CN115353606B - Anti-seepage aqueous polyurethane resin and preparation method and application thereof - Google Patents

Anti-seepage aqueous polyurethane resin and preparation method and application thereof Download PDF

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CN115353606B
CN115353606B CN202211120943.9A CN202211120943A CN115353606B CN 115353606 B CN115353606 B CN 115353606B CN 202211120943 A CN202211120943 A CN 202211120943A CN 115353606 B CN115353606 B CN 115353606B
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acid
polyurethane resin
water
aqueous polyurethane
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CN115353606A (en
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王璐
王明晶
张新宇
别业强
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Zhongshan Daoqum Chemical Group Co ltd
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Zhongshan Daoqum Chemical Group Co ltd
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • 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
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Abstract

The invention discloses an anti-seepage aqueous polyurethane resin and a preparation method and application thereof, and belongs to the technical field of aqueous paint. The anti-bleeding aqueous polyurethane resin is composed of the following raw materials in parts by weight: 5-30 parts of hydrolysis-resistant polyol, 2-12 parts of water-soluble monomer, 5-25 parts of isocyanate monomer, 3-12 parts of functional monomer, 3-10 parts of chain extender, 0.6-5 parts of catalyst and 4-7 parts of amine. The anti-bleeding water-based polyurethane resin improves the hydrolysis resistance and solvent resistance of the resin through the collocation of the hydrolysis-resistant polyol and the functional monomer, realizes the improvement of the stability and anti-bleeding comprehensive performance of the resin, and can be used for preparing water-based paint or applied to a coating process.

Description

Anti-seepage aqueous polyurethane resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to an anti-seepage water-based polyurethane resin and a preparation method and application thereof.
Background
The traditional coating process adopts three-coating and two-baking, namely, after a layer of paint is coated, baking is carried out, and then a layer of paint is coated, so that the coating bleeding can be effectively avoided, but volatilization of VOCs and energy consumption can be caused in the baking process. The novel coating process is also innovatively developed under the influence of VOCs pollution emission regulations in the aspect of environmental protection, so that the cost is reduced, the environment is protected, the baking temperature is reduced, the baking time is shortened, the coating process is shortened, or the cooperation of multiple coatings is completed under the condition of no baking, but the coating of the coating process is easy to cause bleeding, and high requirements are provided for the anti-bleeding performance of the coating.
The aqueous polyurethane takes water as a main medium, contains no or only a small amount of organic solvent, has the characteristics of low VOCs content, small smell, green environmental protection and the like, and has been widely used in aqueous middle paint for automobiles and aqueous colored paint for automobiles. However, the conventional aqueous polyurethane has poor hydrolysis resistance and solvent resistance, and cannot maintain the long-time stability and the anti-bleeding performance of the resin.
Disclosure of Invention
The invention aims to at least overcome one of the defects in the prior art, and provides an anti-bleeding water-based polyurethane resin, a preparation method and application thereof, which solve the problem of poor anti-bleeding performance of water-based paint, improve the hydrolysis resistance and solvent resistance effects of the water-based polyurethane resin and improve the long-time stability.
In a first aspect, an embodiment of the present invention provides an anti-color-leakage aqueous polyurethane resin, which is implemented by the following technical scheme:
the water-based polyurethane resin with the anti-seepage effect comprises the following raw materials in parts by weight: 5-30 parts of hydrolysis-resistant polyol, 2-12 parts of water-soluble monomer, 5-25 parts of isocyanate, 3-12 parts of functional monomer, 3-10 parts of chain extender, 0.6-5 parts of catalyst and 4-7 parts of amine.
The anti-bleeding aqueous polyurethane resin provided by the embodiment of the invention has at least the following beneficial effects:
according to the invention, through collocation of hydrolysis-resistant polyol and functional monomer, functional monomer is inserted into the resin, so that the resin has steric hindrance and hydrophobic effect, can effectively block hydrolysis of chemical bonds, improve chemical resistance, improve hydrolysis resistance and solvent resistance of the resin, and realize improvement of resin stability and anti-bleeding comprehensive performance.
The water-soluble monomer can improve the stability of the water-based polyurethane resin with anti-seepage performance, so that the resin can stably exist in water.
