CN115584207A - High-temperature-resistant cooker pigment and preparation method thereof - Google Patents

Abstract

The invention provides a high-temperature-resistant cooker pigment and a preparation method thereof, belonging to the technical field of pigments. Tetrabutyl titanate is dissolved in an organic solvent, an aqueous solution containing a pore-forming agent and an emulsifier is added, an emulsification reaction is carried out to obtain TiO2 porous hollow nano microspheres, then the porous hollow nano microspheres are added into an aqueous solution dissolved with soluble aluminum salt and soluble iron salt, a complexing agent is added, the temperature is raised to form dried gel, the dried gel is ignited and ball milled to obtain aluminum-titanium-iron oxide composite nano microspheres, the aluminum-titanium-iron oxide composite nano microspheres are added into an ethoxy silane ethanol solution to obtain coated nano microspheres, then the coated nano microspheres are dispersed in water, a composite silane coupling agent is added, a heating reaction is carried out to obtain modified coated nano microspheres, the modified coated nano microspheres and the emulsifier are added into the aqueous phase obtained by adding the water, and the modified coated nano microspheres and the emulsifier are added into an oil phase dissolved with aminosilane and fluorine-containing silane, and the modified coated nano microspheres are emulsified and stirred to react to obtain the high-temperature resistant cooker pigment.

Description

High-temperature-resistant cooker pigment and preparation method thereof

Technical Field

The invention relates to the technical field of pigments, in particular to a high-temperature-resistant cooker pigment and a preparation method thereof.

Background

The metallic pigment is prepared by finely grinding metal or alloy particles or flakes, has metallic luster, can endow the product with metallic appearance, forms a smooth thin coating film, has unique decoration and covering power, and is widely used in the coating industry. Because of their chemical properties, metallic pigments are often limited in their stability in the environment and are prone to safety and product quality issues, metallic pigment preparations are often surface modified to ameliorate these problems.

CN1229110A discloses a multilayer interference pigment with a blue mass tone, which consists of a platelet-shaped carrier material and a coating layer, and the coating layer consists of the following structure; (I) A first layer of a high refractive index, colorless, transparent metal oxide layer, (II) a second layer of a low refractive index, colorless, transparent metal oxide layer, and (III) a third layer of an outer layer of cobalt aluminate, cobalt-containing glass, or cobalt oxide. The first and third layers may also be reversed. The high-refractive-index metal oxides used are titanium dioxide, zirconium dioxide or tin oxide. The low refractive index metal oxide used is silica or alumina.

CN1775869A discloses titanium dioxide pigments comprising rutile or anatase titanium dioxide particles having a coating of zirconia, amorphous silica and hydrated alumina deposited thereon, the particles preferably also having an organic coating adsorbed or bonded thereon.

US5324355A discloses a thermally decomposed zirconium silicate consisting of crystalline ZrO embedded in an amorphous SiO2 phase ₂ And (4) forming.

However, the above pigment has poor high temperature resistance, and thus, cannot be applied to a cooker which is exposed to a high temperature environment for a long time, and therefore, it is also required to develop a high temperature resistant pigment which can be applied to a surface coating material for a cooker.

In addition, the existing cooker is widely applied to non-stick pan coating, if the surface of an object has super-hydrophobic and oleophobic properties, water drops and oil drops cannot be soaked on the surface of the object, so that dirt can be taken away to achieve the self-cleaning effect, and meanwhile, the cooker is not easy to stick a pan in the using process. The coating with the self-cleaning effect and no pan sticking has been more and more paid attention to the market due to the advantages of convenient use, reduction of cleaning procedures and the like, and has commercial value.

Disclosure of Invention

The invention aims to provide a high-temperature-resistant cooker pigment and a preparation method thereof, and the prepared high-temperature-resistant cooker pigment not only has better corrosion resistance and high-temperature resistance, but also has good mechanical property, and simultaneously has a self-cleaning effect, can resist pollution for a long time, is applied to a coating of a non-stick cooker, has better non-stick property, and thus has wide application prospect.

The technical scheme of the invention is realized as follows:

the invention provides a preparation method of a high-temperature resistant cooker pigment, which comprises the steps of dissolving tetrabutyl titanate in an organic solvent, adding an aqueous solution containing a pore-forming agent and an emulsifier, and carrying out an emulsification reaction to obtain TiO ₂ Adding porous hollow nano-microspheres into an aqueous solution in which soluble aluminum salt and soluble ferric salt are dissolved, adding a complexing agent, heating to form dry gel, igniting and ball-milling to obtain aluminum-titanium-iron oxide composite nano-microspheres, adding the aluminum-titanium-iron oxide composite nano-microspheres into an ethoxysilane ethanol solution to obtain coated nano-microspheres, dispersing the coated nano-microspheres in water, adding a composite silane coupling agent, heating to react to obtain modified coated nano-microspheres, adding an emulsifier into an aqueous phase obtained by adding the modified coated nano-microspheres into the water, adding an oil phase in which aminosilane and fluorine-containing silane are dissolved, emulsifying, and stirring to react to obtain the high-temperature resistant cooker pigment.

