A nanomaterial modified waterborne epoxy resin paint, a preparation method and use thereof

Abstract

The present application relates to a kind of nanomaterial modified waterborne epoxy resin paint and its preparation method and purposes.The nanomaterial modified waterborne epoxy resin paint includes waterborne epoxy resin, water and curing agent, the nanomaterial modified waterborne epoxy resin paint also includes nanometer aluminium oxide and titanium dioxide nanotube, the mass ratio of nanometer aluminium oxide and titanium dioxide nanotube is 10-20:1.Preferably, the nanometer aluminium oxide is silane coupling agent modified nanometer aluminium oxide, and the titanium dioxide nanotube is silane coupling agent modified titanium dioxide nanotube.The present application is by the compounding of nanometer aluminium oxide and titanium dioxide nanotube, and control specific mass ratio of both, can make waterborne epoxy resin paint have excellent various performances such as electrical property, mechanical property, thermal stability and chemical stability.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of nanomaterial modified waterborne epoxy resin paint and its preparation method and use. BACKGROUND

[0002] With the continuous improvement of environmental protection requirements of society, the environmental protection drawbacks of traditional solvent type insulating paint are increasingly significant, and the use of environmentally friendly water-based impregnating paint is more and more, as a supporting surface paint, the demand for water-based surface paint is also increasing. At present, the industry basically prepares water-based paint in the modified epoxy resin by adding emulsifier, curing agent and the like, and then prepares water-based epoxy surface paint. Although the VOC content of the water-based epoxy surface paint is greatly reduced compared with the traditional solvent type insulating paint, the water-based epoxy resin is environmentally friendly, but the water-based epoxy insulating surface paint prepared at present has many deficiencies, such as short arc resistance time, poor thermal stability, poor corrosion resistance, poor wear resistance, etc., which limits its application and development.

[0003] In order to further improve the performance of water-based surface paint, the method of doping inorganic particle materials is generally used. Studies have found that nanometer inorganic materials (such as nanometer titanium dioxide material) can improve the flame retardant performance of the material while improving its thermal performance and mechanical properties. The commonly used doping materials include silicon dioxide, aluminum oxide, boron nitride, titanium dioxide, etc., but the above-mentioned doping particle size is generally large, and the compatibility with the epoxy resin matrix is poor, which leads to uneven dispersion in the epoxy resin paint, resulting in insufficient overall performance of the epoxy resin paint, such as electrical properties, mechanical properties, thermal stability and chemical stability. SUMMARY

[0004] The technical problem to be solved by the present application is to provide an improved nanomaterial modified waterborne epoxy resin paint, which has excellent performance such as electrical properties, mechanical properties, thermal stability and chemical stability.

[0005] To solve the above technical problems, the technical solution adopted by the present application is as follows:

[0006] A nanomaterial modified waterborne epoxy resin paint comprises waterborne epoxy resin, water and curing agent, and further comprises nanometer aluminum oxide and titanium dioxide nanotube, and the mass ratio of the nanometer aluminum oxide and titanium dioxide nanotube is 10-20:1.

[0007] In some embodiments, the mass ratio of the total mass of the nanometer aluminum oxide and titanium dioxide nanotube to the mass of the waterborne epoxy resin is 0.04-0.20:1.

[0008] In some embodiments, the nanometer alumina trihydrate is a silane coupling agent modified nanometer alumina trihydrate, and the titanium dioxide nanotube is a silane coupling agent modified titanium dioxide nanotube.

[0009] In some embodiments, the silane coupling agent modified nanometer alumina trihydrate and the silane coupling agent modified titanium dioxide nanotube are prepared by mixing nanometer alumina trihydrate and titanium dioxide nanotube with an ethanol solution of silane coupling agent, and drying.

[0010] In some embodiments, the silane coupling agent in the ethanol solution of silane coupling agent accounts for 0.5-1.0% of the total mass of the nanometer alumina trihydrate and the titanium dioxide nanotube.

[0011] In some embodiments, the aqueous epoxy resin is prepared by reacting bisphenol A, epichlorohydrin and hydrophilic modifier diethanolamine, and the mass ratio of bisphenol A, epichlorohydrin and hydrophilic modifier diethanolamine is 1-2:1:0.1-0.2.

