CN114230864A - Modified zirconia nanoparticle alcohol dispersion system, preparation method and application thereof, and ultraviolet-curable resin material - Google Patents
Modified zirconia nanoparticle alcohol dispersion system, preparation method and application thereof, and ultraviolet-curable resin material Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 170
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000006185 dispersion Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 150000007529 inorganic bases Chemical class 0.000 claims description 13
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 12
- 230000033444 hydroxylation Effects 0.000 claims description 11
- 238000005805 hydroxylation reaction Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000011345 viscous material Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000020477 pH reduction Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- -1 perhydroxyl anions Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of zirconia nano materials, and provides a modified zirconia nano particle alcohol dispersion system, a preparation method and application thereof, and an ultraviolet curing resin material. The modified zirconia nanoparticle alcohol dispersion system provided by the invention comprises modified zirconia nanoparticles and an alcohol dispersant; the modified zirconia nanoparticles include hydroxylated zirconia nanoparticles and oily functional groups grafted on the surface of the hydroxylated zirconia nanoparticles. According to the invention, oily functional groups are grafted on the surfaces of the zirconia nanoparticles, so that the dispersibility of the zirconia nanoparticles in the ultraviolet curing resin is improved; the refractive index of the ultraviolet curing resin material can be greatly improved. The data of the embodiment show that the refractive index of the ultraviolet curing resin material provided by the invention is 1.70-1.75.
Description
Technical Field
The invention relates to the technical field of zirconia nano materials, in particular to a modified zirconia nano particle and a preparation method and application thereof.
Background
Augmented Reality (AR) technology and Virtual Reality (VR) technology are areas of technology that have attracted much attention in recent years. Both near-eye display systems of AR and VR technology project a distant virtual image of pixels on a display through a series of optical imaging elements into the human eye. The difference lies in that: AR glasses need to see both the real outside world and virtual information, so the imaging system cannot be kept out of sight. The diffraction light waveguide technology is not the second choice for AR glasses to have the appearance of ordinary glasses and really go to the consumer market.
"total reflection" is a significant problem with diffractive optical waveguide technology, which requires that the light travel in a given path without loss and leakage, since the remote virtual image must be conducted and projected into the human eye. Therefore, it is desirable to produce a material that can be coated on glass and is transparent, but has a much higher refractive index than glass. The ultraviolet light curing resin is a high molecular material containing acrylate, vinyl ether and epoxy groups, can be cured into a film under the irradiation of ultraviolet light, and is a common material for glass surface coatings. How to increase the refractive index of the uv curable resin is one of the most important issues.
Research shows that the refractive index of the ultraviolet curing resin can be obviously improved by adding a certain amount of zirconium oxide nano particles into the ultraviolet curing resin; moreover, the more zirconia nano particles are added, the more obvious the improvement of the refractive index of the ultraviolet curing resin is. However, the zirconia nanoparticles are inorganic particles, and the uv curable resin is an organic material, which are incompatible, and it is difficult to uniformly disperse the zirconia nanoparticles in the uv curable resin. In the prior art, various methods for modifying zirconia nanoparticles are disclosed, but the obtained modified nano zirconia particles have poor dispersibility in ultraviolet curing resin, and the improvement of the refractive index of the ultraviolet curing resin is influenced.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified zirconia nanoparticle alcohol dispersion system, a preparation method and an application thereof, and an ultraviolet curable resin material. The modified zirconia nanoparticles in the modified zirconia nanoparticle alcohol dispersion system provided by the invention have good dispersibility.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a modified zirconia nanoparticle alcohol dispersion system, which comprises modified zirconia nanoparticles and an alcohol dispersant;
the modified zirconia nanoparticles include hydroxylated zirconia nanoparticles and oily functional groups grafted on the surface of the hydroxylated zirconia nanoparticles.
Preferably, the oily functional group is an oily functional group containing a carbonyl group and having a carbon atom number of not less than 4.
Preferably, the alcohol dispersant comprises a lower alcohol.