As a further improvement of the invention, the method comprises the following steps:

S1.TiO ₂ preparing porous hollow nano microspheres: dissolving tetrabutyl titanate in an organic solvent to obtain an oil phase; dissolving a pore-foaming agent and an emulsifier in water to obtain a water phase; adding the water phase into the oil phase, emulsifying, centrifuging, washing and drying to obtain TiO ₂ Porous hollow nanospheres;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: will be solubleDissolving aluminum salt and soluble ferric salt in water to obtain an aqueous solution, and adding the TiO prepared in the step S1 ₂ Uniformly dispersing the porous hollow nano microspheres, adding a complexing agent, and heating to evaporate the solvent to obtain sol; then raising the temperature, reducing the vacuum degree to obtain dry gel, taking out the dry gel, igniting the dry gel, and performing ball milling to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving ethoxysilane in ethanol, adding the aluminum-titanium-iron oxide composite nano microspheres prepared in the step S2, stirring at a constant speed, and drying to obtain coated nano microspheres;

s4, preparing modified coated nano microspheres: dispersing the coated nano-microspheres prepared in the step S3 in water, adding a composite silane coupling agent, heating for reaction, centrifuging, washing and drying to obtain modified coated nano-microspheres;

s5, preparing the high-temperature resistant cooker pigment: dissolving aminosilane and fluorine-containing silane in an organic solvent to obtain an oil phase; uniformly dispersing the modified coated nano microspheres prepared in the step S4 in water, adding an emulsifier, dissolving and stirring uniformly, and adjusting the pH value of the solution to be alkaline to obtain a water phase; and adding the water phase into the oil phase, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain the high-temperature-resistant cooker pigment.

As a further improvement of the invention, in step S1, the content of tetrabutyl titanate in the oil phase is 25 to 30wt%, the content of pore-forming agent in the water phase is 1 to 3wt%, the content of emulsifier is 1 to 2wt%, the mass ratio of the water phase to the oil phase is 3 to 5 to 7, and the emulsification condition is 12000 to 15000r/min for 3 to 5min; the pore-foaming agent comprises a macroporous pore-foaming agent and a mesoporous pore-foaming agent, wherein the macroporous pore-foaming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether; the mesoporous pore-forming agent is selected from at least one of cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106.

As a further improvement of the invention, the pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 3-5.

As a further improvement of the present invention, in step S2, the soluble aluminum salt is selected from at least one of aluminum nitrate, aluminum chloride and aluminum sulfate; the soluble ferric salt is selected from at least one of ferric sulfate, ferric chloride and ferric nitrate; the complexing agent is selected from at least one of disodium EDTA, ethylenediamine, citric acid and sodium citrate; the soluble aluminum salt, soluble iron salt and TiO ₂ The mass ratio of the porous hollow nano-microspheres to the complexing agent is (5-7); the heating temperature is 60-80 ℃, the temperature is increased to 140-170 ℃ in the heater, and the vacuum degree is reduced to 0.01-0.1MPa; the ball milling time is 7-10h.

As a further improvement of the invention, the mass ratio of the ethoxysilane to the aluminum-titanium-iron oxide composite nanospheres in step S3 is 5-7; the rotation speed of the uniform stirring is 500-700r/min, and the time is 1-2h.

As a further improvement of the invention, the mass ratio of the coated nano-microspheres to the composite silane coupling agent in the step S4 is 10; the composite silane coupling agent is selected from at least two of KH550, KH560, KH570, KH580, KH590, KH602 and KH792, preferably a mixture of KH550 and KH602, and the mass ratio is 3-5:1; heating to 50-70 deg.C, and reacting for 1-2h.

In a further improvement of the present invention, in step S5, the aminosilane is at least one selected from the group consisting of γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldiethoxysilane, and diethylenetriaminopropyltrimethoxysilane; the fluorine-containing silane is selected from 1H, 2H-perfluorodecyltriethoxysilane, 1H, 2H-perfluorodecyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, dodecafluoroethyltriethoxysilane, and octafluorosilane at least one of 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 1H, 2H-perfluorooctyltriethoxysilane, or 1H, 2H-perfluorooctyltrimethoxysilane; the mass ratio of the aminosilane to the fluorine-containing silane is 1-3; the pH value of the adjusting solution is 9-10; the emulsification condition is 12000-15000r/min for 3-5min; the mass ratio of the modified coated nano-microspheres to the emulsifier is 10; the mass ratio of the water phase to the oil phase is 3-5.

As a further improvement of the invention, the method specifically comprises the following steps:

S1.TiO ₂ preparing porous hollow nano microspheres: dissolving tetrabutyl titanate in an organic solvent to obtain an oil phase containing 25-30wt% of tetrabutyl titanate; dissolving a pore-foaming agent and an emulsifier in water to obtain a water phase containing 1-3wt% of the pore-foaming agent and 1-2wt% of the emulsifier; adding 3-5 weight parts of water phase into 5-7 weight parts of oil phase, emulsifying at 12000-15000r/min for 3-5min, centrifuging, washing, and drying to obtain TiO ₂ Porous hollow nanospheres;

the pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio is 3-5;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: dissolving 5-7 parts by weight of soluble aluminum salt and 2-4 parts by weight of soluble iron salt in 100 parts by weight of water to obtain an aqueous solution, and adding 4-6 parts by weight of the TiO prepared in step S1 ₂ Uniformly dispersing porous hollow nano microspheres by ultrasonic, adding 12-17 parts by weight of complexing agent, heating to 60-80 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 140-170 ℃ in the heater, reducing the vacuum degree to 0.01-0.1MPa to obtain dry gel, taking out the dry gel, igniting the dry gel, and carrying out ball milling for 7-10h to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving 5-7 parts by weight of ethoxysilane in 20 parts by weight of ethanol, adding 3-5 parts by weight of the aluminum-titanium-iron oxide composite nano-microspheres prepared in the step S2, stirring at a constant speed of 500-700r/min for 1-2h, and drying to obtain coated nano-microspheres;

