CN115584207B - High Wen Chuiju resistant pigment and preparation method thereof - Google Patents

Abstract

The invention provides a high Wen Chuiju resistant pigment and a preparation method thereof, and belongs to the technical field of pigments. Dissolving tetrabutyl titanate in an organic solvent, adding an aqueous solution containing a pore-forming agent and an emulsifying agent, performing an emulsification reaction to obtain TiO2 porous hollow nano-microspheres, then adding an aqueous solution containing soluble aluminum salt and soluble ferric salt, adding a complexing agent, heating to form xerogel, igniting and ball milling to obtain aluminum-titanium-iron oxide composite nano-microspheres, adding ethoxysilane ethanol solution to obtain coated nano-microspheres, dispersing the coated nano-microspheres in water, adding a composite silane coupling agent, performing a heating reaction to obtain modified coated nano-microspheres, adding an aqueous phase obtained by adding the modified coated nano-microspheres and the emulsifying agent into water, adding an oil phase containing aminosilane and fluorine-containing silane, performing an emulsification reaction, and stirring to obtain the high Wen Chuiju pigment which has better corrosion resistance and high temperature resistance, good mechanical property, and also has a self-cleaning effect and long-acting pollution resistance.

Description

High Wen Chuiju resistant pigment and preparation method thereof

Technical Field

The invention relates to the technical field of pigments, in particular to a high-resistance Wen Chuiju pigment and a preparation method thereof.

Background

The metallic pigment is prepared by grinding particles or flakes of metal or alloy, has metallic luster, can give metallic appearance to products, forms smooth thin coating film, has unique decorative property and hiding power, and is widely used in the coating industry. Metallic pigment products are often surface modified to ameliorate the above problems due to their chemical nature, their stability in the environment, and the ease of safety and product quality issues.

CN1229110a discloses a multilayer interference pigment with a blue dominant color, consisting of a platelet-shaped carrier material and a coating consisting of the following structure; (I) The first layer is a colorless, transparent metal oxide layer with high refractive index, (II) the second layer is a colorless, transparent metal oxide layer with low refractive index, and (III) the third layer is an external layer of cobalt aluminate, cobalt-containing glass or cobalt oxide. The first and third layers may also be reversed. The high refractive index metal oxide used is 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 thereto.

US5324355a discloses thermally decomposed zirconium silicate consisting of crystalline ZrO embedded in an amorphous SiO2 phase ₂ Composition is prepared.

However, the above pigment has poor high temperature resistance and thus cannot be applied to cookers which are exposed to high temperature environments for a long period of time, and thus there is a need to develop a high temperature resistant pigment which can be applied to the surface coating of cookers.

In addition, the non-stick pan coating is widely applied to the existing cooker, if the surface of an object has super-hydrophobic and oleophobic properties, water drops and oil drops cannot infiltrate into the surface of the object, dirt can be taken away, the self-cleaning effect is achieved, and meanwhile, the cooker is not easy to stick to a pan in the using process. The paint with self-cleaning effect and non-stick pan has been increasingly valued in the market due to the advantages of convenient use, reduced cleaning procedures, etc., and has commercial value.

Disclosure of Invention

The invention aims to provide a high Wen Chuiju resistant pigment and a preparation method thereof, and the prepared high temperature resistant pigment has good corrosion resistance and high temperature resistance, good mechanical property, self-cleaning effect, long-acting pollution resistance, good non-stick property and wide application prospect, and can be applied to non-stick cookware paint.

The technical scheme of the invention is realized as follows:

the invention provides a preparation method of high Wen Chuiju resistant pigment, which comprises the steps of dissolving tetrabutyl titanate in an organic solvent, and adding water containing a pore-forming agent and an emulsifying agentThe solution is subjected to emulsion reaction to obtain TiO ₂ Adding porous hollow nano-microsphere into water solution containing soluble aluminium salt and soluble ferric salt, adding complexing agent, heating to form xerogel, igniting, ball-milling to obtain aluminium-titanium-iron oxide composite nano-microsphere, adding ethoxysilane ethanol solution to obtain coated nano-microsphere, dispersing in water, adding composite silane coupling agent, heating to react to obtain modified coated nano-microsphere, adding water phase obtained by adding water into emulsifier and oil phase containing aminosilane and fluorine-containing silane, emulsifying, stirring to react to obtain high Wen Chuiju-resistant pigment.

