CN115418159A - Polyimide waterborne polyurethane coating and preparation method and application thereof - Google Patents
Polyimide waterborne polyurethane coating and preparation method and application thereof Download PDFInfo
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- CN115418159A CN115418159A CN202211148778.8A CN202211148778A CN115418159A CN 115418159 A CN115418159 A CN 115418159A CN 202211148778 A CN202211148778 A CN 202211148778A CN 115418159 A CN115418159 A CN 115418159A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention belongs to the technical field of waterborne polyurethane coatings. The invention provides a polyimide waterborne polyurethane coating. The paint comprises 10-15 parts of waterborne polyimide resin, 45-65 parts of waterborne polyurethane resin, 5-10 parts of curing agent, 0.5-2 parts of flatting agent, 0.5-1 part of dispersing agent, 0.1-0.5 part of defoaming agent, 10-20 parts of pigment, 50-100 parts of filler and 50-100 parts of water. The invention also provides a preparation method and application of the polyimide waterborne polyurethane coating. The polyimide waterborne polyurethane coating disclosed by the invention is good in stability, high in water resistance, low in curing temperature, short in curing time, environment-friendly, non-toxic, low in requirement on use environment and convenient to use.
Description
Technical Field
The invention relates to the technical field of aqueous polyurethane coatings, in particular to a polyimide aqueous polyurethane coating and a preparation method and application thereof.
Background
Polyurethanes are those obtained by the polyaddition of isocyanates and polyethers. At present, a great number of different polyurethane coating systems with outstanding quality are formed. The coating has the advantages of good waterproof effect, high resistance, strong ground-holding power, high flexibility, excellent high and low temperature tolerance, high corrosion resistance, convenient maintenance and the like, is highly valued and favored by the waterproof industry, is widely applied to the construction of underground tunnels, roofs, subways, dams, pipelines, dense underground water layers and other projects, and is the waterproof coating which is most widely used and consumed.
In recent years, although the use of polyurethane coatings containing solvents and organic fillers to promote hydration of polyurethane coatings has been widely used, it has also severely limited environmental awareness and concerns over their health, as well as environmental regulations that place strict demands on Volatile Organic Compound (VOCs) emissions and harmful solvent content-powder development and high solids content.
The waterborne polyurethane is safer in use and can not volatilize a large amount of toxic and harmful gases polluting the environment, so that the waterborne polyurethane becomes a hotspot in the coating world in recent years. But compared with the traditional solvent type polyurethane coating, the water resistance is poor, the mechanical strength is low, and the aging resistance and the thermal stability are not strong enough.
Therefore, the research and development of the waterborne polyurethane coating with good water resistance, good aging resistance, strong thermal stability and high mechanical strength has good prospect.
Disclosure of Invention
The invention aims to provide a polyimide waterborne polyurethane coating and a preparation method and application thereof aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyimide waterborne polyurethane coating which comprises the following components in parts by weight:
10 to 15 parts of water-based polyimide resin, 45 to 65 parts of water-based polyurethane resin, 5 to 10 parts of curing agent, 0.5 to 2 parts of flatting agent, 0.5 to 1 part of dispersing agent, 0.1 to 0.5 part of defoaming agent, 10 to 20 parts of pigment, 50 to 100 parts of filler and 50 to 100 parts of water.
Preferably, the preparation method of the aqueous polyurethane resin comprises the following steps:
1) 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and 3, 5-dihydroxy benzoic acid react under the condition of concentrated sulfuric acid to obtain a product 1;
2) Reacting the urea formic acid with the product 1 to obtain a product 2;
3) Reacting 4-hydroxyphthalic acid with the product 2 under the condition of dicyclohexylcarbodiimide to obtain a product 3;
4) And (3) reacting the 4-hydroxybenzenesulfonic acid with the product 3 to obtain the waterborne polyurethane resin.
Preferably, the mass of the concentrated sulfuric acid in the step 1) accounts for 1-3% of the total mass of the 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and the 3, 5-dihydroxybenzoic acid; the mol ratio of the 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone, the 3, 5-dihydroxybenzoic acid, the urea formic acid, the 4-hydroxyphthalic acid, the dicyclohexyl carbodiimide and the 4-hydroxybenzenesulfonic acid is 2-20: 2 to 20:3 to 21:0.5 to 2:0.05 to 0.2:0.5 to 2; the reaction temperature of the steps 1) to 4) is 120-160 ℃, and the reaction time is 1-2 h.
