyether defoamers; The dispersant includes one or a combination of anionic wetting dispersants and polymeric super dispersants; The catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, and zinc neodecanoate.

8. The epoxy-modified polyurethane waterproof coating according to claim 7, characterized in that: The epoxy modified polyurethane waterproof coating meets at least one of the following characteristics: d1. The polyether diol comprises one or a combination of DL-2000D and DL-1000D; e1. The polyether triol includes one or a combination of EP330N and MN1000; g1. The polyisocyanate includes one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethyl-m-xylylene diisocyanate; h1. The additives include: 180 to 350 parts by weight of pigments and fillers; 1 to 3 parts by weight of defoamers; 0.1 to 0.5 parts by weight of dispersants; and 0.3 to 1.5 parts by weight of catalysts.

9. The epoxy-modified polyurethane waterproof coating according to claim 1, characterized in that: The preparation method satisfies at least one of the following conditions: i. In the step of mixing predetermined weight portions of polyether diol, polyether triol, epoxy plasticizer, polyisocyanate and additive under a first environmental condition to obtain a first reactant, the first environmental condition includes mixing polyether diol, polyether triol, epoxy plasticizer, defoamer, dispersant and pigments and fillers, stirring and heating to 100°C to 110°C, dehydrating under a vacuum condition of -0.08MPa to -0.1MPa for 2h to 3h, cooling to 70°C to 80°C, adding diisocyanate under stirring, and then heating to 75°C to 85°C, reacting for 2h to 3h to obtain the first reactant; j. In the step of mixing the first reactant and the epoxy-terminated modified resin under a second environmental condition to obtain a second reactant, the second environmental condition includes cooling the first reactant to 70° C. to 80° C., adding the epoxy-terminated modified resin and the catalyst under stirring, and reacting for 2 h to 3 h to obtain the second reactant; k. In the step of mixing the second reactant with the latent curing agent and the reactive diluent under the third environmental condition to obtain the epoxy-modified polyurethane waterproof coating, the third environmental condition includes cooling the second reactant to below 50° C., adding the latent curing agent and the reactive diluent, and reacting for 0.5 h to 1 h; filling with nitrogen for protection, and discharging the material to obtain the epoxy-modified polyurethane waterproof coating; 1. In the step of mixing the first reactant and the epoxy-terminated modified resin under a second environmental condition to obtain the second reactant, the epoxy-terminated modified resin is obtained by a free radical polymerization reaction of bisphenol A epoxy resin and glyceryl methacrylate.

10. A waterproof product comprising: A waterproof coating and a substrate covering the waterproof coating, wherein the waterproof coating is formed by the epoxy-modified polyurethane waterproof coating according to any one of claims 1 to 9.

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