s4, preparing modified coated nano microspheres: dispersing 10 parts by weight of the coated nano-microspheres prepared in the step S3 in water, adding 2-3 parts by weight of a composite silane coupling agent, heating to 50-70 ℃, reacting for 1-2h, centrifuging, washing and drying to obtain modified coated nano-microspheres;

the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio of the KH550 to the KH602 is 3-5:1;

s5, preparing the high-temperature resistant cooker pigment: dissolving 10-30 parts by weight of aminosilane and 10 parts by weight of fluorine-containing silane in 100 parts by weight of organic solvent to obtain an oil phase; uniformly dispersing 10 parts by weight of the modified coated nano microspheres prepared in the step S4 in 50 parts by weight of water, adding 1 emulsifier, dissolving and stirring uniformly, and adjusting the pH value of the solution to 9-10 to obtain a water phase; adding 30-50 parts by weight of water phase into 50-70 parts by weight of oil phase, emulsifying at 12000-15000r/min for 3-5min, stirring for reaction for 3-5h, centrifuging, washing, and drying to obtain the high temperature resistant cooker pigment.

Preferably, the emulsifier is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfide, sodium tetradecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfonate, sodium octadecyl benzene sulfonate, and sodium octadecyl sulfate.

Preferably, the organic solvent is at least one selected from dichlorohexane, dichloromethane, chloroform, ethyl acetate, petroleum ether, methyl acetate, butyl acetate, n-hexane and cyclohexane.

The invention further protects the high-temperature resistant cooker pigment prepared by the preparation method.

The invention has the following beneficial effects:

the invention prepares TiO by sol-gel reaction ₂ Mixing and emulsifying an oil phase containing tetrabutyl titanate and a water phase containing a pore-foaming agent and an emulsifier to obtain porous hollow oxide nano microspheres, and centrifuging to remove water and oil in the microspheres to obtain the TiO nano microspheres ₂ Porous hollow nanospheres;

further, the obtained TiO ₂ Adding porous hollow nano-microsphere into water containing soluble aluminum salt and soluble iron salt, and adding complexing agent to obtain the final product ₂ The complexing agent-aluminum is formed inside and outside the surface of the porous hollow nano microsphereHeating the complex, the complexing agent-iron complex and the complexing agent-aluminum-iron complex to obtain dry gel, igniting the dry gel, and performing long-time ball milling to obtain the aluminum-titanium-iron oxide composite nano microspheres;

the aluminum-titanium-iron oxide composite nano-microsphere is a good high-temperature-resistant pigment, and is compounded by aluminum oxide, iron oxide and titanium oxide, so that the formed oxide has an attractive color, different colors of the pigment can be adjusted by adjusting the contents of the aluminum oxide, the iron oxide and the titanium oxide, and meanwhile, the high-temperature resistance of the pigment is greatly improved;

furthermore, the surface of the aluminum-titanium-iron oxide composite nano microsphere is coated by ethoxysilane, so that the stability of the aluminum-titanium-iron oxide composite nano microsphere can be obviously improved, the storage stability of the pigment is prolonged, and the compactness and the anti-corrosion effect can be obviously improved.

And then, modifying the surface of the prepared coated nano microsphere by using a composite silane coupling agent (the composite silane coupling agent is a mixture of KH550 and KH 602), so that abundant amino groups are connected to the surface of the microsphere, the microsphere can stably exist in an alkaline solution in subsequent reactions, meanwhile, an alkaline water phase containing the modified coated nano microsphere is added into an oil phase containing aminosilane and fluorine-containing silane, and then is emulsified to form a tiny water-in-oil droplet, abundant aminosilane and fluorine-containing silane are gathered on an interface, the amino group of the aminosilane faces to the internal water phase, and the amino group can be protonated to become an amphiphilic molecule along with the reaction to stabilize the silane droplet. Meanwhile, the protonation of the amino group and the alkaline aqueous phase can catalyze silane to generate sol-gel reaction, so that a silicon oxide shell layer is formed on an interface. The fluorine-containing group is hydrophobic and can spontaneously face the outside of the shell layer, so that the high-temperature resistant cooker pigment containing rich fluorine-containing groups on the outside is obtained, the fluorine-containing group has extremely low surface energy and better hydrophobic and oleophobic properties, and can be applied to the coating of non-stick cookers, so that the high-temperature resistant cooker pigment not only has better corrosion resistance and high temperature resistance and good mechanical property, but also has a self-cleaning effect, can resist pollution for a long time, has better non-stick property, and has wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 shows TiO prepared in example 1 ₂ TEM image of porous hollow nanospheres.

FIG. 2 is a TEM image of the high temperature resistant cookware pigment prepared in example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The embodiment provides a preparation method of a high-temperature-resistant cooker pigment, which specifically comprises the following steps:

S1.TiO ₂ preparing porous hollow nano microspheres: dissolving tetrabutyl titanate in dichloromethane to obtain an oil phase containing 25wt% of tetrabutyl titanate; dissolving a pore-foaming agent and sodium dodecyl benzene sulfonate in water to obtain a water phase containing 1wt% of the pore-foaming agent and 1wt% of an emulsifier; adding 3 weight parts of water phase into 5 weight parts of oil phase, emulsifying at 12000r/min for 3min, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 deg.C for 2h to obtain TiO ₂ Porous hollow nanospheres; FIG. 1 shows the TiO produced ₂ The TEM image of the porous hollow nano-microsphere shows that the nano-microsphere is a hollow structure.

The pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio is 3;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: dissolving 5 parts by weight of aluminum sulfate and 2 parts by weight of ferric sulfate in 100 parts by weight of water to obtain an aqueous solution, and adding 4 parts by weight of TiO prepared in the step S1 ₂ Carrying out ultrasonic dispersion on the porous hollow nano microspheres at 1000W for 30min, adding 12 parts by weight of EDTA disodium, heating to 60 ℃ and evaporating the solvent to obtain sol; then raising the temperature to 140 ℃ in the heater, reducing the vacuum degree to 0.01MPa to obtain dry gel, taking out the dry gel, igniting the dry gel, and performing ball milling for 7 hours to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving 5 parts by weight of ethoxysilane in 20 parts by weight of ethanol, adding 3 parts by weight of the aluminum-titanium-iron oxide composite nano microspheres prepared in the step S2, uniformly stirring at 500r/min for 1h, and drying at 70 ℃ for 2h to obtain coated nano microspheres;

s4, preparing the modified coated nano microspheres: adding 10 parts by weight of the coated nano-microspheres prepared in the step S3 into water, performing ultrasonic dispersion at 1000W for 20min, adding 2 parts by weight of a composite silane coupling agent, heating to 50 ℃ for reaction for 1h, centrifuging at 3000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified coated nano-microspheres;

the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio of the composite silane coupling agent to the KH602 is 3:1;

s5, preparing the high-temperature resistant cooker pigment: dissolving 10 parts by weight of N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 10 parts by weight of 1H, 2H-perfluorodecyltriethoxysilane in 100 parts by weight of dichloromethane to obtain an oil phase; adding 10 parts by weight of the modified coated nano-microspheres obtained in the step S4 into 50 parts by weight of water, performing ultrasonic dispersion at 1000W for 15min, adding 1 tetradecyl sodium benzenesulfonate, dissolving and stirring uniformly, and adjusting the pH value of the solution to 9 to obtain a water phase; adding 30 parts by weight of water phase into 50 parts by weight of oil phase, emulsifying for 3min at 12000r/min, stirring for reaction for 3h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain the high-temperature-resistant cooker pigment. FIG. 2 is a TEM image of the prepared high temperature resistant cookware pigment, from which it can be seen that the pigment surface layer is aggregated with a silica shell layer.

Example 2

The embodiment provides a preparation method of a high-temperature-resistant cooker pigment, which specifically comprises the following steps:

S1.TiO ₂ preparing porous hollow nano microspheres: dissolving tetrabutyl titanate in butyl acetate to obtain an oil phase containing 30wt% of tetrabutyl titanate; dissolving a pore-foaming agent and tetradecyl sodium sulfide in water to obtain a water phase containing 3wt% of the pore-foaming agent and 2wt% of an emulsifier; adding 5 weight parts of water phase into 7 weight parts of oil phase, emulsifying at 15000r/min for 5min, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain TiO ₂ Porous hollow nanospheres;

the pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio is 5;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: dissolving 7 parts by weight of aluminum nitrate and 4 parts by weight of ferric nitrate in 100 parts by weight of water to obtain an aqueous solution, and adding 6 parts by weight of the TiO prepared in the step S1 ₂ Carrying out ultrasonic dispersion on the porous hollow nano microspheres at 1000W for 30min, adding 17 parts by weight of citric acid, heating to 80 ℃, and evaporating the solvent to obtain sol; then raising the temperature to 170 ℃ in the heater, reducing the vacuum degree to 0.1MPa to obtain dry gel, taking out the dry gel, igniting the dry gel, and performing ball milling for 10 hours to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving 7 parts by weight of ethoxysilane in 20 parts by weight of ethanol, adding 5 parts by weight of the aluminum-titanium-iron oxide composite nano-microspheres prepared in the step S2, uniformly stirring at 700r/min for 2h, and drying at 70 ℃ for 2h to obtain coated nano-microspheres;

s4, preparing modified coated nano microspheres: adding 10 parts by weight of the coated nano-microspheres prepared in the step S3 into water, performing ultrasonic dispersion at 1000W for 20min, adding 3 parts by weight of a composite silane coupling agent, heating to 70 ℃, reacting for 2h, centrifuging at 3000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified coated nano-microspheres;

the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 5:1;

s5, preparing the high-temperature resistant cooker pigment: dissolving 30 parts by weight of gamma-aminopropyltrimethoxysilane and 10 parts by weight of dodecafluoroheptyl-propyl-trimethoxysilane in 100 parts by weight of butyl acetate to obtain an oil phase; adding 10 parts by weight of the modified coated nano microspheres prepared in the step S4 into 50 parts by weight of water, performing ultrasonic dispersion for 15min at 1000W, adding 1 octadecyl sodium sulfate, dissolving and stirring uniformly, and adjusting the pH value of the solution to 10 to obtain a water phase; adding 50 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 5min at 15000r/min, stirring for reaction for 5h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain the high-temperature-resistant cooker pigment.

