CN115894795A - Preparation method and application of zirconium-containing nano organosol - Google Patents
Preparation method and application of zirconium-containing nano organosol Download PDFInfo
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- CN115894795A CN115894795A CN202310010884.8A CN202310010884A CN115894795A CN 115894795 A CN115894795 A CN 115894795A CN 202310010884 A CN202310010884 A CN 202310010884A CN 115894795 A CN115894795 A CN 115894795A
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Abstract
The invention belongs to the technical field of nanoimprint lithography, and particularly discloses a preparation method and application of a zirconium-containing nano organosol. The material is prepared by a condensation reaction and a grafting reaction of zirconium alkoxide under the protection of various compounds. Specifically, double bonds are introduced and the hydrolysis rate is controlled after the double bonds are chelated by zirconium alkoxide and beta-diketone containing the double bonds; the compatibility of the organic resin is improved by introducing aromatic rings on side chains; and finally forming nano particles through hydrolytic condensation, and dispersing the nano particles in organic resin to form a stable dispersion system. The resin can be cured into a film under ultraviolet light, the refractive index can reach 1.7177 under the wavelength of 589 nanometers, and the average transmittance of a visible light waveband can reach 98.6%. The organic sol can be compounded with other organic resin to prepare high-refractive-index nanoimprint lithography glue, obtain a high-resolution nanostructure through ultraviolet nanoimprint lithography, and can also be directly used for preparing high-refractive-index coating.
Description
Technical Field
The invention belongs to the technical field of nanoimprint lithography, and relates to a preparation method and application of a zirconium-containing nano organosol.
Background
The Refractive Index (RI) is one of the most important and fundamental properties of optical materials. In recent years, high-refractive index polymers are more and more widely applied to various advanced micro-nano optical devices, however, the refractive indexes of most of the polymers cannot meet the performance requirements at present. The nanoimprint technology, particularly the ultraviolet nanoimprint technology, is cured at room temperature by using ultraviolet rays, so that the processing efficiency is high, and the nanoimprint technology is a mainstream process for industrially producing micro-nano optical devices. The ultraviolet nanoimprint principle is very simple: and pressing the transparent template with the nano-scale convex-concave structure into the prepolymer film, and after ultraviolet curing, crosslinking the polymer to convert the viscous liquid into a hard three-dimensional network structure, so that the nano-structure filled in the die cavity is shaped. And removing the template to obtain the required nano structure on the surface of the material.
The addition of inorganic nanoparticles with high refractive index to polymers is an effective method for increasing the refractive index of polymers, and zirconia nanoparticles are a potential candidate due to light color and high stability. So far, sol-gel methods, hydrothermal reactions and solvothermal reactions are the most commonly used methods for synthesizing nanoparticle dispersions. Such documents are abundant, for example document 1 (Peter D. Southon, john R. Bartlett, james L. Woolfrey, besim Ben-Nissan, formation and Characterization of an Aqueous Zirconium Hydroxide Colloid, chem. Mater. 2002, 14 (10), 4313-4319) which uses zirconyl nitrate solution as a raw material, uses Zirconium carbonate as an alkali to promote a reaction, and forms nano-sized Zirconium Hydroxide Colloid particles by controlled polycondensation between zirconyl species. Document 2 (Iryna Chemona, roman Smotraev, valentyn Kaibolotsky, volodymy Streelko, colloidal and chemical industries of nanosized hydrated zirconium dioxide synthesized via a gel-gel process, journal of Colloidal and Interface Science,2011, 356 (2), 404-411) uses zirconium oxychloride solution as a precursor and sodium acetate buffer as a stabilizer. For the stabilized hydrous zirconia sols prepared by homogeneous hydrolysis of zirconium oxychloride at constant pH and different molar ratios NaOH/Zr = 1.3 ‒ 1.53.53, the average particle sizes were 20 to 35 nanometers, respectively. Document 3 (CN 109761274a, a method for preparing self-stabilized nano zirconia sol at low temperature) discloses a system using zirconium oxychloride as a raw material, ammonia water as a precipitant, and ethylenediamine as an auxiliary agent to prepare self-stabilized nano zirconia sol. Although the sol-gel method is a common industrial method for preparing zirconium oxide nano sol, the method has insurmountable difficulty when being used for preparing high-refractive index ultraviolet nano imprinting glue, and the essential point is that the obtained sol is an aqueous dispersion system and cannot be compatible with a resin-organic solvent system.