[0012] In some embodiments, the reaction temperature is 70-90℃.

[0013] In some embodiments, the nanomaterial modified aqueous epoxy resin paint further comprises a film forming agent, a dispersing agent and a curing accelerator, and the mass ratio of the film forming agent, the dispersing agent, the curing agent, the curing accelerator and the aqueous epoxy resin is 0.1-0.2:0.001-0.005:0.3-0.4:0.01-0.05:1.

[0014] In some embodiments, the film forming agent is 2,2,4-methyl-1,3-pentanediol monoisobutyl ester acid.

[0015] In some embodiments, the dispersing agent is a block copolymer containing a pigment affinity group.

[0016] In some embodiments, the block copolymer is selected from Germany BYK-163 of Bichemical or Germany MOK-5032 of Merck Chemical.

[0017] In some embodiments, the curing accelerator is Japan Ajinomoto PN-23.

[0018] In some embodiments, the curing agent is prepared by the following preparation method: addition reaction of diethylenetriamine and polypropylene glycol diglycidyl ether to obtain an adduct, and reaction of the adduct with an epoxy resin to obtain the curing agent, and the mass ratio of diethylenetriamine, polypropylene glycol diglycidyl ether and epoxy resin is 1-5:0.4-0.6:1.

[0019] In some embodiments, the addition reaction and the temperature of the reaction are both 60-70℃.

[0020] In some embodiments, the epoxy resin is a composite of epoxy resin E-20 and epoxy resin E-12; the mass ratio of the epoxy resin E-20 to the epoxy resin E-12 in the composite is 2-5:1.

[0021] In some embodiments, the nano-material modified waterborne epoxy resin paint further comprises other additives selected from the group consisting of one or more of emulsifiers, wetting agents, defoamers, anti-rust agents, leveling agents, and thickening agents.

[0022] In some embodiments, the wetting agent is a polyether-modified siloxane copolymer.

[0023] In some embodiments, the polyether-modified siloxane copolymer is selected from the group consisting of BASF Hydropalat 875 or Dow Chemical HW-1000.

[0024] In some embodiments, the defoamer is a silicone-free defoaming polymer, preferably BYK-A500 from BYK-Chemie, Germany.

[0025] In some embodiments, the anti-rust agent is a waterborne silane coupling agent, preferably a combination of one or more of KH450, KH566, and KH578.

[0026] In some embodiments, the leveling agent is BYK380 from BYK-Chemie, Germany.

[0027] In some embodiments, the thickening agent is a non-ionic polyurethane-based associative thickening agent, preferably HT-820 from Nantong Hantai Chemical or MA-2 from Nantong Hantai Chemical.

[0028] The present application further provides a method for preparing the nano-material modified waterborne epoxy resin paint as described above, the method comprising the following steps: mixing a waterborne epoxy resin, optionally a film-forming agent, and part of water, and optionally adding an emulsifier to obtain a mixture; adding the nano-aluminum oxide and titanium dioxide nanotubes to the mixture; and then sequentially adding a curing agent, optionally adding a dispersant, optionally adding a wetting agent, optionally adding a defoamer, optionally adding a leveling agent, optionally adding a curing accelerator, optionally adding an anti-rust agent, optionally adding a thickening agent, and the rest of water, and mixing to obtain the nano-material modified waterborne epoxy resin paint.

[0029] In the present application, the optional component can be added or not added, and when the corresponding nano-material modified waterborne epoxy resin paint contains the component, the component is added. The selective addition means that when the corresponding nano-material modified waterborne epoxy resin paint contains the component, the component is added, and when the corresponding nano-material modified waterborne epoxy resin paint does not contain the component, the component is not added.

[0030] In some embodiments, the method further comprises the step of mixing the nano-aluminum trioxide and titanium dioxide nanotube with an ethanol solution of silane coupling agent, drying and modifying before adding the nano-aluminum trioxide and titanium dioxide nanotube.

[0031] In some embodiments, the method further comprises the step of preparing the titanium dioxide nanotube by hydrothermal reaction using anatase phase titanium dioxide powder.

