CN111849336B - Odorless aromatic two-component waterborne polyurethane coating - Google Patents
Odorless aromatic two-component waterborne polyurethane coating Download PDFInfo
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Abstract
The invention discloses a odorless aromatic double-component waterborne polyurethane coating which is independently packaged and used according to the mass ratio of 10: (2-3) mixing the component A and the component B; the raw materials of the component A comprise: 50-70 parts of water-based hydroxyl acrylic resin, 10-30 parts of pigment, 2-3 parts of dispersing agent, 0.2-0.4 part of defoaming agent, 0.2-0.5 part of flatting agent and 1-3 parts of sodium carbonate; the component B comprises the following raw materials: 70-90 parts of isocyanate curing agent, 15-25 parts of solvent and 30-50 parts of aromatic slow-release particles, wherein the aromatic slow-release particles are mesoporous TiO loaded with plant essential oil2Mesoporous TiO2The surface of the complex is modified with complex of polyvinyl imidazole and Cu (II). According to the invention, the aromatic slow-release particles are added into the coating, and the release of the perfume loaded in the aromatic slow-release particles is controlled by mixing the two components, so that the volatilization loss of the perfume in the storage process of the coating is reduced, and the indoor air can be improved for a long time.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a odorless aromatic two-component waterborne polyurethane coating.
Background
In recent years, people pay more attention to the influence of indoor air quality on human health, and more attention is paid to health and environmental protection of decoration materials. In selecting coatings, environmentally friendly and healthy odor-free products have become a major consumer demand. The current environmental protection odor-free coating is generally used for reducing the release of volatile organic compounds by using a water-based coating instead of a traditional organic solvent coating, and adding perfume into the coating to mask the odor of the coating.
For example, patent publication No. CN111100522A discloses an interior wall coating with a long-lasting fragrance, which uses a polymer latex in which EO groups form strong hydrogen bonds with hydrophilic fragrances, resulting in slow release of the fragrances. The fragrant coating can be used as sleeping-aid and air-purifying coating in bedroom, and is safe and non-irritant.
However, the perfume in the existing perfume paint has large volatilization loss in the paint storage process, so that the durability of the perfume after use is insufficient, and the indoor air cannot be continuously improved.
Disclosure of Invention
The invention aims to solve the problems that the fragrance in the existing fragrant coating is relatively large in volatilization loss in the coating storage process, the fragrance is not sufficient in persistence after the coating is used, and the indoor air cannot be improved continuously, and provides a odorless fragrant two-component waterborne polyurethane coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
a odorless aromatic double-component waterborne polyurethane coating comprises components in parts by mass as follows, wherein the components are independently packaged and used according to a mass ratio of 10: (2-3) mixing the component A and the component B; the component A comprises the following raw materials in parts by weight: 50-70 parts of water-based hydroxyl acrylic resin, 10-30 parts of pigment, 2-3 parts of dispersing agent, 0.2-0.4 part of defoaming agent, 0.2-0.5 part of flatting agent and 1-3 parts of sodium carbonate, wherein the solid content of the water-based hydroxyl acrylic resin is 40-45 wt%; the component B comprises the following raw materials in parts by weight: 70-90 parts of isocyanate curing agent, 15-25 parts of film forming solvent and 30-50 parts of aromatic slow release particles, wherein the aromatic slow release particles are mesoporous TiO loaded with plant essential oil2Said mesoporous TiO2The surface of the complex is modified with complex of polyvinyl imidazole and Cu (II).