Preferably, the structural formula of the aqueous polyurethane resin is as follows:
wherein n is any natural number from 2 to 20.
Preferably, the curing agent is one or more of triglycidyl isocyanurate, polyisocyanate, m-xylylenediamine and isophorone diamine; the leveling agent is one or more of polydimethylsiloxane, diacetone alcohol, polyacrylate and nitrocellulose.
Preferably, the dispersant is one or more of sulfated castor oil, sodium polyethylene glycol alkyl aryl ether sulfonate and sulfate ester salt;
the defoaming agent is a polyether defoaming agent;
the pigment is one or more of titanium dioxide, cadmium red, molybdate orange, chromium oxide green, phthalocyanine blue and iron black;
the filler is one or more of calcium carbonate, barite powder, talcum powder, kaolin, white carbon black, mica powder and bentonite.
The invention provides a preparation method of a polyimide waterborne polyurethane coating, which comprises the following steps:
1) Mixing the water-based polyimide resin, the water-based polyurethane resin, the flatting agent, the dispersing agent, part of the defoaming agent and the first part of water, and then reacting to obtain a mixture I;
2) Mixing the mixture I, the pigment, the filler, the residual defoaming agent and the second part of water, and grinding to obtain a mixture II;
3) And mixing the mixture II, a curing agent and the residual water to obtain the polyimide waterborne polyurethane coating.
Preferably, the mixing time in the step 1) is 1-2 h, the reaction temperature is 110-130 ℃, and the reaction time is 1-2 h; the grinding time in the step 2) is 1-3 h; the mixing time in the step 3) is 5-10 min, and the mixing rotating speed is 600-800 r/min.
Preferably, the mass ratio of the first part of water in the step 1), the second part of water in the step 2) and the residual water in the step 3) is 1-3: 3 to 5:1 to 3; the mass ratio of the partial defoaming agent in the step 1) to the residual defoaming agent in the step 2) is 1-2: 2 to 3.
The invention also provides the application of the polyimide waterborne polyurethane coating, which is to mix the polyimide waterborne polyurethane coating with water and then coat the mixture;
the mass ratio of the polyimide waterborne polyurethane coating to water is (2-4): 1; the coating is carried out in two times, and the second coating is carried out after 10-25 min after the first coating is finished.
The beneficial effects of the invention include the following:
1) The benzenesulfonic acid group contained in the waterborne polyurethane resin can promote the polyurethane resin to be self-emulsified, can be ground into color paste together with the pigment, and has better paint making performance compared with the polyurethane resin with an external emulsifier; in addition, the self-emulsifying polyurethane emulsion is more stable, emulsion breaking is not easy to occur under the high-temperature condition, special equipment is not needed after the emulsion is settled, the emulsion can be dispersed by slightly stirring, and the use is convenient.
2) According to the polyimide waterborne polyurethane coating, an imide structure with good stability and heat resistance is added on the basis of a polyurethane structure, the introduction of the rigid group not only enhances the thermal stability, chemical corrosion resistance and wear resistance of the polyurethane, but also forms hydrogen bonds among carbonyl groups on the imide group, enhances intermolecular force and microphase separation, and enables the material to have more excellent mechanical properties and stronger water resistance.
3) The polyimide waterborne polyurethane coating contains a triazole structure, wherein the triazole structure is a plane divalent segment with strong rigidity, and can enhance the mechanical property and mechanical property of the coating; in addition, the addition of the triazole ring can obviously improve the thermal property of the polyurethane resin, enhance the water resistance of the coating and reduce the curing time and the curing temperature of the coating.
4) The polyimide waterborne polyurethane coating disclosed by the invention is low in volatility, can be stored for a long time, is harmless to workers when being prepared and coated, does not need to wear gas masks, is convenient to use, saves time and labor, and has low requirements on use environments.