According to some embodiments of the invention, the raw materials for preparing the color-proof aqueous polyurethane resin further comprise water.
According to some embodiments of the invention, the color-impermeable aqueous polyurethane resin has a hydroxyl value of 5-35mgKOH/g, a viscosity of 30-800 mPa.s, a molecular weight of 3500-80000, and a solids content of 28% -43%. The aqueous polyurethane resin contains hydroxyl groups, and can carry out intermolecular crosslinking reaction with amino resin to obtain better crosslinking density, so that the coating has better water resistance and adhesive force.
Further, the glass transition temperature of the anti-bleeding aqueous polyurethane resin is 10-30 ℃.
According to some embodiments of the invention, the hydrolysis-resistant polyol is prepared from at least two of a polyacid, a polyol, an anhydride, an epoxy monomer, and caprolactone, and at least comprises a polyol.
Further, the polyacid is selected from isophthalic acid, terephthalic acid, succinic acid, adipic acid, dimer acid, maleic acid, 1, 4-cyclohexanedicarboxylic acid.
Further, the anhydride is selected from phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride.
Further, the polyol is selected from the group consisting of 1, 6-hexanediol, ethylene glycol, glycerol, 1, 4-cyclohexanedimethanol, 2-butyl-2-ethyl-1, 3-propanediol, hydroxypivalyl hydroxypivalate, 1, 2-propanediol.
Further, the epoxy monomer is selected from propylene oxide and/or ethylene oxide.
According to some embodiments of the invention, the isocyanate comprises a polyisocyanate and/or an isocyanate prepolymer.
Further, the polyisocyanate is selected from the group consisting of di-isocyanates, tri-isocyanates; the isocyanate prepolymer is selected from the group consisting of isocyanate dimers and isocyanate trimers.
Still further, the isocyanate includes at least one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, tetramethylxylylene diisocyanate.
According to some embodiments of the invention, the water-soluble monomer comprises at least one of dimethylolbutyric acid, dimethylolpropionic acid, sodium 1, 4-butanediol-2-sulfonate, sodium 1, 2-propanediol-3-sulfonate, ethylene glycol, methacrylic acid, acrylic acid, and quaternary amine salt.
According to some embodiments of the invention, the functional monomer comprises at least one of glycidyl versatate, gamma-aminopropyl triethoxysilane, 3-methyl-1, 5-pentanediol, linoleic acid, soy oleic acid, eleostearic acid, gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
According to some embodiments of the invention, the chain extender comprises at least one of ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, ethylenediamine, hexamethylenediamine, dipropylene glycol, castor oil.
According to some embodiments of the invention, the amine comprises at least one of triethylamine, triethanolamine, N '-dimethylethanolamine, N' -diisopropylethylamine, diisopropylamine.
According to some embodiments of the invention, the catalyst comprises organotin, organobismuth.
In a second aspect, an embodiment of the present invention provides a method for preparing the above aqueous polyurethane resin, which is implemented by the following technical scheme:
the preparation method of the aqueous polyurethane resin comprises the following steps:
(1) Mixing and reacting the hydrolysis-resistant polyol and isocyanate in a protective gas atmosphere;
(2) Adding the water-soluble monomer and the catalyst for reaction;
(3) Adding the functional monomer for reaction;
(4) Adding the chain extender for reaction;
(5) Adding amine for neutralization;
(6) Dispersing the neutralized product in water.
The preparation method of the color-proof aqueous polyurethane resin provided by the embodiment of the invention has at least the following beneficial effects:
the preparation method disclosed by the invention is simple in operation method, suitable for industrial production, and capable of reducing the emission of VOCs and reducing the pollution to the environment by taking water as a dispersing agent.
According to some embodiments of the invention, in step (1), the reaction is preceded by: adding a first solvent and mixing with the water-soluble monomer and the catalyst.
According to some embodiments of the invention, the shielding gas in step (1) is selected from one of nitrogen, helium, neon, and argon.
According to some embodiments of the invention, the reaction temperature in step (1) is 70-100 ℃.
According to some embodiments of the invention, the reaction time in step (1) is 1-3h.
According to some embodiments of the invention, the reaction temperature in step (2) is 80-100 ℃.
According to some embodiments of the invention, the reaction time in step (2) is 1-3h.
