CN115232552A - Flame-retardant polyurethane exterior wall coating and preparation method thereof - Google Patents
Flame-retardant polyurethane exterior wall coating and preparation method thereof Download PDFInfo
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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
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
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- 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
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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
- C08G18/67—Unsaturated compounds having active hydrogen
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention relates to the technical field of exterior wall coatings, in particular to a flame-retardant polyurethane exterior wall coating and a preparation method thereof. The flame-retardant polyurethane exterior wall coating comprises a component A and a component B; the component A comprises the following substances: (1) unsaturated polyurethane resin emulsion; (2) The antibacterial cross-linking agent is prepared by esterification reaction of dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate and alkyl alcohol containing halogenated hydrocarbon, and quaternization reaction of the dicarboxylic acid, the monohydroxy acrylate and the alkyl alcohol containing halogenated hydrocarbon with tertiary amine containing unsaturated bonds; (3) a photoinitiator; (4) an auxiliary agent; the auxiliary agent comprises light calcium, kaolin, titanium dioxide, a dispersing agent, a defoaming agent and a thickening agent; the component B comprises diisocyanate and an ultraviolet resistant curing agent. The prepared exterior wall coating is flame retardant polyurethane exterior wall coating with durable antibacterial property, durable ultraviolet resistance and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of exterior wall coatings, in particular to a flame-retardant polyurethane exterior wall coating and a preparation method thereof.
Background
The polyurethane exterior wall coating is a basic material in building engineering, is directly exposed outdoors and is subjected to external effects of wind, sunshine, rain, snow, and the like; therefore, important indexes of performance are ultraviolet irradiation resistance and water resistance. Meanwhile, in order to increase the functionality of the exterior wall coating, the flame retardant, antibacterial and other properties are generally increased. Wherein, the antibacterial function can inhibit the pollution such as surface mildew and the like and reduce the hydrolysis and pulverization phenomena; the flame retardant function can reduce the spread situation of fire and increase the safety. However, in the prior art, for example, in a gray heat-insulating flame-retardant exterior wall coating disclosed in patent No. cn201310068838.X and a heat-insulating exterior wall coating disclosed in patent No. CN202210559735.2, additives such as an antibacterial agent, a flame retardant, an ultraviolet resistant agent and the like which are low in reactivity are mixed with resin, and the additives have a migration phenomenon and are used for a long time, so that the performance is reduced; and the adhesive efficiency is low, and the pulverization is easy to occur.
On the other hand, although the aqueous polyurethane coating has environmental protection performance, the segment of the aqueous polyurethane coating contains hydrophilic groups and is in a linear structure, so that the curing efficiency is low, the internal crosslinking performance is insufficient, and the mechanical strength is poor. The single photocuring polyurethane coating has large shrinkage, so that the coating has the problems of large brittleness, low adhesive force, poor mechanical strength and cracking.
In conclusion, the preparation of the flame-retardant polyurethane exterior wall coating is of great significance in solving the problems.
Disclosure of Invention
The invention aims to provide a flame-retardant polyurethane exterior wall coating and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a flame-retardant polyurethane exterior wall coating comprises a component A and a component B;
the component A comprises the following substances: (1) unsaturated polyurethane resin emulsion; (2) The antibacterial cross-linking agent is prepared by esterification reaction of dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate and alkyl alcohol containing halogenated hydrocarbon, and quaternization reaction of the dicarboxylic acid, monohydroxy acrylate and alkyl alcohol containing halogenated hydrocarbon with tertiary amine containing unsaturated bonds; (3) a photoinitiator; (4) an auxiliary agent; the auxiliary agent comprises light calcium, kaolin, titanium dioxide, a dispersing agent, a defoaming agent and a thickening agent;
the component B comprises diisocyanate and an anti-ultraviolet curing agent.
In addition, the molar ratio of dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate, alkyl alcohol containing halogenated hydrocarbon and tertiary amine containing unsaturated bonds in the antibacterial cross-linking agent is 1.
Furthermore, the antibacterial cross-linking agent is prepared by esterification reaction of itaconic acid, hydroxyethyl acrylate and 4-chloro-1-butanol and quaternization reaction of N, N-dimethyl allylamine.