Preferably, the preparation method of the aromatic sustained-release particles comprises the following steps:
(1) dissolving P123 in absolute ethyl alcohol, dropwise adding butyl titanate while stirring, stirring and reacting for 30-60 min, then dropwise adding a mixed solution of ethanol and water, and stirring and reacting for 1-2 h to obtain a precursor solution;
(2) placing the precursor solution in a hydrothermal reaction kettle, performing crystallization reaction at 80-120 ℃ for 8-12 h, cooling to room temperature, filtering, washing and drying the product to obtain TiO2A crystal;
(3) adding TiO into the mixture2Roasting the crystal in air atmosphere at 180-220 ℃ for 60-90 min, then heating to 350-400 ℃ and roasting for 2-3 h to obtain mesoporous TiO2；
(4) Making mesoporous TiO2Dispersing in toluene, adding gamma-methacryloxypropyltrimethoxysilane, stirring at 120-130 ℃ for reaction for 6-8 h, filtering, washing and drying the product to obtain the silanized mesoporous TiO2；
(5) Silanized mesoporous TiO2Dispersing in N, N-dimethylformamide, adding a 1-vinylimidazole monomer, stirring for 20-30 min to obtain a dispersion, adding azodiisobutyronitrile into the dispersion under the protection of nitrogen, stirring and reacting at 80-85 ℃ for 8-12 h, filtering, washing a product, and drying in vacuum to obtain the polyvinyl imidazole modified mesoporous TiO2；
(6) Mesoporous TiO modified by polyvinyl imidazole2Dispersing in plant essential oil, stirring for reaction for 10-12 h, filtering, and washing the product with deionized water to obtain the mesoporous TiO loaded with the plant essential oil2；
(7) Loading mesoporous TiO with plant essential oil2Dispersing in HEPES buffer solution with pH of 7.2-7.4, stirring for 20-30 min, and adding CuCl2And stirring the solution for reacting for 8-10 h, filtering, washing and drying the product to obtain the aromatic slow-release particles.
In the two-component polyurethane coating, the component A contains water-based hydroxyl acrylic resin, the component B contains isocyanate curing agent, and after the components A and B are mixed in use, hydroxyl in the water-based hydroxyl acrylic resin can react with-NCO group in the curing agent to be cured into a film. Meanwhile, the aromatic slow-release particles loaded with the plant essential oil are added into the polyurethane coating, the plant essential oil can volatilize and release the aromatic smell of plants so as to cover the pungent smell of the coating, and meanwhile, the plant essential oil also has good antibacterial and antiseptic effects and can purify indoor air.
In the preparation process of the aromatic slow-release particles, the mesoporous TiO is prepared through the steps (1) to (3)2With mesoporous TiO2As a carrier for loading plant essential oil, the plant essential oil is adsorbed and loaded in the mesoporous TiO2The pore canal can realize the slow release of the plant essential oil, prolong the fragrance releasing and air purifying effects of the coating, and simultaneously add TiO2The weathering resistance of the coating can also be improved.
For preventing plant essential oil inThe invention relates to a method for preparing a coating with high volatility loss in the storage process, which comprises the steps (4) and (5) and utilizes the polymerization reaction of 1-vinyl imidazole monomer and gamma-methacryloxypropyl trimethoxy silane to prepare mesoporous TiO2Modifying the surface with polyvinyl imidazole, and then performing step (6) to obtain mesoporous TiO2After the pore canal is loaded with the plant essential oil, the step (7) is carried out to lead the mesoporous TiO to be2The polyvinyl imidazole on the surface is complexed with the added copper ions to form a complex, so that the polymer is connected and covered on the mesoporous TiO2The surface is sealed with mesoporous TiO2The plant essential oil loaded in the pore channels cannot be released. When the aromatic slow-release particles are added into the component B for storage, the volatilization loss of the plant essential oil is greatly reduced.
Meanwhile, sodium carbonate is added into the component A of the polyurethane coating, so that the component A can be used as a pH regulator, and the coordination capacity of carbonate and copper ions is stronger than that of imidazole and copper ions, so that when the component A and the component B are mixed for use, after the aromatic slow-release particles meet the carbonate, the carbonate ions can deprive the copper ions from a complex of polyvinyl imidazole and Cu (II) on the surface of the aromatic slow-release particles, the complex effect is destroyed, and the mesoporous TiO is damaged2The polymers on the surface are mutually separated, the pore passages are opened, and the plant essential oil is released.