The invention also provides a preparation method of the modified zirconia nanoparticle alcohol dispersion system, which comprises the following steps:
mixing basic zirconium carbonate, inorganic base and water, and carrying out hydrothermal reaction to obtain a system containing zirconium oxide nanoparticles;
mixing the system containing the zirconia nanoparticles, hydrogen peroxide and inorganic acid, and carrying out hydroxylation modification to obtain hydroxylated zirconia nanoparticles;
mixing the hydroxylated zirconia nanoparticles with fatty acid, carrying out surface modification, evaporating the obtained surface modification feed liquid to be viscous, and dispersing the obtained viscous substance by using an alcohol dispersing agent to obtain the modified zirconia nanoparticle alcohol dispersion system.
Preferably, the inorganic base comprises sodium hydroxide or potassium hydroxide; the temperature of the hydrothermal reaction is 110-150 ℃, and the time is 5-8 h.
Preferably, the concentration of the hydrogen peroxide is 0.4 mol/L; the dosage ratio of the basic zirconium carbonate to the hydrogen peroxide is 20 g: (5-7) mL.
Preferably, the temperature of the hydroxylation modification is 10-30 ℃.
Preferably, the mass ratio of the hydroxylated zirconia nanoparticles to the fatty acid is 1.0: (0.5 to 1).
The invention also provides an application of the modified zirconia nanoparticle alcohol dispersion system in the technical scheme or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method in the technical scheme in an ultraviolet curing resin material.
The invention also provides an ultraviolet curing resin material, which comprises: ultraviolet light curing resin and modified zirconia nano particles;
the modified zirconia nanoparticles are derived from the modified zirconia nanoparticle alcohol dispersion system in the technical scheme or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method in the technical scheme.
The invention provides a modified zirconia nanoparticle alcohol dispersion system, which comprises modified zirconia nanoparticles and an alcohol dispersant; the modified zirconia nanoparticles include hydroxylated zirconia nanoparticles and oily functional groups grafted on the surface of the hydroxylated zirconia nanoparticles. According to the invention, oily functional groups are grafted on the surfaces of the zirconia nanoparticles, and the zirconia nanoparticles are dispersed in the alcohol solvent, so that when the zirconium oxide nanoparticles are used in the ultraviolet curing resin material, the dispersibility of the zirconia nanoparticles in the ultraviolet curing resin is improved.
The invention also provides a preparation method of the modified zirconia nanoparticle alcohol dispersion system, which comprises the following steps: mixing the system containing the zirconia nanoparticles, hydrogen peroxide and inorganic acid, and carrying out hydroxylation modification to obtain hydroxylated zirconia nanoparticles; mixing the hydroxylated zirconia nanoparticles with fatty acid, carrying out surface modification, evaporating the obtained surface modification feed liquid to be viscous, and dispersing the obtained viscous substance by using an alcohol dispersing agent to obtain the modified zirconia nanoparticle alcohol dispersion system. Firstly, carrying out hydrothermal reaction on inorganic base and basic zirconium carbonate to prepare zirconium oxide nanoparticles; carrying out hydroxylation modification on the zirconium oxide nanoparticles by adopting hydrogen peroxide and dilute nitric acid to obtain hydroxylated zirconium oxide nanoparticles; then, carrying out surface modification on the hydroxylated zirconia nanoparticles by using fatty acid, evaporating the surface modification liquid to be viscous, and dissolving the viscous liquid by using alcohol so that the modified zirconia nanoparticles are uniformly dispersed in the alcohol and cannot be agglomerated; when the ultraviolet curing resin material is applied to an ultraviolet curing resin material, the dispersibility is good, and the refractive index of the ultraviolet curing resin material can be greatly improved. Meanwhile, the preparation method provided by the invention is simple to operate.
The invention also provides an application of the modified zirconia nanoparticle alcohol dispersion system in the technical scheme or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method in the technical scheme in an ultraviolet curing resin material.
