阅读说明：本技术 一种形貌可控的透明单分散纳米氧化锆液相分散体的制备方法 (Preparation method of transparent monodisperse nano-zirconia liquid-phase dispersion with controllable morphology ) 是由 王洁欣 夏怡 王丹 曾晓飞 蒲源 陈建峰 于 2018-06-07 设计创作，主要内容包括：本发明公开了一种形貌可控的透明单分散纳米氧化锆液相分散体的制备方法,包括如下步骤：以水作为溶剂,向其中加入锆盐,配制锆盐溶液；以水作为溶剂,向其中加入水解促进剂,配制水解促进剂溶液；将锆盐溶液和水解促进剂溶液混合,得到反应液；将反应液进行洗涤,洗涤后前驱体分散到水中,得到前驱体分散体；取有机溶剂作为溶剂,向其中加入表面活性剂,配制表面活性剂溶液；将前驱体分散体及表面活性剂溶液进行混合,并对其水热处理；得到纳米氧化锆颗粒；水热处理后,将纳米氧化锆颗粒进行洗涤,再分散到液相介质中,即得产物。该分散体中纳米氧化锆颗粒为亲油性纳米颗粒,一维尺寸为1～30nm；具有单分散性；静置≥6个月仍无沉降。(the invention discloses a preparation method of a transparent monodisperse nano zirconia liquid phase dispersion with controllable appearance, which comprises the following steps: adding zirconium salt into water as a solvent to prepare a zirconium salt solution; adding a hydrolysis promoter into water serving as a solvent to prepare a hydrolysis promoter solution; mixing a zirconium salt solution and a hydrolysis promoter solution to obtain a reaction solution; washing the reaction solution, and dispersing the washed precursor into water to obtain a precursor dispersion; taking an organic solvent as a solvent, adding a surfactant into the solvent, and preparing a surfactant solution; mixing the precursor dispersion and a surfactant solution, and carrying out hydrothermal treatment on the mixture; obtaining nano zirconium oxide particles; after hydrothermal treatment, washing the nano zirconia particles, and dispersing the nano zirconia particles into a liquid phase medium to obtain a product. The nano zirconium oxide particles in the dispersion are lipophilic nano particles, and the one-dimensional size is 1-30 nm; has monodispersity; still standing for more than or equal to 6 months without sedimentation.)

1. A preparation method of a transparent monodisperse nano zirconia liquid phase dispersion body with controllable appearance is characterized by comprising the following steps:

1) Adding zirconium salt into water as a solvent to prepare a zirconium salt solution;

2) adding a hydrolysis promoter into water serving as a solvent to prepare a hydrolysis promoter solution;

3) mixing a zirconium salt solution and a hydrolysis promoter solution for reaction to obtain a reaction solution;

4) washing the reaction solution, and dispersing the washed precursor into water to obtain a water-phase precursor dispersion;

5) taking an organic solvent as a solvent, adding a surfactant into the solvent, and preparing a surfactant solution;

6) mixing the precursor dispersion and a surfactant solution, and carrying out hydrothermal treatment on the mixture; obtaining nano zirconium oxide particles;

7) After hydrothermal treatment, washing the obtained nano zirconia particles, and dispersing the nano zirconia particles into a liquid-phase medium to obtain the transparent nano zirconia liquid-phase dispersion.

2. The preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in step 1), the zirconium salt is selected from one or more of the following substances: zirconium nitrate, zirconyl nitrate, zirconium oxychloride, zirconium acetylacetonate, zirconium basic carbonate, zirconium chloride;

preferably, in step 1), the concentration of the zirconium salt solution is 1 wt.% to 30 wt.%; more preferably, in step 1), the concentration of the zirconium salt solution is 1 wt.% to 15 wt.%; most preferably, in step 1), the concentration of the zirconium salt solution is between 1 wt.% and 5 wt.%.