Hydrothermal and solvothermal methods are also common methods for preparing nanoparticles in the laboratory, and the obtained nanoparticles are mixed into resin, so that the refractive index can be improved. However, the nanoparticles prepared by the method have low concentration during preparation, need high temperature and high pressure reaction for a long time at high temperature, need high-speed centrifugation for separation after reaction, need solvent washing for removing the auxiliary agent used during synthesis, need surface modification and re-disperse in a proper solvent, and not only consume time and energy, cause great environmental pollution, but also have extremely high cost and extremely low production efficiency. In addition, it is also possible to disperse the nanopowder in the medium by a mechanical method to reduce agglomeration in the resin and improve the dispersion property, for example, document 4 (CN 101547866B, zirconia particle dispersion liquid, photocurable composition containing zirconia particles, and cured film) discloses a zirconia dispersion liquid in which zirconia particles and a metal complex are dispersed in a dispersion medium by ball milling for preparing a transparent cured film of high refractive index. The method needs long-time ball milling, has high energy consumption and transmittance lower than 90 percent, and is difficult to meet the requirement of high-performance optical devices.
Therefore, the development of an environment-friendly, high-production-efficiency and low-cost nano-particle preparation method has important significance for the high-refractive-index nano-imprinting adhesive.
Disclosure of Invention
Aiming at the defect that the prior art can not prepare the high-concentration zirconium-containing nano organosol cheaply and efficiently, the invention provides a preparation method of the zirconium-containing nano organosol, the zirconium-containing nano organosol is obtained by controlled condensation under the grafting and protection of an organic monomer, and the zirconium-containing nano organosol can be used for preparing the high-refractive-index ultraviolet curing nanoimprint lithography glue.
The technical solution for realizing the purpose of the invention is as follows:
a preparation method of zirconium-containing nano organic sol comprises the following steps of carrying out chelation reaction on alkoxy zirconium and beta-diketone containing double bonds to introduce the double bonds; the compound containing o-phenylphenoxy is reacted to introduce an aromatic ring on a side chain to improve the compatibility of the nano-particles with organic monomers and solvents; the nano particles are gradually formed through slow hydrolytic condensation reaction and can be dissolved in an organic solvent to obtain a transparent solution, and the solution and the organic resin are compounded to obtain the high-refractive-index ultraviolet curing resin which can be used for ultraviolet nano imprinting and preparing high-refractive-index polymer coatings.
The zirconium-containing nano organic sol is prepared by the following steps:
1) Uniformly mixing alkoxy zirconium and double-bond beta-diketone at normal temperature and stirring until the mixture is transparent;
2) Adding a compound containing o-phenylphenoxy, and continuously stirring until the mixture is transparent;
3) Slowly adding deionized water, and continuously stirring at normal temperature;
4) Performing vacuum rotary evaporation;
5) After cooling, adding an organic solvent to obtain the zirconium-containing nano organosol.
Preferably, in the step 1), the zirconium alkoxide is zirconium n-butoxide.
Preferably, in the steps 1) and 2), the molar ratio of the zirconium alkoxide, the double bond-containing beta-diketone and the o-phenylphenoxy-containing compound is 10:1:1.
preferably, in the step 3), the molar ratio of the deionized water to the zirconium alkoxide is 1 to 5-1.
Preferably, in the step 3), the stirring time is 0.5 to 72 hours.
Preferably, in the step 4), the rotary steaming temperature is 50 to 160 ℃, the rotary steaming time is 2 to 24 hours, and the vacuum degree is-0.09 to-0.098 MPa;
preferably, in step 5), the organic solvent is selected from one of anisole, toluene, xylene, chlorobenzene, ethylene glycol monomethyl ether, methyl methacrylate, propylene glycol methyl ether acetate or tert-butyl methacrylate.
The invention also provides application of the zirconium-containing nano organic sol in preparing a polymer film of the ultraviolet curing nano imprinting adhesive, wherein ultraviolet curing resin and a photoinitiator are dissolved in the zirconium-containing nano organic sol together, and corresponding dilution is carried out according to the required film thickness to obtain the ultraviolet curing nano imprinting adhesive.
Preferably, the photoinitiator is one or more selected from 2-hydroxy-methyl phenyl propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone.
The invention also provides application of the zirconium-containing nano organic sol in preparing a polymer film of the ultraviolet curing nanoimprint lithography glue, wherein the ultraviolet curing nanoimprint lithography glue is spin-coated on a substrate, and the polymer film is obtained after ultraviolet curing for a certain time.
The invention also provides application of the zirconium-containing nano organic sol in preparing a high-folding imprinting structure of ultraviolet curing nano imprinting glue.
Preferably, the curing temperature is normal temperature, and the curing time is 4 to 10 minutes.
Compared with the prior art, the invention has the advantages that: the zirconium-containing nano organosol prepared by the invention has simple preparation process and high production efficiency, does not need to adopt an organic solvent during preparation, does not need forced dispersion such as ultrasonic dispersion, ball milling and the like during dispersion, can obtain good dispersion by directly stirring, and can be directly used by adding an organic monomer into the organosol.
