An epoxy polyurethane dispersion, its preparation method and use
By preparing an epoxy polyurethane dispersion, combining modified epoxy resin with polyurethane prepolymer, and introducing double bonds and silane coupling agents to form a hard core and soft shell structure, the problems of low-temperature film formation and insufficient bonding strength of single-component water-based paints are solved, achieving the effects of rapid self-drying, anti-blocking and high bonding strength.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGZHOU JOINTAS CHEM
- Filing Date
- 2023-12-18
- Publication Date
- 2026-06-12
AI Technical Summary
Existing single-component water-based paints have poor film-forming properties, low adhesion strength, and are prone to sticking at low temperatures. Existing improvement methods are either costly or ineffective.
By preparing an epoxy-polyurethane dispersion, a modified epoxy resin is combined with a polyurethane prepolymer, and double bonds and silane coupling agents are introduced to increase the crosslinking density. Nonionic and anionic segments are also introduced into the polyurethane chain segments to form a hard-core soft-shell structure.
It achieves rapid self-drying, good anti-blocking properties, excellent bonding strength and storage stability of the coating, good low-temperature film-forming properties, less than 5% of the area of adhesion damage after 5 hours of self-drying, less than 1% after 24 hours, pencil hardness up to H grade, and bonding strength of 4-5.8 MPa.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of water-based industrial coatings technology, specifically relating to an epoxy polyurethane dispersion, its preparation method, and its application. Background Technology
[0002] Epoxy resin, polyurethane resin, acrylic resin, and alkyd resin are some of the most commonly used resins in water-based coatings. These resins can be used in both one-component and two-component paints. Due to their higher crosslinking density, two-component water-based paints offer superior overall performance compared to one-component water-based paints, particularly in terms of chemical resistance, corrosion resistance, hardness, scratch resistance, anti-tack properties, and abrasion resistance. However, one-component water-based paints are less expensive, their basic properties meet the requirements for light corrosion protection, and they are easier to apply, making them increasingly popular in the field of water-based industrial coatings, including anti-tack water-based paints. Tack generally refers to the adhesion of paint films when components are stacked, especially during the early drying stage or at high ambient temperatures. Currently, high-Tg acrylic resins are commonly used as film-forming resins to improve the drying speed and early hardness of the paint film, thereby enhancing its anti-tack properties. However, high-Tg acrylic resins have poor film-forming properties, requiring the addition of large amounts of film-forming aids to lower the film-forming temperature. Epoxy esters obtained by modifying epoxy resins with vegetable oils are also commonly used in water-based industrial coatings for preventing tackiness. However, they take a long time to build up hardness, the final hardness of the film is not very high, and the anti-tack effect is generally average. To improve the anti-tack effect, some water-based paints add a large amount of filler to improve the drying properties of the film, but this reduces the sealing and adhesion of the film. Some water-based paints add a small amount of film-forming aids to increase the drying speed of the film, but the low-temperature film-forming properties of the film are poor, and the application environment temperature is generally higher than 15°C. Some water-based paints use scratch-resistant, abrasion-resistant, or hardening agents, but the effect is minimal and the cost is high.
[0003] The above methods only focus on the drying speed, hardness, and high-temperature anti-blocking of the paint film, while neglecting the low-temperature film-forming properties and bonding strength of the paint film. In order to solve the problems of early adhesion, poor low-temperature film-forming properties, and low bonding strength of single-component anti-tack water-based industrial coatings, it is imperative to provide an epoxy polyurethane dispersion. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the present invention aims to provide an epoxy polyurethane dispersion, its preparation method, and its application. By selecting the raw materials and controlling their dosage, the obtained epoxy polyurethane dispersion, when used in coatings, can enable the coatings to possess excellent anti-tack properties, low-temperature film-forming properties, hardness, adhesive strength, and storage stability.
[0005] To achieve this objective, the present invention adopts the following technical solution:
[0006] In a first aspect, the present invention provides an epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include a combination of modified epoxy resin, polyurethane prepolymer, neutralizing agent and water; the mass ratio of the modified epoxy resin to the polyurethane prepolymer is (1-4):1; the raw materials for preparing the modified epoxy resin include a combination of fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinyl siloxane and epoxy resin; and the mass percentage of the vinyl siloxane is 3-10%, based on the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinyl siloxane and epoxy resin being 100%.
[0007] The epoxy polyurethane dispersion provided by this invention, by modifying the epoxy resin, can introduce double bonds and silane coupling agents, thereby increasing the curing crosslinking modes and improving the crosslinking density of the epoxy polyurethane dispersion. When used in coatings, it can accelerate the self-drying speed of the coating and give the coating good early anti-blocking properties and bonding strength.
[0008] The mass ratio of the modified epoxy resin to the polyurethane prepolymer is (1-4):1, for example, it can be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, etc.
[0009] Based on the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinyl siloxanes, and epoxy resins as 100%, the mass percentage of vinyl siloxanes is 3-10%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, and specific values between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values included in the range.
[0010] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.
[0011] As a preferred technical solution, the fatty acids containing conjugated double bonds include dehydrated castor oil and / or tung oil acid.