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

S1.TiO ₂ preparing porous hollow nano microspheres: tetrabutyl titanate is dissolved in an organic solvent to obtain an oil phase; dissolving a pore-forming agent and an emulsifying agent 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 nano-microspheres;

s2, preparing aluminum-titanium-iron oxide composite nano microspheres: dissolving soluble aluminum salt and soluble ferric salt in water to obtain aqueous solution, and adding TiO prepared in the step S1 ₂ Porous hollow nano-microspheres are uniformly dispersed, complexing agent is added, and solvent is heated and evaporated to obtain sol; then the temperature is increased, the vacuum degree is reduced, xerogel is obtained, the xerogel is taken out, the xerogel is ignited, and the aluminum-titanium-iron oxide composite nano microsphere is obtained by ball milling;

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

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 a 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 uniformly stirring, and regulating the pH value of the solution to be alkaline to obtain a water phase; adding the water phase into the oil phase, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain the high Wen Chuiju resistant pigment.

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

As a further improvement of the present invention, the soluble aluminum salt in step S2 is selected from at least one of aluminum nitrate, aluminum chloride, aluminum sulfate; the soluble ferric salt is selected from at least one of ferric sulfate, ferric chloride and ferric nitrate; the complexing agent is at least one of EDTA disodium, EDTA, ethylenediamine, citric acid and sodium citrate; the soluble aluminum salt, soluble ferric salt and TiO ₂ The mass ratio of the porous hollow nano microsphere to the complexing agent is 5-7:2-4:4-6:12-17; the heating temperature is 60-80 ℃, the temperature in the heater is 140-170 ℃, 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 nano microsphere in the step S3 is 5-7:3-5; 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-microsphere to the composite silane coupling agent in the step S4 is 10:2-3; the compound silane coupling agent is at least two selected from KH550, KH560, KH570, KH580, KH590, KH602 and KH792, preferably, the compound of KH550 and KH602 with the mass ratio of 3-5:1, a step of; the temperature is heated to 50-70 ℃ and the reaction is carried out for 1-2h.

As a further improvement of the present invention, the aminosilane in step S5 is selected from at least one of γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, N- β (aminoethyl) - γ -aminopropyl trimethoxysilane, N- β (aminoethyl) - γ -aminopropyl triethoxysilane, N- β (aminoethyl) - γ -aminopropyl methyldimethoxysilane, N- β (aminoethyl) - γ -aminopropyl methyldiethoxysilane, diethylenetriaminopropyl trimethoxysilane; the fluorine-containing silane is selected from 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro decyl trimethoxysilane, dodecafluoro heptyl propyl methyl dimethoxy silane 3, 3-trifluoropropyl methyl dimethoxy silane, 3-trifluoropropyl trimethoxy silane at least one of 1h,2 h-perfluorooctyltriethoxysilane or 1h,2 h-perfluorooctyltrimethoxysilane; the ratio of the amounts of the aminosilane and the fluorosilane-containing material is 1-3:1; the pH value of the solution is adjusted to 9-10; the emulsifying condition is 12000-15000r/min for 3-5min; the mass ratio of the modified coated nano microsphere to the emulsifier is 10:1-2; the mass ratio of the water phase to the oil phase is 3-5:5-7.

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-forming agent and an emulsifying agent in water to obtain a water phase containing 1-3wt% of the pore-forming agent and 1-2wt% of the emulsifying agent; adding 3-5 weight parts of water phase into 5-7 weight parts of oil phase, emulsifying for 3-5min at 12000-15000r/min, centrifuging, washing, and drying to obtain TiO ₂ Porous hollow nano-microspheres;

the pore-forming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 3-5:2;

s2, preparing 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, and adding 4-6 parts by weight of TiO prepared in the step S1 ₂ Uniformly dispersing porous hollow nano microspheres by ultrasonic, adding 12-17 parts by weight of complexing agent, heating to 60-80 ℃ and evaporating solvent to obtain sol; then the temperature is increased to 140-170 ℃ in the heater, the vacuum degree is reduced to 0.01-0.1MPa, xerogel is obtained, the xerogel is taken out and ignited, and the ball milling is carried out for 7-10 hours, thus obtaining the aluminum-titanium-iron oxide composite nano microsphere;

s3, preparing 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 microsphere prepared in the step S2, stirring at a constant speed of 500-700r/min for 1-2h, and drying to obtain a coated nano microsphere;

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

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

s5, preparing a 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 emulsifying agent, dissolving and uniformly stirring, and regulating 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 for 3-5min at 12000-15000r/min, stirring for 3-5h, centrifuging, washing, and drying to obtain the high-resistance Wen Chuiju pigment.

