CN115386025B - Preparation method of sulfur-containing resin and high refractive index composite material based on sulfur-containing resin - Google Patents

Abstract

The invention relates to a preparation method of a sulfur-containing resin and a high refractive index composite material with the sulfur-containing resin as a substrate, wherein the sulfur-containing resin is at least one of compounds shown in formulas 1 to 3; according to the invention, the sulfur-containing resin is used as a substrate, the metal nano particles subjected to surface hydroxylation treatment are used to obtain the stable organic-inorganic composite material, the preparation of the high-refractive-index composite material is realized, the flexible functional material with high transparency, good stability and excellent optical performance is obtained, the refractive index is regulated by regulating the doping amount of the metal nano particles, the requirements of various application scenes are met, and the application field of the optoelectronic device is greatly expanded.

Description

Preparation of a sulfur-containing resin and a high refractive index composite material based on the sulfur-containing resin Preparation method

Technical field

The invention belongs to the technical field of high refractive index composite materials and relates to a sulfur-containing resin and a preparation method of a high refractive index composite material based on the sulfur-containing resin.

Background technique

With the continuous development of optoelectronic devices, their application scenarios continue to expand, and the shortcomings of traditional optoelectronic devices gradually become apparent. Among them, optical glass that is widely used in devices currently has shortcomings such as being difficult to bend and having an unadjustable refractive index. Therefore, flexible materials with adjustable refractive index have gradually become a research hotspot.

At present, the preparation of flexible materials with high refractive index is usually organic-inorganic hybrid materials, that is, by doping metal nanoparticles in the resin to increase the refractive index, and by changing the solid content to make the refractive index adjustable. Gradient refractive index layer. At the same time, the prepared organic-inorganic hybrid material is bendable and can therefore be used in the preparation of flexible optoelectronic devices. However, during the preparation process of organic-inorganic hybrid materials, there are still problems such as poor dispersion of metal nano-ions and low compatibility with resin, resulting in low or uncontrollable refractive index, which limits the use of organic-inorganic hybrid materials. Promotion of high refractive index materials.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and propose a method for preparing a sulfur-containing resin and a high-refractive index composite material based on the sulfur-containing resin, which can effectively improve the dispersion of metal nanoparticles in water or organic solvents. At the same time, after the hydroxylation reaction, the metal nanoparticles obtained have good compatibility with the sulfur-containing resin, so that the prepared high-refractive index composite material based on the sulfur-containing resin has better transparency and controllable refractive index. As well as excellent thermal stability, it can be widely used in optoelectronic devices.

In order to achieve the above objects, the present invention adopts the following technical solutions:

The first aspect of the present invention provides a sulfur-containing resin, which is characterized in that it is at least one of the compounds represented by formulas 1 to 3:

X ₂ -R ₄ -SH; Formula 2

In Formula 1, R ₁ and R ₂ are each independently a single bond, a substituted or unsubstituted C1 to C30 branched or linear alkylene group, or a substituted or unsubstituted C1 to C30 alkylene group. Ether group, substituted or unsubstituted C1 to C20 secondary or tertiary amino group, substituted or unsubstituted C6 to C20 arylene group, substituted or unsubstituted C7 to C30 aryl alkylene group, Any one of substituted or unsubstituted C1 to C20 alkyleneoxy groups; alternatively, R ₂ and R ₃ can be connected to S in the formula 1 to form a substituted or unsubstituted C1-C20 alkylene group. Unsaturated monocyclic or polycyclic functional group; the R ₃ is hydrogen, hydroxyl or amine group;

In formula 2, R ₄ is a substituted or unsubstituted C1 to C30 branched or linear alkylene group, a substituted or unsubstituted C1 to C30 alkyl ether group, a substituted or unsubstituted C1 to C30 alkyl ether group, C20 secondary amino or tertiary amino, Any one of them, where * is the connection site;

X ₁ and X ₂ are each independently any one of Equations 4 to 6:

Among them, * is the connection site, Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group;

In Formula 3, W is a single bond, any one of S or O; R ₅ and R ₆ are each independently a single bond, a substituted or unsubstituted C1 to C30 branched or linear alkylene group, Substituted or unsubstituted C1 to C30 alkylene ether group, substituted or unsubstituted C7 to C30 aryl alkylene group, substituted or unsubstituted C1 to C30 arylene group, Any one of them; where L ₁ is a single bond, a branched or linear alkylene group from C1 to C30 substituted or unsubstituted by hydroxyl; L ₂ is hydrogen or

R ₇ and R ₈ are each independently hydrogen, substituted or unsubstituted C1 to C30 branched or linear alkyl, any of them.