Further, the A component comprises the following substances: 120-150 parts of unsaturated polyurethane resin emulsion, 8-12 parts of antibacterial cross-linking agent, 2-4 parts of photoinitiator, 5-8 parts of light calcium, 4-6 parts of kaolin, 12-16 parts of titanium dioxide, 0.2-0.5 part of dispersing agent, 0.5-1 part of defoaming agent and 2-4 parts of thickening agent.
Further, the component B comprises the following substances: 5 to 6 parts of diisocyanate and 8 to 10 parts of ultraviolet-resistant curing agent by weight.
Further, the anti-ultraviolet curing agent is prepared from phytic acid, monohydroxy acrylate, hydroxybenzotriazole and diisocyanate in a molar ratio of 1 (1) - (2) (3) - (4); the diisocyanate is at least one of hexamethyl diisocyanate, toluene diisocyanate, isophorone diisocyanate and lysine diisocyanate.
Further, the preparation method of the flame-retardant polyurethane exterior wall coating comprises the following steps:
step 1: mixing light calcium carbonate, kaolin and titanium dioxide uniformly, adding the mixture into unsaturated polyurethane resin emulsion, adding a dispersing agent, and stirring uniformly; adding antibacterial cross-linking agent, and homogenizing; adding a defoaming agent and a thickening agent, and uniformly stirring; adding a pH regulator, and regulating the pH to be 8 to 9; adding a photoinitiator in a dark place, and uniformly stirring to obtain a component A;
and 2, step: uniformly mixing diisocyanate and an anti-ultraviolet curing agent to obtain a component B;
and step 3: and uniformly mixing the component A and the component B to obtain the flame-retardant polyurethane exterior wall coating.
Further, the preparation method of the antibacterial cross-linking agent comprises the following steps: sequentially adding dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate, alkyl alcohol containing halogenated hydrocarbon, p-toluenesulfonic acid and an organic solvent into a reaction kettle; stirring for 3 to 4 hours at 60 to 65 ℃ under a nitrogen atmosphere, reacting for 0.5 to 1 hour at 70 to 75 ℃, washing and drying; dispersing the material in ethanol, setting the temperature at 45 to 50 ℃ under the nitrogen atmosphere, dropwise adding a tertiary amine-ethanol dispersion liquid containing an unsaturated bond, reacting for 2 to 3 hours, washing and drying to obtain the antibacterial cross-linking agent.
Further, the preparation method of the anti-ultraviolet curing agent comprises the following steps: sequentially adding phytic acid, monohydroxy acrylate, hydroxybenzotriazole, p-toluenesulfonic acid and an organic solvent into a reaction kettle, and uniformly mixing; putting the mixture into a microwave reactor, reacting at 100 to 120 ℃ for 60 to 120 seconds, washing and drying; dispersing the solution in dimethyl sulfoxide to obtain a solution A; dropwise adding the mixture into a reaction kettle containing diisocyanate, stirring for 2 to 4 hours at the temperature of 30 to 40 ℃, and performing rotary evaporation to remove the solvent to obtain the ultraviolet-resistant curing agent.
Further, the preparation method of the unsaturated polyurethane resin emulsion comprises the following steps: sequentially adding polyether polyol, diisocyanate, dimethylformamide and a catalyst into a reaction kettle, reacting for 3 to 5 hours at 70 to 80 ℃ under the atmosphere of nitrogen, cooling to 50 to 60 ℃, and adding a chain extender to react for 2 to 3 hours; and cooling to room temperature, adding triethylamine for neutralization, and adding deionized water for emulsification to obtain the unsaturated polyurethane resin emulsion.
In the technical scheme, the cross-linking agent with antibacterial property and the curing agent with ultraviolet resistance are prepared and used in polyurethane emulsion containing unsaturated groups to form the dual-curing exterior wall coating. The prepared exterior wall coating has durable antibacterial property, durable ultraviolet performance and excellent mechanical performance.
(1) In the scheme, carboxyl in dicarboxylic acid containing unsaturated bonds is used for generating esterification graft with hydroxyl in monohydroxy acrylate and alkyl alcohol containing halogenated hydrocarbon, and quaternary amination reaction is generated between halogenated groups in alkyl alcohol containing halogenated hydrocarbon and tertiary amine, so that the antibacterial cross-linking agent is prepared. Wherein, the contained acrylate group and the unsaturated polyurethane emulsion have similar compatibility, and the unsaturated group can generate ultraviolet curing crosslinking; meanwhile, the quaternary ammonium salt group is a hydrophilic structure, so that the dispersibility and the antibacterial property of the quaternary ammonium salt group can be improved.