[0032] The present application also provides the use of the aforementioned nano-material modified waterborne epoxy resin paint for insulating paint.

[0033] Thanks to the use of the above technical solutions, the present application has the following advantages compared with the prior art:

[0034] The present application uses the specific compound of nano-aluminum trioxide and titanium dioxide nanotube, controls the specific mass ratio of the two, and uses the specific compound nano-material for modification of waterborne epoxy resin paint. The compound nano-material can form a stable and uniformly dispersed particle and nanotube mixed system in the waterborne epoxy resin paint, in which the titanium dioxide nanotube can separate the nano-aluminum trioxide particles, so that the nano-aluminum trioxide particles are not easy to agglomerate, thereby avoiding the problem of unsatisfactory modification caused by the difficulty in controlling the uniformity of nano-particles, the dispersibility in insulating paint and the high inconsistency of the interface with the insulating paint in the traditional nano-aluminum trioxide / silica particle system. In addition, the modification of nano-aluminum trioxide and titanium dioxide nanotube with silane coupling agent can improve its compatibility with the waterborne epoxy resin matrix. The waterborne epoxy resin paint modified by the above specific compound nano-material has excellent performance such as electrical performance, mechanical performance, thermal stability and chemical stability. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The morphology of the nano-aluminum trioxide and titanium dioxide nanotube mixture modified in Example 1. DETAILED DESCRIPTION

[0036] The technical solutions of the present application will be described in detail below with reference to specific examples, so that those skilled in the art can better understand and implement the technical solutions of the present application, but the present application is not limited in the scope of the described examples.

[0037] Example 1

[0038] The embodiment provides a nanomaterial modified water-based epoxy resin paint, and a preparation method thereof.

[0039] 1) Preparation of titanium dioxide nanotubes: in a high-pressure reaction kettle, titanium dioxide powder in an anatase phase (particle size of about 500 nanometers) and a 10M concentration NaOH solution are added according to a mass ratio of 1:5, the high-pressure reaction kettle is sealed, and then hydrothermal reaction is carried out at 140 DEG C for 72 hours; after the reaction kettle is cooled, the white solid is removed from the high-pressure reaction kettle and washed with a 0.1M hydrochloric acid (HCl) solution, and then washed with a large amount of deionized water until the pH value of the effluent solution is neutral. Finally, the titanium dioxide nanotube product is dried at 80 DEG C to obtain the titanium dioxide nanotubes.

[0040] 2) Preparation of modified nanometer aluminum trioxide and modified titanium dioxide nanotubes: a mixture of nanometer aluminum trioxide particles and the titanium dioxide nanotubes obtained in step 1) (mass ratio of 15:1) is added to an anhydrous ethanol solution of a silane coupling agent KH560 (volume ratio of the silane coupling agent and the anhydrous ethanol is 1:10), the mass percentage of the mixture in the anhydrous ethanol solution is 10%, and ultrasonic dispersion treatment is carried out for 10 minutes; then, oil bath treatment is carried out at 400 DEG C for 4 hours; after the oil bath treatment, the flocculation obtained by the reaction is repeatedly washed with anhydrous ethanol and deionized water, suction filtered, and naturally dried at room temperature to obtain a mixture of modified nanometer aluminum trioxide and modified titanium dioxide nanotubes, and the morphology of the mixture is as shown in Figure 1 .

[0041] 3) Preparation of a water-based epoxy resin: bisphenol A and diethanolamine are dissolved in a 15% mass concentration NaOH aqueous solution, and epoxy chloropropane is rapidly added at 90 DEG C for reaction, wherein the mass ratio of bisphenol A, diethanolamine and epoxy chloropropane is 1:0.1:1; the temperature is controlled to be maintained at 90 DEG C, and after the reaction is completed, the system is left to stand; after the upper alkaline water is removed, the remaining substance is washed with hot water until neutral to remove residual alkali and by-products in the resin, and the obtained product is vacuum dehydrated to obtain a light yellow transparent viscous liquid, which is the water-based epoxy resin.