Further, the compound of Formula 2 is represented by at least one of Formula 2-1 to Formula 2-3;

Further, the compound of Formula 3 is represented by at least one of Formula 3-1 to Formula 3-3;

A second aspect of the present invention provides a method for preparing a high refractive index composite material based on sulfur-containing resin, which includes the following steps:

S1. Purification of metal nanooxides;

S2. Disperse the purified metal nanooxide obtained in S1 in a solution to perform a hydroxylation reaction to obtain surface hydroxylated metal nanooxide; the particle size of the metal nanooxide is ≤100 nm; further preferably, The particle size of the metal nanooxide is ≤20nm;

S3. Compound the surface hydroxylated metal nanooxide obtained in S2 with the sulfur-containing resin to obtain an organic-inorganic hybrid resin;

S4. Add a photoinitiator to the organic-inorganic hybrid resin obtained in S3, and solidify it to form a film through ultraviolet light irradiation to obtain a high refractive index composite material.

Further, the metal nanooxide in S1 includes at least one of zirconium oxide, titanium oxide, nickel oxide, zinc oxide, and aluminum oxide; the specific steps for purifying the metal nanooxide in S1 are: The oxide is dispersed in absolute ethanol, ultrasonicated for 10 to 20 minutes, then stirred at 500 to 700 rpm for 1 to 3 hours, centrifuged, and the white precipitate in the lower layer is removed. Repeat the above process 2 to 3 times and dry to obtain purified metal nanoparticles. oxide, the weight ratio of the metal nanooxide to ethanol is 1: (10-40).

Further, the hydroxylation reaction of the metal nanooxide in S2 is specifically: dispersing the purified metal nanooxide obtained in S1 in the solution, ultrasonic treatment for 20 to 50 minutes, and then at 25°C to 50°C. Stir at 300-650 rpm for 10-30 hours, let it settle for 30-60 minutes, then discard the supernatant, add tetrahydrofuran to adjust the pH to 4-6, and let it settle. The white precipitate in the lower layer is the metal nanooxide after surface hydroxylation.

Further, in S2, the purified metal nanooxide is dispersed in a solution to perform a hydroxylation reaction, specifically: the purified metal nanooxide is dispersed in an acid solution to perform a hydroxylation reaction, or the purified metal nanooxide is dispersed in an acid solution to perform a hydroxylation reaction. The metal nanooxide is dispersed in an alkali solution to perform a hydroxylation reaction, or the purified metal nanooxide is first dispersed in an alkali solution and then dispersed in an acid solution to perform a hydroxylation reaction;

The pH value of the acid solution is ≤ 3, and the acid solution is at least one of hydrochloric acid aqueous solution, sulfuric acid aqueous solution, nitric acid aqueous solution, carbonic acid aqueous solution, phosphoric acid aqueous solution, formic acid aqueous solution, acetic acid aqueous solution, butyric acid aqueous solution and hexanoic acid aqueous solution; the pH of the alkaline solution Value ≥ 9, the alkali solution is at least one of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, ammonium hydroxide aqueous solution, ammonia water, pyridine, and triethylamine. The alkali solution can also be a mixture of the above solution and hydrogen peroxide aqueous solution. mixture.

Further, the specific S3 is: dispersing the surface hydroxylated metal nanooxide obtained in S2 in a solvent, adding the above-mentioned sulfur-containing resin, ultrasonic dispersion for 10 to 30 minutes, and dispersing at 25°C to 55°C and 500 to 700rpm. Stir for 0.5 to 2 hours under conditions, filter to obtain a clear and transparent solution, and rotary evaporate to remove the solvent to obtain an organic-inorganic hybrid resin.

Further, the solvent in S3 is water, methanol, ethanol, propanol, butanol, toluene, benzyl alcohol, phenol, acetonitrile, oleic acid, oleylamine, caproic acid, caprylic acid, pyridine, N, N-dimethyl At least one of formamide, N,N-dimethylacetamide, dimethyl sulfoxide, and acetone.