Preferably, the emulsifier is at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, 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 the group consisting of 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 the TiO by sol-gel reaction ₂ Mixing and emulsifying the oil phase containing tetrabutyl titanate and the water phase containing pore-forming agent and emulsifying agent to obtain porous hollow oxide nanometer microsphere, centrifuging to remove water and oil in the microsphere, thereby obtaining TiO ₂ Porous hollow nano-microspheres;

further, the obtained TiO ₂ Adding the porous hollow nano microsphere into water containing soluble aluminum salt and soluble ferric salt, and adding complexing agent, thereby obtaining TiO (titanium dioxide) ₂ Forming complexing agent-aluminum complex, complexing agent-iron complex and complexing agent-aluminum-iron complex inside and outside the surface of the porous hollow nano microsphere, heating to obtain xerogel, igniting the xerogel, and performing long-time ball milling to obtain the aluminum-titanium-iron oxide composite nano microsphere;

the aluminum-titanium-iron oxide composite nano microsphere is a better high-temperature resistant pigment, and the composite of aluminum oxide, iron oxide and titanium oxide not only has beautiful color, but also can adjust different colors of the pigment by adjusting the contents of the aluminum oxide, the iron oxide and the titanium oxide, and simultaneously greatly improves the high-temperature resistant performance of the pigment;

further, 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 can be prolonged, and the compactness and the anti-corrosion effect can be obviously improved.

Then, 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, and the amino groups can stably exist in alkaline solution in subsequent reactions. Simultaneously, amino protonation and alkaline water phase can catalyze silane to generate sol-gel reaction, so that a silicon oxide shell layer is formed at the interface. The fluorine-containing group spontaneously faces the outer part of the shell layer due to the hydrophobicity, so that the high-temperature resistant cooker pigment with rich fluorine-containing groups is obtained, the fluorine-containing group has extremely low surface energy and good hydrophobic and oleophobic performance, and can be applied to the coating of the non-stick cooker, so that the self-cleaning type high-temperature resistant cooker pigment has good corrosion resistance and high-temperature resistance, has good mechanical property, has self-cleaning effect, can resist pollution for a long time, has good non-stick performance, and has wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.

FIG. 1 is a diagram of TiO as prepared in example 1 ₂ TEM image of porous hollow nanospheres.

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

Detailed Description

The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

The embodiment provides a preparation method of a high Wen Chuiju resistant pigment, which specifically comprises the following steps:

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

The pore-forming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 3:2;

s2, preparing 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 The porous hollow nano microsphere is subjected to 1000W ultrasonic dispersion for 30min, 12 parts by weight of EDTA disodium is added, and the mixture is heated to 60 ℃ to evaporate the solvent to obtain sol; then the temperature is increased to 140 ℃ in the heater, the vacuum degree is reduced to 0.01MPa, xerogel is obtained, the xerogel is taken out, ignited, ball-milled for 7 hours, and the aluminum-titanium-iron oxide composite nano microsphere is obtained;

s3, preparing 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-microsphere prepared in the step S2, uniformly stirring for 1h at 500r/min, and drying at 70 ℃ for 2h to obtain a coated nano-microsphere;

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

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

s5, preparing a high-temperature resistant cooker pigment: 10 parts by weight of N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and 10 parts by weight of 1H, 2H-perfluoro decyl triethoxy silane are dissolved in 100 parts by weight of methylene dichloride to obtain an oil phase; adding 10 parts by weight of the modified coated nano-microsphere prepared in the step S4 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 15min, adding 1 tetradecyl sodium benzenesulfonate, dissolving and stirring uniformly, and regulating 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 at 70 ℃ for 2h to obtain the high-resistance Wen Chuiju pigment. Fig. 2 is a TEM image of the resulting high temperature resistant cookware pigment, which is seen to have a silica shell layer assembled on the surface layer.