Example 3

The embodiment provides a preparation method of a high-temperature-resistant cooker pigment, which specifically comprises the following steps:

S1.TiO ₂ preparing porous hollow nano microspheres: dissolving tetrabutyl titanate in ethyl acetate to obtain an oil phase containing 27wt% of tetrabutyl titanate; dissolving a pore-foaming agent and sodium hexadecyl benzene sulfonate in water to obtain a water phase containing 2wt% of the pore-foaming agent and 1.5wt% of an emulsifier; adding 4 weight parts of water phase into 6 weight parts of oil phase, emulsifying at 13500r/min for 4min, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain TiO ₂ Porous hollow nanospheres;

the pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the hexadecyl trimethyl ammonium bromide is 4;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: dissolving 6 parts by weight of aluminum chloride and 3 parts by weight of ferric chloride in 100 parts by weight of water to obtain an aqueous solution, and adding 5 parts by weight of the TiO prepared in step S1 ₂ Carrying out ultrasonic dispersion on porous hollow nano microspheres at 1000W for 30min, adding 15 parts by weight of sodium citrate, and heating to 70 ℃ to evaporate a solvent to obtain sol; then raising the temperature to 155 ℃ in the heater, reducing the vacuum degree to 0.05MPa to obtain dry gel, taking out the dry gel, igniting the dry gel, and carrying out ball milling for 8 hours to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving 6 parts by weight of ethoxysilane in 20 parts by weight of ethanol, adding 4 parts by weight of the aluminum-titanium-iron oxide composite nano-microspheres prepared in the step S2, uniformly stirring at 600r/min for 1.5h, and drying at 70 ℃ for 2h to obtain coated nano-microspheres;

s4, preparing modified coated nano microspheres: adding 10 parts by weight of the coated nano-microspheres prepared in the step S3 into water, performing ultrasonic dispersion at 1000W for 20min, adding 2.5 parts by weight of a composite silane coupling agent, heating to 60 ℃, reacting for 1.5h, centrifuging at 3000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified coated nano-microspheres;

the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio of the KH550 to the KH602 is 4:1;

s5, preparing the high-temperature resistant cooker pigment: dissolving 20 parts by weight of N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane and 10 parts by weight of 3, 3-trifluoropropylmethyldimethoxysilane in 100 parts by weight of ethyl acetate to obtain an oil phase; adding 10 parts by weight of the modified coated nano microspheres prepared in the step S4 into 50 parts by weight of water, performing ultrasonic dispersion for 15min at 1000W, adding 1 octadecyl sodium sulfate, dissolving and stirring uniformly, and adjusting the pH value of the solution to 9.5 to obtain a water phase; adding 40 parts by weight of water phase into 60 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring and reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain the high-temperature-resistant cooker pigment.

Example 4

Compared with example 3, the difference is that the pore-forming agent is a single polyoxyethylene sorbitan fatty acid ester.

Example 5

The difference compared to example 3 is that the porogen is hexadecyltrimethylammonium bromide alone.

Example 6

Compared with example 3, the difference is that the composite silane coupling agent is single KH550.

Example 7

Compared with example 3, the difference is that the composite silane coupling agent is single KH602.

Comparative example 1

Compared with example 3, the difference is that no pore-forming agent is added in step S1.

Comparative example 2

The difference from example 3 is that step S1 is not performed.

Comparative example 3

The difference compared to example 3 is that no aluminum chloride was added in step S2.

Comparative example 4

The difference from example 3 is that no ferric chloride was added in step S2.

Comparative example 5

The difference from example 3 is that step S3 is not performed.

Comparative example 6

The difference from example 3 is that step S4 is not performed.

Comparative example 7

The difference compared to example 3 is that N- β (aminoethyl) - γ -aminopropyltriethoxysilane was not added in step S5.

Comparative example 8

Compared with example 3, except that 3,3, 3-trifluoropropylmethyldimethoxysilane was not added in step S5.

Comparative example 9

The difference from example 3 is that steps S4 and S5 are not performed.

Comparative example 10

The difference from example 3 is that steps S3, S4, and S5 are not performed.

Test example 1 high temperature resistance

The high temperature resistant cooker pigments prepared in examples 1 to 7 and comparative examples 1 to 10 were added to a silicone resin (brand: W30-1) at a content of 30wt%, the raw resin was a resin to which the high temperature resistant cooker pigment was not added, uniformly coated on the surface of the cooker, maintained at a temperature of 220 ℃, 240 ℃, 260 ℃, 280 ℃,300 ℃, 320 ℃ for 10min, the color at normal temperature was selected as a reference, the color was measured at each temperature, and the average value of the 5-point colors was taken as the color test result at that temperature. The color measuring system adopts a Lab color system, and takes the color difference value dE larger than 3 as a failure point.

TABLE 1

As can be seen from the above table, the high temperature resistant cookware pigment prepared in the embodiments 1-3 of the present invention can significantly improve the high temperature resistance of the resin when added to the resin.

Test example 2

The high temperature resistant cooker pigments prepared in examples 1 to 7 and comparative examples 1 to 10 were added to a silicone resin (brand: W30-1) at a content of 30wt%, and the base resin was a resin to which the high temperature resistant cooker pigment was not added, and uniformly coated on the surface of the cooker, to perform a performance test.

Heat resistance: baking the coated cooker at 180 ℃ for 2h, putting the cooker into a constant temperature box type electric furnace checked by a potential difference meter, raising the temperature by 10 ℃/min, starting timing along with the temperature of the furnace to 280 ℃, taking out the sample after the high temperature of 10min, cooling to room temperature, observing the surface condition of the coating, wherein the coating has good heat resistance if no cracking or dropping phenomenon occurs, and the coating has poor heat resistance if no cracking or dropping phenomenon occurs.