[0012] Preferably, based on the total mass of the fatty acid containing conjugated double bonds, the fatty acid without conjugated double bonds, the vinylsiloxane, and the epoxy resin as 100%, the mass percentage of the fatty acid containing conjugated double bonds is 3-17%, for example, it can be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, or 17%, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0013] Preferably, the fatty acid without conjugated double bonds includes any one or a combination of at least two of linoleic acid, linolenic acid, oleic acid, or arachidonic acid.
[0014] Preferably, based on the total mass of the fatty acids containing conjugated double bonds, the fatty acids without conjugated double bonds, the vinylsiloxane, and the epoxy resin as 100%, the mass percentage of the fatty acids without conjugated double bonds is 12-56%, for example, it can be 12%, 15%, 18%, 20%, 25%, 28%, 30%, 35%, 40%, 45%, 50%, 55%, or 56%, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0015] Preferably, the vinylsiloxane includes any one or a combination of at least two of vinyltriisopropoxysiloxane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, or vinylmethyldiethoxysilane.
[0016] Preferably, the epoxy resin comprises liquid bisphenol A epoxy resin.
[0017] Preferably, the liquid bisphenol A epoxy resin includes any one or a combination of at least two of E-51, E-44, E-42, E-54, E-35 or E-31.
[0018] Preferably, the epoxy equivalent of the epoxy resin is 170-430, for example, it can be 170, 200, 220, 240, 250, 280, 300, 320, 350, 380, 400 or 430, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0019] Preferably, based on the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinylsiloxane, and epoxy resin as 100%, the mass percentage of the epoxy resin is 35-62%, for example, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, or 62%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0020] Preferably, the modified epoxy resin is prepared by the following method, which includes the following steps:
[0021] (S1) The fatty acid containing conjugated double bonds undergoes an addition reaction with vinylsiloxane to obtain the reaction product;
[0022] (S2) The reaction product, the epoxy resin, and the fatty acid without conjugated double bonds are subjected to an esterification reaction to obtain the modified epoxy resin.
[0023] Preferably, the temperature of the addition reaction is 70-110°C, for example, it can be 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C or 110°C, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0024] Preferably, the addition reaction time is 1-3 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours, as well as specific values between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values included in the range.
[0025] Preferably, the temperature of the esterification reaction is 120-160℃, for example, it can be 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃ or 160℃, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0026] Preferably, the esterification reaction time is 1-3 hours, for example, it can be 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 3 hours, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0027] Preferably, the esterification reaction in step (S2) is carried out in the presence of a solvent, a polymerization inhibitor, and a catalyst.
[0028] Preferably, the solvent includes N-methylpyrrolidone and / or methylpentyl ketone.
[0029] Preferably, the mass ratio of epoxy resin to solvent is (2.5-14):1, for example, it can be 2.5:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1 or 14:1, etc.
[0030] Preferably, the polymerization inhibitor comprises p-hydroxyanisole and / or hydroquinone.
[0031] Preferably, based on 100% of the epoxy resin, the mass of the polymerization inhibitor is 0.3-1.5%, for example, it can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0032] Preferably, the catalyst comprises any one or a combination of at least two of dimethylaniline, tetrabutylammonium bromide, or triphenylphosphine.
[0033] Preferably, the mass of the catalyst is 0.3-1.5% based on 100% of the epoxy resin, for example, it can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0034] Preferably, the modified epoxy resin in the raw materials for preparing the epoxy polyurethane dispersion has a mass percentage content of 18-30%, for example, it can be 18%, 20%, 22%, 24%, 26%, 28% or 30%, and specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0035] Preferably, the raw materials for preparing the polyurethane prepolymer include the following components by mass percentage: 40-70% diol, 3-6% hydroxy acid, 15-45% diisocyanate, and 5-10% amino-terminated polyether.
[0036] This invention uses hydroxy acid and amino-terminated polyether as two raw materials for preparing polyurethane prepolymers, which can introduce nonionic and anionic segments into the polyurethane chain. When the resulting epoxy polyurethane is used in coatings, the coatings can have good dispersion stability and storage stability.
[0037] The diol is 40-70%, for example, it can be 40%, 45%, 50%, 55%, 60%, 65% or 70%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0038] The hydroxy acid is 3-6%, for example, it can be 3%, 3.5%, 4%, 4.5%, 5%, 5.5% or 6%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0039] The diisocyanate is 15-45%, for example, it can be 15%, 20%, 25%, 30%, 35%, 40% or 45%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0040] The terminal amino polyether is 5-10%, for example, it can be 5%, 6%, 7%, 8%, 9% or 10%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0041] Preferably, the diol comprises a combination of hydroxyl-terminated polysiloxane and polytetrahydrofuran ether diol.
[0042] Preferably, the molar ratio of the hydroxyl-terminated polysiloxane to the polytetrahydrofuran ether diol is 1:(1-3), for example, it can be 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8 or 1:3.
[0043] Preferably, the hydroxyl-terminated polysiloxane comprises polydimethylsiloxane with hydroxypropyl end-capped ends and / or polydimethylsiloxane with dihydroxy end-capped ends.