The introduction of the antibacterial cross-linking agent improves the long-chain structure of polyurethane, the cross-linking of the antibacterial cross-linking agent is in the coating, three-dimensional cross-linking is formed, the internal cross-linking property is improved, the curing efficiency and the mechanical property are improved, the migration of an antibacterial agent is effectively inhibited, and the antibacterial durability is improved. Meanwhile, the crosslinking density is improved, the internal pores are reduced, and the water resistance is effectively improved. Wherein, the content of the antibacterial cross-linking agent is limited, the content is reduced, and the performance is reduced; the content is increased, the crosslinking density is too high, and microphase separation exists between excessive crosslinking agent and polyurethane, so that the brittleness is increased, and the mechanical property is reduced. In addition, the introduction of the antibacterial cross-linking agent increases the viscosity of the coating and enhances the adhesive force of the coating.
(2) In the scheme, carboxyl in phytic acid, monohydroxy acrylate and hydroxyl in hydroxybenzotriazole are used for carrying out half-esterification reaction (grafting acrylate and phenylpropyl triazole) in a microwave reactor; and then, reacting and grafting the residual phosphoric acid group with one isocyanate group in diisocyanate to obtain the anti-ultraviolet curing agent. The benzotriazole is an excellent organic ultraviolet-resistant additive, can effectively improve the ultraviolet resistance, and can be reacted and grafted on a curing agent to inhibit the migration, so that the durability of the ultraviolet resistance is improved; and the acrylate may be photo-curable grafted. The anti-ultraviolet curing agent is prepared on the basis of phytic acid, is similar to a snowflake shape in shape, improves the toughness of the coating, and improves the mechanical property of the polyurethane outer wall coating by cooperating with the antibacterial cross-linking agent. In addition, the ultraviolet-resistant curing agent also improves the viscosity of the coating and enhances the adhesive force of the coating.
(3) In the scheme, the waterborne polyurethane is prepared by preparing a prepolymer from polyether polyol and diisocyanate and then chain extending the prepolymer from 3- (perfluorobutyl) -2-hydroxy propyl methacrylate and monohydroxy acrylate, wherein the introduced fluorine-containing group effectively improves the water resistance.
(4) The prepared exterior wall coating has flame retardance due to the existence of more fillers (light calcium, kaolin and titanium dioxide), and can be used for improving the flame retardance of the exterior wall coating by cooperating with the phosphorus-containing ultraviolet-resistant curing agent and the triazole-containing antibacterial cross-linking agent, so that the polyurethane exterior wall coating has flame retardance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a chemical equation for the preparation of an antibacterial cross-linking agent in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The following examples are pilot plant processes; wherein the product number of itaconic acid (Chongqing Rui ya Biotech Co., ltd.) is 97-65-4; hydroxyethyl acrylate (sigma aldrich shanghai trade ltd) has a cat No. 292818; 4-chloro-1-butanol (sigma aldrich shanghai trade, ltd.) has a cat No. 278823; n, N-dimethylallylamine (Shanghai Ji to Biochemical technologies, inc.) under the trade designation N16220; the product number of hydroxybenzotriazole (Hebei Zhentian food additive Co., ltd.) is ZT-21407; isophorone diisocyanate (sigma aldrich shanghai trade ltd) has a product number of 8185860250; the product number of polytetrahydrofuran ether glycol (Hebei Zhentian food additive Co., ltd.) is ZT-19033667; the PPG-210 (Shanghai Bike chemical Co., ltd.) is PPG1000; the product number of 3- (perfluorobutyl) -2-hydroxymethylacrylic acid propyl ester (Nanjing QIAOFENG and pharmaceutical science and technology Co., ltd.) was CHLF-01-362.
Example 1:
step 1: (1) Sequentially adding 2.6g of itaconic acid, 2.3g of hydroxyethyl acrylate, 2.2g of 4-chloro-1-butanol, 0.05g of p-toluenesulfonic acid and 15g of N, N-dimethylformamide into a reaction kettle; stirring for 3.5 hours at 65 ℃ under the nitrogen atmosphere, reacting for 1 hour at 70 ℃, washing and drying; dispersing the antibacterial cross-linking agent in 15g of ethanol, setting the temperature at 50 ℃ under the nitrogen atmosphere, dropwise adding 1.5gN, N-dimethylallylamine-5 g of ethanol dispersion liquid at the dropwise adding speed of about 30 drops/min, reacting for 3 hours, washing and drying to obtain the antibacterial cross-linking agent.