[0042] 4) Preparation of curing agent: under the condition of dry nitrogen protection, diethylenetriamine was added into a four-necked flask equipped with a thermometer, a reflux condenser, a mechanical stirrer and a dropping funnel, the temperature was raised to 68℃, and then polypropylene glycol diglycidyl ether was slowly added into the flask, and the reaction was carried out at the temperature to obtain diethylenetriamine-polypropylene glycol diglycidyl ether adduct; distillation was carried out, and then a certain amount of diethylene glycol butyl ether was added in the later stage of distillation, and the diethylene glycol butyl ether and a small amount of diethylenetriamine were distilled out together; under the condition of 70℃ and nitrogen protection, a compound solution of epoxy resin E-20 and epoxy resin E-12 (the mass ratio of epoxy resin E-20 and epoxy resin E-12 was 3:1) dispersed in propylene glycol methyl ether was added dropwise into the diethylenetriamine-polypropylene glycol diglycidyl ether adduct, and the reaction was carried out to prepare the curing agent. The mass ratio of diethylenetriamine, polypropylene glycol diglycidyl ether and epoxy resin was 1:0.4:1.

[0043] 5) Preparation of modified water-based epoxy resin paint: 100 g of the water-based epoxy resin prepared in step 3), 20 g of 2,2,4-methyl-1,3-pentanediol monoisobutylate acid, 2 g of French Xingchuang SYNTHRO-COR 609B and 80 g of deionized water were weighed and fully stirred on a stirrer to form a mixture; 8 g of the mixture of modified nano-aluminum oxide and modified titanium dioxide nanotubes prepared in step 2) was added to the mixture under stirring, and after the addition was completed, the stirring was continued for 30 minutes to obtain a uniform mixed slurry; 40 g of the curing agent prepared in step 4), 0.5 g of German BYK-163, 0.5 g of Dow HW-1000, 0.5 g of German BYK-A500, 0.5 g of German BYK380, 5 g of Japanese Ajinomoto PN-23, 2 g of KH566, 1 g of Nantong Hantai Chemical HT-820 and 20 g of deionized water were sequentially added to the mixed slurry to obtain the modified water-based epoxy resin paint.

[0044] Example 2

[0045] The embodiment provides a kind of nanomaterial modified water-based epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in that: step 5) is different, step 5) specifically: 100g water-based epoxy resin prepared in step 3), 30g 2,2,4-methyl-1,3-pentanediol monoisobutyl ester acid, 3g France Xianchuang SYNTHRO-COR 609B and 100g deionized water are placed on stirrer and stirred uniformly to form mixed solution;Under the condition of stirring, 9g the mixture of modified nanometer aluminium trioxide and modified titanium dioxide nanotube prepared in step 2) is added to mixed solution, after adding, continue to stir 30 minutes, obtain uniform mixed slurry;0.4g Germany BYK-163 of Bichemical, 0.4g Dow Chemical HW-1000, 0.4g Germany BYK-A500 of Bichemical, 0.4g Germany BYK380 of Bichemical, 4g Japan Ajinomoto PN-23, 1g KH566, 0.8g Nantong Hantai Chemical HT-820 and 15g deionized water are sequentially added to mixed slurry, and modified water-based epoxy resin paint is obtained.

[0046] Embodiment 3

[0047] The embodiment provides a kind of nanomaterial modified water-based epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in that: step 5) is different, step 5) specifically: 100g water-based epoxy resin prepared in step 3), 30g 2,2,4-methyl-1,3-pentanediol monoisobutyl ester acid, 3g France Xianchuang SYNTHRO-COR 609B and 100g deionized water are placed on stirrer and stirred uniformly to form mixed solution;Under the condition of stirring, 9g the mixture of modified nanometer aluminium trioxide and modified titanium dioxide nanotube prepared in step 2) is added to mixed solution, after adding, continue to stir 30 minutes, obtain uniform mixed slurry;0.4g Germany BYK-163 of Bichemical, 0.4g Dow Chemical HW-1000, 0.4g Germany BYK-A500 of Bichemical, 0.4g Germany BYK380 of Bichemical, 4g Japan Ajinomoto PN-23, 1g KH566, 0.8g Nantong Hantai Chemical HT-820 and 15g deionized water are sequentially added to mixed slurry, and modified water-based epoxy resin paint is obtained.