The invention also provides an ultraviolet curing resin material, which comprises: ultraviolet light curing resin and modified zirconia nano particles; the modified zirconia nanoparticles are derived from the modified zirconia nanoparticle alcohol dispersion system in the technical scheme or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method in the technical scheme. The modified zirconia nanoparticles provided by the invention are grafted with oily groups, so that the modified zirconia nanoparticles have good dispersibility in the ultraviolet curing resin, and the refractive index of the ultraviolet curing resin material can be improved.
The data of the examples show that: the refractive index of the ultraviolet curing resin material provided by the invention is 1.70-1.75.
Drawings
FIG. 1 is a refractive index chart of a UV-curable resin in which modified zirconia nanoparticles were dispersed, obtained in example 1;
FIG. 2 is a graph showing a distribution of particle diameters of modified zirconia nanoparticles in the ethanol dispersion of modified zirconia nanoparticles obtained in example 1;
FIG. 3 is a refractive index chart of the UV-curable resin in which modified zirconia nanoparticles were dispersed obtained in example 2;
FIG. 4 is a graph showing a distribution of particle diameters of modified zirconia nanoparticles in the ethanol dispersion of modified zirconia nanoparticles obtained in example 2;
FIG. 5 is a refractive index chart of the UV-curable resin with dispersed modified zirconia nanoparticles obtained in example 3;
FIG. 6 is a graph showing refractive indexes of the ultraviolet-curable resin in which the zirconium oxide nanoparticles obtained in comparative example 1 were dispersed;
fig. 7 is a refractive index diagram of the ultraviolet curable resin in which the zirconia nanoparticles were dispersed obtained in comparative example 2.
Detailed Description
The invention provides a modified zirconia nanoparticle alcohol dispersion system, which comprises modified zirconia nanoparticles and an alcohol dispersant;
the modified zirconia nanoparticles include hydroxylated zirconia nanoparticles and oily functional groups grafted on the surface of the hydroxylated zirconia nanoparticles.
In the invention, the particle size of the zirconia nanoparticles is 5-50 nm.
In the present invention, the oily functional group is preferably an oily phase functional group containing a carbonyl group, the number of carbon atoms of which is not less than 4; further preferably comprises-CO-R or-CO-C (CH)3)＝CH2(ii) a R in the-CO-R is preferably pentyl, undecyl or heptyl.
In the present invention, the alcohol dispersant preferably includes a lower alcohol, and the lower alcohol preferably includes ethanol.
In the present invention, the oily functional group is attached to the hydroxylated zirconia nanoparticle through an ester group.
The invention also provides a preparation method of the modified zirconia nanoparticle alcohol dispersion system, which comprises the following steps:
mixing basic zirconium carbonate, inorganic base and water, and carrying out hydrothermal reaction to obtain a system containing zirconium oxide nanoparticles;
mixing the system containing the zirconia nanoparticles, hydrogen peroxide and inorganic acid, and carrying out hydroxylation modification to obtain hydroxylated zirconia nanoparticles;
mixing the hydroxylated zirconia nanoparticles with fatty acid, carrying out surface modification, evaporating the obtained surface modification feed liquid to be viscous, and dispersing the obtained viscous substance by using an alcohol dispersing agent to obtain the modified zirconia nanoparticle alcohol dispersion system.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention mixes basic zirconium carbonate, inorganic alkali and water to carry out hydrothermal reaction, and obtains a system containing zirconia nano particles.
In the present invention, the inorganic base preferably includes sodium hydroxide or potassium hydroxide, and more preferably sodium hydroxide. In the present invention, the inorganic base is preferably used in the form of an aqueous solution of an inorganic base, and the concentration of the aqueous solution of an inorganic base is not particularly limited in the present invention as long as the ratio of the amount of the inorganic base to the amount of the basic zirconium carbonate used can satisfy the following requirements.
In the present invention, the molar ratio of hydroxide radicals in the basic zirconium carbonate and the inorganic base is preferably not less than 1: 4.
in the invention, the temperature of the hydrothermal reaction is preferably 110-150 ℃, and more preferably 120-140 ℃; the time is preferably 5 to 8 hours, and more preferably 6 to 7 hours.