3. The preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in step 2), the hydrolysis promoter is selected from one or more of the following substances: potassium hydroxide, sodium hydroxide, ammonia water, triethanolamine and ethylenediamine;

preferably, in step 2), the concentration of the hydrolysis promoter is 0.1 wt.% to 20 wt.%; more preferably, in step 2), the concentration of the hydrolysis promoter is 0.1 wt.% to 10 wt.%; most preferably, in step 2), the concentration of the hydrolysis enhancer is between 0.1 wt.% and 5 wt.%.

4. the preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in the step 3), before mixing the hydrolysis promoter and the zirconium salt solution, fully and uniformly stirring the zirconium salt solution and the hydrolysis promoter solution respectively, dropwise adding the hydrolysis promoter solution into the zirconium salt solution at a constant speed in a stirring state, controlling the final pH of the reaction solution to be 0-7, controlling the stirring speed to be more than or equal to 300r/min, and controlling the adding process temperature to be 0-65 ℃;

preferably, in the step 3), the final pH of the reaction solution is controlled to be 0.5-6, the stirring speed is more than or equal to 500r/min, and the adding process temperature is 10-50 ℃; more preferably, in the step 3), the final pH of the reaction solution is controlled to be 1-5, and the adding temperature is 20-35 ℃;

5. The preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in the step 3), the mixing mode of the zirconium salt solution and the hydrolysis promoter solution can also be as follows: and respectively placing the zirconium salt solution and the hydrolysis promoter solution in a storage tank, preheating to a reaction temperature, and adding the preheated zirconium salt solution and the hydrolysis promoter solution into a molecular mixing and strengthening reactor in proportion for reaction to obtain a reaction solution with the final pH of 0-7.

6. The preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in the step 3), the reaction temperature is 0-65 ℃, and the reaction is carried out in a molecular mixing and strengthening reactor; the molecular mixing strengthening reactor is a supergravity rotating packed bed reactor, a stator-rotor reactor, a micro-channel reactor or a static mixing reactor; more preferably, the reaction temperature is 10-50 ℃; most preferably, the reaction temperature is 20-35 ℃.

7. The preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in the step 4), the washing mode is one or more of filtration (suction filtration or filter pressing), dialysis, ultrafiltration, nanofiltration and centrifugation; more preferably, in the step 4), the washing mode is one or more of suction filtration, dialysis and ultrafiltration;

preferably, in the step 4), the solid content of the precursor in the precursor dispersion is 0.1 wt.% to 50 wt.%; more preferably, in the step 4), the solid content of the precursor in the precursor dispersion is 0.2 wt.% to 20 wt.%; most preferably, in step 4), the precursor has a solid content of 0.5 wt.% to 15 wt.% in the precursor dispersion.

8. the preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in step 5), the surfactant is selected from one or more of the following substances: polyethylene glycol 4000, polyethylene glycol 8000, polyethylene glycol 20000, polyvinylpyrrolidone, sodium lauryl sulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, ethyl 3, 4-dihydroxycinnamate, phenethyl caffeate, allylmalonic acid, trimethylpropane monoallyl ester, octadecene, dopamine, n-butyric acid, valeric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, linoleic acid, oleylamine, oleic acid, oleyl amine, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, oleyl amine, stearic acid, and mixtures thereof, Sodium oleate;

more preferably, in step 5), the surfactant is selected from one or more of the following: polyethylene glycol 8000, sodium dodecyl sulfate, dodecylbenzene sulfonic acid, gamma-methacryloxypropyltrimethoxysilane, octadecene, dopamine, n-butyric acid, valeric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, linoleic acid, oleylamine, sodium oleate;

preferably, in the step 5), the solvent in the surfactant solution is one or more of methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, N-propanol, isopropanol, N-butanol, isobutanol, acetonitrile, N-dimethylformamide, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, benzyl alcohol, xylene, cyclohexane, N-hexane, pyridine, ethyl acetate, methyl acetate and butyl acetate;

preferably, in step 5), the concentration of the surfactant is 0.1 wt.% to 50 wt.%; more preferably, in step 5), the concentration of the surfactant is 0.1 wt.% to 20 wt.%.