According to some embodiments of the invention, the reaction time in step (3) is 2-4h.
According to some embodiments of the invention, the reaction time in step (4) is 1-4h.
According to some embodiments of the invention, before the step (5), the method further comprises: adding a second solvent into the reactant obtained in the step (4) for mixing. The addition of the second solvent can avoid excessive viscosity of the system.
Further, the first solvent and the second solvent may be at least one selected from butanone, ethylene glycol butyl ether, propylene glycol methyl ether acetate, butyl acetate, acetone, methyl isobutyl ketone, N-methylpyrrolidone, diethylene glycol butyl ether, respectively.
According to some embodiments of the invention, the step (6) further comprises an operation of removing the solvent when the first solvent and/or the second solvent are added.
Further, the method for removing the solvent is reduced pressure suction filtration.
In a third aspect, the embodiment of the invention provides a water-based paint, which contains the anti-bleeding water-based polyurethane resin.
According to some embodiments of the invention, the aqueous coating comprises an aqueous mid coat, an aqueous color coat.
According to some embodiments of the invention, the bulk resin of the aqueous coating further comprises at least one of an acrylic dispersion, an amino resin.
In a fourth aspect, the embodiment of the invention provides an application of the anti-bleeding aqueous polyurethane resin in a coating process.
According to some embodiments of the invention, the coating process comprises sequentially coating an intermediate coating and a color coating, wherein the intermediate coating and/or the color coating is prepared from a raw material comprising the water-impermeable polyurethane resin.
According to some embodiments of the invention, the middle coating is dried by a first sun-drying.
Further, the temperature of the first airing of the middle coating is room temperature.
Further, the first airing time of the middle coating is 3-5 minutes.
According to some embodiments of the invention, the color coat is dried sequentially by a second sun-drying and baking.
Further, the temperature of the second airing is room temperature.
Further, the second airing time is 4-6 minutes.
Further, the baking temperature is 70-90 ℃.
Further, the baking time is 4-6 minutes.
Detailed Description
For the purposes of clarity, technical solutions and advantages of the present application, the following will be described in further detail with reference to specific embodiments. The embodiments described herein are only some of the embodiments of the present application and should not be construed as limiting the scope of the present application.
Example 1
Preparation of water-based polyurethane resin with anti-seepage performance:
15 parts of phthalic anhydride, 15 parts of terephthalic acid, 10 parts of glycerol and 20 parts of 1, 4-cyclohexanedimethanol are mixed, isopropyl titanate is selected as a catalyst, butanone is selected as a solvent, and the mixture is reacted for 20 hours at the temperature of 150-220 ℃ to prepare the hydrolysis-resistant polyol.
Under the protection of nitrogen, adding 20 parts of hydrolysis-resistant polyol, 15 parts of isophorone diisocyanate trimer, 3 parts of hexamethylene diisocyanate and 20 parts of butanone into a reactor, and reacting for 3 hours at 85 ℃; adding 6 parts of dimethylolbutyric acid and 1 part of tin dilaurate, and reacting for 2 hours; adding 3 parts of soybean oleic acid, and reacting for 1h; 3 parts of 1, 2-propylene glycol is added for chain extension, and the reaction is stirred for 1h. 5 parts of butanone are added, and after the reaction is completed, 6 parts of triethylamine are added for neutralization. The resin was added to 115 parts deionized water under high shear conditions and stirred for 1h. The solvent was removed by suction filtration under reduced pressure to obtain an aqueous polyurethane resin. The resin content was 30%, the viscosity was 550 mPas, the molecular weight of the resin was 18000, and the glass transition temperature was 25 ℃.
Example 2
Preparation of water-based polyurethane resin with anti-seepage performance:
15 parts of dimer acid, 15 parts of terephthalic acid, 10 parts of 1, 6-hexanediol, 18 parts of ethylene glycol and 5 parts of glycerol are mixed, isopropyl titanate is used as a catalyst, butanone is used as a solvent, and the mixture is reacted for 20 hours at 150-220 ℃ to prepare the hydrolysis-resistant polyol.