In the present invention, the hydrothermal reaction is preferably carried out in a high-temperature hydrothermal reaction vessel.
After the system containing the zirconia nano particles is obtained, the method can be directly used for the next reaction without post-treatment.
In the present invention, the hydrothermal reaction can react an inorganic base with zirconium basic carbonate to obtain zirconia nanoparticles.
After a system containing zirconia nanoparticles is obtained, the system containing the zirconia nanoparticles, hydrogen peroxide and inorganic acid are mixed and subjected to hydroxylation modification to obtain hydroxylated zirconia nanoparticles.
In the invention, the temperature of the hydroxylation modification is preferably 10-30 ℃.
In the invention, the hydroxylation modification comprises AHP reaction and acidification treatment which are sequentially carried out.
In the present invention, the AHP reaction preferably comprises the steps of: and mixing the system containing the zirconia nanoparticles with hydrogen peroxide to perform AHP reaction. In the invention, the pH value of the AHP reaction is preferably 12-13. In the present invention, the pH of the AHP reaction is preferably achieved by adjusting the pH of the system containing the zirconia nanoparticles; namely, after the pH value of the zirconium oxide-containing nanoparticle system is adjusted to 12-13, hydrogen peroxide is added to carry out AHP reaction. In the present invention, the agent for adjusting the pH of the system containing zirconia nanoparticles preferably comprises water. In the invention, the mass concentration of the hydrogen peroxide is preferably 0.4 mol/L. In the invention, the dosage ratio of the basic zirconium carbonate and the hydrogen peroxide is preferably 20 g: (5-7) mL. In the present invention, the hydrogen peroxide is preferably added while stirring the system containing the zirconia nanoparticles. In the invention, the temperature of the AHP reaction is preferably 10-30 ℃, and the time is preferably 5-8 h.
After the AHP reaction is finished, the method preferably further comprises the steps of centrifuging the obtained AHP reaction feed liquid, washing the obtained solid, and obtaining the precipitate. In the present invention, the washing reagent is preferably water, and the amount of the washing reagent and the number of times of washing are not particularly limited as long as the washing can be carried out to a pH of 7.
In the present invention, the acidification treatment preferably comprises the following steps: and (4) carrying out acidification treatment on the system obtained by AHP reaction. In the invention, the pH value of the acidification treatment is preferably 1-3. In the present invention, the agent for the acidification treatment preferably includes nitric acid; the reagent for the acidification treatment is not particularly limited, and the pH value of the acidification treatment can be 1-3. In the invention, the temperature of the acidification treatment is preferably 10-30 ℃, and the time is preferably 3-5 h.
After the acidification treatment, the invention preferably further comprises evaporating the obtained acidification treatment system to dryness. The operation of the evaporation to dryness is not particularly limited in the present invention, as long as the solvent can be evaporated to dryness.
In the invention, the hydroxylation treatment comprises AHP reaction and acidification treatment; in alkaline environment, zirconium oxide nano particles (ZrO) are promoted by perhydroxyl anions (HOO) generated by hydrogen peroxide2NPs) growth of surface hydroxyl groups; ZrO (ZrO)2And acidifying the Zr-O-structure on the surface of the NPs to form Zr-OH, thus obtaining the hydroxylated zirconia nano particles.
After the hydroxylated zirconia nanoparticles are obtained, the hydroxylated zirconia nanoparticles and fatty acid are mixed for surface modification, the obtained surface modification feed liquid is evaporated to be viscous, and the obtained viscous substance is dispersed by an alcohol dispersing agent to obtain the modified zirconia nanoparticle alcohol dispersion system.
In the present invention, the fatty acid preferably includes caproic acid, methacrylic acid, dodecanoic acid or octanoic acid, and more preferably caproic acid.