9. the preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in the step 6), the hydrothermal reaction temperature is 130-250 ℃, and the hydrothermal reaction time is 1-96 h; more preferably, in the step 6), the hydrothermal reaction temperature is 150-240 ℃, and the hydrothermal reaction time is 2-96 hours; most preferably, in the step 6), the hydrothermal reaction temperature is 160-240 ℃, and the hydrothermal reaction time is 10-72 hours.

10. The preparation method of the transparent monodisperse nano-zirconia liquid phase dispersion with controllable morphology according to claim 1, characterized in that: in the step 7), the liquid-phase medium is an organic solvent; the organic solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, triethylene glycol, propylene glycol, glycerol, N-propanol, isopropanol, N-butanol, isobutanol, acetic acid, acetonitrile, N-dimethylformamide, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, chloroform, benzene, toluene, xylene, petroleum ether at 30-60 ℃ and 60-90 ℃ respectively, naphtha, white oil, fish oil, castor oil, peanut oil, N-hexane, cyclohexane, N-heptane, N-decane, methyl isobutyl ketone, propylene glycol methyl ether acetate, pyridine, ethyl acetate, methyl acetate and butyl acetate;

More preferably, in step 7), the organic solvent is selected from one or more of the following: ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, isobutanol, acetic acid, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, chloroform, benzene, xylene, petroleum ether at 30-60 ℃, petroleum ether at 60-90 ℃, naphtha, white oil, fish oil, castor oil, peanut oil, cyclohexane, n-heptane, n-decane, methyl isobutyl ketone, propylene glycol methyl ether, pyridine, ethyl acetate, methyl acetate and butyl acetate.

Technical Field

the invention relates to the technical field of nano materials. More particularly, relates to a preparation method of a transparent monodisperse nano zirconia liquid phase dispersion, in particular to a preparation method of a morphology-controllable transparent monodisperse nano zirconia liquid phase dispersion.

background

the nano zirconia has the characteristics of high melting point (2700 ℃), high boiling point, low thermal conductivity, small thermal expansion coefficient, good wear resistance, high refractive index and excellent corrosion resistance, and can be widely applied to the fields of fuel cells, heat insulation, information, electronics, bionic materials, functional ceramics, precious stone industry, catalyst industry, solid electrolyte, environmental protection and the like. The refractive index of the material can be adjusted by using the nano zirconia, which is very valuable for optical lenses, solar cells, broadcasting materials, antireflection films of optical devices, LED packaging and the like.

The zirconia is used as the inorganic filler with high refractive index to be applied to optical materials, particularly in the field of optical coatings, the good crystallinity and dispersibility of the zirconia are important, and the small and uniform particle size distribution is important, particularly, the secondary particle size of the zirconia is less than one tenth of the wavelength (400-800nm), namely less than 40nm, so that the transparency and other optical properties of the zirconia and the composite material can be ensured not to be influenced.

At present, the technology for preparing monodisperse nano zirconia at home and abroad is relatively mature, and the common preparation method is to prepare a zirconium hydroxide precursor by hydrolyzing organic zirconium salt and form crystallized monodisperse zirconia by calcining or hydrothermal method. For example: the preparation method of the Chinese patent application No. 201810018467.7 is that organic zirconium salt reacts with electrolyte solution in inert gas environment, and the product is prepared through precipitation, washing, drying and calcination, wherein the zirconia nano-particles have regular shapes, but the particles have agglomeration phenomenon due to high-temperature calcination treatment, are large (about 120nm in particle size) and cannot be transparently dispersed. The preparation method of the traditional Chinese patent with the application number of 201310544689.X is that organic zirconium salt is hydrolyzed to prepare a zirconium hydroxide precursor, and the zirconium hydroxide precursor is subjected to solvothermal, washing and redispersion to prepare the product, wherein zirconium oxide nanoparticles have small particle size and uniform appearance, but the particles are slightly agglomerated. The common defect of the preparation method is that the raw material organic zirconium salt is high in price and is not easy to store. Therefore, it is very important to find a synthesis method which has cheap raw materials, does not need calcination and can obtain a product with uniform appearance, particle size less than 40nm, high crystallinity and no agglomeration.