Detailed Description
The invention provides a polyimide waterborne polyurethane coating which comprises the following components in parts by weight:
10 to 15 parts of water-based polyimide resin, 45 to 65 parts of water-based polyurethane resin, 5 to 10 parts of curing agent, 0.5 to 2 parts of flatting agent, 0.5 to 1 part of dispersing agent, 0.1 to 0.5 part of defoaming agent, 10 to 20 parts of pigment, 50 to 100 parts of filler and 50 to 100 parts of water.
The polyimide aqueous polyurethane coating material of the present invention contains 10 to 15 parts of an aqueous polyimide resin, preferably 11 to 14 parts, more preferably 12 to 13 parts, and still more preferably 12.5 parts.
In the present invention, the aqueous polyimide resin is preferably a PMR-II type polyimide resin.
The polyimide aqueous polyurethane coating material of the present invention contains 45 to 65 parts of an aqueous polyurethane resin, preferably 50 to 60 parts, more preferably 53 to 57 parts, and still more preferably 55 parts.
In the invention, the preparation method of the waterborne polyurethane resin comprises the following steps:
1) 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and 3, 5-dihydroxy benzoic acid react under the condition of concentrated sulfuric acid to obtain a product 1;
2) Reacting the urea formic acid with the product 1 to obtain a product 2;
3) Reacting 4-hydroxyphthalic acid with the product 2 under the condition of dicyclohexylcarbodiimide to obtain a product 3;
4) And (3) reacting the 4-hydroxybenzenesulfonic acid with the product 3 to obtain the waterborne polyurethane resin.
In the invention, the mass of the concentrated sulfuric acid in the step 1) accounts for 1-3% of the total mass of the 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and the 3, 5-dihydroxybenzoic acid, preferably 1.5-2.5%, and more preferably 2%; the mol ratio of the 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone, the 3, 5-dihydroxybenzoic acid, the urea formic acid, the 4-hydroxyphthalic acid, the dicyclohexyl carbodiimide and the 4-hydroxybenzenesulfonic acid is 2-20: 2 to 20:3 to 21:0.5 to 2:0.05 to 0.2:0.5 to 2, preferably 5 to 17:5 to 17:6 to 18:0.8 to 1.7:0.08 to 0.17:0.8 to 1.7, more preferably 10 to 12:10 to 12:10 to 14:1.1 to 1.4:0.11 to 0.14:1.1 to 1.4, more preferably 11:11:12:1.2:0.12:1.2; the reaction temperature in the steps 1) to 4) is independently 120-160 ℃, preferably 130-150 ℃, more preferably 135-145 ℃, and more preferably 140 ℃; the reaction time is independently 1 to 2 hours, preferably 1.2 to 1.8 hours, more preferably 1.4 to 1.6 hours, and still more preferably 1.5 hours.
In the present invention, the concentrated sulfuric acid is preferably a 98% concentrated sulfuric acid by mass concentration.
In the invention, the reaction equation for preparing the aqueous polyurethane resin is as follows:
wherein n is any natural number from 2 to 20, preferably any natural number from 8 to 14, and more preferably any natural number from 10 to 12.
The polyimide aqueous polyurethane coating of the present invention contains 5 to 10 parts of a curing agent, preferably 6 to 9 parts, more preferably 7 to 8 parts, and still more preferably 7.5 parts.
In the invention, the curing agent is one or more of triglycidyl isocyanurate, polyisocyanate, m-xylylenediamine and isophorone diamine, preferably triglycidyl isocyanurate, polyisocyanate or m-xylylenediamine, and further preferably triglycidyl isocyanurate or polyisocyanate; the leveling agent is one or more of polydimethylsiloxane, diacetone alcohol, polyacrylate and nitrocellulose, preferably diacetone alcohol, polyacrylate or nitrocellulose, and further preferably diacetone alcohol or polyacrylate.
The polyimide waterborne polyurethane coating comprises 0.5-2 parts of leveling agent, preferably 1-1.5 parts, and more preferably 1.2-1.3 parts.
In the invention, the leveling agent is one or more of polydimethylsiloxane, diacetone alcohol, polyacrylate and nitrocellulose, preferably polydimethylsiloxane, diacetone alcohol or polyacrylate, and further preferably polydimethylsiloxane or diacetone alcohol.