In the present invention, the hydroxylated zirconia nanoparticles are preferably used in the form of a dispersion of hydroxylated zirconia nanoparticles; the solvent of the dispersion of the hydroxylated zirconia nanoparticles is preferably water; the concentration of the dispersion of the hydroxylated zirconia nanoparticles of the present invention is not particularly limited.
In the present invention, the fatty acid is preferably used in the form of a fatty acid solution; the solvent of the fatty acid solution is preferably a polar solvent, and the polar solvent preferably includes ethanol, ethyl acetate, N-methylpyrrolidone (NMP) or N, N-Dimethylformamide (DMF), and is further preferably ethanol; the dosage ratio of the fatty acid to the solvent in the fatty acid solution is preferably (0.5-0.8) g: (10-20) mL.
In the present invention, the mass ratio of the hydroxylated zirconia nanoparticles to the fatty acid is preferably 1.0 g: (0.5-1) g.
In the invention, the temperature of the surface modification is preferably 10-30 ℃, and the time is preferably 5-8 h. In the present invention, the surface modification is preferably performed under stirring.
The operation of the evaporation is not particularly limited in the present invention as long as the surface-modifying material can be evaporated to be viscous.
In the present invention, the alcohol dispersant preferably includes a lower alcohol, and the lower alcohol preferably includes ethanol.
The surface modification material liquid is evaporated to be viscous, a part of solvent can be reserved, and the viscous substance is dissolved in alcohol, so that the modified zirconia nanoparticles can be uniformly dispersed.
In the invention, in the surface modification process, the-OH grafted on the surface of the zirconium oxide nano-ions can react with-COOH in the fatty acid, so that the surfaces of the zirconium oxide nano-particles are connected with oily functional groups through ester groups, the dispersibility of the modified zirconium oxide nano-particles in the ultraviolet curing resin is improved, and the refractive index of the ultraviolet curing resin material can be greatly improved.
The invention also provides an application of the modified zirconia nanoparticle alcohol dispersion system in the technical scheme or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method in the technical scheme in an ultraviolet curing resin material.
The invention also provides an ultraviolet curing resin material, which comprises ultraviolet curing resin and modified zirconia nano particles; the modified zirconia nanoparticles are derived from the modified zirconia nanoparticle alcohol dispersion system in the technical scheme or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method in the technical scheme.
In the present invention, the uv curable resin preferably includes one or more of pentaerythritol triacrylate, hydroxyethyl acrylate, and CN 975.
In the invention, the mass ratio of the ultraviolet curing resin to the modified zirconia nanoparticles in the ultraviolet curing resin material is not particularly limited and can be adjusted according to actual needs.
The following will describe the modified zirconia nanoparticle alcohol dispersion system, the preparation method and the application thereof, and the uv curable resin material in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 20g of NaOH in 40mL of deionized water, adding 20g of basic zirconium carbonate into the NaOH solution, and uniformly stirring; pouring the mixed solution into a 50mL high-temperature hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6h at the temperature of 110 ℃; taking out the reacted mixed solution, adding 85mL of water to adjust the pH value to 13, stirring at 50 ℃, adding 5.1mL of 0.4mol/L hydrogen peroxide while stirring, and reacting for 5 hours at room temperature; centrifuging, washing the precipitate with water to pH 7; adding 1.5mol/L HNO into the precipitate34.36g are reacted for 3 h; slowly and rotatably steaming the obtained mixed solution until the solution is evaporated to dryness, and adding deionized water to disperse particles to obtain a clear zirconium oxide nano particle water dispersion solution; taking 5g of zirconium oxide aqueous dispersion (wherein, the hydroxylated zirconium oxide nano particles are 0.9g), adding 0.7g of caproic acid and 15mL of ethanol for surface modification, and stirring and reacting for 5h at room temperature; after reactionThe mixed solution is slowly and spirally steamed to 5mL, and 10.58g of ethanol is added into 5mL of the dope to obtain clear ethanol dispersion liquid of the modified zirconia nano particles.