(2) Sequentially adding 13.2g of phytic acid, 2.3g of hydroxyethyl acrylate, 3.5g of hydroxybenzotriazole, 0.02g of p-toluenesulfonic acid and 20g of N, N-dimethylformamide into a reaction kettle, and uniformly mixing; putting the mixture into a microwave reactor, reacting for 100 seconds at 115 ℃, washing and drying; dispersing the solution in 60g of dimethyl sulfoxide to obtain a solution A; and dropwise adding the solution A into a reaction kettle containing 16g of isophorone diisocyanate, stirring for 4 hours at 35 ℃ at the dropwise adding speed of 20 drops/minute, and removing dimethyl sulfoxide by rotary evaporation to obtain the anti-ultraviolet curing agent.
(3) Adding 50g of polytetrahydrofuran ether glycol, 5g of polyoxypropylene glycol, 25g of isophorone diisocyanate and 0.15g of dibutyltin dilaurate into a reaction kettle in sequence, reacting at 75 ℃ for 4 hours under a nitrogen atmosphere, cooling to 55 ℃, adding 1g of 1, 4-dibutyl alcohol, 8g of 3- (perfluorobutyl) -2-hydroxy propyl methacrylate and 3g of hydroxyethyl acrylate, and reacting for 2 hours; and (3) cooling to 30 ℃, adding 8g of triethylamine, stirring for 20 minutes, adding deionized water, and emulsifying at 1200rpm to obtain unsaturated polyurethane resin emulsion with solid content of 50 wt%.
(4) Uniformly mixing 6g of light calcium carbonate, 5g of kaolin and 15g of titanium dioxide, adding the mixture into 140g of unsaturated polyurethane resin emulsion, adding 0.5g of byk 190, uniformly stirring, adding 10g of antibacterial cross-linking agent, homogenizing at 1200rpm for 15 minutes, adding 0.5g of diisobutyl ketone of polysiloxane and 3g of sodium alginate, stirring for 15 minutes, adding a pH regulator, and adjusting the pH to be =8.5; adding 3g of photoinitiator TPO in a dark place, and stirring for 30 minutes to obtain a component A;
step 2: and (3) uniformly mixing 6g of isophorone diisocyanate and 8g of ultraviolet-resistant curing agent to obtain a component B.
And 3, step 3: and uniformly mixing the component A and the component B to obtain the flame-retardant polyurethane exterior wall coating.
Example 2:
step 1: (1) 2.6g of itaconic acid, 2.3g of hydroxyethyl acrylate, 2.2g of 4-chloro-1-butanol, 0.05g of p-toluenesulfonic acid and 15g of N, N-dimethylformamide are sequentially added into a reaction kettle; stirring for 3 hours at 65 ℃ under the nitrogen atmosphere, reacting for 1 hour at 70 ℃, washing and drying; dispersing the antibacterial cross-linking agent in 15g of ethanol, setting the temperature at 50 ℃ under the nitrogen atmosphere, dropwise adding 1.7gN, N-dimethylallylamine-5 g of ethanol dispersion liquid at the dropping speed of about 30 drops/minute, reacting for 3 hours, washing and drying to obtain the antibacterial cross-linking agent.
(2) Sequentially adding 13.2g of phytic acid, 2.3g of hydroxyethyl acrylate, 2.7g of hydroxybenzotriazole, 0.02g of p-toluenesulfonic acid and 20g of N, N-dimethylformamide into a reaction kettle, and uniformly mixing; putting the mixture into a microwave reactor, reacting for 120 seconds at 100 ℃, washing and drying; dispersing the solution in 60g of dimethyl sulfoxide to obtain a solution A; dropwise adding the solution A into a reaction kettle containing 13.3g of isophorone diisocyanate at the dropping speed of 20 drops/min, stirring for 2 hours at the temperature of 30 ℃, and performing rotary evaporation to remove dimethyl sulfoxide to obtain the anti-ultraviolet curing agent.