Chinese patent 201510309304.0 discloses a transparent nano zirconia liquid phase dispersion and its preparation method; the preparation method of the nano zirconia liquid phase dispersion comprises the following steps: 1) taking a water, an organic solvent, a mixture of the organic solvent and the water which are mutually soluble with the water or a mixture of different organic solvents as a solvent, adding zirconium salt into the solvent to prepare a zirconium salt solution; 2) taking a water, an organic solvent, a mixture of the organic solvent and water which are mutually soluble with water or a mixture of different organic solvents as a solvent, adding a hydrolysis accelerator into the solvent, and preparing a hydrolysis accelerator solution; 3) mixing a zirconium salt solution and a hydrolysis promoter solution to obtain an acidic reaction solution; 4) aging the acidic reaction solution, and washing the aged acidic reaction solution to obtain a precursor dispersion; 5) and carrying out hydrothermal treatment on the precursor dispersion to obtain the product transparent nano zirconia liquid-phase dispersion. By the method, the nano zirconia liquid phase dispersion is prepared: the solid content is 1 wt% to 50 wt%, the zirconia crystal has small grain size and uniform distribution, the one-dimensional size is 1-12 nm, and the average grain size is only 6 nm; standing for more than or equal to 6 months without sedimentation. However, the zirconia particles in the nano zirconia liquid phase dispersion are not monodisperse, are hydrophilic particles and are not suitable for occasions needing lipophilic particles

Disclosure of Invention

the invention aims to provide a preparation method of a transparent monodisperse nano zirconia liquid phase dispersion with controllable appearance. The transparent monodisperse nano zirconia liquid phase dispersion prepared by the method has lipophilic nano-particles and solid content of 1-60 wt%; the zirconia crystal has small grain diameter, and the one-dimensional size is 1-30 nm; the product has monodispersity, uniform particle size distribution and good dispersibility; the nanometer zirconia particles are in spindle shape, square shape, rice particle shape, rod shape and leaf shape; in addition, the liquid phase dispersion product has high transmittance and high purity, and does not settle after standing for more than or equal to 6 months.

in order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a transparent monodisperse nano zirconia liquid phase dispersion with controllable morphology comprises the following steps:

1) Adding zirconium salt into water as a solvent to prepare a zirconium salt solution;

2) Adding a hydrolysis promoter into water serving as a solvent to prepare a hydrolysis promoter solution;

3) Mixing a zirconium salt solution and a hydrolysis promoter solution for reaction to obtain a reaction solution;

4) washing the reaction solution, and dispersing the washed precursor into water to obtain a water-phase precursor dispersion;

5) taking an organic solvent as a solvent, adding a surfactant into the solvent, and preparing a surfactant solution;

6) Mixing the precursor dispersion and a surfactant solution, and carrying out hydrothermal treatment on the mixture; obtaining nano zirconium oxide particles;

7) after hydrothermal treatment, washing the obtained nano zirconia particles, and dispersing the nano zirconia particles into a liquid-phase medium to obtain the transparent nano zirconia liquid-phase dispersion.

as a further improvement of the technical solution, in step 1), the zirconium salt is selected from one or more of the following substances: zirconium nitrate, zirconyl nitrate, zirconium oxychloride, zirconium acetylacetonate, zirconium basic carbonate, zirconium chloride.

preferably, in step 1), the concentration of the zirconium salt solution is 1 wt.% to 30 wt.%; more preferably, in step 1), the concentration of the zirconium salt solution is 1 wt.% to 15 wt.%; most preferably, in step 1), the concentration of the zirconium salt solution is between 1 wt.% and 5 wt.%.

as a further improvement of the technical solution, in the step 2), the hydrolysis promoter is selected from one or more of the following substances: potassium hydroxide, sodium hydroxide, ammonia water, triethanolamine and ethylenediamine.