Further, the specific steps of S4 are: add a photoinitiator to the organic-inorganic hybrid resin obtained in S3, stir evenly, coat it on the surface of the glass substrate, and irradiate it with 20-120 mW/cm ² ultraviolet light for 10- After 100 seconds of curing, a high-refractive composite material is obtained. The refractive index of the high-refractive composite material is 1.500 to 1.800, the curing rate is 90% to 97%, and the light transmittance is 95% to 99%. The amount of the photoinitiator added It is 0.1~5% of the weight of organic-inorganic hybrid resin;

Preferably, the photoinitiator is a triazine-based photoinitiator, an acetophenone-based photoinitiator, a benzophenone-based photoinitiator, a thioxanthone-based photoinitiator, a benzoin-based photoinitiator. At least one of a photoinitiator, a phosphorus-based photoinitiator, and an oxime-based photoinitiator.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention improves the dispersibility of metal nanooxides in solvents by performing surface hydroxylation modification on metal nanooxides, and effectively improves the stability and transparency of organic-inorganic hybrid resins.

2. The specific sulfur-containing resin selected in the present invention has high flexibility, and at the same time forms an intermolecular force with the surface hydroxylated metal nano-oxide, effectively improving the compatibility between the sulfur-containing resin and the metal nano-oxide. properties; at the same time, sulfur-containing resin can form hydrogen bonds with the surface of metal nanooxides, effectively improving the stability and transparency of organic-inorganic hybrid resin.

3. The present invention can adjust the refractive index by adjusting the weight ratio of the hydroxylated metal nanooxide and the specific sulfur-containing resin to meet the requirements of various application scenarios and greatly expand the application field of optoelectronic devices.

4. The present invention uses sulfur-containing resin as the base and uses metal nanooxides that have been surface hydroxylated to obtain stable organic-inorganic hybrid resins to achieve the preparation of high-refractive composite materials. The prepared high-refractive composite materials are transparent Flexible functional materials with high resistance, good stability and adjustable refractive index.

Other features and advantages of the invention will become apparent from the following detailed description of exemplary embodiments of the invention with reference to the accompanying drawings.

Description of drawings

The accompanying drawings are incorporated in and constitute a part of this specification, and together with the description, serve to explain the principles of the invention.

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those of ordinary skill in the art, It is said that other drawings can be obtained based on these drawings without exerting creative labor.

Figure 1 is the infrared spectrum of the hydroxylation product after acid treatment and hydroxylation modification of titanium oxide metal nanoparticles in step 2 of Example 2 of the present invention;

Figure 2 is an infrared spectrum of the hydroxylation product after alkali treatment and hydroxylation modification of alumina metal nanoparticles in step 2 of Example 3 of the present invention;

Figure 3 is the infrared spectrum of the hydroxylation product after acid and alkali treatment and hydroxylation modification of alumina metal nanoparticles in step 2 of Example 3 of the present invention.

Detailed ways

Exemplary embodiments will be described in detail herein, examples of which are illustrated in the accompanying drawings. When the following description refers to the drawings, the same numbers in different drawings refer to the same or similar elements unless otherwise indicated. The implementations described in the following exemplary embodiments do not represent all implementations consistent with the invention. Rather, they are merely examples of means consistent with aspects of the invention as detailed in the appended claims.

The preparation of the high refractive index composite material based on sulfur-containing resin proposed by the present invention is further described in detail through examples below:

Example 1:

This embodiment provides a method for preparing a high refractive index composite material based on sulfur-containing resin:

S1. Purification of metal nanooxides:

Take 3.0g of metal nano-zinc oxide and disperse it in 60 mL of absolute ethanol. After ultrasonic treatment for 15 minutes, stir at 600 rpm for 3 hours. Centrifuge at 7800 rpm for 15 minutes. Discard the supernatant and collect the white precipitate in the lower layer. Repeat the above process three times. , dry the collected lower white precipitate to obtain purified metal nano-zinc oxide.

S2. Hydroxylation of metal nanooxides:

Take the above purified metal nano-zinc oxide, disperse it in 60 mL of a mixed solution of 1M H ₃ PO ₄ and 1M HCl, ultrasonicate for 20 minutes, stir and react at 500 rpm at 37°C for 24 hours, wait for natural cooling to room temperature, and let it settle for 30 minutes. Discard the supernatant, add tetrahydrofuran solution, adjust the pH of the system to 5, and let it settle for another 30 minutes to collect the lower white precipitate to obtain surface hydroxylated metal nanooxides.