Drawings
FIG. 1 is a dispersion curve of an imprint resist film after UV curing;
FIG. 2 is a dispersion curve of a high refractive index nanoimprint resist;
FIG. 3 is a graph showing the transmittance of the film at different wavelengths after photocuring;
FIG. 4 is a perspective view, a plan view, and a cross-sectional profile view of the stamped feature.
Detailed Description
The following further describes particular embodiments of the present invention to facilitate further understanding of the present invention by those skilled in the art, and does not limit the claims.
Example 1
A preparation method of a zirconium-containing nano organic sol comprises the following steps:
1) 2.14g of acetoacetic acid ethylene glycol methacrylate (0.01 mol) and 48.0g of n-butyl zirconium (0.1mol, 80wt%) were mixed uniformly, and then stirred at room temperature until clear;
2) 2.68g of o-phenylphenoxyethyl acrylate (0.01 mol) is added, and the mixture is stirred at room temperature until the mixture is clear;
3) 0.36g of deionized water (0.02 mol) was slowly added at room temperature with stirring;
4) Performing vacuum rotary evaporation for 24 hours at the temperature of 50 ℃, wherein the vacuum degree is-0.095 MPa;
5) Cooling to room temperature, adding anisole, and dissolving completely to obtain the final product with average particle diameter of 22 nm.
Example 2
A preparation method of a zirconium-containing nano organic sol comprises the following steps:
1) Mixing 10.7g of acetoacetic acid ethylene glycol methacrylate (0.05 mol) and 48.0g of n-butyl zirconium (0.1mol, 80wt%), stirring at room temperature until the mixture is clear;
2) Adding 2.68g of o-phenylphenoxyethyl acrylate (0.01 mol), and stirring at room temperature until the mixture is clear;
3) 0.36g of deionized water (0.02 mol) was slowly added at room temperature with stirring;
4) Performing vacuum rotary evaporation for 24 hours at the temperature of 50 ℃, wherein the vacuum degree is-0.095 MPa;
5) Cooling to room temperature, adding anisole, and dissolving completely to obtain the final product with average particle diameter of 17 nm.
Example 3
A preparation method of a zirconium-containing nano organic sol comprises the following steps:
1) 2.14g of acetoacetic acid ethylene glycol methacrylate (0.01 mol) and 48.0g of n-butyl zirconium (0.1mol, 80wt%) were mixed uniformly, and then stirred at room temperature until clear;
2) Adding 5.36g of o-phenylphenoxyethyl acrylate (0.02 mol) and uniformly mixing, and stirring at room temperature until the mixture is clear;
3) Slowly adding 0.36g of deionized water (0.02 mol) while stirring at room temperature, and then continuously stirring for 12 hours;
4) Performing vacuum rotary evaporation for 12 hours at 70 ℃, wherein the vacuum degree is-0.095 MPa;
5) Cooling to room temperature, adding anisole, and dissolving completely to obtain the final product with average particle diameter of 21 nm.
Example 4
A preparation method of a zirconium-containing nano organic sol comprises the following steps:
1) 2.14g of acetoacetic acid ethylene glycol methacrylate (0.01 mol) and 48.0g of zirconium n-butoxide (0.1mol, 80wt%) are mixed uniformly and stirred at room temperature until clear;
2) Adding 3.40g of o-phenylphenol (0.02 mol), uniformly mixing, and stirring at room temperature until the mixture is clear;
3) Slowly adding 0.36g of deionized water (0.02 mol) while stirring at room temperature, and then continuously stirring for 12 hours;
4) Performing vacuum rotary evaporation for 12 hours at 90 ℃ and the vacuum degree is-0.095 MPa;
5) Cooling to room temperature, adding anisole, and dissolving completely to obtain the final product with average particle diameter of 24 nm.
In examples 1 to 4, the anisole added in step 5) may be replaced by other organic solvents, and specifically, the organic solvent may be one selected from anisole, toluene, xylene, chlorobenzene, ethylene glycol monomethyl ether, methyl methacrylate, propylene glycol methyl ether acetate, and t-butyl methacrylate.
Example 5
To the zirconium-containing nanoorganosol obtained in example 1 were added o-phenylphenoxyethyl acrylate (OPPEA) and triallyl isocyanurate (TAIC), the solids content of the sol: OPPEA TAIC =8:1.5:0.5 (mass ratio), and adding 1-hydroxycyclohexyl phenyl ketone (3 wt% relative to the total mass of solid components in the sol, OPPEA and TAIC), dissolving and diluting with anisole to prepare 15wt% of imprinting glue solution, obtaining golden yellow transparent solution, and showing obvious tyndall phenomenon (figure 1). And sealing in dark for later use.
The imprinting glue solution was spin-coated on a clean silicon wafer and uv-cured in air at room temperature for 4 minutes to obtain a polymer film. As shown in FIG. 2, the dispersion curve was measured to show a refractive index of 1.7177 at 589 nm.