Example 2

The embodiment provides a preparation method of a high Wen Chuiju resistant pigment, which specifically comprises the following steps:

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

the pore-forming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 5:2;

s2, preparing 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 TiO prepared in the step S1 ₂ Porous hollow nanometer microsphere, 1000W ultrasonic dispersing for 30min, adding 17 weight parts of citric acid, and heating toEvaporating the solvent at 80 ℃ to obtain sol; then the temperature is increased to 170 ℃ in the heater, the vacuum degree is reduced to 0.1MPa, xerogel is obtained, the xerogel is taken out, ignited, ball-milled for 10 hours, and the aluminum-titanium-iron oxide composite nano microsphere is obtained;

s3, preparing 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-microsphere prepared in the step S2, uniformly stirring at 700r/min for 2h, and drying at 70 ℃ for 2h to obtain a coated nano-microsphere;

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

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

s5, preparing a high-temperature resistant cooker pigment: 30 parts by weight of gamma-aminopropyl trimethoxysilane and 10 parts by weight of dodecafluoro heptyl propyl trimethoxysilane are dissolved in 100 parts by weight of butyl acetate to obtain an oil phase; adding 10 parts by weight of the modified coated nano-microsphere prepared in the step S4 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 15min, adding 1 octadecyl sodium sulfate, dissolving and stirring uniformly, and regulating the pH value of the solution to 10 to obtain a water phase; 50 parts by weight of the water phase is added into 70 parts by weight of the oil phase, 15000r/min is emulsified for 5min, stirring reaction is carried out for 5h,3000r/min is centrifuged for 15min, clear water washing is carried out, and drying is carried out at 70 ℃ for 2h, thus obtaining the high-resistant Wen Chuiju pigment.

Example 3

The embodiment provides a preparation method of a high Wen Chuiju resistant pigment, which specifically comprises the following steps:

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

the pore-forming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 4:2;

s2, preparing aluminum-titanium-iron oxide composite nano microspheres: 6 parts by weight of aluminum chloride and 3 parts by weight of ferric chloride are dissolved in 100 parts by weight of water to obtain an aqueous solution, and 5 parts by weight of TiO prepared in the step S1 is added ₂ The porous hollow nano microsphere is subjected to 1000W ultrasonic dispersion for 30min, 15 parts by weight of sodium citrate is added, and the mixture is heated to 70 ℃ to evaporate the solvent to obtain sol; then the temperature is increased to 155 ℃ in the heater, the vacuum degree is reduced to 0.05MPa, xerogel is obtained, the xerogel is taken out, ignited, ball-milled for 8 hours, and the aluminum-titanium-iron oxide composite nano microsphere is obtained;

s3, preparing 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-microsphere prepared in the step S2, stirring at a constant speed of 600r/min for 1.5h, and drying at 70 ℃ for 2h to obtain a coated nano-microsphere;

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

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

s5, preparing a high-temperature resistant cooker pigment: dissolving 20 parts by weight of N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane and 10 parts by weight of 3, 3-trifluoropropyl methyl dimethoxysilane in 100 parts by weight of ethyl acetate to obtain an oil phase; adding 10 parts by weight of the modified coated nano-microsphere prepared in the step S4 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 15min, adding 1 octadecyl sodium sulfate, dissolving and stirring uniformly, and regulating 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 for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70deg.C for 2h to obtain high-resistance Wen Chuiju pigment.

Example 4

The difference compared to example 3 is that the porogen is a single polyoxyethylene sorbitan fatty acid ester.

Example 5

The difference compared to example 3 is that the porogen is a single cetyltrimethylammonium bromide.

Example 6

The difference compared to example 3 is that the complex silane coupling agent is a single KH550.

Example 7

The difference compared to example 3 is that the complex silane coupling agent is a single KH602.

Comparative example 1

The difference compared to example 3 is that no porogen is added in step S1.

Comparative example 2

In comparison with example 3, the difference 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 compared to example 3 is that no ferric chloride is added in step S2.

Comparative example 5

In comparison with example 3, the difference is that step S3 is not performed.