(3) Adding 50g of polytetrahydrofuran ether glycol, 5g of polyoxypropylene glycol, 25g of isophorone diisocyanate and 0.15g of dibutyltin dilaurate into a reaction kettle in sequence, reacting at 70 ℃ for 5 hours under a nitrogen atmosphere, cooling to 50 ℃, adding 1g of 1, 4-dibutyl alcohol, 8g of 3- (perfluorobutyl) -2-hydroxy propyl methacrylate and 3g of hydroxyethyl acrylate, and reacting for 3 hours; and (3) cooling to 30 ℃, adding 8g of triethylamine, stirring for 20 minutes, adding deionized water, and emulsifying at 1200rpm to obtain unsaturated polyurethane resin emulsion with solid content of 50 wt%.
(4) Uniformly mixing 5g of light calcium carbonate, 6g of kaolin and 16g of titanium dioxide, adding the mixture into 150g of unsaturated polyurethane resin emulsion, adding 0.5g of Bike 190, uniformly stirring, adding 12g of antibacterial cross-linking agent, homogenizing at 1200rpm for 15 minutes, adding 1g of diisobutyl ketone of polysiloxane and 2g of sodium alginate, stirring for 15 minutes, adding a pH regulator, and adjusting the pH to be =8.5; adding 4g of photoinitiator TPO in a dark place, and stirring for 30 minutes to obtain a component A;
and 2, step: and 5g of isophorone diisocyanate and 10g of ultraviolet-resistant curing agent are uniformly mixed to obtain a component B.
And step 3: and uniformly mixing the component A and the component B to obtain the flame-retardant polyurethane exterior wall coating.
Example 3:
step 1: (1) 2.6g of itaconic acid, 2.3g of hydroxyethyl acrylate, 2.2g of 4-chloro-1-butanol, 0.05g of p-toluenesulfonic acid and 15g of N, N-dimethylformamide are sequentially added into a reaction kettle; stirring for 4 hours at 60 ℃ under the nitrogen atmosphere, reacting for 0.5 hour at 75 ℃, washing and drying; dispersing the antibacterial cross-linking agent in 15g of ethanol, setting the temperature at 45 ℃ in the nitrogen atmosphere, dropwise adding 1.4gN, N-dimethylallylamine-5 g of ethanol dispersion liquid at the dropping speed of about 30 drops/minute, reacting for 2 hours, washing and drying to obtain the antibacterial cross-linking agent.
(2) Sequentially adding 13.2g of phytic acid, 2.3g of hydroxyethyl acrylate, 5.4g of hydroxybenzotriazole, 0.02g of p-toluenesulfonic acid and 20g of N, N-dimethylformamide into a reaction kettle, and uniformly mixing; putting the mixture into a microwave reactor, reacting for 60 seconds at 120 ℃, washing and drying; dispersing the solution in 60g of dimethyl sulfoxide to obtain a solution A; dropwise adding the solution A into a reaction kettle containing 17.7g of isophorone diisocyanate at the dropping speed of 20 drops/min, stirring for 4 hours at the temperature of 40 ℃, and performing rotary evaporation to remove dimethyl sulfoxide to obtain the anti-ultraviolet curing agent.
(3) Sequentially adding 50g of polytetrahydrofuran ether glycol, 5g of polypropylene oxide glycol, 25g of isophorone diisocyanate and 0.15g of dibutyltin dilaurate into a reaction kettle, reacting at 80 ℃ for 3 hours under the atmosphere of nitrogen, cooling to 60 ℃, adding 1g of 1, 4-dibutyl alcohol, 8g of 3- (perfluorobutyl) -2-hydroxy propyl methacrylate and 3g of hydroxyethyl acrylate, and reacting for 2 hours; and cooling to 30 ℃, adding 8g of triethylamine, stirring for 20 minutes, adding deionized water, and emulsifying at 1200rpm to obtain the unsaturated polyurethane resin emulsion with the solid content of 50 wt%.
(4) Uniformly mixing 8g of light calcium carbonate, 4g of kaolin and 12g of titanium dioxide, adding the mixture into 120g of unsaturated polyurethane resin emulsion, adding 0.2g of byk 190, uniformly stirring, adding 8g of antibacterial cross-linking agent, homogenizing at 1200rpm for 15 minutes, adding 0.5g of diisobutyl ketone of polysiloxane and 4g of sodium alginate, stirring for 15 minutes, adding a pH regulator, and regulating the pH to be 8.5; adding 2g of photoinitiator TPO in a dark place, and stirring for 30 minutes to obtain a component A;
step 2: and (3) uniformly mixing 6g of isophorone diisocyanate and 8g of ultraviolet-resistant curing agent to obtain a component B.