[0044] The molecular structural formula of the double-hydroxypropyl-terminated polydimethylsiloxane is: The molecular structural formula of the dihydroxyl-terminated polydimethylsiloxane is:
[0045] Preferably, the number average molecular weight of the terminal hydroxyl polysiloxane is 1000-2000, for example, it can be 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0046] Preferably, the number average molecular weight of the polytetrahydrofuran ether diol is 1000-2000, for example, it can be 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0047] Preferably, the hydroxy acid includes dimethylolbutyric acid and / or dimethylolpropionic acid.
[0048] Preferably, the diisocyanate includes any one or a combination of at least two of toluene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, or 1,4-cyclohexane diisocyanate.
[0049] Preferably, the amino-terminated polyether has the structure of Formula I:
[0050]
[0051] Where R is -H or -CH3.
[0052] x is an integer selected from 1 to 20, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20, etc.
[0053] y is selected from integers from 1 to 35, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32 or 34, etc.
[0054] Preferably, the number average molecular weight of the terminal amino polyether is 500-2000, for example, it can be 500, 600, 800, 900, 1000, 1100, 1200, 1400, 1600, 1800 or 2000, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0055] Preferably, the polyurethane prepolymer is prepared by the following method, which includes the following steps:
[0056] (X1) The diol, the hydroxy acid and the diisocyanate are mixed and reacted to obtain an isocyanate-terminated polyurethane prepolymer.
[0057] (X2) The isocyanate-terminated polyurethane prepolymer is reacted with the amino-terminated polyether to obtain the polyurethane prepolymer.
[0058] Preferably, the reaction in step (X1) is carried out in the presence of an organic solvent.
[0059] Preferably, the organic solvent includes acetone.
[0060] Preferably, based on the mass of the diol, hydroxy acid, diisocyanate, amino-terminated polyether, and organic solvent as 100%, the mass of the organic solvent is 4-10%, for example, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, and specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0061] Preferably, the reaction temperature in step (X1) is 70-85°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C or 85°C, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0062] Preferably, the reaction time in step (X1) is 1-3 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours, as well as specific values between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values included in the range.
[0063] Preferably, the reaction temperature in step (X2) is 30-60°C, for example, it can be 30°C, 32°C, 35°C, 40°C, 42°C, 45°C, 50°C, 52°C, 58°C or 60°C, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0064] Preferably, the reaction time in step (X2) is 1-3 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours, as well as specific values between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values included in the range.
[0065] Preferably, the neutralizing agent comprises any one or a combination of at least two of triethylamine, ammonia, or N,N-dimethylethanolamine.
[0066] Preferably, the neutralizing agent in the raw materials for preparing the epoxy polyurethane dispersion has a mass percentage content of 0.15-0.5%, for example, it can be 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%, and specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0067] Preferably, the water content in the raw materials for preparing the epoxy polyurethane dispersion is 60-65% by mass, for example, 60%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 64.5%, or 65%, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0068] In a second aspect, the present invention provides a method for preparing an epoxy polyurethane dispersion as described in the first aspect, the method comprising the following steps:
[0069] (1) The modified epoxy resin and polyurethane prepolymer are reacted to obtain the reaction product;
[0070] (2) The reaction product is neutralized with a neutralizing agent, and the resulting reaction product is mixed with water to obtain the epoxy polyurethane dispersion.
[0071] Preferably, the reaction temperature in step (1) is 70-85℃, for example, it can be 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0072] Preferably, the reaction time in step (1) is 1-3 hours, for example, it can be 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 3 hours, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0073] Preferably, the temperature of the neutralization reaction is 30-50℃, for example, it can be 30℃, 32℃, 34℃, 36℃, 38℃, 40℃, 42℃, 44℃, 46℃, 48℃ or 50℃, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0074] Preferably, the neutralization reaction time is 20-50 min, for example, it can be 20 min, 25 min, 30 min, 32 min, 35 min, 40 min, 42 min, 45 min or 50 min, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0075] Preferably, after the reaction product is mixed with water, the step of removing the organic solvent is further included.
[0076] Preferably, the method for removing the organic solvent includes vacuum distillation.
[0077] Preferably, the temperature of the vacuum distillation is 35-55℃, for example, it can be 35℃, 36℃, 38℃, 40℃, 42℃, 44℃, 46℃, 48℃, 50℃, 52℃, 54℃ or 55℃, as well as specific values between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0078] Preferably, the vacuum distillation time is 30-60 min, for example, it can be 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min, as well as specific values between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values included in the range.
[0079] Thirdly, the present invention provides a water-based industrial coating, the water-based industrial coating comprising the epoxy polyurethane dispersion as described in the first aspect.
[0080] Compared with the prior art, the present invention has the following beneficial effects:
[0081] (1) The epoxy polyurethane dispersion provided by the present invention combines polyurethane and epoxy resin through chemical grafting and introduces branched structure, double bond and silane coupling agent. It has multiple curing and crosslinking methods, high crosslinking density, and contains more cyclic structures. When used in coatings, it can accelerate the self-drying speed of the coating and make the coating have good early anti-blocking and bonding strength.
[0082] (2) The polyurethane segments in the epoxy polyurethane dispersion provided by the present invention contain carboxyl groups and are partially end-capped with amino-terminated polyethers, exhibiting good hydrophilicity. Simultaneously, the segments also contain polysiloxane and polyether segments, resulting in good flexibility. During dispersion and emulsification, the hydrophilic polyurethane segments can encapsulate the hydrophobic epoxy resin segments, forming a "hard core, soft shell" structure, which is beneficial for improving the film-forming properties of the coating film.