S3. Preparation of organic-inorganic hybrid resin:

Disperse 2.0g of the above-mentioned surface hydroxylated metal nano-zinc oxide in 15mL of ethanol and methanol (volume ratio: 1:1) mixed solution, and add 2.0g of sulfur-containing resin formula 1-2 (Shanghai Yuyuan Pharmaceutical Technology Co., Ltd. ), ultrasonically disperse for 20 min, stir for 0.7 h at 25°C and 650 rpm, filter to obtain a clear and transparent solution, and rotary evaporate to remove the solvent to obtain an organic-inorganic hybrid resin.

S4. Preparation of high refractive composite materials:

Add 3% TPO photoinitiator of the total weight of the organic-inorganic hybrid resin to the organic-inorganic hybrid resin obtained in S3, stir evenly, and apply it to the surface of the glass substrate and then irradiate it with 100mW/cm ² ultraviolet light After curing for 30 seconds, a high-refractive composite material with a refractive index of 1.71 and a transmittance of 97.5% was obtained.

Example 2

A method for preparing a high refractive index composite material based on sulfur-containing resin:

S1. Purification of metal nanooxides:

Take 3.0 g of metal nano-titanium oxide and disperse it in 60 mL of absolute ethanol. Repeat the ultrasonic and centrifugal cleaning work described in Example 1 4 times, and dry the collected lower white precipitate to obtain purified metal nano-oxide.

S2. Hydroxylation of metal nanooxides:

Take the above-purified metal nanotitanium oxide and disperse it in 60 mL of 1M HNO ₃ solution. After ultrasonic treatment for 30 minutes, heat and stir at 45°C for 28 hours. After naturally cooling to room temperature, let it settle for 40 minutes, discard the supernatant, add tetrahydrofuran solution to adjust the pH of the system to 6, and let it settle for another 30 minutes to collect the lower white precipitate to obtain surface hydroxylated metal nanooxides.

As shown in Figure 1, in the infrared spectrum, the hydroxyl peak (3600-3015cm ^-1 in the figure) of metal nanoparticles after acid treatment increases significantly. The acid treatment has an obvious surface modification effect on metal nanoparticles, and the surface hydroxyl groups Chemical modification effectively improves the dispersion of nanoparticles in various solvents.

S3. Preparation of organic-inorganic hybrid resin:

Take 2.5g of the above-mentioned surface hydroxylated metal titanium oxide nanoparticles and disperse it in 10mL of ethanol and methanol (volume ratio is 1:2) mixed solution, add 2.0g of sulfur-containing resin, and ultrasonic for 20min Formula 2-2 (Shanghai Yuyuan Pharmaceutical Technology Co., Ltd.), ultrasonic dispersion for 20 min, stirring for 0.7 h at 25°C and 600 rpm, filtered to obtain a clear and transparent solution, and the solvent was removed by rotary evaporation to obtain an organic-inorganic hybrid resin.

S4. Preparation of high refractive composite materials:

Add 3% TPO photoinitiator based on the total weight of the organic-inorganic hybrid resin to the organic-inorganic hybrid resin obtained in S3, stir evenly, and apply 100mW/cm ² ultraviolet light to the surface of the glass substrate. After 30 seconds of irradiation and curing, a high-refractive composite material with a refractive index of 1.77 and a transmittance of 98.0% was obtained.

Example 3

A method for preparing a high refractive index composite material based on sulfur-containing resin:

S1. Purification of metal nanooxides:

Take 3.0g of metal nano-alumina, disperse it in 60 mL of absolute ethanol, repeat the ethanol dispersion, ultrasonic, and centrifugal cleaning work described in Example 1 5 times, and dry the collected lower white precipitate to obtain purified metal nano-alumina. aluminum oxide.

S2. Hydroxylation of metal nanooxides:

Dissolve 1.6g NaOH in 10mL deionized water, heat and stir at 50°C for 10min. And drop in 5.1 mL of 30% concentration H ₂ O ₂ (0.4 M) to form a mixed solution.

Take the above-mentioned purified metal nano-alumina, disperse it in the above-mentioned mixed aqueous solution of sodium hydroxide and hydrogen peroxide, conduct ultrasonic treatment for 30 minutes, and stir for 18 hours at 45°C.

After natural cooling, let it settle for 30 minutes, discard the supernatant, and collect the alkali-treated alumina nanoparticles in the lower layer.