Preferably, in step 2), the concentration of the hydrolysis promoter is 0.1 wt.% to 20 wt.%; more preferably, in step 2), the concentration of the hydrolysis promoter is 0.1 wt.% to 10 wt.%; most preferably, in step 2), the concentration of the hydrolysis enhancer is between 0.1 wt.% and 5 wt.%.

As a further improvement of the technical scheme, in the step 3), before mixing the hydrolysis promoter and the zirconium salt solution, the zirconium salt solution and the hydrolysis promoter solution need to be respectively and fully stirred uniformly, and the hydrolysis promoter solution is dropwise added into the zirconium salt solution at a constant speed in a stirring state, the final pH of the reaction solution is controlled to be 0-7, the stirring speed is more than or equal to 300r/min, and the adding process temperature is 0-65 ℃;

preferably, in the step 3), the final pH of the reaction solution is controlled to be 0.5-6, the stirring speed is more than or equal to 500r/min, and the adding process temperature is 10-50 ℃; more preferably, in the step 3), the final pH of the reaction solution is controlled to be 1-5, and the adding temperature is controlled to be 20-35 ℃.

Preferably, in step 3), the mixing manner of the zirconium salt solution and the hydrolysis promoter solution can also be: and respectively placing the zirconium salt solution and the hydrolysis promoter solution in a storage tank, preheating to a reaction temperature, and adding the preheated zirconium salt solution and the hydrolysis promoter solution into a molecular mixing and strengthening reactor in proportion for reaction to obtain a reaction solution with the final pH of 0-7.

Preferably, in the step 3), the reaction temperature is 0-65 ℃, and the reaction is carried out in a molecular mixing and strengthening reactor; the molecular mixing strengthening reactor is a supergravity rotating packed bed reactor, a stator-rotor reactor, a micro-channel reactor or a static mixing reactor; more preferably, the reaction temperature is 10-50 ℃; most preferably, the reaction temperature is 20-35 ℃.

As a further improvement of the technical scheme, in the step 4), the washing mode is one or more of filtration (suction filtration or pressure filtration), dialysis, ultrafiltration, nanofiltration and centrifugation; more preferably, in the step 4), the washing mode is one or more of suction filtration, dialysis and ultrafiltration.

Preferably, in the step 4), the solid content of the precursor in the precursor dispersion is 0.1 wt.% to 50 wt.%; more preferably, in the step 4), the solid content of the precursor in the precursor dispersion is 0.2 wt.% to 20 wt.%; most preferably, in step 4), the precursor has a solid content of 0.5 wt.% to 15 wt.% in the precursor dispersion.

Preferably, in step 5), the surfactant is selected from one or more of the following: polyethylene glycol 4000, polyethylene glycol 8000, polyethylene glycol 20000, polyvinylpyrrolidone, sodium lauryl sulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, ethyl 3, 4-dihydroxycinnamate, phenethyl caffeate, allylmalonic acid, trimethylpropane monoallyl ester, octadecene, dopamine, n-butyric acid, valeric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, linoleic acid, oleylamine, oleic acid, oleyl amine, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, oleyl amine, stearic acid, and mixtures thereof, Sodium oleate.

More preferably, in step 5), the surfactant is selected from one or more of the following: polyethylene glycol 8000, sodium dodecyl sulfate, dodecylbenzene sulfonic acid, gamma-methacryloxypropyltrimethoxysilane, octadecene, dopamine, n-butyric acid, valeric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, linoleic acid, oleylamine and sodium oleate.

Preferably, in the step 5), the solvent in the surfactant solution is one or more of methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, N-propanol, isopropanol, N-butanol, isobutanol, acetonitrile, N-dimethylformamide, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, benzyl alcohol, xylene, cyclohexane, N-hexane, pyridine, ethyl acetate, methyl acetate and butyl acetate;

Preferably, in step 5), the concentration of the surfactant is 0.1 wt.% to 50 wt.%; more preferably, in step 5), the concentration of the surfactant is 0.1 wt.% to 20 wt.%.

preferably, in the step 6), the hydrothermal reaction temperature is 130-250 ℃, and the hydrothermal reaction time is 1-96 hours; more preferably, in the step 6), the hydrothermal reaction temperature is 150-240 ℃, and the hydrothermal reaction time is 2-96 hours; most preferably, in the step 6), the hydrothermal reaction temperature is 160-240 ℃, and the hydrothermal reaction time is 10-72 hours.