[0083] (3) The polyurethane segments in the epoxy polyurethane dispersion provided by the present invention introduce nonionic and anionic segments, which can make the coating have good dispersion stability and storage stability.
[0084] (4) The epoxy polyurethane dispersion provided by the present invention has excellent anti-tack properties when applied to coatings. After 5 hours of self-drying, the adhesion grade is BC and the damaged area is ≤5%. After 24 hours of self-drying, the adhesion grade is AC and the damaged area is ≤1%. It has good low-temperature film-forming properties, high hardness, and the highest pencil hardness grade can reach H. It has good adhesive strength, with an adhesive strength of 4-5.8 MPa. It also has good storage stability. Detailed Implementation
[0085] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.
[0086] The sources of some components in the examples and comparative examples are as follows:
[0087] (1) Vinyltriisopropoxysiloxane: purchased from Nanjing Nengde New Material Technology Co., Ltd.;
[0088] (2) Epoxy resin E51: purchased from Nantong Xingchen Synthetic Materials Co., Ltd., with an epoxy equivalent of 184-195;
[0089] (3) Monoamino-terminated polyether: Purchased from Zibo Zhengda Polyurethane Co., Ltd., with a number-average molecular weight of 600 and molecular structural formula as follows:
[0090] (4) Bis-hydroxypropyl-terminated polydimethylsiloxane: purchased from Hubei Xinyuhong Biomedical Technology Co., Ltd., with a number average molecular weight of 1000;
[0091] (5) Polytetrahydrofuran ether diol: purchased from Jining Huakai Resin Co., Ltd., with a number average molecular weight of 1000;
[0092] (6) Dehydrated castor oil: purchased from Jining Huakai Resin Co., Ltd.
[0093] Preparation Example 1
[0094] A modified epoxy resin A is prepared from raw materials including dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid; based on the total mass of the dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid as 100%, the mass percentage of vinyltriisopropoxysiloxane is 8.9%.
[0095] The preparation method of the modified epoxy resin A includes the following steps:
[0096] (S1) Add 56.0g of dehydrated castor oil and 46.5g of vinyltriisopropoxysiloxane to the reactor, purge with nitrogen, mix thoroughly, and react at 90°C for 2 hours.
[0097] (S2) Add 196.0g of epoxy resin E51, 111.5g of linoleic acid, 112.1g of linoleic acid, 28.0g of N-methylpyrrolidone, 1.6g of p-hydroxyanisole and 1.6g of tetrabutylammonium bromide to the above reactor, mix evenly, heat to 140℃ and react for 2.5h to obtain the modified epoxy resin A.
[0098] Preparation Example 2
[0099] A modified epoxy resin B is prepared from raw materials including dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid; based on the total mass of the dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid as 100%, the mass percentage of vinyltriisopropoxysiloxane is 4.9%.
[0100] The preparation method of the modified epoxy resin B includes the following steps:
[0101] (S1) Add 28.0g of dehydrated castor oil and 23.3g of vinyltriisopropoxysiloxane to the reactor, purge with nitrogen, mix thoroughly, and react at 90°C for 2 hours;
[0102] (S2) Add 196.0g of epoxy resin E51, 111.5g of linolenic acid, 112.2g of linoleic acid, 25.0g of N-methylpyrrolidone, 1.4g of p-hydroxyanisole and 1.4g of tetrabutylammonium bromide to the above reactor, mix well, heat to 140℃ and react for 2.5h to obtain the modified epoxy resin B.
[0103] Preparation Example 3
[0104] A modified epoxy resin C is prepared from raw materials including dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid; based on the total mass of the dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid as 100%, the mass percentage of vinyltriisopropoxysiloxane is 3.2%.
[0105] The preparation method of the modified epoxy resin C includes the following steps:
[0106] (S1) Add 18.3g of dehydrated castor oil and 15.0g of vinyltriisopropoxysiloxane to reactor, purge with nitrogen, mix thoroughly, and react at 90°C for 2 hours;
[0107] (S2) Add 196.0g of epoxy resin E51, 121.1g of linoleic acid, 122.0g of linoleic acid, 25.0g of N-methylpyrrolidone, 1.4g of p-hydroxyanisole and 1.4g of tetrabutylammonium bromide to the above reactor, mix evenly, heat to 140℃ and react for 2.5h to obtain the modified epoxy resin C.
[0108] Preparation Example 4
[0109] A polyurethane prepolymer and its preparation method, the preparation method comprising the following steps:
[0110] (X1) Add 155.7g isophorone diisocyanate (IPDI), 100.0g hydroxyl-terminated polysiloxane, 100.0g polytetrahydrofuran ether diol, 15.2g dimethylolbutyric acid and 21.5g acetone to the reactor, purge with nitrogen, mix thoroughly, and react at 80°C for 1.5h.
[0111] (X2) Add 30.0 g of amino-terminated polyether to the above reactor, mix well, and react at 30°C for 1 h to obtain the polyurethane prepolymer.
[0112] Preparation of Comparative Example 1
[0113] A modified epoxy resin D is prepared from raw materials including dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid; the vinyltriisopropoxysiloxane has a mass percentage content of 1% based on the total mass of the dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid as 100%.