The infrared spectrum is shown in Figure 2. The hydroxyl peak (3678-3030 cm ^-1 in the figure) of alumina nanoparticles after alkali treatment increases significantly, indicating that alkali treatment has an obvious surface modification effect on metal nanoparticles.

Redisperse the particles in 30 mL of 1M HNO ₃ solution, stir the reaction at 600 rpm for 24 hours at room temperature, let it settle for 50 minutes, discard the supernatant, add tetrahydrofuran solution to adjust the system pH = 5, and let it settle for 30 minutes to collect the hydroxylated metal Alumina nanoparticle precipitates. The infrared spectrum is shown in Figure 3. The hydroxyl peak of metal nanoparticles (3680-3050 cm ^-1 in the figure) increases significantly after acid and alkali treatment. The mixed acid and alkali treatment has an obvious surface modification effect on the metal nanoparticles.

S3. Preparation of organic-inorganic hybrid resin:

Disperse 2.0g of the above-mentioned surface hydroxylated metal aluminum oxide nanoparticles in 3mL of benzyl alcohol, ultrasonic for 10 minutes, add 1.5g of sulfur-containing resin formula 3-2 (Shangfluoro Technology), ultrasonic and disperse for 15 minutes, at 25°C, 650rpm Stir under the conditions for 0.7h, filter, and obtain a clear and transparent solution, which is the organic-inorganic hybrid resin.

S4. Preparation of high refractive composite materials:

Add 3% TPO photoinitiator of the total weight of the organic-inorganic hybrid resin to the organic-inorganic hybrid resin obtained in S3, stir evenly, and apply it to the surface of the glass substrate and then irradiate it with 100mW/cm ² ultraviolet light After curing for 30 seconds, a cured composite film with a refractive index of 1.68 and a transmittance of 97.5% was obtained.

Example 4

A method for preparing a high refractive index composite material based on sulfur-containing resin:

S1. Purification of metal nanooxides:

Take 3.0g of metal nano-metal zirconia, disperse it in 60 mL of absolute ethanol, repeat the ethanol dispersion, ultrasonic, and centrifugal cleaning work described in Example 1 three times, and dry the collected lower white precipitate to obtain purified metal nanoparticles. Zirconia.

S2. Hydroxylation of metal nanooxides:

Take the above purified metal nano-zirconia, disperse it in 1M HNO ₃ solution, ultrasonic treatment for 30 minutes, and then heat and stir at 45°C for 48 hours. After naturally cooling to room temperature, let it settle for 30 minutes, discard the supernatant, and add tetrahydrofuran solution to adjust the pH of the system to 4. The white precipitate of metal zirconium oxide nanoparticles after hydroxylation treatment was collected after settling for 40 minutes.

S3. Preparation of organic-inorganic hybrid resin:

Disperse 2.0g of surface hydroxylated metal zirconia nanoparticles in 2mL of N,N-dimethylformamide solution, ultrasonically disperse for 5 minutes, and add 1.0g of sulfur-containing resin formula 2-3 (Shanghai Baishun Biotechnology Co., Ltd. ), ultrasonically disperse for 10 minutes, stir for 0.7h at 25°C and 650rpm, filter, and obtain a clear and transparent solution, which is the organic-inorganic hybrid resin.

S4. Preparation of high refractive composite materials:

Add 5% TPO photoinitiator of the total weight of the organic-inorganic hybrid resin to the organic-inorganic hybrid resin obtained in S3, stir evenly, and apply it to the surface of the glass substrate and then irradiate it with 100mW/cm ² ultraviolet light After curing for 30 seconds, a cured composite film with a refractive index of 1.73 and a transmittance of 98% was obtained.

The organic-inorganic hybrid resin in this patent is soluble in a variety of solvents, and high-boiling point solvents with good solubility are introduced into the composite system, which effectively solves the problem of viscosity increase and increases the upper limit of doping of metal nanoparticles.

The above descriptions are only specific embodiments of the present invention, enabling those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be practiced in other embodiments without departing from the spirit or scope of the invention.