[0048] Embodiment 4

[0049] The embodiment provides a kind of nanomaterial modified water-based epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in that: in step 2) the mixture of nanometer aluminium trioxide particle and titanium dioxide nanotube, the mass ratio of two is replaced by 10:1 from 15:1.

[0050] Embodiment 5

[0051] The present example provides a kind of nanomaterial modified waterborne epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in: in the mixture of nanometer aluminium oxide particles and titanium dioxide nanotube in step 2), the mass ratio of the two is replaced from 10:1 to 20:1.

[0052] Comparative example 1

[0053] The present comparative example provides a kind of nanomaterial modified waterborne epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in: different in step 2), step 2) prepares the mixture of modified nanometer aluminium oxide, modified nanometer silicon dioxide, specific steps are as follows: the mixture (the mass ratio of the two is 10:1) of nanometer aluminium oxide particles and nanometer silicon dioxide particles (particle size is about 50 nanometers) is added to the anhydrous ethanol solution (the volume ratio of silane coupling agent and anhydrous ethanol is 1:10) of silane coupling agent KH560, the mass percentage of mixture in anhydrous ethanol solution is 10%, and ultrasonic dispersion treatment is handled for 10 minutes;Subsequently, oil bath treatment is carried out at 400 DEG C for 4 hours;After oil bath, the flocculation obtained by reaction is repeatedly cleaned using anhydrous ethanol, deionized water, suction filtration, and natural drying at room temperature, to obtain the mixture of modified nanometer aluminium oxide and modified silicon dioxide.And the mixture of modified nanometer aluminium oxide and modified titanium dioxide nanotube in step 5) of embodiment 1 is replaced with the mixture of modified nanometer aluminium oxide and modified silicon dioxide prepared in step 2).

[0054] Comparative example 2

[0055] The present comparative example provides a kind of nanomaterial modified waterborne epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in: in the mixture of nanometer aluminium oxide particles and titanium dioxide nanotube in step 2), the mass ratio of the two is replaced from 10:1 to 30:1.

[0056] Comparative example 3

[0057] The present comparative example provides a kind of nanomaterial modified waterborne epoxy resin paint, its preparation method is basically same with embodiment 1, the difference is only in: in step 2), only nanometer aluminium oxide is modified, and in step 5), the mixture of modified nanometer aluminium oxide and modified titanium dioxide nanotube is replaced with modified aluminium oxide obtained in step 2).

[0058] Comparative example 4

[0059] The comparative example provides a nano-material modified water-based epoxy resin paint, and its preparation method is basically the same as that of example 1, the difference is only that step 2) is different, step 2) is used to prepare a mixture of modified nano-aluminum oxide and modified nano-titanium dioxide particles, and the specific steps are as follows: a mixture of nano-aluminum oxide particles and nano-titanium dioxide particles (particle size is about 50 nanometers) (mass ratio of the two is 10:1) is added into an anhydrous ethanol solution of silane coupling agent KH566 (volume ratio of silane coupling agent and anhydrous ethanol is 1:10), the mass percentage of the mixture in the anhydrous ethanol solution is 10%, and ultrasonic dispersion treatment is performed for 10 minutes; then oil bath treatment is performed at 400 DEG C for 4 hours; after the oil bath is completed, the flocculation obtained by reaction is repeatedly cleaned with anhydrous ethanol and deionized water, suction filtration is performed, and natural drying is performed at room temperature to obtain a mixture of modified nano-aluminum oxide and modified nano-titanium dioxide particles. And the mixture of modified nano-aluminum oxide and modified nano-titanium dioxide nanotubes in step 5) of example 1 is replaced with the mixture of modified nano-aluminum oxide and modified nano-titanium dioxide particles prepared in step 2).

[0060] After the modified water-based epoxy resin paint prepared in examples 1-5 and comparative examples 1-4 is sprayed on a substrate, the performance of the cured coating film is tested according to GB / 15022.2-2017, and the results are shown in Table 1.