Adding 3.6g of pentaerythritol triacrylate into the modified zirconia nanoparticle ethanol dispersion liquid (wherein the mass of the modified zirconia nano ions is 0.9g) obtained by the method, stirring and mixing, and removing the ethanol in vacuum to obtain the high-refraction modified zirconia nanoparticle dispersed ultraviolet curing resin.
The refractive index of the obtained modified zirconia nanoparticle dispersed uv curable resin was measured using an ellipsometer, and the result is shown in fig. 1. As can be seen from fig. 1: the refractive index of the ultraviolet curing resin dispersed by the modified zirconia nano particles at 500nm is 1.70.
The clear ethanol dispersion liquid of the modified zirconia nano particles is kept stand at room temperature, and the obtained dispersion liquid can stably exist for more than 30 days without precipitation.
The measured distribution graph of the particle size of the modified zirconia nanoparticles in the clarified ethanol dispersion of the modified zirconia nanoparticles is shown in fig. 2. As can be seen from fig. 2: the particle size of the modified zirconia nanoparticles obtained in the embodiment is 5-50 nm, and the hydrodynamic particle size is 18.87 nm.
Example 2
Dissolving 20g of NaOH in 40mL of deionized water, adding 20g of basic zirconium carbonate into the NaOH solution, and uniformly stirring; pouring the mixed solution into a 50mL high-temperature hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6h at the temperature of 110 ℃; taking out the reacted mixed solution, adding 87mL of water to adjust the pH value to 13, stirring at 50 ℃, adding 5mL of 0.4mol/L hydrogen peroxide while stirring, and reacting for 5 hours at room temperature; centrifuging, washing the precipitate with water to pH 7; adding 1.5mol/L HNO into the precipitate34.40g are reacted for 3 h; slowly and rotatably steaming the obtained mixed solution until the solution is evaporated to dryness, and adding deionized water to disperse particles to obtain a clear zirconium oxide nano particle water dispersion solution; taking 5g of zirconium oxide aqueous dispersion (wherein, 1.1g of hydroxylated zirconium oxide nano particles) and adding 0.7g of caproic acid and 15mL of ethanol for surface modification, and stirring and reacting for 5h at room temperature; slowly evaporating the mixed solution after reaction to 5mL in a rotary manner6.83g of ethanol was added to 5mL of the dope to obtain a clear ethanol dispersion of modified zirconia nanoparticles.
Adding 6.8g of CN975 into 8.53g of modified zirconia nanoparticle ethanol dispersion liquid (wherein the mass of the modified zirconia nano ions is 1.7g), stirring and mixing, and removing ethanol in vacuum to obtain the high-refraction modified zirconia nanoparticle dispersed ultraviolet curing resin.
The refractive index of the obtained modified zirconia nanoparticle dispersed uv curable resin was measured using an ellipsometer, and the result is shown in fig. 3. As can be seen from fig. 3: the refractive index of the obtained ultraviolet curing resin dispersed by the modified zirconia nano particles at 500nm is 1.72.
The clear ethanol dispersion liquid of the modified zirconia nano particles is kept stand at room temperature, and the obtained dispersion liquid can stably exist for 30 days without precipitation.
Fig. 4 shows the measured distribution diagram of the particle diameters of the modified zirconia nanoparticles in the obtained clarified ethanol dispersion of the modified zirconia nanoparticles. As can be seen from fig. 4: the hydrodynamic diameter of the modified zirconia nanoparticles obtained in this example was 103.98 nm.
Example 3
The differences from example 1 are: the mass of the modified zirconia nanoparticles and the mass of the pentaerythritol triacrylate were 1g and 1.5g, respectively.
The refractive index of the obtained modified zirconia nanoparticle dispersed uv curable resin was measured using an ellipsometer, and the result is shown in fig. 5. As can be seen from fig. 5: the refractive index of the ultraviolet curing resin dispersed by the modified zirconia nano particles at 500nm is 1.75.