Comparative example 6

In comparison with example 3, the difference is that step S4 is not performed.

Comparative example 7

In comparison with example 3, the difference is that N- β (aminoethyl) - γ -aminopropyl triethoxysilane is not added in step S5.

Comparative example 8

The difference compared with example 3 is that 3, 3-trifluoropropylmethyldimethoxysilane was not added in step S5.

Comparative example 9

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

Comparative example 10

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

Test example 1 high temperature resistance

The high temperature resistant cooker pigment prepared in examples 1 to 7 and comparative examples 1 to 10 was added to a silicone resin (trade name: W30-1) at a content of 30wt%, the base resin was a resin to which no high temperature resistant cooker pigment was added, uniformly coated on the cooker surface, kept at a temperature of 220 ℃, 240 ℃, 260 ℃, 280 ℃,300 ℃, 320 ℃ for 10 minutes, and the color at normal temperature was selected as a reference, the color was tested at each temperature, and an average value of the color at 5 points was taken as a color test result at that temperature. The color measurement system adopts a Lab color system, and takes a 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 cooker pigment prepared in the embodiments 1-3 of the invention can obviously improve the high temperature resistance of the resin after being added into 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 (trade name: W30-1) at a content of 30wt%, and the raw resin was a resin to which no high temperature resistant cooker pigment was added, and was uniformly coated on the cooker surface, to perform a performance test.

Heat resistance: the cooker with the coating film is baked for 2 hours at 180 ℃, then is put into a constant temperature box type electric furnace checked by a potentiometer, the temperature is increased according to 10 ℃/min, the time is counted along with the temperature of the furnace to 280 ℃, the sample is taken out after the sample is subjected to the high temperature for 10min, and is cooled to room temperature, and the surface condition of the coating is observed, if no cracking and falling phenomenon exists, the good heat resistance of the coating is demonstrated, and if no cracking and falling phenomenon exists, the poor heat resistance of the coating is demonstrated.

Non-stick properties: heating the coated cooker to 90 ℃, placing a shelled raw egg on the surface of the cooker, keeping the temperature until the egg is completely fried, slightly pushing the egg by a shovel, and naturally peeling off the egg, wherein the non-tackiness is good; slightly adhered (adhesion area is less than 30%), and the non-tackiness is general; the adhesion was severe (adhesion area greater than 60%), even did not peel, and the tack was poor.

Boiling resistance: the cooker with the coating film is baked at 180 ℃ for 2 hours, cooled to room temperature, then placed in boiling water at 100 ℃ and heated until the coating film is destroyed, and phenomena such as bubbles, light loss, color change, cracking and the like appear, the longer the time is, the better the boiling resistance is seen.

Wear resistance: detection is 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 cooker pigment prepared in examples 1 to 3 of the invention can obviously improve the heat resistance, non-tackiness, boiling resistance and wear resistance of the resin after being 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 (trade name: W30-1) at a content of 30wt%, the base resin was a resin to which no high temperature resistant cooker pigment was added, uniformly coated on a glass slide, and after heat curing treatment, water and hexadecane were dropped on the surface of the glass slide, and the measurement was carried out using a contact angle meter, and the results are shown in Table 3.