As a further improvement of the technical scheme, in the step 7), the liquid-phase medium is an organic solvent; the organic solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, triethylene glycol, propylene glycol, glycerol, N-propanol, isopropanol, N-butanol, isobutanol, acetic acid, acetonitrile, N-dimethylformamide, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, chloroform, benzene, toluene, xylene, petroleum ether at 30-60 ℃ and petroleum ether at 60-90 ℃, naphtha, white oil, fish oil, castor oil, peanut oil, N-hexane, cyclohexane, N-heptane, N-decane, methyl isobutyl ketone, propylene glycol methyl ether acetate, pyridine, ethyl acetate, methyl acetate and butyl acetate.

More preferably, in step 7), the organic solvent is selected from one or more of the following: ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, isobutanol, acetic acid, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, chloroform, benzene, xylene, petroleum ether at 30-60 ℃, petroleum ether at 60-90 ℃, naphtha, white oil, fish oil, castor oil, peanut oil, cyclohexane, n-heptane, n-decane, methyl isobutyl ketone, propylene glycol methyl ether, pyridine, ethyl acetate, methyl acetate and butyl acetate.

It is further noted that any range recited herein includes the endpoints and any values therebetween and any subranges subsumed therein or any values therebetween unless otherwise specified.

the invention has the following beneficial effects:

1) The transparent monodisperse nano zirconia liquid phase dispersion prepared by the invention has the advantages that the nano zirconia particles are lipophilic nano particles, and the solid content is 1-60 wt%;

2) the nanometer zirconia crystal has small grain diameter, and the one-dimensional size is 1-30 nm; the product has monodispersity, uniform particle size distribution and good dispersibility; the nanometer zirconia particles are in spindle shape, square shape, rice particle shape, rod shape and leaf shape;

3) The prepared nano zirconium oxide liquid phase dispersion product has high transmittance and high purity, and has no sedimentation after standing for more than or equal to 6 months.

drawings

the following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 shows a transmission electron micrograph of a product obtained in example 1 of the present invention;

FIG. 2 shows a transmission electron micrograph of a product obtained in example 2 of the present invention;

FIG. 3 shows a transmission electron micrograph of a product obtained in example 3 of the present invention;

FIG. 4 shows a transmission electron micrograph of a product obtained in example 4 of the present invention;

FIG. 5 shows a transmission electron micrograph of a product obtained in example 5 of the present invention;

FIG. 6 shows a photograph of a transparent dispersion of the product obtained in example 6 of the present invention after it was left standing for 6 months;

FIG. 7 shows a photograph of a transparent dispersion of the product obtained in example 9 of the present invention after it has been left standing for 6 months;

FIG. 8 shows a photograph of a transparent dispersion of a product obtained in comparative example 5 of the present invention after it was left standing for 6 months;

Figure 9 shows the XRD pattern of the product obtained in example 6 of the present invention.

Detailed Description

in order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

the invention relates to a preparation method of a transparent monodisperse nano zirconia liquid phase dispersion with controllable appearance, which comprises the following steps:

1) adding zirconium salt into water as a solvent to prepare a zirconium salt solution;

2) adding a hydrolysis promoter into water serving as a solvent to prepare a hydrolysis promoter solution;

3) Mixing a zirconium salt solution and a hydrolysis promoter solution to obtain a reaction solution;

4) washing the reaction solution, and dispersing the washed precursor into water to obtain a water-phase precursor dispersion;

5) taking an organic solvent as a solvent, adding a surfactant into the solvent, and preparing a surfactant solution;

6) Mixing the precursor dispersion and a surfactant solution, and carrying out hydrothermal treatment on the mixture; obtaining nano zirconium oxide particles;

7) After hydrothermal treatment, washing the obtained nano zirconia particles, and dispersing the nano zirconia particles into a liquid-phase medium to obtain the transparent nano zirconia liquid-phase dispersion.