Comparative example 1
The differences from example 1 are: 2.8g of pentaerythritol triacrylate was added to 5mL of a commercially available ethanol dispersion of zirconia nanoparticles (wherein the mass of the commercially available zirconia nanoparticles was 0.7g), and after stirring and mixing, ethanol was removed in vacuo to obtain a high-refractive ultraviolet-curable resin in which zirconia nanoparticles were dispersed.
The refractive index of the obtained ultraviolet curable resin in which the zirconia nanoparticles were dispersed was measured using an ellipsometer, and the result is shown in fig. 6. As can be seen from fig. 6: the refractive index of the obtained zirconia nanoparticle dispersed ultraviolet curing resin at 500nm is 1.51.
Comparative example 2
The difference from example 3 is that the modified zirconia nano-ions were replaced with commercially available zirconia nanoparticles.
The refractive index of the obtained ultraviolet curable resin in which the zirconia nanoparticles were dispersed was measured using an ellipsometer, and the result is shown in fig. 7. As can be seen from fig. 7: the refractive index of the obtained zirconia nanoparticle dispersed ultraviolet curing resin at 500nm is 1.51.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The modified zirconia nanoparticle alcohol dispersion system is characterized by comprising modified zirconia nanoparticles and an alcohol dispersant;
the modified zirconia nanoparticles include hydroxylated zirconia nanoparticles and oily functional groups grafted on the surface of the hydroxylated zirconia nanoparticles.
2. The alcohol dispersion system of claim 1, wherein the oily functional group is an oily functional group containing a carbonyl group and having not less than 4 carbon atoms.
3. The modified zirconia nanoparticle alcohol dispersion of claim 1 wherein the alcohol dispersant comprises a lower alcohol.
4. A process for the preparation of an alcohol dispersion of modified zirconia nanoparticles according to any one of claims 1 to 3 comprising the steps of:
mixing basic zirconium carbonate, inorganic base and water, and carrying out hydrothermal reaction to obtain a system containing zirconium oxide nanoparticles;
mixing the system containing the zirconia nanoparticles, hydrogen peroxide and inorganic acid, and carrying out hydroxylation modification to obtain hydroxylated zirconia nanoparticles;
mixing the hydroxylated zirconia nanoparticles with fatty acid, carrying out surface modification, evaporating the obtained surface modification feed liquid to be viscous, and dispersing the obtained viscous substance by using an alcohol dispersing agent to obtain the modified zirconia nanoparticle alcohol dispersion system.
5. The method of claim 4, wherein the inorganic base comprises sodium hydroxide or potassium hydroxide; the temperature of the hydrothermal reaction is 110-150 ℃, and the time is 5-8 h.
6. The preparation method according to claim 4, wherein the concentration of the hydrogen peroxide is 0.4 mol/L; the dosage ratio of the basic zirconium carbonate to the hydrogen peroxide is 20 g: (5-7) mL.
7. The method according to claim 4 or 6, wherein the temperature of the hydroxylation modification is 10-30 ℃.
8. The preparation method according to claim 4, wherein the mass ratio of the hydroxylated zirconia nanoparticles to the fatty acid is 1.0: (0.5 to 1).
9. Use of the modified zirconia nanoparticle alcohol dispersion system according to any one of claims 1 to 3 or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method according to any one of claims 4 to 8 in an ultraviolet curable resin material.
10. An ultraviolet-curable resin material, comprising: ultraviolet light curing resin and modified zirconia nano particles;
the modified zirconia nanoparticles are derived from the modified zirconia nanoparticle alcohol dispersion system of any one of claims 1 to 3 or the modified zirconia nanoparticle alcohol dispersion system obtained by the preparation method of any one of claims 4 to 8.
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| WO2009088043A1 (en) * | 2008-01-09 | 2009-07-16 | Asahi Glass Company, Limited | Surface-modified zirconia particle, process for producing the same, and resin composition |
| WO2012156199A1 (en) * | 2011-05-16 | 2012-11-22 | Evonik Degussa Gmbh | Metal oxide dispersion based on organic solvent |
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