Under the protection of nitrogen, adding 20 parts of hydrolysis-resistant polyol, 25 parts of hexamethylene diisocyanate and 20 parts of methyl isobutyl ketone into a reactor for reaction for 2 hours at 90 ℃; adding 6 parts of dimethylolpropionic acid and 1.5 parts of organic bismuth, and reacting for 1h; adding 3 parts of gamma-aminopropyl triethoxysilane, and reacting for 2 hours; then 6 parts of 1, 6-hexanediol is added for chain extension, and the reaction is stirred for 2 hours. 4 parts of butanone are added, and after the reaction is completed, 5 parts of N, N' -dimethylethanolamine are added for neutralization. The resin was added to 105 parts deionized water under high shear conditions and stirred for 2h. The solvent was removed by suction filtration under reduced pressure to obtain an aqueous polyurethane resin. The resin had a solids content of 36%, a viscosity of 750 mPas, a molecular weight of 53500 and a glass transition temperature of 18 ℃.
Example 3
Preparation of water-based polyurethane resin with anti-seepage performance:
15 parts of maleic acid, 12 parts of 1, 4-cyclohexanedicarboxylic acid, 5 parts of terephthalic acid, 10 parts of glycerol, 3 parts of ethylene glycol and 18 parts of 1, 4-cyclohexanedimethanol are mixed, isopropyl titanate is selected as a catalyst, butanone is selected as a solvent, and the mixture is reacted for 20 hours at 150-220 ℃ to prepare the hydrolysis-resistant polyol.
Under the protection of nitrogen, adding 20 parts of hydrolysis-resistant polyol, 25 parts of tetramethyl xylylene diisocyanate and 12 parts of N-methylpyrrolidone into a reactor, and reacting for 1h at 90 ℃; adding 5 parts of dimethylolpropionic acid and 1 part of organic bismuth, and reacting for 1.5 hours; adding 5 parts of tertiary glycidyl ester E10p, and reacting for 2 hours; adding 3 parts of 1, 4-butanediol for chain extension, stirring for reaction for 1h, adding 10 parts of N-methylpyrrolidone, and adding 4 parts of N, N' -diisopropylethanolamine for neutralization after the reaction is complete. The resin was added to 150 parts deionized water under high shear conditions and stirred for 1h. The solvent was removed by suction filtration under reduced pressure to obtain an aqueous polyurethane resin. The resin had a solids content of 32%, a viscosity of 120 mPas, a molecular weight of 6800 and a glass transition temperature of 15 ℃.
Example 4
Preparation of water-based polyurethane resin with anti-seepage performance:
5 parts of isophthalic acid, 12 parts of phthalic anhydride, 15 parts of succinic acid, 20 parts of 1, 2-propylene glycol, 10 parts of propylene oxide and 3 parts of ethylene oxide are mixed, isopropyl titanate is selected as a catalyst, butanone is selected as a solvent, and the mixture is reacted for 20 hours at 150-220 ℃ to prepare the hydrolysis-resistant polyol.
Under the protection of nitrogen, adding 25 parts of hydrolysis-resistant polyol, 15 parts of hexamethylene diisocyanate, 5 parts of tetramethyl xylylene diisocyanate and 15 parts of acetone into a reactor, and reacting for 4 hours at 80 ℃; adding 6 parts of dimethylol butyric acid and 1 part of stannous chloride, and reacting for 1h; 3 parts of linoleic acid and 3 parts of hexamethylenediamine are added for reaction for 1 hour, chain extension is carried out, and the reaction is carried out for 1 hour under stirring. 8 parts of acetone is added, and after the reaction is completed, 6 parts of N, N' -dimethylethanolamine is added for neutralization reaction. The resin was added to 150 parts deionized water under high shear conditions and stirred for 1h. The solvent was removed by suction filtration under reduced pressure to obtain an aqueous polyurethane resin. The resin had a solid content of 31%, a viscosity of 200 mPas, a molecular weight of 10200 and a glass transition temperature of 10 ℃.
Comparative example 1
Preparation of aqueous polyurethane resin: under the protection of nitrogen, adding 35 parts of polyester polyol, 10 parts of dicyclohexylmethane diisocyanate and 10 parts of hexamethylene diisocyanate into a reactor for reaction at 90 ℃ for 2 hours; adding 9 parts of dimethylolbutyric acid and 3 parts of trimethylolpropane, and reacting for 2 hours; and cooling after the reaction is finished, and adding 9 parts of triethylamine to perform neutralization reaction for 0.5h. Adding deionized water and ethylenediamine under high shear condition, and stirring for 2h to obtain the aqueous polyurethane resin. The resin content was 32% and the viscosity was 50 mPas.