[0114] The preparation method of the modified epoxy resin D includes the following steps:
[0115] (S1) Add 5.5g of dehydrated castor oil and 4.7g of vinyltriisopropoxysiloxane to the reactor, purge with nitrogen, mix thoroughly, and react at 90°C for 2 hours.
[0116] (S2) Add 196.0g of epoxy resin E51, 133.6g of linoleic acid, 134.6g of linoleic acid, 25.0g of N-methylpyrrolidone, 1.4g of p-hydroxyanisole and 1.4g of tetrabutylammonium bromide to the above reactor, mix well, heat to 140℃ and react for 2.5h to obtain the modified epoxy resin D.
[0117] Preparation of Comparative Example 2
[0118] A modified epoxy resin E is prepared from raw materials including dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid; the vinyltriisopropoxysiloxane has a mass percentage content of 15% based on the total mass of the dehydrated castor oil, vinyltriisopropoxysiloxane, epoxy resin E51, linoleic acid, and linoleic acid as 100%.
[0119] The preparation method of the modified epoxy resin E includes the following steps:
[0120] (S1) Add 84.0g of dehydrated castor oil and 69.8g of vinyltriisopropoxysiloxane to the reactor, purge with nitrogen, mix thoroughly, and react at 90°C for 2 hours.
[0121] (S2) Add 196.0g of epoxy resin E51, 57.0g of linolenic acid, 57.4g of linoleic acid, 25.0g of N-methylpyrrolidone, 1.4g of p-hydroxyanisole and 1.4g of tetrabutylammonium bromide to the above reactor, mix evenly, heat to 140℃ and react for 2.5h to obtain the modified epoxy resin E.
[0122] Example 1
[0123] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin A, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin A to the polyurethane prepolymer is 4:1.
[0124] The preparation method of the epoxy polyurethane dispersion includes the following steps:
[0125] (1) Add 400.0g of modified epoxy resin A and 100.0g of polyurethane prepolymer to the reactor, mix well, and react at 80℃ for 1.5h.
[0126] (2) Cool the reactor to 40°C, add 2.6g of triethylamine, neutralize for 40 min, add 431.0g of water and disperse for 20 min, then add another 431.0g of water and disperse for 30 min; vacuum distill at 35°C for 40 min to remove acetone and obtain the epoxy polyurethane dispersion.
[0127] Example 2
[0128] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin A, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin A to the polyurethane prepolymer is 7:3.
[0129] The preparation method of the epoxy polyurethane dispersion includes the following steps:
[0130] (1) Add 350.0g of modified epoxy resin A and 150.0g of polyurethane prepolymer to the reactor, mix well, and react at 80℃ for 1.5h.
[0131] (2) Cool the reactor to 40°C, add 3.9g of triethylamine, neutralize for 40 min, add 432.3g of water and disperse for 20 min, then add another 432.3g of water and disperse for 30 min; vacuum distill at 35°C for 40 min to remove acetone and obtain the epoxy polyurethane dispersion.
[0132] Example 3
[0133] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin A, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin A to the polyurethane prepolymer is 1.5:1.
[0134] The preparation method of the epoxy polyurethane dispersion includes the following steps:
[0135] (1) Add 300.0g of modified epoxy resin A and 200.0g of polyurethane prepolymer to the reactor, mix well, and react at 80℃ for 1.5h.
[0136] (2) Cool the reactor to 40°C, add 5.2g of triethylamine, neutralize for 40 min, add 433.5g of water and disperse for 20 min, then add another 433.5g of water and disperse for 30 min; vacuum distill at 35°C for 40 min to remove acetone and obtain the epoxy polyurethane dispersion.
[0137] Example 4
[0138] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin A, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin A to the polyurethane prepolymer is 1:1.
[0139] The preparation method of the epoxy polyurethane dispersion includes the following steps:
[0140] (1) Add 250.0g of modified epoxy resin A and 250.0g of polyurethane prepolymer to the reactor, mix well, and react at 80℃ for 1.5h.
[0141] (2) Cool the reactor to 40°C, add 6.5g of triethylamine, neutralize for 40 min, add 434.8g of water and disperse for 20 min, then add another 434.8g of water and disperse for 30 min; vacuum distill at 35°C for 40 min to remove acetone and obtain the epoxy polyurethane dispersion.
[0142] Example 5
[0143] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin B, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin B to the polyurethane prepolymer is 1.5:1.
[0144] The preparation method of the epoxy polyurethane dispersion differs from that of Example 3 only in that modified epoxy resin A is replaced with modified epoxy resin B in an equal amount; all other raw materials, process parameters, and steps are the same as in Example 3.
[0145] Example 6
[0146] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin C, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin C to the polyurethane prepolymer is 1.5:1.
[0147] The preparation method of the epoxy polyurethane dispersion differs from that of Example 3 only in that modified epoxy resin A is replaced with modified epoxy resin C in equal amounts; all other raw materials, process parameters, and steps are the same as in Example 3.
[0148] Comparative Example 1
[0149] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin A, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin A to the polyurethane prepolymer is 9:1.