Non-stick property: heating the coated cooker to 90 deg.C, placing a shelled egg on the surface, heating until the egg is completely fried, slightly pushing the egg with a shovel, and naturally peeling off the egg with good non-stickiness; slightly adhering (the adhering area is less than 30 percent), and the non-adhesiveness is normal; the adhesion was severe (adhesion area was more than 60%), and even could not be peeled off, the non-tackiness was poor.

Boiling resistance: baking the coated cooker at 180 ℃ for 2h, cooling to room temperature, then placing the cooker in boiling water at 100 ℃, heating until the paint film is damaged, and phenomena such as bubbles, light loss, discoloration, cracking and the like appear, recording the required time, wherein the longer the time, the better the boiling resistance of the cooker.

Wear resistance: detection was carried out according to the method of GB/T1768-2006.

The results are shown in Table 2.

TABLE 2

As can be seen from the above table, the high temperature resistant cookware pigment prepared by the examples 1-3 of the present invention can significantly improve the heat resistance, non-stick property, water boiling resistance and wear resistance of the resin when added into the resin.

Test example 3

The high temperature resistant cooker pigments prepared in examples 1 to 7 and comparative examples 1 to 10 were added to a silicone resin (brand: W30-1) at a content of 30wt%, the base resin was a resin to which the high temperature resistant cooker pigment was not added, uniformly coated on a glass slide, water and hexadecane were dropped on the surface of the glass slide after a heat curing treatment, and the results were measured using a contact angle measuring instrument, as shown in table 3.

TABLE 3

As can be seen from the above table, the high temperature resistant cookware pigment prepared in the embodiments 1-3 of the invention can obviously improve the hydrophobic and oleophobic properties of the resin and the self-cleaning ability of the resin after being added into the resin.

Examples 4 and 5 are different from example 3 in that the porogen is a single polyoxyethylene sorbitan fatty acid ester or cetyltrimethylammonium bromide, and the high temperature resistance and heat resistance are reduced. Compared with example 3, the difference of comparative example 1 is that no pore-forming agent is added in step S1, and the high temperature resistance and heat resistance are obviously reduced. The invention prepares TiO by sol-gel reaction ₂ Mixing and emulsifying an oil phase containing tetrabutyl titanate and a water phase containing a pore-forming agent and an emulsifying agent to obtain porous hollow oxide nano microspheres, and centrifuging to remove water and oil in the microspheres to obtain the TiO ₂ Porous hollow nanospheres. Pore-forming agent in macroporeUnder the synergistic action of polyoxyethylene sorbitan fatty acid ester and mesoporous pore-forming agent hexadecyl trimethyl ammonium bromide, the formation of porous TiO can be ensured ₂ The hollow nano-microsphere provides sufficient space for the subsequent adhesion of aluminum and iron-complex compounds on the surface and inside of the nano-microsphere, thereby ensuring the formation of the stable aluminum-titanium-iron oxide composite nano-microsphere and improving the high temperature resistance and the aesthetic property of the pigment.

Examples 6 and 7 are different from example 3 in that the composite silane coupling agent is single KH550 or KH602, and the abrasion resistance, the non-stick property and the hydrophobic and oleophobic property are reduced. Comparative example 6 is different from example 3 in that step S4 is not performed, and abrasion resistance, non-stick property, and water and oil repellent property are remarkably decreased. The surface of the prepared coated nano microsphere is modified by a composite silane coupling agent (the composite silane coupling agent is a mixture of KH550 and KH 602), so that abundant amino groups are connected to the surface of the microsphere, the microsphere can stably exist in an alkaline solution in subsequent reactions, meanwhile, after an alkaline water phase containing the modified coated nano microsphere is added into an oil phase containing aminosilane and fluorine-containing silane, a tiny water-in-oil liquid drop is formed through emulsification, abundant aminosilane and fluorine-containing silane are gathered at an interface, the amino group of the aminosilane faces towards the internal water phase, and the amino group can be protonated and changed into an amphiphilic molecule along with the reaction, so that the silane liquid drop is stabilized. Meanwhile, the protonation of the amino group and the alkaline aqueous phase can catalyze silane to generate sol-gel reaction, and a silicon oxide shell layer is further formed on an interface, so that the wear resistance of the pigment is improved, a large number of fluorine-containing groups are connected outside the shell layer, and the hydrophobicity and oleophobicity of the pigment are improved.

Comparative example 2 is different from example 3 in that step S1 is not performed, and the heat resistance and high temperature resistance are reduced. Comparative example 3 is different from example 3 in that aluminum chloride is not added in step S2, and the high temperature resistance is lowered. Comparative example 4 is different from example 3 in that iron chloride is not added in step S2, and abrasion resistance and high temperature resistance are reduced. The aluminum-titanium-iron oxide composite nano-microsphere is a better high-temperature-resistant pigment, and is compounded by aluminum oxide, iron oxide and titanium oxide, so that the formed oxide has an attractive color, different colors of the pigment can be adjusted by adjusting the contents of the aluminum oxide, the iron oxide and the titanium oxide, and meanwhile, the high-temperature resistance of the pigment is greatly improved;

comparative example 5 is compared with example 3 except that the boiling resistance is lowered without performing step S3. The surface of the aluminum-titanium-iron oxide composite nano microsphere is coated by ethoxysilane, so that the stability of the aluminum-titanium-iron oxide composite nano microsphere can be obviously improved, the storage stability of the pigment is prolonged, and the compactness and the corrosion prevention effect can be obviously improved.