The polyimide aqueous polyurethane coating material of the present invention contains 0.5 to 1 part of a dispersant, preferably 0.6 to 0.9 part, and more preferably 0.7 to 0.8 part.
In the invention, the dispersant is one or more of sulfated castor oil, sodium polyethylene glycol alkyl aryl ether sulfonate and sulfate ester salt, preferably sulfated castor oil and/or sodium polyethylene glycol alkyl aryl ether sulfonate, and further preferably sulfated castor oil and sodium polyethylene glycol alkyl aryl ether sulfonate.
The polyimide aqueous polyurethane coating material of the present invention contains 0.1 to 0.5 part of a defoaming agent, preferably 0.2 to 0.4 part, and more preferably 0.3 part.
In the invention, the defoaming agent is a polyether defoaming agent, preferably GP330 glycerol polyether defoaming agent and polyoxypropylene polyoxyethylene glycerol ether GPE-3000.
The polyimide aqueous polyurethane coating material of the present invention contains 10 to 20 parts of a pigment, preferably 12 to 18 parts, more preferably 14 to 16 parts, and still more preferably 15 parts.
In the invention, the pigment is one or more of titanium dioxide, cadmium red, molybdenum chromium orange, chromium oxide green, phthalocyanine blue and iron black, preferably one or more of titanium dioxide, cadmium red, molybdenum chromium orange and chromium oxide green.
The polyimide aqueous polyurethane coating material of the present invention contains 50 to 100 parts of a filler, preferably 60 to 90 parts, more preferably 70 to 80 parts, and still more preferably 75 parts.
In the invention, the filler is one or more of calcium carbonate, barite powder, talcum powder, kaolin, white carbon black, mica powder and bentonite, and preferably calcium carbonate, barite powder, talcum powder or kaolin.
The polyimide aqueous polyurethane coating material of the present invention contains 50 to 100 parts of water, preferably 60 to 90 parts, more preferably 70 to 80 parts, and still more preferably 75 parts.
The invention provides a preparation method of a polyimide waterborne polyurethane coating, which comprises the following steps:
1) Mixing the water-based polyimide resin, the water-based polyurethane resin, the flatting agent, the dispersing agent, part of the defoaming agent and the first part of water, and then reacting to obtain a mixture I;
2) Mixing the mixture I, the pigment, the filler, the residual defoaming agent and the second part of water, and grinding to obtain a mixture II;
3) And mixing the mixture II, a curing agent and the residual water to obtain the polyimide waterborne polyurethane coating.
In the invention, the mixing time in the step 1) is 1-2 h, preferably 1.2-1.8 h, more preferably 1.4-1.6 h, and more preferably 1.5h; the reaction temperature is 110-130 ℃, preferably 115-125 ℃, and further preferably 120 ℃; the reaction time is 1-2 h, preferably 1.2-1.8 h, more preferably 1.4-1.6 h, and more preferably 1.5h; the grinding time in the step 2) is 1-3 h, preferably 1.5-2.5 h, further preferably 1.8-2.2 h, and more preferably 2h; the mixing time in the step 3) is 5-10 min, preferably 6-9 min, and more preferably 7-8 min; the mixing speed is 600 to 800r/min, preferably 650 to 750r/min, more preferably 680 to 720r/min, and still more preferably 700r/min.
In the invention, the mass ratio of the first part of water in the step 1), the second part of water in the step 2) and the residual water in the step 3) is 1-3: 3 to 5:1 to 3, preferably 1.5 to 2.5: 3.5-4.5: 1.5 to 2.5, more preferably 2:4:2; the mass ratio of the partial defoaming agent in the step 1) to the residual defoaming agent in the step 2) is 1-2: 2 to 3, preferably 1.2 to 1.8:2.2 to 2.8, more preferably 1.4 to 1.6:2.4 to 2.6.
The invention also provides the application of the polyimide waterborne polyurethane coating, which is to mix the polyimide waterborne polyurethane coating with water and then coat the mixture;
the mass ratio of the polyimide waterborne polyurethane coating to water is 2-4: 1, preferably 2.5 to 3.5:1, more preferably 3:1; the coating is carried out in two times, and the second coating is carried out for 10-25 min after the first coating is finished, preferably 15-20 min, and more preferably 18min.