[0150] The preparation method of the epoxy polyurethane dispersion includes the following steps:
[0151] (1) Add 450.0g of modified epoxy resin A and 50.0g of polyurethane prepolymer to the reactor, mix well, and react at 80℃ for 1.5h.
[0152] (2) Cool the reactor to 40°C, add 1.3g of triethylamine, neutralize for 40 min, add 429.8g of water and disperse for 20 min, then add another 429.8g of water and disperse for 30 min; vacuum distill at 35°C for 40 min to remove acetone and obtain the epoxy polyurethane dispersion.
[0153] Comparative Example 2
[0154] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin A, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin A to the polyurethane prepolymer is 3:7.
[0155] The preparation method of the epoxy polyurethane dispersion includes the following steps:
[0156] (1) Add 150.0g of modified epoxy resin A and 350.0g of polyurethane prepolymer to the reactor, mix well, and react at 80℃ for 1.5h.
[0157] (2) Cool the reactor to 40°C, add 9.0g of triethylamine, neutralize for 40 min, add 437.4g of water and disperse for 20 min, then add another 437.4g of water and disperse for 30 min; vacuum distill at 35°C for 40 min to remove acetone and obtain the epoxy polyurethane dispersion.
[0158] Comparative Example 3
[0159] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin D, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin D to the polyurethane prepolymer is 1.5:1.
[0160] The preparation method of the epoxy polyurethane dispersion differs from that of Example 3 only in that modified epoxy resin A is replaced with modified epoxy resin D in equal amounts; all other raw materials, process parameters, and steps are the same as in Example 3.
[0161] Comparative Example 4
[0162] An epoxy polyurethane dispersion, wherein the raw materials for preparing the epoxy polyurethane dispersion include modified epoxy resin E, polyurethane prepolymer provided in Preparation Example 4, triethylamine and water; the mass ratio of the modified epoxy resin E to the polyurethane prepolymer is 1.5:1.
[0163] The preparation method of the epoxy polyurethane dispersion differs from that of Example 3 only in that modified epoxy resin A is replaced with modified epoxy resin E in an equal amount; all other raw materials, process parameters, and steps are the same as in Example 3.
[0164] The epoxy polyurethane dispersions provided in Examples 1-6 and Comparative Examples 1-4 were formulated into coatings according to Table 1 below. The coatings were then subjected to performance tests according to the following methods. The test results are shown in Tables 2 and 3.
[0165] Table 1
[0166]
[0167]
[0168] The sources of each substance are as follows in Table 1:
[0169] (1) Hydrophobically modified hydroxyethyl cellulose HE3KB: purchased from Ashland;
[0170] (2) Dispersant Orotan 731A: purchased from Dow;
[0171] (3) Nonionic wetting agent NOVELUTION GT406K: purchased from Sasol;
[0172] (4) Defoamer Tego 901w: purchased from Digo;
[0173] (5) Drying agent OXY-Coat1101: Purchased from OMG in the USA;
[0174] (6) Anti-flash rust agent Ascoli H14: purchased from Ascoli;
[0175] (7) Coadd, a freeze-thaw stabilizer TM FD-101: Purchased from Puwei Additives;
[0176] (8) Defoamer FoamStar ST 2437: purchased from BASF;
[0177] (9) Associative polyurethane thickener WT-105A: purchased from Haimingsideqian.
[0178] Performance testing:
[0179] (1) Pencil hardness test method: determined according to GB / T 6739-2022;
[0180] (2) Storage stability test method: determined according to section 5.4.2 of HG / T 4758-2014;
[0181] (3) The bond strength is expressed as the pull-off adhesion, and the test method is determined in accordance with GB / T 5210-2006;
[0182] (4) Anti-adhesion test method: ① Take two 150mm*70mm*1mm cold-rolled steel plates, sand them with 100-grit sandpaper, clean them with alcohol, and prepare the plates by air spraying. The plates are cured under standard conditions. The dry film thickness of the paint film is 60±5μm, and the curing time (self-drying time) is 5h. ② Stack the two plates with paint film face to face and put them in a 60℃ forced-air drying oven. Place a 5kg weight vertically on the top cold-rolled plate and keep it at 60℃ for 24h. Then take out the plates and observe the ease of separation and estimate the area of paint film damage. The ease of separation of the plates is represented by natural separation (A), slight tapping separation (B), separation with slight force (C), separation with medium force (D), separation with strong force (E), and separation using tools (F), i.e., the adhesion level. The adhesion level and the area of paint film damage are tested with the same test steps when the curing time is 24h.
[0183] (5) Low-temperature film-forming property test method: ① Take a flat steel plate, polish it with 100-grit sandpaper, wipe it clean with alcohol, and set it aside; ② Place the flat steel plate, wet film preparation device (200um) and coating at 5℃ for 30min to pre-cool; ③ Use the wet film preparation device in ② to scrape a 200um wet film on the flat steel plate, place the wet film at 5℃ for 4h, then take it out and observe whether there are any abnormalities on the surface of the paint film; test the low-temperature film-forming property at 0℃ using the same test steps.