Therefore, the plant essential oil cannot volatilize and lose in the storage process of the two-component polyurethane coating, and the two-component polyurethane coating cannot be oxidized and deteriorated to influence the use of the coating; after the component A and the component B are mixed for use, the aromatic slow-release particles start to continuously release the plant essential oil, so that the smell of the coating can be covered, the indoor air can be purified for a long time, and the fragrance release time is long.
Preferably, the mass-to-volume ratio of the P123 to the absolute ethyl alcohol, the butyl titanate and the mixed solution in the step (1) is 1 g: (10-15 mL): (3.5-4 mL): (15-20 mL), wherein the volume ratio of ethanol to water in the mixed solution is (1-2): 1.
preferably, the mesoporous TiO in the step (4)2Toluene and gamma-methacryloxypropyltrimethoxysilane were added in a proportion of 1 g: (10-15 mL): (1 to 1.5g)。
Preferably, the silanized mesoporous TiO in the step (5)2The addition ratio of the N, N-dimethylformamide to the 1-vinylimidazole monomer to the azobisisobutyronitrile is 10g (100-200 mL): (1.5-2.5 g): (0.3-0.4 g).
Preferably, the plant essential oil in step (6) is one or more selected from lavender essential oil, rose essential oil, jasmine essential oil, rosemary essential oil, clove essential oil and chamomile essential oil, and the polyvinyl imidazole modified mesoporous TiO is2The mass volume ratio of the plant essential oil to the plant essential oil is 1 g: (20-30 mL).
Preferably, the plant essential oil-loaded mesoporous TiO described in the step (7)2The mass-to-volume ratio of the buffer solution to the HEPES buffer solution is 1 g: (100-200 mL) of mesoporous TiO loaded with plant essential oil2With CuCl2Cu in solution2+In a ratio of 1 g: (2-4 mmol).
Preferably, the pigment in the component A is selected from one of phthalocyanine blue, titanium dioxide, carbon black, medium chrome yellow and iron oxide red.
Preferably, the film forming solvent in the component B is one or more selected from ethylene glycol butyl ether, diethylene glycol hexyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether.
Therefore, the invention has the following beneficial effects:
(1) the polyurethane coating mainly takes water as a dispersion medium, so that the release amount of volatile organic compounds is small, and the polyurethane coating is healthy and environment-friendly; meanwhile, the aromatic slow-release particles loaded with the plant essential oil are added into the polyurethane coating, the plant essential oil can volatilize and release the aromatic smell of plants so as to cover the pungent smell of the coating, and meanwhile, the plant essential oil also has good antibacterial and antiseptic effects and can purify indoor air;
(2) when the aromatic slow-release particles are added into the component B for storage, the loaded plant essential oil cannot be volatilized, lost or oxidized and deteriorated, and the plant essential oil is released after the component A and the component B are mixed for use, so that the fragrance releasing time is long, and the long-acting purification of indoor air is realized.
Detailed Description
The invention is further described with reference to specific embodiments.
The waterborne hydroxy acrylic resin used in the invention is waterborne hydroxy acrylic resin with Bayer company model number BayhydrolA 145, the dispersant is Dispex Ultra PA4580 series product of Pasteur, the defoamer is winning TEGO Airex 901W polydimethylsiloxane defoamer, the leveling agent is ACRTSOL RM-8W series product of the Dow chemical (China) Limited company, the isocyanate curing agent is waterborne isocyanate curing agent DIC5500 of the Japan Di Aisheng company, and the rose essential oil is rose essential oil of the Guangzhou seven-color cosmetics manufacturing Limited company.