[0061] Table 1 Performance of the cured coating film

[0062]

[0063]

[0064] From the above table 1, it can be seen that by compounding nano-aluminum oxide and nano-titanium dioxide nanotubes and controlling the specific mass ratio of the two, the water-based epoxy resin paint containing the same has excellent performance such as electrical performance, mechanical performance, thermal stability and chemical stability.

[0065] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application should be covered within the protection scope of the present application.

[0066] The endpoints of the ranges and any values in the ranges disclosed herein are not limited to the precise values recited as the exact dimensions are not, and should not be, to be construed as being critical to the scope of the application. Each integer value within a range is to be considered to be a new range. The ranges are intended to encompass any and all sub-ranges. For values which are less than one, one unit is considered to be a sub-range. For values which are not less than one, "one" is considered to be a sub-range.

Claims

1. A nanomaterial-modified waterborne epoxy resin paint comprising a waterborne epoxy resin, water, and a curing agent, characterized by: The nano-material modified water-based epoxy resin paint further comprises nano-aluminum oxide and titanium dioxide nanotubes, and the mass ratio of the nano-aluminum oxide and the titanium dioxide nanotubes is 10-20:

1. The mass ratio of the total mass of the nano-aluminum oxide and the titanium dioxide nanotubes to the mass of the water-based epoxy resin is 0.04-0.20:

1. The nano-aluminum oxide is silane coupling agent modified nano-aluminum oxide, and the titanium dioxide nanotubes are silane coupling agent modified titanium dioxide nanotubes.

2. The nanomaterial-modified waterborne epoxy resin paint according to claim 1, characterized in that: The water-based epoxy resin is prepared by reacting bisphenol A, epichlorohydrin and a hydrophilic modifier diethanolamine, and the feeding mass ratio of the bisphenol A, the epichlorohydrin and the hydrophilic modifier diethanolamine is 1-2:1:0.1-0.

2.

3. The nanomaterial-modified waterborne epoxy resin paint according to claim 1, characterized in that: The nano-material modified water-based epoxy resin paint further comprises a film forming agent, a dispersant and a curing accelerator, and the mass ratio of the film forming agent, the dispersant, the curing agent, the curing accelerator and the water-based epoxy resin is 0.1-0.2:0.001-0.005:0.3-0.4:0.01-0.05:

1.

4. The nanomaterial-modified waterborne epoxy resin paint according to claim 1, characterized in that: The curing agent is prepared by the following preparation method: addition reaction of diethylenetriamine and polypropylene glycol diglycidyl ether to obtain an addition product, and reaction of the addition product with an epoxy resin to obtain the curing agent, and the feeding mass ratio of the diethylenetriamine, the polypropylene glycol diglycidyl ether and the epoxy resin is 1-5:0.4-0.6:

1.

5. The nanomaterial-modified waterborne epoxy resin paint according to claim 4, characterized in that: The epoxy resin is a composite of epoxy resin E-20 and epoxy resin E-12, and the feeding mass ratio of the epoxy resin E-20 to the epoxy resin E-12 in the composite is 2-5:

1.

6. The nanomaterial-modified waterborne epoxy resin paint according to claim 1, characterized in that: The nano-material modified water-based epoxy resin paint further comprises other additives, and the other additives are selected from the combination of one or more of emulsifiers, wetting agents, defoaming agents, anti-flash rust agents, leveling agents and thickening agents.

7. A method for preparing the nanomaterial-modified waterborne epoxy resin paint according to any one of claims 1-6, characterized in that: The method comprises the following steps: mixing the water-based epoxy resin, the optional film forming agent and part of the water, and optionally adding an emulsifier to obtain a mixed solution; adding the nano-aluminum oxide and the titanium dioxide nanotubes to the mixed solution; and then sequentially adding the curing agent, optionally adding a dispersant, optionally adding a wetting agent, optionally adding a defoaming agent, optionally adding a leveling agent, optionally adding a curing accelerator, optionally adding an anti-flash rust agent, optionally adding a thickening agent and the remaining water, and mixing to obtain the nano-material modified water-based epoxy resin paint.

8. Use of the nano-material modified water-based epoxy resin paint according to any one of claims 1-6 for insulation paint.

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