[0184] Table 2
[0185]
[0186]
[0187] Table 3
[0188]
[0189] Examples 1-4 and Comparative Examples 1-2 show that an appropriate amount of polyurethane prepolymer can improve the low-temperature film-forming properties and storage stability of the coating film. Excessive amounts will reduce the hardness, anti-tack properties, and adhesive strength of the coating film. Examples 3 and Comparative Examples 3-4 show that an appropriate amount of vinylsiloxane is beneficial for improving the adhesive strength, hardness, and anti-tack properties of the coating film, especially early anti-tack properties. Excessive amounts will worsen the storage stability of the coating, while insufficient amounts will reduce the adhesive strength of the coating film.
[0190] The applicant declares that the detailed process equipment and process flow of this invention are illustrated through the above embodiments, but this invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that this invention must rely on the above detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the products of this invention, additions of auxiliary components, and selection of specific methods, all fall within the protection scope and disclosure scope of this invention.
Claims
1. An epoxy polyurethane dispersion characterized in that, The raw materials for preparing the epoxy polyurethane dispersion include a combination of modified epoxy resin, polyurethane prepolymer, neutralizer and water; The mass ratio of the modified epoxy resin to the polyurethane prepolymer is (1-4):1; The raw materials for preparing the polyurethane prepolymer include the following components by mass percentage: 40-70% diol, 3-6% hydroxy acid, 15-45% diisocyanate, and 5-10% amino-terminated polyether; The raw materials for preparing the modified epoxy resin include a combination of fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinyl siloxanes, and epoxy resins. The epoxy resin includes liquid bisphenol A epoxy resin; The modified epoxy resin is prepared by the following method, which includes the following steps: (S1) The fatty acid containing conjugated double bonds undergoes an addition reaction with vinylsiloxane to obtain the reaction product; (S2) The reaction product, the epoxy resin, and the fatty acid without conjugated double bonds are subjected to an esterification reaction to obtain the modified epoxy resin; Based on the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinyl siloxanes, and epoxy resin as 100%, the mass percentage of vinyl siloxanes is 3-10%.
2. The epoxy polyurethane dispersion according to claim 1, characterized in that, The fatty acids containing conjugated double bonds include dehydrated castor oil and / or tung oil acid.
3. The epoxy polyurethane dispersion according to claim 1, characterized in that, Based on the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinyl siloxanes, and epoxy resin as 100%, the mass percentage of the fatty acids containing conjugated double bonds is 3-17%.
4. The epoxy polyurethane dispersion according to claim 1, characterized in that, The fatty acids that do not contain conjugated double bonds include any one or a combination of at least two of linoleic acid, linolenic acid, oleic acid, or arachidonic acid.
5. The epoxy polyurethane dispersion according to claim 1, characterized in that, Based on the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinylsiloxane, and epoxy resin as 100%, the mass percentage of the fatty acids without conjugated double bonds is 12-56%.
6. The epoxy polyurethane dispersion according to claim 1, characterized in that, The vinylsiloxane includes any one or a combination of at least two of vinyltriisopropoxysiloxane, vinyltri(2-methoxyethoxy)silane, vinyltriethoxysilane, or vinylmethyldiethoxysilane.
7. The epoxy polyurethane dispersion according to claim 1, characterized in that, The liquid bisphenol A epoxy resin includes any one or a combination of at least two of E-51, E-44, E-42, E-54, E-35 or E-31.
8. The epoxy polyurethane dispersion according to claim 1, characterized in that, The epoxy equivalent of the epoxy resin is 170-430.
9. The epoxy polyurethane dispersion according to claim 1, characterized in that, The epoxy resin has a mass percentage of 35-62%, calculated as 100% of the total mass of the fatty acids containing conjugated double bonds, fatty acids without conjugated double bonds, vinylsiloxane, and epoxy resin.
10. The epoxy polyurethane dispersion according to claim 1, characterized in that, The addition reaction is performed at a temperature of 70-110℃.
11. The epoxy polyurethane dispersion according to claim 1, characterized in that, The addition reaction takes 1-3 hours.
12. The epoxy polyurethane dispersion according to claim 1, characterized in that, The esterification reaction is carried out at a temperature of 120-160℃.
13. The epoxy polyurethane dispersion according to claim 1, characterized in that, The esterification reaction takes 1-3 hours.
14. The epoxy polyurethane dispersion according to claim 1, characterized in that, The esterification reaction in step (S2) is carried out in the presence of a solvent, a polymerization inhibitor, and a catalyst.
15. The epoxy polyurethane dispersion according to claim 14, characterized in that, The solvent includes N-methylpyrrolidone and / or methylpentyl ketone.
16. The epoxy polyurethane dispersion according to claim 14, characterized in that, The mass ratio of the epoxy resin to the solvent is (2.5-14):
1.
17. The epoxy polyurethane dispersion according to claim 14, characterized in that, The polymerization inhibitors include p-hydroxyanisole and / or hydroquinone.
18. The epoxy polyurethane dispersion according to claim 14, characterized in that, Based on the epoxy resin as 100% by mass, the polymerization inhibitor is 0.3-1.5% by mass.
19. The epoxy polyurethane dispersion according to claim 14, characterized in that, The catalyst comprises any one or a combination of at least two of dimethylaniline, tetrabutylammonium bromide, or triphenylphosphine.
20. The epoxy polyurethane dispersion according to claim 14, characterized in that, The mass of the catalyst is 0.3-1.5% based on the mass of the epoxy resin being 100%.