Example 1:
a odorless aromatic two-component waterborne polyurethane coating comprises an A component and a B component which are independently packaged; the component A comprises the following raw materials in parts by weight: 60 parts of water-based hydroxy acrylic resin (solid content is 41%), 20 parts of phthalocyanine blue, 2.5 parts of dispersing agent, 0.3 part of defoaming agent, 0.3 part of flatting agent and 2 parts of sodium carbonate; the component B comprises the following raw materials in parts by weight: 80 parts of isocyanate curing agent, 20 parts of ethylene glycol butyl ether and 40 parts of aromatic slow-release particles.
The preparation method of the aromatic sustained-release particles comprises the following steps:
(1) dissolving P123 in absolute ethyl alcohol, dropwise adding butyl titanate under a stirring state, dropwise adding a mixed solution of ethanol and water after stirring reaction for 40min, and stirring reaction for 1.5h to obtain a precursor solution, wherein the mass-volume ratio of P123 to the absolute ethyl alcohol, the butyl titanate and the mixed solution is 1 g: 12mL of: 3.7 mL: 18mL, wherein the volume ratio of ethanol to water in the mixed solution is 1.5: 1;
(2) placing the precursor solution in a hydrothermal reaction kettle, carrying out crystallization reaction for 10h at 100 ℃, cooling to room temperature, filtering, washing and drying the product to obtain TiO2A crystal;
(3) adding TiO into the mixture2The crystal is firstly roasted for 80min at 200 ℃ in the air atmosphere, and then the temperature is raised to 380 ℃ for roasting for 2.5h to obtain mesoporous TiO2；
(4) Making mesoporous TiO2Dispersing in toluene, adding gamma-methacryloxypropyltrimethoxysilane and mesoporous TiO2Toluene and gamma-methacryloxypropyltrimethoxysilane were added in a proportion of 1 g: 12mL of: 1.2g, stirring and reacting for 7h at 125 ℃, filtering, washing and drying the product to obtain the silanized mesoporous TiO2；
(5) Silanized mesoporous TiO2Dispersing in N, N-dimethylformamide, adding 1-vinylimidazole monomer, stirring for 25min to obtain dispersion, adding azobisisobutyronitrile under the protection of nitrogen, stirring at 82 deg.C for 10h, and silylanizing the mesoporous TiO2The addition proportion of N, N-dimethylformamide, 1-vinyl imidazole monomer and azodiisobutyronitrile is 10g: 150mL of: 2 g: 0.35g, filtering, washing a product, and drying in vacuum to obtain the polyvinyl imidazole modified mesoporous TiO2；
(6) Mesoporous TiO modified by polyvinyl imidazole2Mesoporous TiO modified by polyvinyl imidazole dispersed in rose essential oil2The mass volume ratio of the rose essential oil to the rose essential oil is 1 g: 25mL, stirring and reacting for 11h, filtering, and cleaning the product with deionized water to obtain the mesoporous TiO loaded with the plant essential oil2；
(7) Loading mesoporous TiO with plant essential oil2Dispersed in HEPES buffer solution with pH of 7.2 and loaded with plant essential oil2The mass-to-volume ratio of the buffer solution to the HEPES buffer solution is 1 g: 150mL, stirring for 25min and adding CuCl2Solution of mesoporous TiO loaded with plant essential oil2With CuCl2Cu in solution2+In a ratio of 1 g: 3mmol, stirring and reacting for 9h, filtering, washing and drying the product to obtain the aromatic slow-release particles.
Example 2:
a odorless aromatic two-component waterborne polyurethane coating comprises an A component and a B component which are independently packaged; the component A comprises the following raw materials in parts by weight: 50 parts of water-based hydroxy acrylic resin (with the solid content of 40%), 10 parts of iron oxide red, 2 parts of dispersing agent, 0.2 part of defoaming agent, 0.2 part of flatting agent and 1 part of sodium carbonate; the component B comprises the following raw materials in parts by weight: 70 parts of isocyanate curing agent, 15 parts of ethylene glycol butyl ether and 30 parts of aromatic slow-release particles.