Comparative example 2
Preparation of aqueous polyurethane resin: under the protection of nitrogen, adding 30 parts of polyether glycol, 2 parts of 1, 4-dihydroxy-2-butane sodium sulfonate, 25 parts of cyclohexane dimethylene diisocyanate and 1.2 parts of stannous chloride into a reactor, heating to 75 ℃, and reacting for 4 hours; adding 2 parts of trimethylolpropane, further reacting for 2 hours, adding 3 parts of hexamethylenediamine, stirring for reacting for 2 hours, cooling, and adding 6 parts of N, N' -diisopropylethylamine for neutralization reaction; 135 parts of deionized water is added under the high shearing condition, and the mixture is stirred for 3 hours to obtain the aqueous polyurethane resin, wherein the solid content of the resin is 35.3%, and the viscosity is 5500 mPa.s.
The resins of examples 1 to 4 and comparative examples 1 to 2 were stored at 50℃for 1 month, and the resins were hydrolyzed to give carboxylic acids, which caused an increase in acid value, and the hydrolysis resistance of the resins was judged based on the measured acid value concentration reflecting the hydrolysis resistance level, and the test results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the resins prepared in examples 1-4 have a hydrolysis resistance of 1 level due to the use of the specific hydrolysis-resistant polyol and the functional monomer, which improves the hydrolysis resistance of the resin, and the resin has a longer shelf life. The comparative examples 1 and 2, because of using common polyester and polyether as raw materials, have relatively poor stability, are easy to hydrolyze, have short storage time, and cannot be stored for a long time.
Waterborne basecoat was prepared according to the formulation of table 2, wherein the waterborne polyurethane resin was selected from the color-resistant waterborne polyurethane resins prepared in examples 1-4 and comparative examples 1-2, respectively.
TABLE 2
Material Weight (g)
Color paste 32
Zhanxin 6803 acrylic acid Dispersion 12
Aqueous polyurethane resin 18
Zhanxin 305 amino resin 4
BYK-052 defoamer 0.1
BYK-AT204 dispersant 0.1
BYK-349 leveling agent 0.2
Deionized water 8
Aqueous color paints were prepared according to the formulation of table 3, wherein the aqueous polyurethane resins were selected from the barrier aqueous polyurethane resins prepared in examples 1-4 and comparative examples 1-2, respectively.
TABLE 3 Table 3
The aqueous basecoat and aqueous colorcoat prepared using the aqueous polyurethane resins of the respective examples and comparative examples were applied, the application comprising two layers of a basecoat and a colorcoat, the basecoat being air-cured at room temperature for 4 minutes, the colorcoat being air-cured at room temperature for 5 minutes and then baked at 80 ℃ for 5 minutes, the basecoat having a coating thickness of 20 μm and the colorcoat having a coating thickness of 15 μm, the coated substrate being a PC plastic board, the test results being shown in table 4:
TABLE 4 Table 4
The test results in Table 4 show that on the premise of fixing the coating formulation, the resins in examples 1-4 have steric hindrance and hydrophobic effect, can effectively block the hydrolysis of chemical bonds, improve the chemical resistance, and have better anti-biting ability than those in comparative examples 1 and 2, so that the coatings prepared in examples 1-4 are added to have no anti-biting or flowering phenomenon during spraying, the surface of the board is flat, and the matched coating has good appearance and adhesion. Comparative examples 1 and 2 had lower permeation resistance than examples 1-4, and localized permeation and blushing occurred when the coatings were prepared using comparative examples 1 and 2, ultimately resulting in poor overall appearance and adhesion of the coatings.
The properties of the coatings prepared using the aqueous polyurethane resins of examples 1-4 were tested and the test results are shown in Table 5:
TABLE 5
The test results in Table 5 show that the water resistance and acid and alkali resistance of the paint can meet the requirements.