TABLE 3 Table 3

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As can be seen from the above table, the high temperature resistant cooker pigment prepared in the examples 1-3 of the invention can obviously improve the water and oil repellency of the resin and the self-cleaning capability 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 cetyl trimethylammonium bromide, and the high temperature resistance and heat resistance are reduced. The comparative example 1 is different from example 3 in that no porogen is added in the step S1, and the high temperature resistance and the heat resistance are remarkably reduced. The invention prepares the TiO by sol-gel reaction ₂ Mixing and emulsifying the oil phase containing tetrabutyl titanate and the water phase containing pore-forming agent and emulsifying agent to obtain porous hollow oxide nanometer microsphere, centrifuging to remove water and oil in the microsphere, thereby obtaining TiO ₂ Porous hollow nano-microspheres. Under the synergistic effect of macroporous pore-forming agent polyoxyethylene sorbitan fatty acid ester and mesoporous pore-forming agent cetyl trimethyl ammonium bromide, porous TiO can be ensured to be formed ₂ The hollow nano microsphere provides sufficient space for attaching aluminum and iron-complex on the surface and inside of the nano microsphere, thereby ensuring the formation of 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 KH550 or KH602 alone, and the abrasion resistance, non-tackiness and water/oil repellency are reduced. Comparative example 6 is different from example 3 in that step S4 is not performed, and abrasion resistance, non-tackiness property, water-repellent and oleophobic property are 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, and can stably exist in alkaline solution in subsequent reaction, 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 tiny water-in-oil liquid drops, the abundant aminosilane and fluorine-containing silane are aggregated at an interface, the amino groups of the aminosilane face to an inner water phase, and are protonated along with the reaction, become amphiphilic molecules and stabilize the silane liquid drops. Simultaneously, amino protonation and alkaline aqueous phase can catalyze silane to generate sol-gel reaction, and then a silicon oxide shell layer is formed at the 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 heat resistance and high temperature resistance are lowered. 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 no ferric chloride was added in step S2, and the wear resistance and the high temperature resistance were lowered. The aluminum-titanium-iron oxide composite nano microsphere is a better high-temperature resistant pigment, and the composite of aluminum oxide, iron oxide and titanium oxide not only has beautiful color, but also can adjust different colors of the pigment by adjusting the contents of the aluminum oxide, the iron oxide and the titanium oxide, and simultaneously greatly improves the high-temperature resistant performance of the pigment;

comparative example 5 is different from example 3 in that step S3 is not performed and the boiling resistance is lowered. 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 can be prolonged, and the compactness and the anti-corrosion effect can be obviously improved.

Comparative example 7 is different from example 3 in that N- β (aminoethyl) - γ -aminopropyl triethoxysilane is not added in step S5, and heat resistance, boiling resistance, abrasion resistance, water repellency and oleophobicity are lowered. Comparative example 8 is different from example 3 in that 3, 3-trifluoropropyl methyl dimethoxy silane is not added in step S5, and the non-tackiness and the water-oleophobic performance are 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, and can stably exist in alkaline solution in subsequent reaction, 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 tiny water-in-oil liquid drops, the abundant aminosilane and fluorine-containing silane are aggregated at an interface, the amino groups of the aminosilane face to an inner water phase, and are protonated along with the reaction, become amphiphilic molecules and stabilize the silane liquid drops. Simultaneously, amino protonation and alkaline water phase can catalyze silane to generate sol-gel reaction, so that a silicon oxide shell layer is formed at the interface. The fluorine-containing group spontaneously faces the outer part of the shell layer due to the hydrophobicity, so that the high-temperature resistant cooker pigment with rich fluorine-containing groups is obtained, the fluorine-containing group has extremely low surface energy and good hydrophobic and oleophobic performance, and can be applied to the coating of the non-stick cooker, so that the self-cleaning type high-temperature resistant cooker pigment has good corrosion resistance and high-temperature resistance, has good mechanical property, has self-cleaning effect, can resist pollution for a long time, has good non-stick performance, and has wide application prospect.

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

Comparative example 10 is different from example 3 in that steps S3, S4, S5 are not performed, and heat resistance, non-sticking property, abrasion resistance, water repellency and oil repellency are remarkably reduced.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (8)

1. A method for preparing a high Wen Chuiju-resistant pigment, which is characterized by comprising the following steps:

S1.TiO ₂ preparation of porous hollow nano microsphere: tetrabutyl titanate is dissolved in an organic solvent to obtain an oil phase; dissolving a pore-forming agent and an emulsifying agent 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 nano-microspheres; the mass ratio of the water phase to the oil phase is 3-5:5-7; the pore-forming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 3-5:2;

s2, preparing aluminum-titanium-iron oxide composite nano microspheres: dissolving soluble aluminum salt and soluble ferric salt in water to obtain aqueous solution, and adding TiO prepared in the step S1 ₂ Porous hollow nano-microspheres are uniformly dispersed, complexing agent is added, and solvent is heated and evaporated to obtain sol; then the temperature is increased, the vacuum degree is reduced, xerogel is obtained, the xerogel is taken out, the xerogel is ignited, and the aluminum-titanium-iron oxide composite nano microsphere is obtained by ball milling; the soluble aluminum salt, soluble ferric salt and TiO ₂ The mass ratio of the porous hollow nano microsphere to the complexing agent is 5-7:2-4:4-6:12-17;

s3, preparing coated nano microspheres: dissolving ethoxysilane in ethanol, adding the aluminum-titanium-iron oxide composite nano-microsphere prepared in the step S2, stirring at a constant speed, and drying to obtain a coated nano-microsphere; the mass ratio of the ethoxysilane to the aluminum-titanium-iron oxide composite nano microsphere is 5-7:3-5;