The preparation method of the aromatic sustained-release particles comprises the following steps:
(1) dissolving P123 in absolute ethyl alcohol, dropwise adding butyl titanate under a stirring state, dropwise adding a mixed solution of ethanol and water after stirring reaction for 30min, and stirring reaction for 1h to obtain a precursor solution, wherein the mass-volume ratio of P123 to the absolute ethyl alcohol, the butyl titanate and the mixed solution is 1 g: 10mL of: 3.5 mL: 15mL, wherein the volume ratio of ethanol to water in the mixed solution is 1: 1;
(2) placing the precursor solution in a hydrothermal reaction kettle, carrying out crystallization reaction at 80 ℃ for 12h, cooling to room temperature, filtering, washing and drying the product to obtain TiO2A crystal;
(3) adding TiO into the mixture2The crystal is firstly roasted for 90min at 180 ℃ in the air atmosphere, and then the temperature is raised to 400 ℃ for roasting for 2h to obtain mesoporous TiO2；
(4) Making mesoporous TiO2Dispersing in toluene, adding gamma-methacryloxypropyltrimethoxysilane and mesoporous TiO2Toluene and gamma-methacryloxypropyltrimethoxysilane were added in a proportion of 1 g: 10mL of: 1g, stirring and reacting for 8 hours at 120 ℃, filtering, washing and drying the product to obtain the silanized mesoporous TiO2；
(5) Silanized mesoporous TiO2Dispersing in N, N-dimethylformamide, adding 1-vinylimidazole monomer, stirring for 20min to obtain dispersion, adding azobisisobutyronitrile under the protection of nitrogen, stirring at 80 deg.C, reacting for 12h, and silylanizing the mesoporous TiO2The addition proportion of N, N-dimethylformamide, 1-vinyl imidazole monomer and azodiisobutyronitrile is 10g: 100mL of: 1.5 g: 0.3g, filtering, washing a product, and drying in vacuum to obtain the polyvinyl imidazole modified mesoporous TiO2；
(6) Mesoporous TiO modified by polyvinyl imidazole2Mesoporous TiO modified by polyvinyl imidazole dispersed in rose essential oil2The mass volume ratio of the rose essential oil to the rose essential oil is 1 g: 20mL, stirring and reacting for 10h, filtering, and cleaning the product with deionized water to obtain the mesoporous TiO loaded with the plant essential oil2；
(7) Loading mesoporous TiO with plant essential oil2Dispersed in HEPES buffer solution with pH of 7.4 and loaded with plant essential oil2The mass-to-volume ratio of the buffer solution to the HEPES buffer solution is 1 g: 100mL, stirring for 20min, and adding CuCl2Solution of mesoporous TiO loaded with plant essential oil2With CuCl2Cu in solution2+In a ratio of 1 g: 2mmol, stirring and reacting for 8h, filtering, washing and drying the product to obtain the aromatic slow-release particles.
Example 3:
a odorless aromatic two-component waterborne polyurethane coating comprises an A component and a B component which are independently packaged; the component A comprises the following raw materials in parts by weight: 70 parts of water-based hydroxy acrylic resin (solid content is 45%), 30 parts of carbon black, 3 parts of dispersing agent, 0.4 part of defoaming agent, 0.5 part of flatting agent and 3 parts of sodium carbonate; the component B comprises the following raw materials in parts by weight: 90 parts of isocyanate curing agent, 25 parts of ethylene glycol butyl ether and 50 parts of aromatic slow-release particles.