In the present invention, the surface of the coated object needs to be pretreated before the coating.
The pretreatment is a process of removing floating dust and rust on the surface of the coated object and making the surface of the coated object basically flat.
In the invention, after pretreatment, washing and drying are carried out in sequence; the washing is carried out by adopting clean water; the drying temperature is 80-150 ℃, preferably 100-130 ℃, more preferably 110-120 ℃, and more preferably 115 ℃; the drying time is 10 to 20min, preferably 12 to 18min, more preferably 14 to 16min, and still more preferably 15min.
In the present invention, the coating method is preferably brush coating.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
17g of 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and 30.8g of 3, 5-dihydroxybenzoic acid are reacted for 1H under the conditions that 0.478g of concentrated sulfuric acid with the mass concentration of 98% and the temperature is 120 ℃, so as to obtain a product 1; reacting 41.6g of urea formic acid with the product 1 at 130 ℃ for 2h to obtain a product 2; 9.1g of 4-hydroxyphthalic acid and the product 2 react for 1h under the condition of 1.03g of dicyclohexylcarbodiimide and the temperature of 130 ℃ to obtain a product 3; 8.7g of 4-hydroxybenzenesulfonic acid and the product 3 are reacted for 2 hours at the temperature of 140 ℃ to obtain the aqueous polyurethane resin with the n of 2.
Mixing 10g of PMR-II type polyimide resin, 45g of waterborne polyurethane resin, 0.5g of polydimethylsiloxane, 0.5g of diacetone alcohol, 1g of sulfated castor oil, 0.1g of GP330 glycerol polyether defoamer and 20g of water for 1 hour, and then reacting for 1 hour at the temperature of 110 ℃ to obtain a mixture I; mixing the mixture I, 5g of titanium dioxide, 10g of cadmium red, 5g of molybdenum chromium orange, 50g of talcum powder, 20g of mica powder, 20g of bentonite, 10g of barite powder, 0.2g of GP330 glycerol polyether defoamer and 60g of water, and grinding for 1h to obtain a mixture II; and mixing the mixture II, 5g of m-xylylenediamine and 20g of water for 5min under the condition that the rotating speed is 600r/min to obtain the polyimide waterborne polyurethane coating.
Removing floating dust and rust on the surface of the coated object, washing the surface of the coated object with clear water after the surface is basically flat, and drying the surface in an oven at the temperature of 80 ℃ for 10min; 2g of the polyimide waterborne polyurethane coating and 1g of water are mixed and then brushed on the surface of an object to be coated, and after 10min, the second brushing is carried out.
Example 2
Reacting 25.5g of 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and 46.2g of 3, 5-dihydroxybenzoic acid in 2.151g of concentrated sulfuric acid with the mass concentration of 98% at the temperature of 140 ℃ for 1.5H to obtain a product 1; reacting 62.4g of urea formic acid with the product 1 at 145 ℃ for 1h to obtain a product 2; reacting 18.2g of 4-hydroxyphthalic acid with the product 2 for 2h at the temperature of 150 ℃ in the presence of 2.06g of dicyclohexylcarbodiimide to obtain a product 3; reacting 17.4g of 4-hydroxybenzene sulfonic acid with the product 3 at 160 ℃ for 1h to obtain the waterborne polyurethane resin with n being 3.
Mixing 15g of PMR-II type polyimide resin, 65g of aqueous polyurethane resin, 0.5g of polyacrylate, 0.2g of sodium polyethylene glycol alkyl aryl ether sulfonate, 0.3g of ammonium lauryl sulfate, 0.2g of GP330 glycerol polyether defoamer and 20g of water for 2 hours, and then reacting at 130 ℃ for 2 hours to obtain a mixture I; mixing the mixture I, 5g of iron oxide black, 3g of chromium oxide green, 2g of phthalocyanine blue, 10g of calcium carbonate, 20g of mica powder, 10g of kaolin, 10g of white carbon black, 0.3g of GP330 glycerol polyether defoaming agent and 40g of water, and grinding for 3 hours to obtain a mixture II; and mixing the mixture II, 5g of triglycidyl isocyanurate, 5g of isophorone diamine and 20g of water for 10min under the condition that the rotating speed is 800r/min to obtain the polyimide waterborne polyurethane coating.