And 3, step 3: and uniformly mixing the component A and the component B to obtain the flame-retardant polyurethane exterior wall coating.
Comparative example 1: the same procedure as in example 1 was repeated except that Rocima361, a fungicide, was used as an antibacterial agent and hexafluorobutyl acrylate was used as a crosslinking agent;
wherein, (4) 6g of light calcium carbonate, 5g of kaolin and 15g of titanium dioxide are uniformly mixed, added into 140g of unsaturated polyurethane resin emulsion, 0.5g of Bike 190 is added, the mixture is uniformly stirred, 2.5g of mildew preventive Rocima361 and 10g of hexafluorobutyl acrylate are added, the mixture is homogenized for 15 minutes at 1200rpm, 0.5g of polysiloxane diisobutyl ketone and 3g of sodium alginate are added, the mixture is stirred for 15 minutes, and a pH regulator is added to regulate the pH value to be 8.5; adding 3g of photoinitiator TPO in a dark place, and stirring for 30 minutes to obtain a component A;
comparative example 2: the using amount of the antibacterial cross-linking agent is increased, and the rest is the same as that of the embodiment 1;
wherein, (4) 6g of light calcium carbonate, 5g of kaolin and 15g of titanium dioxide are uniformly mixed, added into 140g of unsaturated polyurethane resin emulsion, 0.5g of Bike 190 is added, the mixture is uniformly stirred, 15g of antibacterial cross-linking agent is added, the mixture is homogenized for 15 minutes at 1200rpm, 0.5g of diisobutyl ketone of polysiloxane and 3g of sodium alginate are added, the mixture is stirred for 15 minutes, and a pH regulator is added to regulate the pH value to be =8.5; adding 3g of photoinitiator TPO in a dark place, and stirring for 30 minutes to obtain a component A;
comparative example 3: the antibacterial cross-linking agent is not introduced with hydroxyethyl acrylate, and the rest is the same as the example 1;
wherein (1) 2.6g of itaconic acid, 4.4g of 4-chloro-1-butanol, 0.05g of p-toluenesulfonic acid and 15g of N, N-dimethylformamide are sequentially added into a reaction kettle; stirring for 3.5 hours at 60 to 65 ℃ under the nitrogen atmosphere, reacting for 1 hour at 70 ℃, washing and drying; dispersing the antibacterial cross-linking agent in 15g of ethanol, setting the temperature at 50 ℃ under the nitrogen atmosphere, dropwise adding 1.5g of N, N-dimethylallylamine-5 g of ethanol dispersion liquid at the dropwise adding speed of about 30 drops/minute, reacting for 3 hours, washing and drying to obtain the antibacterial cross-linking agent.
Comparative example 4: the grafting amount of hydroxyethyl acrylate is increased in the antibacterial cross-linking agent, the grafting amount of 4-chloro-1-butanol is reduced, and the rest is the same as that in the embodiment 1;
(1) Sequentially adding 2.6g of itaconic acid, 3.48g of hydroxyethyl acrylate, 1.1g of 4-chloro-1-butanol, 0.05g of p-toluenesulfonic acid and 15g of N, N-dimethylformamide into a reaction kettle; stirring for 3.5 hours at 60 to 65 ℃ under the nitrogen atmosphere, reacting for 1 hour at 70 ℃, washing and drying; dispersing the antibacterial cross-linking agent in 15g of ethanol, setting the temperature at 50 ℃ under the nitrogen atmosphere, dropwise adding 1.5gN, N-dimethylallylamine-5 g of ethanol dispersion liquid at the dropwise adding speed of about 30 drops/min, reacting for 3 hours, washing and drying to obtain the antibacterial cross-linking agent.
Comparative example 5: the hydroxybenzotriazole is directly introduced, the rest is the same as in example 1;
wherein, (4) 6g of light calcium carbonate, 5g of kaolin and 15g of titanium dioxide are uniformly mixed, added into 140g of unsaturated polyurethane resin emulsion, 0.5g of Bike 190 is added, the mixture is uniformly stirred, 10g of antibacterial cross-linking agent and 2g of hydroxybenzotriazole are added, the mixture is homogenized for 15 minutes at 1200rpm, 0.5g of diisobutyl ketone of polysiloxane and 3g of sodium alginate are added, the mixture is stirred for 15 minutes, and a pH regulator is added to regulate the pH value to be =8.5; adding 3g of photoinitiator TPO in a dark place, and stirring for 30 minutes to obtain a component A;
and 2, step: 12g of isophorone diisocyanate were used as B component.