The imprinting glue solution was spin-coated on a clean quartz plate and UV-cured in air at room temperature for 4 minutes to obtain a polymer film. As shown in fig. 3, the transmittance of the film was measured by an ultraviolet-visible spectrophotometer, and the average transmittance was 98.6% at a wavelength of 380 nm to 710 nm.
And spin-coating the imprinting adhesive solution on a clean silicon wafer, covering a PDMS template, carrying out ultraviolet curing in the air for 4 minutes at room temperature, demolding, and removing the PDMS template to obtain the high-folding imprinting structure. As shown in fig. 4, the morphology was measured with an atomic force microscope.
Claims (10)
1. The preparation method of the zirconium-containing nano organic sol is characterized by comprising the following steps:
1) Uniformly mixing alkoxy zirconium and double-bond beta-diketone at normal temperature and stirring until the mixture is transparent;
2) Adding a compound containing o-phenylphenoxy, and continuously stirring until the mixture is transparent;
3) Slowly adding deionized water, and continuously stirring at normal temperature;
4) Performing vacuum rotary evaporation;
5) After cooling, adding an organic solvent to obtain the zirconium-containing nano organosol.
2. The method for preparing the nano organosol containing zirconium according to claim 1, wherein in the step 1), the zirconium alkoxide is zirconium n-butoxide.
3. The method for preparing the nano organosol containing zirconium according to claim 1, wherein in the step 1) and the step 2), the molar ratio of the zirconium alkoxide, the beta-diketone containing the double bond and the compound containing the o-phenylphenoxy group is 10:1:1.
4. the method for preparing the zirconium-containing nano organosol according to claim 1, wherein in the step 3), the molar ratio of the deionized water to the zirconium alkoxide is 1 to 5 to 1, and the stirring time is 0.5 to 72 hours.
5. The method for preparing the nano organosol containing zirconium according to claim 1, wherein in the step 4), the rotary evaporation temperature is 50 to 160 ℃, the rotary evaporation time is 2 to 24 hours, and the vacuum degree is-0.09 to-0.098 MPa.
6. The method for preparing the nano organosol containing zirconium as claimed in claim 1, wherein the organic solvent in step 5) is selected from one of anisole, toluene, xylene, chlorobenzene, ethylene glycol monomethyl ether, methyl methacrylate, propylene glycol methyl ether acetate or t-butyl methacrylate.
7. The use of the zirconium-containing nanoorganosol of claim 1 in the preparation of UV-curable nanoimprint lithography adhesives, wherein the UV-curable resin is dissolved in the zirconium-containing nanoorganosol together with a photoinitiator, and the UV-curable nanoimprint lithography adhesives are obtained by diluting the zirconium-containing nanoorganosol according to the desired film thickness.
8. The use of the zirconium-containing nanoorganosol according to claim 1 for preparing a polymer film of a uv-curable nanoimprint lithography glue, wherein the uv-curable resin is dissolved in the zirconium-containing nanoorganosol together with a photoinitiator and diluted accordingly according to the desired film thickness to obtain the uv-curable nanoimprint lithography glue, the uv-curable nanoimprint lithography glue is spin-coated on a substrate, and the polymer film is obtained after uv-curing for a certain time.
9. The use of the zirconium-containing nanoorganosol according to claim 1 for the preparation of high-folding imprinted structures of uv-curable nanoimprint lithography, wherein uv-curable resins are dissolved in the zirconium-containing nanoorganosol together with photoinitiators and diluted accordingly according to the desired film thickness to obtain uv-curable nanoimprint lithography, which is spin-coated onto a substrate, covered with a transparent template, and demolded after uv-curing for a certain period of time to obtain high-folding imprinted structures.
10. Use according to any one of claims 7 to 9, wherein the photoinitiator is selected from one or more of 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone.
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| CN114149589A (en) * | 2021-11-18 | 2022-03-08 | 常熟理工学院 | High-refractive-index ultraviolet-curing nanoimprint lithography adhesive |
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2023
- 2023-01-05 CN CN202310010884.8A patent/CN115894795A/en active Pending
Patent Citations (7)
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| KR20110062521A (en) * | 2009-12-03 | 2011-06-10 | 주식회사 블루폴리텍 | Ultraviolet cured organic-inorganic hybrid resin and the resin composition for optical film |
| CN105278246A (en) * | 2014-07-04 | 2016-01-27 | 富士胶片株式会社 | Hardened composition, hardened film manufacturing method, harden film, touch screen and display device |
| CN108445717A (en) * | 2018-03-08 | 2018-08-24 | 常熟理工学院 | A kind of photocuring titaniferous nano impression glue, preparation method and its application in not anti-sticking template directly imprints |
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