Removing floating dust and rust on the surface of the coated object, basically flattening the surface, washing with clear water, and drying in a drying oven at 150 ℃ for 14min; 4g of the polyimide waterborne polyurethane coating and 1g of water are mixed and then brushed on the surface of an object to be coated, and after 25min, the second brushing is carried out.
Example 3
The aqueous polyurethane resin having n of 2 obtained in example 1 was used.
Mixing 12g of PMR-II type polyimide resin, 50g of waterborne polyurethane resin, 2g of nitrocellulose, 0.3g of sulfated castor oil, 0.5g of sodium polyethylene glycol alkyl aryl ether sulfonate, 0.025g of polyoxypropylene polyoxyethylene glycerol ether GPE-3000 and 15g of water for 1.5h, and then reacting for 1.5h at 120 ℃ to obtain a mixture I; mixing the mixture I, 5g of iron oxide black, 10g of chromium oxide green, 10g of calcium carbonate, 25g of bentonite, 15g of mica powder, 10g of kaolin, 10g of white carbon black, 0.075g of polyoxypropylene polyoxyethylene glycerol ether GPE-3000 and 25g of water, and grinding for 2 hours to obtain a mixture II; and mixing the mixture II, 3g of m-xylylenediamine, 5g of triglycidyl isocyanurate and 10g of water for 8min under the condition that the rotating speed is 700r/min to obtain the polyimide waterborne polyurethane coating.
Removing floating dust and rust on the surface of the coated object, basically flattening the surface of the coated object, washing the coated object by using clean water, and drying the coated object in a drying oven at 100 ℃ for 16min; and mixing 3g of the polyimide waterborne polyurethane coating and 1g of water, brushing the mixture on the surface of the coated object, and brushing for the second time after 20 min.
Comparative example 1
After a commercially available high temperature water resistant polyurethane coating (polyurethane finish paint of Dow PUCM 200) was formulated according to the specification, it was coated on the surface of the coated object by brush coating according to the method of example 1.
Comparative example 2
A commercially available aqueous polyurethane waterproofing paint (model: AH-1704B-2) was prepared according to the instructions and was applied by brush coating to the surface of the coated article in the same manner as in example 2.
The coating properties of examples 1 to 2 and comparative examples 1 to 2 were tested, and the items and methods of the tests were as follows
1. Film hardness: measuring the hardness of the paint film by a GB/T6739-2006 colored paint and varnish pencil method;
2. corrosion resistance: GB/T38020.2-2019 watch case and its attachment gold alloy coating part 2: testing the purity, thickness, corrosion resistance and adhesion;
and 3, VOC: measuring the release amount of Volatile Organic Compounds (VOC) in the GB/T37884-2019 coating;
4. high-temperature stability: GB/T1735-1979 paint film heat resistance determination method;
5. the anti-sagging property: GB/T9264-2012 colored paint and varnish sag resistance assessment;
6. water resistance: GB/T1733-1993 paint film water resistance assay;
7. color: visual colorimetry of GB/T9761-2008 colored paints and clear coat colored paints;
the results of the performance test of the coatings of examples 1 to 2 and comparative examples 1 to 2 are shown in table 1.
TABLE 1 Performance test results of the coatings of examples 1 to 2 and comparative examples 1 to 2
As can be seen from Table 1: the performances of the polyimide waterborne polyurethane coatings prepared in the examples 1-2 are superior to those of the common commercial waterborne polyurethane coatings used in the comparative examples 1-2, wherein the high-temperature stability is obviously superior to that of the comparative example 2, and the water resistance is obviously superior to that of the comparative example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The polyimide waterborne polyurethane coating is characterized by comprising the following components in parts by weight:
10 to 15 portions of water-based polyimide resin, 45 to 65 portions of water-based polyurethane resin, 5 to 10 portions of curing agent, 0.5 to 2 portions of flatting agent, 0.5 to 1 portion of dispersant, 0.1 to 0.5 portion of defoamer, 10 to 20 portions of pigment, 50 to 100 portions of filler and 50 to 100 portions of water.