The preparation method of the aromatic sustained-release particles comprises the following steps:
(1) dissolving P123 in absolute ethyl alcohol, dropwise adding butyl titanate under a stirring state, dropwise adding a mixed solution of ethanol and water after stirring reaction for 60min, and stirring reaction for 2h to obtain a precursor solution, wherein the mass-volume ratio of P123 to the absolute ethyl alcohol, the butyl titanate and the mixed solution is 1 g: 15mL of: 4mL of: 20mL, wherein the volume ratio of ethanol to water in the mixed solution is 2: 1;
(2) placing the precursor solution in a hydrothermal reaction kettle, performing crystallization reaction at 120 ℃ for 8 hours, cooling to room temperature, filtering, washing and drying the product to obtain TiO2A crystal;
(3) adding TiO into the mixture2The crystal is firstly roasted for 60min at 220 ℃ in air atmosphere, and then is roasted for 3h after being heated to 350 ℃ to obtain mesoporous TiO2；
(4) Making mesoporous TiO2Dispersing in toluene, adding gamma-methacryloxypropyltrimethoxysilane and mesoporous TiO2Toluene and gamma-methacryloxypropyltrimethoxysilane were added in a proportion of 1 g: 15mL of: 1.5g, stirring and reacting at 130 ℃ for 6h, filtering and obtaining the productWashing and drying the substance to obtain silanized mesoporous TiO2；
(5) Silanized mesoporous TiO2Dispersing in N, N-dimethylformamide, adding 1-vinylimidazole monomer, stirring for 30min to obtain dispersion, adding azobisisobutyronitrile under the protection of nitrogen, stirring at 85 deg.C, reacting for 8 hr, and silylanizing the mesoporous TiO2The addition proportion of N, N-dimethylformamide, 1-vinyl imidazole monomer and azodiisobutyronitrile is 10g: 200mL of: 2.5 g: 0.4g, filtering, washing a product, and drying in vacuum to obtain the polyvinyl imidazole modified mesoporous TiO2；
(6) Mesoporous TiO modified by polyvinyl imidazole2Mesoporous TiO modified by polyvinyl imidazole dispersed in rose essential oil2The mass volume ratio of the rose essential oil to the rose essential oil is 1 g: 30mL, stirring for reaction for 12h, filtering, and washing the product with deionized water to obtain the mesoporous TiO loaded with the plant essential oil2；
(7) Loading mesoporous TiO with plant essential oil2Dispersed in HEPES buffer solution with pH of 7.4 and loaded with plant essential oil2The mass-to-volume ratio of the buffer solution to the HEPES buffer solution is 1 g: 200mL, stirring for 20min, and adding CuCl2Solution of mesoporous TiO loaded with plant essential oil2With CuCl2Cu in solution2+In a ratio of 1 g: 4mmol, stirring and reacting for 8h, filtering, washing and drying the product to obtain the aromatic slow-release particles.
Comparative example 1:
the component A of comparative example 1 was the same as that of example 1 except that no sodium carbonate was added.
Comparative example 2:
the preparation method of the aromatic sustained-release particles in comparative example 2 includes the steps of:
(1) dissolving P123 in absolute ethyl alcohol, dropwise adding butyl titanate under a stirring state, dropwise adding a mixed solution of ethanol and water after stirring reaction for 40min, and stirring reaction for 1.5h to obtain a precursor solution, wherein the mass-volume ratio of P123 to the absolute ethyl alcohol, the butyl titanate and the mixed solution is 1 g: 12mL of: 3.7 mL: 18mL, wherein the volume ratio of ethanol to water in the mixed solution is 1.5: 1;
(2) placing the precursor solution in a hydrothermal reaction kettle, carrying out crystallization reaction for 10h at 100 ℃, cooling to room temperature, filtering, washing and drying the product to obtain TiO2A crystal;
(3) adding TiO into the mixture2The crystal is firstly roasted for 80min at 200 ℃ in the air atmosphere, and then the temperature is raised to 380 ℃ for roasting for 2.5h to obtain mesoporous TiO2；
(4) Making mesoporous TiO2Dispersing in toluene, adding gamma-methacryloxypropyltrimethoxysilane and mesoporous TiO2Toluene and gamma-methacryloxypropyltrimethoxysilane were added in a proportion of 1 g: 12mL of: 1.2g, stirring and reacting for 7h at 125 ℃, filtering, washing and drying the product to obtain the silanized mesoporous TiO2；
(5) Silanized mesoporous TiO2Dispersing in N, N-dimethylformamide, adding 1-vinylimidazole monomer, stirring for 25min to obtain dispersion, adding azobisisobutyronitrile under the protection of nitrogen, stirring at 82 deg.C for 10h, and silylanizing the mesoporous TiO2The addition proportion of N, N-dimethylformamide, 1-vinyl imidazole monomer and azodiisobutyronitrile is 10g: 150mL of: 2 g: 0.35g, filtering, washing a product, and drying in vacuum to obtain the polyvinyl imidazole modified mesoporous TiO2；
(6) Mesoporous TiO modified by polyvinyl imidazole2Mesoporous TiO modified by polyvinyl imidazole dispersed in rose essential oil2The mass volume ratio of the rose essential oil to the rose essential oil is 1 g: 25mL, stirring and reacting for 11h, filtering, washing a product with deionized water, and drying to obtain the aromatic sustained-release particles.