Comparative example 7 is different from example 3 in that N- β (aminoethyl) - γ -aminopropyltriethoxysilane was not added in step S5, and the heat resistance, boiling resistance, wear resistance, and water and oil repellency were reduced. Comparative example 8 is different from example 3 in that 3,3, 3-trifluoropropylmethyldimethoxysilane was not added in step S5, and the non-stick property and the water and oil repellent property were remarkably reduced. The surface of the prepared coated nano microsphere is modified by a composite silane coupling agent (the composite silane coupling agent is a mixture of KH550 and KH 602), so that abundant amino groups are connected to the surface of the microsphere, the microsphere can stably exist in an alkaline solution in subsequent reactions, meanwhile, after an alkaline water phase containing the modified coated nano microsphere is added into an oil phase containing aminosilane and fluorine-containing silane, a tiny water-in-oil liquid drop is formed through emulsification, abundant aminosilane and fluorine-containing silane are gathered at an interface, the amino group of the aminosilane faces towards the internal water phase, and the amino group can be protonated and changed into an amphiphilic molecule along with the reaction, so that the silane liquid drop is stabilized. Meanwhile, the protonation of the amino group and the alkaline aqueous phase can catalyze silane to generate sol-gel reaction, so that a silicon oxide shell layer is formed on an interface. The fluorine-containing group is hydrophobic and can spontaneously face the outside of the shell layer, so that the high-temperature resistant cooker pigment containing rich fluorine-containing groups on the outside is obtained, the fluorine-containing group has extremely low surface energy and better hydrophobic and oleophobic properties, and can be applied to the coating of non-stick cookers, so that the high-temperature resistant cooker pigment not only has better corrosion resistance and high temperature resistance and good mechanical property, but also has a self-cleaning effect, can resist pollution for a long time, has better non-stick property, and has wide application prospect.

Comparative example 9 is different from example 3 in that steps S4 and S5 are not performed, and the heat resistance, wear resistance, and water and oil repellency are significantly reduced. .

Comparative example 10 is different from example 3 in that the heat resistance, non-stick property, abrasion resistance, water and oil repellency were remarkably reduced without performing steps S3, S4, and S5.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (10)

1. A preparation method of a high-temperature resistant cooker pigment is characterized by dissolving tetrabutyl titanate in an organic solvent, adding an aqueous solution containing a pore-foaming agent and an emulsifier, carrying out an emulsification reaction to obtain TiO2 porous hollow nano microspheres, then adding the aqueous solution dissolved with soluble aluminum salt and soluble iron salt, adding a complexing agent, heating to form xerogel, igniting and carrying out ball milling to obtain aluminum-titanium-iron oxide composite nano microspheres, adding the aluminum-titanium-iron oxide composite nano microspheres into an ethoxysilane ethanol solution to obtain coated nano microspheres, then dispersing the coated nano microspheres in water, adding a composite silane coupling agent, carrying out a heating reaction to obtain modified coated nano microspheres, adding the modified coated nano microspheres and the emulsifier into the water to obtain a water phase, adding the water phase dissolved with aminosilane and fluorine-containing silane, carrying out an emulsification and a stirring reaction to obtain the high-temperature resistant cooker pigment.

2. The method of claim 1, comprising the steps of:

s1, preparing the TiO2 porous hollow nano-microspheres: dissolving tetrabutyl titanate in an organic solvent to obtain an oil phase; dissolving a pore-foaming agent and an emulsifier in water to obtain a water phase; adding the water phase into the oil phase, emulsifying, centrifuging, washing and drying to obtain the TiO2 porous hollow nano microsphere;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: dissolving soluble aluminum salt and soluble ferric salt in water to obtain an aqueous solution, adding the TiO2 porous hollow nano-microspheres prepared in the step S1, uniformly dispersing, adding a complexing agent, and heating to evaporate the solvent to obtain sol; then raising the temperature, reducing the vacuum degree to obtain dry gel, taking out the dry gel, igniting the dry gel, and performing ball milling to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving ethoxysilane in ethanol, adding the aluminum-titanium-iron oxide composite nano microspheres prepared in the step S2, stirring at a constant speed, and drying to obtain coated nano microspheres;

s4, preparing modified coated nano microspheres: dispersing the coated nano-microspheres prepared in the step S3 in water, adding a composite silane coupling agent, heating for reaction, centrifuging, washing and drying to obtain modified coated nano-microspheres;

s5, preparing the high-temperature resistant cooker pigment: dissolving aminosilane and fluorine-containing silane in an organic solvent to obtain an oil phase; uniformly dispersing the modified coated nano microspheres prepared in the step S4 in water, adding an emulsifier, dissolving and stirring uniformly, and adjusting the pH value of the solution to be alkaline to obtain a water phase; and adding the water phase into the oil phase, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain the high-temperature-resistant cooker pigment.

3. The preparation method according to claim 2, wherein in step S1, the content of tetrabutyl titanate in the oil phase is 25 to 30wt%, the content of pore-forming agent in the aqueous phase is 1 to 3wt%, the content of emulsifier is 1 to 2wt%, the mass ratio of the aqueous phase to the oil phase is 3 to 5 to 7, and the emulsification condition is 12000 to 15000r/min for 3 to 5min; the pore-foaming agent comprises a macroporous pore-foaming agent and a mesoporous pore-foaming agent, wherein the macroporous pore-foaming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether; the mesoporous pore-forming agent is selected from at least one of cetyl trimethyl ammonium bromide, an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106.