And step 3: and uniformly mixing the component A and the component B to obtain the flame-retardant polyurethane exterior wall coating.
Experiment: the flame-retardant polyurethane exterior wall coatings prepared in the examples and the comparative examples were coated on a 3mm flat plate at a coating thickness of 120 μm and a set energy of an ultraviolet dryer of 800mj/cm 2 Drying for 30 minutes; drying at 45 ℃ for 1 hour; maintaining for one week to obtain the test plate. Taking a test board with the thickness of 450mm multiplied by 150mm, putting the test board into an artificial environment box, and carrying out an aging resistance test according to the standard of GB/T23987 under the conditions that: irradiating with ultraviolet radiation with intensity of 45W/m 2 Drying at 50 deg.C and relative humidity of 10% for 5 hr, spraying at 25 deg.C for 1 hr, and not controlling humidity; the spraying-drying is carried out in a circulating way, and the abnormal phenomena such as pulverization and the like are observed after 600 hours. Meanwhile, coating the paint on a test piece, taking a test plate with the thickness of 150mm multiplied by 70mm, and determining the adhesive force according to the standard of GB/T1720; testing the antibacterial property to escherichia coli before and after aging by referring to the standard of GB/T21866; the tensile strength before and after aging was measured by tensile testing with a tensile machine in accordance with the JG/T172 standard. The data obtained are shown below:
and (4) conclusion: the data in the table show that the prepared flame-retardant polyurethane exterior wall coating has excellent water resistance and ultraviolet resistance, and meanwhile, the coating has good adhesive force and strong mechanical property. Comparison of the data from example 1 and example 5 shows that: the prepared antibacterial cross-linking agent has obviously improved mechanical properties, and simultaneously, the antibacterial property after aging is reduced due to low reactivity of the antibacterial agent. In comparative example 2, the mechanical properties were degraded due to the excessive introduction amount of the antibacterial crosslinking agent. In comparative example 3, since hydroxyethyl acrylate was not introduced into the antibacterial crosslinking agent, the mechanical properties were significantly reduced. In comparative example 4, the grafting amount of hydroxyethyl acrylate was increased and the grafting amount of 4-chloro-1-butanol was decreased, so that the mechanical properties were slightly decreased, and the introduction of the antibacterial segment was decreased, so that the antibacterial properties were decreased. Also, in comparative example 5, since hydroxybenzotriazole was directly introduced, photocrosslinking was reduced, so that mechanical properties were degraded.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A flame-retardant polyurethane exterior wall coating is characterized in that: the flame-retardant polyurethane exterior wall coating comprises a component A and a component B;
the component A comprises the following substances: (1) unsaturated polyurethane resin emulsion; (2) The antibacterial cross-linking agent is prepared by esterification reaction of dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate and alkyl alcohol containing halogenated hydrocarbon, and quaternization reaction of the dicarboxylic acid, monohydroxy acrylate and alkyl alcohol containing halogenated hydrocarbon with tertiary amine containing unsaturated bonds; (3) a photoinitiator; (4) an auxiliary agent; the auxiliary agent comprises light calcium, kaolin, titanium dioxide, a dispersing agent, a defoaming agent and a thickening agent;
the component B comprises diisocyanate and an anti-ultraviolet curing agent.
2. The flame retardant polyurethane exterior wall coating of claim 1, wherein: the molar ratio of dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate, alkyl alcohol containing halogenated hydrocarbon and tertiary amine containing unsaturated bonds in the antibacterial cross-linking agent is (1).
3. The flame retardant polyurethane exterior wall coating of claim 2, wherein: the antibacterial cross-linking agent is prepared by esterification reaction of itaconic acid, hydroxyethyl acrylate and 4-chloro-1-butanol, and quaternization reaction of N, N-dimethyl allylamine.