The rest is the same as in example 1.
The two-component polyurethane coatings of the above examples and comparative examples were tested for their performance and the results are shown in table 1.
Table 1: and testing the performance of the polyurethane coating and the film.
The two-component polyurethane coating in the above examples and comparative examples is stored in a sealed manner at 50 ℃ for 6 months, and the content of citronellol (the main volatile component in rose essential oil) in the component B is determined by adopting a gas chromatography-mass spectrometry combined method; then, the component A and the component B are mixed according to the mass ratio of 4:1, the mixture is uniformly stirred and coated on a cement fiberboard with the thickness of 20cm multiplied by 20cm, the cement fiberboard is placed in a sealed container to be stored at the constant temperature of 50 ℃, and the fragrance duration is tested, and the results are shown in Table 2.
Table 2: and (5) testing the volatility of the plant essential oil.
As can be seen from tables 1 and 2, the polyurethane coatings prepared by using the raw materials of the present invention in examples 1 to 3 have good storage stability and coating film performance, little volatilization loss of the vegetable essential oil during storage, and long lasting fragrance of the coating after mixed coating, and can achieve the effect of long-term indoor air purification. The coating A in the comparative example 1 is not added with sodium carbonate, so that the plant essential oil is basically not released in the storage process, and the coating after mixed coating is free from fragrance emission, which proves that the pore passages of the fragrance slow-release particles cannot be opened when carbonate ions are not added, and the plant essential oil loaded in the pore passages cannot be released. Comparative example 2 preparation of aromatic sustained-release particles without addition of Cu2+Complex formation, the plant essential oil begins to volatilize in the storage process of the coating, the fragrance duration is short after mixed coating, and the fact that Cu is not added is proved2+When the aromatic slow-release particles form a complex with polyvinyl imidazole, the pore channels of the aromatic slow-release particles cannot be effectively closed.
Claims (6)
1. The odorless aromatic double-component waterborne polyurethane coating is characterized by comprising components which are independently packaged and used according to the mass ratio of 10: (2-3) mixing the component A and the component B; the component A comprises the following raw materials in parts by weight: 50-70 parts of water-based hydroxyl acrylic resin, 10-30 parts of pigment, 2-3 parts of dispersing agent, 0.2-0.4 part of defoaming agent, 0.2-0.5 part of flatting agent and 1-3 parts of sodium carbonate, wherein the water-based hydroxyl acrylic resin is prepared by mixing water-based hydroxyl acrylic resin, pigment, dispersing agent, defoaming agent, leveling agent and sodium carbonateThe solid content of the fat is 40-45 wt%; the component B comprises the following raw materials in parts by weight: 70-90 parts of isocyanate curing agent, 15-25 parts of film forming solvent and 30-50 parts of aromatic slow release particles, wherein the aromatic slow release particles are mesoporous TiO loaded with plant essential oil2Said mesoporous TiO2A complex of polyvinyl imidazole and Cu (II) is modified on the surface;
the preparation method of the aromatic sustained-release particles comprises the following steps:
(1) dissolving P123 in absolute ethyl alcohol, dropwise adding butyl titanate while stirring, stirring and reacting for 30-60 min, then dropwise adding a mixed solution of ethanol and water, and stirring and reacting for 1-2 h to obtain a precursor solution;