Claims (6)

1. The water-based polyurethane resin with the anti-seepage function is characterized by comprising the following raw materials in parts by weight:
5-30 parts of hydrolysis-resistant polyol, 2-12 parts of water-soluble monomer, 5-25 parts of isocyanate, 3-12 parts of functional monomer, 3-10 parts of chain extender, 0.6-5 parts of catalyst and 4-7 parts of amine;
the hydrolysis-resistant polyol is prepared from at least two of polybasic acid, polyhydric alcohol, anhydride, epoxy monomer and caprolactone, and at least comprises polyhydric alcohol; the polybasic acid is selected from isophthalic acid, terephthalic acid, succinic acid, adipic acid, dimer acid, maleic acid and 1, 4-cyclohexane dicarboxylic acid; the anhydride is selected from phthalic anhydride, maleic anhydride and hexahydrophthalic anhydride; the polyalcohol is selected from 1, 6-hexanediol, ethylene glycol, glycerol, 1, 4-cyclohexanedimethanol, 2-butyl-2-ethyl-1, 3-propanediol, hydroxypivalyl hydroxypivalate and 1, 2-propanediol; the epoxy monomer is selected from propylene oxide and/or ethylene oxide;
the water-soluble monomer comprises at least one of dimethylolbutyric acid and dimethylolpropionic acid;
the functional monomer comprises at least one of tertiary glycidyl ester, gamma-aminopropyl triethoxysilane, 3-methyl-1, 5-pentanediol, linoleic acid, soybean oleic acid, eleostearic acid and gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane.
2. The color-impermeable waterborne polyurethane resin according to claim 1, wherein the isocyanate comprises a polyisocyanate and/or an isocyanate prepolymer.
3. The color-impermeable waterborne polyurethane resin according to claim 1, wherein the chain extender comprises at least one of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, ethylene diamine, hexamethylenediamine, dipropylene glycol and castor oil.
4. A process for preparing the color-impermeable aqueous polyurethane resin according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing and reacting the hydrolysis-resistant polyol and isocyanate in a protective gas atmosphere;
(2) Adding the water-soluble monomer and the catalyst for reaction;
(3) Adding the functional monomer for reaction;
(4) Adding the chain extender for reaction;
(5) Adding amine for neutralization;
(6) Dispersing the neutralized product in water.
5. An aqueous coating material comprising the color-impermeable aqueous polyurethane resin according to any one of claims 1 to 3.
6. Use of the color-impermeable aqueous polyurethane resin as claimed in any one of claims 1 to 3 or the color-impermeable aqueous polyurethane resin prepared by the method as claimed in claim 4 in a coating process.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004059894A (en) * 2002-06-04 2004-02-26 Arakawa Chem Ind Co Ltd Water-based polyurethane resin
CN106832882A (en) * 2017-01-18 2017-06-13 广东达志环保科技股份有限公司 A kind of enhanced water resistance, aqueous polyurethane emulsion of high adhesion force and preparation method thereof
CN111909354A (en) * 2020-07-31 2020-11-10 中山大桥化工集团有限公司 Waterborne polyurethane resin and preparation method and application thereof
CN114133541A (en) * 2021-11-12 2022-03-04 广东腐蚀科学与技术创新研究院 High-hydrolysis-resistance polyester polyol, preparation method thereof and application thereof in waterborne polyurethane resin

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201302914A (en) * 2011-05-31 2013-01-16 Ube Industries Aqueous polyurethane resin dispersion and coating composition containing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004059894A (en) * 2002-06-04 2004-02-26 Arakawa Chem Ind Co Ltd Water-based polyurethane resin
CN106832882A (en) * 2017-01-18 2017-06-13 广东达志环保科技股份有限公司 A kind of enhanced water resistance, aqueous polyurethane emulsion of high adhesion force and preparation method thereof
CN111909354A (en) * 2020-07-31 2020-11-10 中山大桥化工集团有限公司 Waterborne polyurethane resin and preparation method and application thereof
CN114133541A (en) * 2021-11-12 2022-03-04 广东腐蚀科学与技术创新研究院 High-hydrolysis-resistance polyester polyol, preparation method thereof and application thereof in waterborne polyurethane resin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
抗渗咬水性聚氨酯的制备及涂料的性能研究;王璐等;《中国涂料》;第35卷(第06期);第31-35页 *

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