4. The preparation method according to claim 3, wherein the pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide in a mass ratio of 3-5.

5. The method according to claim 2, wherein the soluble aluminum salt in step S2 is at least one selected from the group consisting of aluminum nitrate, aluminum chloride, and aluminum sulfate; the soluble ferric salt is selected from at least one of ferric sulfate, ferric chloride and ferric nitrate; the complexing agent is selected from at least one of EDTA disodium, EDTA, ethylenediamine, citric acid and sodium citrate; the mass ratio of the soluble aluminum salt to the soluble ferric salt to the TiO2 porous hollow nano-microsphere to the complexing agent is (5-7); the heating temperature is 60-80 ℃, the temperature is increased to 140-170 ℃ in the heater, and the vacuum degree is reduced to 0.01-0.1MPa; the ball milling time is 7-10h.

6. The preparation method of claim 2, wherein the mass ratio of the ethoxysilane to the aluminum-titanium-iron oxide composite nanospheres in step S3 is 5-7; the rotation speed of the uniform stirring is 500-700r/min, and the time is 1-2h.

7. The preparation method according to claim 2, wherein the mass ratio of the coated nanospheres to the composite silane coupling agent in step S4 is 10 to 2-3; the composite silane coupling agent is selected from at least two of KH550, KH560, KH570, KH580, KH590, KH602 and KH792, preferably a mixture of KH550 and KH602, and the mass ratio is 3-5:1; heating to 50-70 deg.C, and reacting for 1-2h.

8. The method according to claim 2, wherein the aminosilane in step S5 is at least one selected from the group consisting of γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldiethoxysilane, and diethylenetriaminopropyltrimethoxysilane; the fluorine-containing silane is selected from 1H, 2H-perfluorodecyltriethoxysilane, 1H, 2H-perfluorodecyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, dodecafluorodecyltrimethoxysilane, and mixtures thereof at least one of 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 1H, 2H-perfluorooctyltriethoxysilane, or 1H, 2H-perfluorooctyltrimethoxysilane; the mass ratio of the aminosilane to the fluorine-containing silane is 1-3; the pH value of the adjusting solution is 9-10; the emulsification condition is 12000-15000r/min for 3-5min; the mass ratio of the modified coated nano-microspheres to the emulsifier is 10; the mass ratio of the water phase to the oil phase is 3-5.

9. The preparation method according to claim 2, characterized by comprising the following steps:

s1, preparing the TiO2 porous hollow nano-microspheres: dissolving tetrabutyl titanate in an organic solvent to obtain an oil phase containing 25-30wt% of tetrabutyl titanate; dissolving a pore-foaming agent and an emulsifier in water to obtain a water phase containing 1-3wt% of the pore-foaming agent and 1-2wt% of the emulsifier; adding 3-5 parts by weight of water phase into 5-7 parts by weight of oil phase, emulsifying for 3-5min at 12000-15000r/min, centrifuging, washing and drying to obtain TiO2 porous hollow nano microspheres;

the pore-foaming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio is 3-5;

s2, preparing the aluminum-titanium-iron oxide composite nano microspheres: dissolving 5-7 parts by weight of soluble aluminum salt and 2-4 parts by weight of soluble ferric salt in 100 parts by weight of water to obtain an aqueous solution, adding 4-6 parts by weight of the TiO2 porous hollow nano-microspheres prepared in the step S1, uniformly dispersing by ultrasonic, adding 12-17 parts by weight of a complexing agent, heating to 60-80 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 140-170 ℃ in the heater, reducing the vacuum degree to 0.01-0.1MPa to obtain dry gel, taking out the dry gel, igniting the dry gel, and carrying out ball milling for 7-10h to obtain the aluminum-titanium-iron oxide composite nano microspheres;

s3, preparing the coated nano microspheres: dissolving 5-7 parts by weight of ethoxysilane in 20 parts by weight of ethanol, adding 3-5 parts by weight of the aluminum-titanium-iron oxide composite nano-microspheres prepared in the step S2, stirring at a constant speed of 500-700r/min for 1-2h, and drying to obtain coated nano-microspheres;

s4, preparing modified coated nano microspheres: dispersing 10 parts by weight of the coated nano-microspheres prepared in the step S3 in water, adding 2-3 parts by weight of a composite silane coupling agent, heating to 50-70 ℃, reacting for 1-2h, centrifuging, washing and drying to obtain modified coated nano-microspheres;

the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio of the KH550 to the KH602 is 3-5:1;

s5, preparing the high-temperature resistant cooker pigment: dissolving 10-30 parts by weight of aminosilane and 10 parts by weight of fluorine-containing silane in 100 parts by weight of organic solvent to obtain an oil phase; uniformly dispersing 10 parts by weight of the modified coated nano microspheres prepared in the step S4 in 50 parts by weight of water, adding 1 emulsifier, dissolving and stirring uniformly, and adjusting the pH value of the solution to 9-10 to obtain a water phase; adding 30-50 parts by weight of water phase into 50-70 parts by weight of oil phase, emulsifying at 12000-15000r/min for 3-5min, stirring for reaction for 3-5h, centrifuging, washing, and drying to obtain the high temperature resistant cooker pigment.

10. A high temperature resistant cookware pigment made by the method of any of claims 1-9.

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