(2) placing the precursor solution in a hydrothermal reaction kettle, performing crystallization reaction at 80-120 ℃ for 8-12 h, cooling to room temperature, filtering, washing and drying the product to obtain TiO2A crystal;
(3) adding TiO into the mixture2Roasting the crystal in air atmosphere at 180-220 ℃ for 60-90 min, then heating to 350-400 ℃ and roasting for 2-3 h to obtain mesoporous TiO2；
(4) Making mesoporous TiO2Dispersing in toluene, adding gamma-methacryloxypropyltrimethoxysilane, stirring at 120-130 ℃ for reaction for 6-8 h, filtering, washing and drying the product to obtain the silanized mesoporous TiO2；
(5) Silanized mesoporous TiO2Dispersing in N, N-dimethylformamide, adding a 1-vinylimidazole monomer, stirring for 20-30 min to obtain a dispersion, adding azodiisobutyronitrile into the dispersion under the protection of nitrogen, stirring and reacting at 80-85 ℃ for 8-12 h, filtering, washing a product, and drying in vacuum to obtain the polyvinyl imidazole modified mesoporous TiO2(ii) a The silanized mesoporous TiO2The addition ratio of the N, N-dimethylformamide to the 1-vinylimidazole monomer to the azobisisobutyronitrile is 10g (100-200 mL): (1.5-2.5 g): (0.3-0.4 g);
(6) mesoporous TiO modified by polyvinyl imidazole2Dispersing in plant essential oil, stirring for reaction for 10-12 h, filtering, and washing the product with deionized water to obtain the mesoporous TiO loaded with the plant essential oil2；
(7) Loading mesoporous TiO with plant essential oil2Dispersing in HEPES buffer solution with pH of 7.2-7.4, stirring for 20-30 min, and adding CuCl2Stirring the solution for reacting for 8-10 h, filtering, washing and drying the product to obtain the aromatic slow-release particles; the mesoporous TiO loaded with the plant essential oil2The mass-to-volume ratio of the buffer solution to the HEPES buffer solution is 1 g: (100-200 mL) of mesoporous TiO loaded with plant essential oil2With CuCl2Cu in solution2+In a ratio of 1 g: (2-4 mmol).
2. The odorless aromatic two-component waterborne polyurethane coating as claimed in claim 1, wherein the mass-volume ratio of the P123 to the absolute ethyl alcohol, the butyl titanate and the mixed solution in the step (1) is 1 g: (10-15 mL): (3.5-4 mL): (15-20 mL), wherein the volume ratio of ethanol to water in the mixed solution is (1-2): 1.
3. the odorless aromatic two-component waterborne polyurethane coating as claimed in claim 1, wherein the mesoporous TiO in step (4) is2Toluene and gamma-methacryloxypropyltrimethoxysilane were added in a proportion of 1 g: (10-15 mL): (1-1.5 g).
4. The odorless fragrant two-component waterborne polyurethane coating material as claimed in claim 1, wherein the plant essential oil in step (6) is one or more selected from lavender essential oil, rose essential oil, jasmine essential oil, rosemary essential oil, clove essential oil and chamomile essential oil, and the polyvinyl imidazole modified mesoporous TiO is2The mass volume ratio of the plant essential oil to the plant essential oil is 1 g: (20-30 mL).
5. The odorless aromatic two-component waterborne polyurethane coating as claimed in claim 1, wherein the pigment in the component A is one selected from phthalocyanine blue, titanium dioxide, carbon black, medium chrome yellow and iron oxide red.
6. The odor-free aromatic two-component waterborne polyurethane coating as claimed in claim 1, wherein the film forming solvent in the component B is one or more selected from the group consisting of ethylene glycol butyl ether, diethylene glycol hexyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether.
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