21. The epoxy polyurethane dispersion according to claim 1, characterized in that, The modified epoxy resin in the raw materials for preparing the epoxy polyurethane dispersion has a mass percentage content of 18-30%.
22. The epoxy polyurethane dispersion according to claim 1, characterized in that, The diol comprises a combination of hydroxyl-terminated polysiloxane and polytetrahydrofuran ether diol.
23. The epoxy polyurethane dispersion according to claim 22, characterized in that, The molar ratio of the terminal hydroxyl polysiloxane to polytetrahydrofuran ether diol is 1:(1-3).
24. The epoxy polyurethane dispersion according to claim 22, characterized in that, The hydroxyl-terminated polysiloxanes include polydimethylsiloxanes with hydroxypropyl end-capped groups and / or polydimethylsiloxanes with dihydroxy end-capped groups.
25. The epoxy polyurethane dispersion according to claim 22, characterized in that, The number-average molecular weight of the terminal hydroxyl polysiloxane is 1000-2000.
26. The epoxy polyurethane dispersion according to claim 22, characterized in that, The number-average molecular weight of the polytetrahydrofuran ether diol is 1000-2000.
27. The epoxy polyurethane dispersion according to claim 1, characterized in that, The hydroxy acids include dimethylolbutyric acid and / or dimethylolpropionic acid.
28. The epoxy polyurethane dispersion according to claim 1, characterized in that, The diisocyanate includes any one or a combination of at least two of toluene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, or 1,4-cyclohexane diisocyanate.
29. The epoxy polyurethane dispersion according to claim 1, characterized in that, The amino-terminated polyether has the structure shown in Formula I: Formula I; Where R is -H or -CH3; x is an integer selected from 1 to 20; y is an integer selected from 1 to 35.
30. The epoxy polyurethane dispersion according to claim 1, characterized in that, The number-average molecular weight of the terminal amino polyether is 500-2000.
31. The epoxy polyurethane dispersion according to claim 1, characterized in that, The polyurethane prepolymer was prepared by the following method, which includes the following steps: (X1) The diol, the hydroxy acid and the diisocyanate are mixed and reacted to obtain an isocyanate-terminated polyurethane prepolymer; (X2) The isocyanate-terminated polyurethane prepolymer is reacted with the amino-terminated polyether to obtain the polyurethane prepolymer.
32. The epoxy polyurethane dispersion according to claim 31, characterized in that, The reaction described in step (X1) is carried out in the presence of an organic solvent.
33. The epoxy polyurethane dispersion according to claim 32, characterized in that, The organic solvent includes acetone.
34. The epoxy polyurethane dispersion according to claim 32, characterized in that, The organic solvent comprises 4-10% of the mass of the diol, hydroxy acid, diisocyanate, amino-terminated polyether and organic solvent, which together constitute 100% of the total mass.
35. The epoxy polyurethane dispersion according to claim 31, characterized in that, The reaction temperature in step (X1) is 70-85℃.
36. The epoxy polyurethane dispersion according to claim 31, characterized in that, The reaction time in step (X1) is 1-3 hours.
37. The epoxy polyurethane dispersion according to claim 31, characterized in that, The reaction temperature in step (X2) is 30-60℃.
38. The epoxy polyurethane dispersion according to claim 31, characterized in that, The reaction time in step (X2) is 1-3 hours.
39. The epoxy polyurethane dispersion according to claim 1, characterized in that, The neutralizing agent includes any one or a combination of at least two of triethylamine, ammonia, or N,N-dimethylethanolamine.
40. The epoxy polyurethane dispersion according to claim 1, characterized in that, The neutralizing agent in the raw materials for preparing the epoxy polyurethane dispersion has a mass percentage content of 0.15-0.5%.
41. The epoxy polyurethane dispersion according to claim 1, characterized in that, The water content in the raw materials for preparing the epoxy polyurethane dispersion is 60-65% by mass.
42. A method for preparing an epoxy polyurethane dispersion according to any one of claims 1-41, characterized in that, The preparation method includes the following steps: (1) The modified epoxy resin reacts with the polyurethane prepolymer to obtain the reaction product; (2) The reaction product is neutralized with a neutralizing agent, and the resulting reaction product is mixed with water to obtain the epoxy polyurethane dispersion.
43. The preparation method according to claim 42, characterized in that, The reaction temperature in step (1) is 70-85℃.
44. The preparation method according to claim 42, characterized in that, The reaction time in step (1) is 1-3 hours.
45. The preparation method according to claim 42, characterized in that, The neutralization reaction is carried out at a temperature of 30-50°C.
46. The preparation method according to claim 42, characterized in that, The neutralization reaction takes 20-50 minutes.
47. The preparation method according to claim 42, characterized in that, The reaction product, after being mixed with water, also includes a step of removing the organic solvent.
48. The preparation method according to claim 47, characterized in that, The method for removing organic solvents includes vacuum distillation.
49. The preparation method according to claim 48, characterized in that, The temperature of the vacuum distillation is 35-55℃.
50. The preparation method according to claim 48, characterized in that, The vacuum distillation time is 30-60 minutes.
51. A water-based industrial coating, characterized in that, The waterborne industrial coating includes the epoxy polyurethane dispersion as described in any one of claims 1-41.