It should be understood that the present invention is not limited to what has been described above, and various modifications and changes can be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (5)

1. A method for preparing a high refractive index composite material based on sulfur-containing resin, which is characterized in that it includes the following steps: S1. Purification of metal nanooxides. The metal nanooxides in S1 include at least one of zirconium oxide, titanium oxide, nickel oxide, zinc oxide, and aluminum oxide; the specific steps for the purification of metal nanooxides in S1 The steps are: disperse the metal nanooxide in absolute ethanol, ultrasonic for 10 to 20 minutes, then stir at 500 to 700 rpm for 1 to 3 hours, centrifuge, remove the white precipitate, repeat the above process 2 to 3 times, and dry, that is Purified metal nanooxides are obtained, and the weight ratio of the metal nanooxides to ethanol is 1: (10-40); S2. Disperse the purified metal nanooxide obtained in S1 in the solution to perform a hydroxylation reaction to obtain surface hydroxylated metal nanooxide; S3. Compound the surface hydroxylated metal nanooxide obtained in S2 with the sulfur-containing resin to obtain an organic-inorganic hybrid resin; S4. Add a photoinitiator to the organic-inorganic hybrid resin obtained in S3, and solidify it to form a film through ultraviolet light irradiation to obtain a high refractive index composite material, wherein the sulfur-containing resin is one of the compounds represented by formulas 1 to 2. at least one of: X ₂ -R ₄ -SH; Formula 1 In the formula 1, R ₄ is a substituted or unsubstituted C1 to C30 branched or linear alkylene group, a substituted or unsubstituted C1 to C30 alkylene ether group, a substituted or unsubstituted C1 to C30 alkylene ether group, Substituted C1 to C20 secondary or tertiary amino groups, Any one of them, where * is the connection site; X ₁ and X ₂ are each independently any one of formulas 3 to 5: Among them, * is the connection site, Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group; In the formula 2, W is a single bond, any one of S or O; R ₅ and R ₆ are each independently a single bond, a substituted or unsubstituted C1 to C30 branched or linear alkylene group, substituted or unsubstituted C1 to C30 alkylene ether group, substituted or unsubstituted C7 to C30 aryl alkylene group, substituted or unsubstituted C1 to C30 arylene group , Any one of them; where L ₁ is a single bond, a branched or linear alkylene group from C1 to C30 substituted or unsubstituted by hydroxyl; L ₂ is hydrogen or R ₇ and R ₈ are each independently hydrogen, substituted or unsubstituted C1 to C30 branched or linear alkyl, Any one of them, the compound of Formula 1 is represented by at least one of Formula 1-1 to Formula 1-3; The compound of Formula 2 is represented by at least one of Formula 2-1 to Formula 2-3; 2. The preparation method according to claim 1, characterized in that, the metal nanooxides in S2 are dispersed in the solution to perform the hydroxylation reaction, specifically: the purified metal nanooxides obtained in S1 are dispersed in the solution. Medium, ultrasonicate for 20 to 50 minutes, then stir at 300 to 650 rpm for 10 to 30 hours at 25°C to 50°C, let stand for 30 to 60 minutes, then discard the supernatant, add tetrahydrofuran to adjust the pH to 4 to 6, and let stand to settle. , the white precipitate in the lower layer is the metal nanooxide after surface hydroxylation; among them, the purified metal nanooxide is dispersed in an acid solution or an alkali solution to perform a hydroxylation reaction, or the purified metal nanooxide is first Dispersed in an alkaline solution and then dispersed in an acid solution to perform hydroxylation reaction. 3. The preparation method according to claim 1, characterized in that, the S3 specifically includes: dispersing the surface hydroxylated metal nanooxide obtained in S2 in a solvent, adding the above-mentioned sulfur-containing resin, and ultrasonic dispersion for 10 ~30min, stir for 0.5~2h at 25°C~55°C, 500~700rpm, filter, obtain a clear and transparent solution, and rotary evaporate to remove the solvent to obtain organic-inorganic hybrid resin. 4. The preparation method according to claim 3, characterized in that the solvent in the S3 is water, methanol, ethanol, propanol, butanol, toluene, benzyl alcohol, phenol, acetonitrile, oleic acid, oleylamine, hexane At least one of acid, octanoic acid, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and acetone. 5. The preparation method according to claim 1, characterized in that the specific steps of S4 are: adding a photoinitiator to the organic-inorganic hybrid resin obtained in S3, stirring evenly, and coating it on the surface of the glass substrate , through 20-120 mW/cm ² ultraviolet light irradiation and curing for 10-100 seconds, a high-refractive composite material is obtained. The high-refractive composite material has a refractive index of 1.500-1.800, a curing rate of 90%-97%, and a light transmittance of 95 %~99%.