Compared with the prior art of Chinese patent 201510309304.0, the lipophilic monodisperse nano-zirconia particles prepared by the method are suitable for different requirements and can be expected to have better application performance; the key point of the technical improvement of the invention is that: 1) the choice of surfactant, the surfactant mentioned in prior art 201510309304.0, is not suitable for use in this application; 2) during hydrothermal treatment, the solvent comprises water and an organic solvent, and pure water serving as the solvent cannot enable the nano zirconia particles to be modified successfully to obtain the lipophilic nano zirconia particles. 3) The preparation process of the precursor is carried out in a water phase, and is economic and environment-friendly. 4) The step of aging treatment is omitted, the process is simplified, and the preparation period is shortened.

In certain embodiments of the invention, in step 1), the zirconium salt is selected from one or more of the following: zirconium nitrate, zirconyl nitrate, zirconium oxychloride, zirconium acetylacetonate, zirconium basic carbonate, zirconium chloride.

in certain embodiments of the invention, in step 1), the concentration of the zirconium salt solution is 1 wt.% to 30 wt.%; more preferably, in step 1), the concentration of the zirconium salt solution is 1 wt.% to 15 wt.%; most preferably, in step 1), the concentration of the zirconium salt solution is between 1 wt.% and 5 wt.%. The concentration is too high, the product can agglomerate, and the transparency is influenced; the concentration is too low, and the yield of the product prepared in one batch is too low.

in certain embodiments of the invention, in step 2), the hydrolysis enhancer is selected from one or more of the following: potassium hydroxide, sodium hydroxide, ammonia water, triethanolamine and ethylenediamine.

in certain embodiments of the invention, in step 2), the concentration of the hydrolysis enhancer is from 0.1 wt.% to 20 wt.%; more preferably, in step 2), the concentration of the hydrolysis promoter is 0.1 wt.% to 10 wt.%; most preferably, in step 2), the concentration of the hydrolysis enhancer is between 0.1 wt.% and 5 wt.%. The concentration is too high, the product can agglomerate, and the transparency is influenced; the concentration is too low to promote hydrolysis.

In some embodiments of the invention, in step 3), before mixing the hydrolysis promoter and the zirconium salt solution, the zirconium salt solution and the hydrolysis promoter solution are respectively and fully stirred uniformly, and the hydrolysis promoter solution is added dropwise into the zirconium salt solution at a constant speed under a stirring state, the final pH of the reaction solution is controlled to be 0-7, the stirring speed is not less than 300r/min, and the adding process temperature is 0-65 ℃; the pH value of the reaction solution is too large, the product can agglomerate, and the transparency is influenced.

In some preferred embodiments of the invention, in the step 3), the final pH of the reaction solution is controlled to be 0.5-6, the stirring speed is more than or equal to 500r/min, and the temperature of the adding process is 10-50 ℃; more preferably, in the step 3), the final pH of the reaction solution is controlled to be 1-5, and the adding temperature is controlled to be 20-35 ℃. If the temperature is too high or too low, the transparency of the dispersion may be affected.

in certain embodiments of the present invention, in step 3), the mixing of the zirconium salt solution and the hydrolysis promoter solution may also be performed in the following manner: and respectively placing the zirconium salt solution and the hydrolysis promoter solution in a storage tank, preheating to a reaction temperature, and adding the preheated zirconium salt solution and the hydrolysis promoter solution into a molecular mixing and strengthening reactor in proportion for reaction to obtain a reaction solution with the final pH of 0-7.

In some embodiments of the invention, in the step 3), the reaction temperature is 0-65 ℃, and the reaction is performed in a molecular mixing and strengthening reactor; the molecular mixing strengthening reactor is a supergravity rotating packed bed reactor, a stator-rotor reactor, a micro-channel reactor or a static mixing reactor; more preferably, the reaction temperature is 10-50 ℃; most preferably, the reaction temperature is 20-35 ℃.

in certain embodiments of the present invention, in step 4), the washing manner is one or more of filtration (suction filtration or pressure filtration), dialysis, ultrafiltration, nanofiltration, centrifugation; more preferably, in the step 4), the washing mode is one or more of suction filtration, dialysis and ultrafiltration.