4. The flame retardant polyurethane exterior wall coating of claim 1, wherein: the component A comprises the following substances: the polyurethane coating comprises, by weight, 120-150 parts of an unsaturated polyurethane resin emulsion, 8-12 parts of an antibacterial cross-linking agent, 2-4 parts of a photoinitiator, 5-8 parts of light calcium, 4-6 parts of kaolin, 12-16 parts of titanium dioxide, 0.2-0.5 part of a dispersing agent, 0.5-1 part of an antifoaming agent and 2-4 parts of a thickening agent.
5. The flame retardant polyurethane exterior wall coating of claim 1, wherein: the component B comprises the following substances: 5 to 6 parts of diisocyanate and 8 to 10 parts of ultraviolet-resistant curing agent by weight.
6. The flame retardant polyurethane exterior wall coating of claim 5, wherein: the ultraviolet-resistant curing agent is prepared from phytic acid, monohydroxy acrylate, hydroxybenzotriazole and diisocyanate in a molar ratio of 1 (1) - (2) (3) - (4); the diisocyanate is at least one of hexamethyl diisocyanate, toluene diisocyanate, isophorone diisocyanate and lysine diisocyanate.
7. A preparation method of flame-retardant polyurethane exterior wall paint is characterized by comprising the following steps: the method comprises the following steps:
step 1: mixing light calcium carbonate, kaolin and titanium dioxide uniformly, adding the mixture into unsaturated polyurethane resin emulsion, adding a dispersing agent, and stirring uniformly; adding antibacterial cross-linking agent, and homogenizing; adding a defoaming agent and a thickening agent, and uniformly stirring; adding a pH regulator, and regulating the pH to be 8 to 9; adding a photoinitiator in a dark place, and uniformly stirring to obtain a component A;
step 2: uniformly mixing diisocyanate and an anti-ultraviolet curing agent to obtain a component B;
and step 3: and uniformly mixing the component A and the component B to obtain the flame-retardant polyurethane exterior wall coating.
8. The method for preparing the flame retardant polyurethane exterior wall coating according to claim 7, wherein the method comprises the following steps: the preparation method of the antibacterial cross-linking agent comprises the following steps: sequentially adding dicarboxylic acid containing unsaturated bonds, monohydroxy acrylate, alkyl alcohol containing halogenated hydrocarbon, p-toluenesulfonic acid and an organic solvent into a reaction kettle; stirring for 3 to 4 hours at 60 to 65 ℃ under a nitrogen atmosphere, reacting for 0.5 to 1 hour at 70 to 75 ℃, washing and drying; dispersing the material in ethanol, setting the temperature at 45 to 50 ℃ under the nitrogen atmosphere, dropwise adding a tertiary amine-ethanol dispersion liquid containing an unsaturated bond, reacting for 2 to 3 hours, washing and drying to obtain the antibacterial cross-linking agent.
9. The method for preparing the flame retardant polyurethane exterior wall coating material according to claim 7, wherein the method comprises the following steps: the preparation method of the ultraviolet-resistant curing agent comprises the following steps: sequentially adding phytic acid, monohydroxy acrylate, hydroxybenzotriazole, p-toluenesulfonic acid and an organic solvent into a reaction kettle, and uniformly mixing; putting the mixture into a microwave reactor, reacting at 100 to 120 ℃ for 60 to 120 seconds, washing and drying; dispersing the solution in dimethyl sulfoxide to obtain a solution A; dropwise adding the mixture into a reaction kettle containing diisocyanate, stirring the mixture for 2 to 4 hours at the temperature of 30 to 40 ℃, and performing rotary evaporation to remove the solvent to obtain the ultraviolet-resistant curing agent.
10. The method for preparing the flame retardant polyurethane exterior wall coating according to claim 7, wherein the method comprises the following steps: the preparation method of the unsaturated polyurethane resin emulsion comprises the following steps: sequentially adding polyether polyol, diisocyanate, dimethylformamide and a catalyst into a reaction kettle, reacting for 3 to 5 hours at 70 to 80 ℃ under the atmosphere of nitrogen, cooling to 50 to 60 ℃, and adding a chain extender to react for 2 to 3 hours; and cooling to room temperature, adding triethylamine for neutralization, and adding deionized water for emulsification to obtain unsaturated polyurethane resin emulsion.
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| CN116622051A (en) * | 2023-07-25 | 2023-08-22 | 苏州久翔纺织整理有限公司 | Preparation method and application of antibacterial aqueous polyurethane emulsion |
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