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; the mass ratio of the coated nano microsphere to the composite silane coupling agent is 10:2-3; the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 3-5:1, a step of;

s5, preparing a 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 uniformly stirring, and regulating the pH value of the solution to be alkaline to obtain a water phase; adding the water phase into the oil phase, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain the high-resistance Wen Chuiju pigment; the mass ratio of the modified coated nano microsphere to the emulsifier is 10:1-2; the mass ratio of the water phase to the oil phase is 3-5:5-7.

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

3. The method according to claim 1, 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 at least one of EDTA disodium, EDTA, ethylenediamine, citric acid and sodium citrate; the heating temperature is 60-80 ℃, the temperature in the heater is 140-170 ℃, and the vacuum degree is reduced to 0.01-0.1MPa; the ball milling time is 7-10h.

4. The method according to claim 1, wherein the uniform stirring in step S3 is performed at a rotation speed of 500-700r/min for 1-2h.

5. The method according to claim 1, wherein the heating is performed at a temperature of 50 to 70 ℃ for 1 to 2 hours in step S4.

6. The preparation method according to claim 1, wherein the aminosilane in step S5 is at least one selected from the group consisting of γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, N- β (aminoethyl) - γ -aminopropyl trimethoxysilane, N- β (aminoethyl) - γ -aminopropyl triethoxysilane, N- β (aminoethyl) - γ -aminopropyl methyldimethoxysilane, N- β (aminoethyl) - γ -aminopropyl methyldiethoxysilane, and diethylenetriaminopropyl trimethoxysilane; the fluorine-containing silane is selected from 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro decyl trimethoxysilane, dodecafluoro heptyl propyl methyl dimethoxy silane 3, 3-trifluoropropyl methyl dimethoxy silane, 3-trifluoropropyl trimethoxy silane at least one of 1h,2 h-perfluorooctyltriethoxysilane or 1h,2 h-perfluorooctyltrimethoxysilane; the ratio of the amounts of the aminosilane and the fluorosilane-containing material is 1-3:1; the pH value of the solution is adjusted to 9-10; the emulsifying condition is 12000-15000r/min for 3-5min.

7. The preparation method according to claim 1, characterized by comprising 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-forming agent and an emulsifying agent in water to obtain a water phase containing 1-3wt% of the pore-forming agent and 1-2wt% of the emulsifying agent; adding 3-5 weight parts of water phase into 5-7 weight parts of oil phase, emulsifying for 3-5min at 12000-15000r/min, centrifuging, washing, and drying to obtain TiO ₂ Porous hollow nano-microspheres;

the pore-forming agent is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyl trimethyl ammonium bromide, and the mass ratio is 3-5:2;

s2, preparing 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, and adding 4-6 parts by weight of TiO prepared in the step S1 ₂ Uniformly dispersing porous hollow nano microspheres by ultrasonic, adding 12-17 parts by weight of complexing agent, heating to 60-80 ℃ and evaporating solvent to obtain sol; then heating to 140-170deg.C, reducing vacuum degree to 0.01-0.1MPa to obtain xerogel, and taking outIgniting the xerogel, and ball milling for 7-10 hours to obtain the aluminum-titanium-iron oxide composite nano microsphere;

s3, preparing 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 microsphere prepared in the step S2, stirring at a constant speed of 500-700r/min for 1-2h, and drying to obtain a coated nano microsphere;

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

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

s5, preparing a 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 emulsifying agent, dissolving and uniformly stirring, and regulating 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 for 3-5min at 12000-15000r/min, stirring for 3-5h, centrifuging, washing, and drying to obtain the high-resistance Wen Chuiju pigment.

8. A high temperature resistant cookware pigment made by the method of any of claims 1-7.

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