In certain embodiments of the present invention, in step 4), the precursor has a solid content of 0.1 wt.% to 50 wt.% in the precursor dispersion; more preferably, in the step 4), the solid content of the precursor in the precursor dispersion is 0.2 wt.% to 20 wt.%; most preferably, in step 4), the precursor has a solid content of 0.5 wt.% to 15 wt.% in the precursor dispersion. Dispersions which are outside this range do not permit transparency.

in certain embodiments of the invention, in step 5), the surfactant is selected from one or more of the following: polyethylene glycol 4000, polyethylene glycol 8000, polyethylene glycol 20000, polyvinylpyrrolidone, sodium lauryl sulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, ethyl 3, 4-dihydroxycinnamate, phenethyl caffeate, allylmalonic acid, trimethylpropane monoallyl ester, octadecene, dopamine, n-butyric acid, valeric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, linoleic acid, oleylamine, oleic acid, oleyl amine, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, oleyl amine, stearic acid, and mixtures thereof, Sodium oleate.

in certain preferred embodiments of the present invention, in step 5), the surfactant is selected from one or more of the following: polyethylene glycol 8000, sodium dodecyl sulfate, dodecylbenzene sulfonic acid, gamma-methacryloxypropyltrimethoxysilane, octadecene, dopamine, n-butyric acid, valeric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, sodium stearate, arachidic acid, behenic acid, oleic acid, linoleic acid, oleylamine and sodium oleate.

in certain embodiments of the present invention, in step 5), the solvent in the surfactant solution is one or more of water, methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, N-propanol, isopropanol, N-butanol, isobutanol, acetonitrile, N-dimethylformamide, acetone, aniline, dimethylsulfoxide, tetrahydrofuran, benzene, toluene, benzyl alcohol, xylene, cyclohexane, N-hexane, pyridine, ethyl acetate, methyl acetate, butyl acetate;

In certain embodiments of the invention, in step 5), the concentration of the surfactant is from 0.1 wt.% to 50 wt.%; more preferably, in step 5), the concentration of the surfactant is 0.1 wt.% to 20 wt.%.

in some embodiments of the invention, in the step 6), the hydrothermal reaction temperature is 130 ℃ to 250 ℃ and the hydrothermal reaction time is 1 to 96 hours; more preferably, in the step 6), the hydrothermal reaction temperature is 150-240 ℃, and the hydrothermal reaction time is 2-96 hours; most preferably, in the step 6), the hydrothermal reaction temperature is 160-240 ℃, and the hydrothermal reaction time is 10-72 hours. Not in this range the crystallization is incomplete.

In certain embodiments of the invention, in step 7), the liquid-phase medium is selected from one or more of the following: water, organic solvents, mixtures of organic solvents and water; the organic solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, triethylene glycol, propylene glycol, glycerol, N-propanol, isopropanol, N-butanol, isobutanol, acetic acid, acetonitrile, N-dimethylformamide, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, chloroform, benzene, toluene, xylene, petroleum ether at 30-60 ℃ and petroleum ether at 60-90 ℃, naphtha, white oil, fish oil, castor oil, peanut oil, N-hexane, cyclohexane, N-heptane, N-decane, methyl isobutyl ketone, propylene glycol methyl ether acetate, pyridine, ethyl acetate, methyl acetate and butyl acetate.

In certain preferred embodiments of the present invention, in step 7), the organic solvent is selected from one or more of the following: ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, isobutanol, acetic acid, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, chloroform, benzene, xylene, petroleum ether at 30-60 ℃, petroleum ether at 60-90 ℃, naphtha, white oil, fish oil, castor oil, peanut oil, cyclohexane, n-heptane, n-decane, methyl isobutyl ketone, propylene glycol methyl ether, pyridine, ethyl acetate, methyl acetate and butyl acetate.