2. The polyimide aqueous polyurethane coating according to claim 1, wherein the preparation method of the aqueous polyurethane resin comprises the following steps:
1) 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone and 3, 5-dihydroxy benzoic acid react under the condition of concentrated sulfuric acid to obtain a product 1;
2) Reacting the urea formic acid with the product 1 to obtain a product 2;
3) Reacting 4-hydroxyphthalic acid with the product 2 under the condition of dicyclohexylcarbodiimide to obtain a product 3;
4) And (3) reacting the 4-hydroxybenzenesulfonic acid with the product 3 to obtain the waterborne polyurethane resin.
3. The polyimide aqueous polyurethane coating according to claim 2, wherein the mass of the concentrated sulfuric acid in the step 1) is 1 to 3% of the total mass of 1, 2-dihydro-3H-1, 2, 4-triazol-3-one and 3, 5-dihydroxybenzoic acid; the mol ratio of the 1, 2-dihydro-3H-1, 2, 4-triazole-3-ketone, the 3, 5-dihydroxybenzoic acid, the urea formic acid, the 4-hydroxyphthalic acid, the dicyclohexyl carbodiimide and the 4-hydroxybenzenesulfonic acid is 2-20: 2 to 20:3 to 21:0.5 to 2:0.05 to 0.2:0.5 to 2; the reaction temperature in the steps 1) to 4) is independently 120-160 ℃, and the reaction time is independently 1-2 h.
4. The polyimide aqueous polyurethane coating according to claim 3, wherein the structural formula of the aqueous polyurethane resin is:
wherein n is any natural number from 2 to 20.
5. The polyimide waterborne polyurethane coating according to claim 1 or 4, wherein the curing agent is one or more of triglycidyl isocyanurate, polyisocyanate, m-xylylenediamine and isophorone diamine; the leveling agent is one or more of polydimethylsiloxane, diacetone alcohol, polyacrylate and nitrocellulose.
6. The polyimide waterborne polyurethane coating of claim 5, wherein the dispersant is one or more of sulfated castor oil, sodium polyethylene glycol alkyl aryl ether sulfonate and sulfate ester salt;
the defoaming agent is a polyether defoaming agent;
the pigment is one or more of titanium dioxide, cadmium red, molybdate orange, chromium oxide green, phthalocyanine blue and iron black;
the filler is one or more of calcium carbonate, barite powder, talcum powder, kaolin, white carbon black, mica powder and bentonite.
7. The method for preparing a polyimide aqueous polyurethane coating material according to any one of claims 1 to 6, comprising the steps of:
1) Mixing the water-based polyimide resin, the water-based polyurethane resin, the flatting agent, the dispersing agent, part of the defoaming agent and the first part of water, and then reacting to obtain a mixture I;
2) Mixing the mixture I, the pigment, the filler, the residual defoaming agent and the second part of water, and grinding to obtain a mixture II;
3) And mixing the mixture II, a curing agent and the residual water to obtain the polyimide waterborne polyurethane coating.
8. The preparation method of claim 7, wherein the mixing time of step 1) is 1-2 h, the reaction temperature is 110-130 ℃, and the reaction time is 1-2 h; the grinding time in the step 2) is 1-3 h; the mixing time in the step 3) is 5-10 min, and the mixing rotating speed is 600-800 r/min.
9. The preparation method according to claim 8, wherein the mass ratio of the first part of water in step 1), the second part of water in step 2) and the residual water in step 3) is 1 to 3:3 to 5:1 to 3; the mass ratio of the partial defoaming agent in the step 1) to the residual defoaming agent in the step 2) is 1-2: 2 to 3.
10. The use of the aqueous polyimide polyurethane coating according to any one of claims 1 to 6, wherein the aqueous polyimide polyurethane coating is mixed with water and applied;
the mass ratio of the polyimide waterborne polyurethane coating to water is (2-4): 1; the coating is carried out in two times, and the second coating is carried out after 10-25 min after the first coating is finished.
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