阅读说明：本技术 一种高折光树脂及其制备方法和应用 (High-refraction resin and preparation method and application thereof ) 是由 廖恒 左洪亮 刘阳 黄杰 于 2021-05-27 设计创作，主要内容包括：本发明涉及树脂的合成,更具体地,本发明涉及一种高折光树脂及其制备方法和应用。所述树脂的制备原料包括端羟基硅油、烷基醇铪和羟基化合物。本发明提供一种树脂,具有有机铪、硅油和R-(2)的结构,发明人发现,通过铪对硅油,尤其是含有芳基的硅油进行改性,可赋予该树脂高的折光率,用于制备具有高折光率的透明膜,有望作为主体成分制备各种高折光系数材料,应用于各种光学镜头,光通讯器件,光电子器件,电子显示屏,LED发光元件封装,OLED器件折光系数匹配等光学材料中。(The invention relates to synthesis of resin, in particular to high-refraction resin and a preparation method and application thereof. The preparation raw materials of the resin comprise hydroxyl-terminated silicone oil, hafnium alkyl alcohol and a hydroxyl compound. The present invention provides a resin having organohafnium, silicone oil and R 2 The inventor finds that the resin can be endowed with high refractive index by modifying the silicone oil, particularly the aryl-containing silicone oil, through hafnium, is used for preparing a transparent film with high refractive index, is expected to be used as a main component for preparing various high-refractive-index materials, and is applied to optical materials such as various optical lenses, optical communication devices, optoelectronic devices, electronic display screens, LED light-emitting element packaging, OLED device refractive index matching and the like.)

1. A high refractive resin, characterized in that the structural formula of the resin is shown as formula (1):

R₁is a linear alkylene group and/or a branched alkylene group, R₂Is alkyl or an alkyl derivative, R₃One or more selected from alkyl, alkoxy and aryl, R₄Selected from alkyl, alkoxy, arylOne or more of (a);

x is 5 to 50, and y is 10 to 50.

2. The high refractive resin of claim 1, wherein R is₁Is C1-C10 straight chain alkylene and/or C1-C10 branched chain alkylene.

3. The high refractive resin according to claim 1, wherein x is 10 to 30 and y is 15 to 30.

4. The high refractive resin of claim 1, wherein hydrogen atoms in the alkyl groups of the alkyl derivatives are substituted with vinyl, acrylate, methacrylate, or isocyanate groups.

5. The high refractive resin according to any one of claims 1 to 4, wherein the preparation raw materials of the resin comprise hydroxyl-terminated silicone oil, hafnium alkyl alcohol and hydroxyl compound, and the molar ratio is 1: (2-2.5): (6-6.5).

6. The high refractive resin of claim 5, wherein the hydroxyl terminated silicone oil has a formula of formula (2):

R₁is a linear and/or branched alkyl radical, R₃One or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl;

x is 5 to 50, and y is 10 to 50.

7. The high refractive resin of claim 5, wherein the hydroxy compound has the formula R₂OH，R₂Is an alkyl group or an alkyl derivative.

8. The high refractive resin of claim 6, wherein the hydroxyl-terminated silicone oil is prepared from a raw material comprising a hydrogen-terminated silicone oil and an alkenyl alcohol, and the hydrogen-terminated silicone oil has a structural formula shown in formula (3):

R₃one or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl; x is 5-50, y is 10-50;

the structural formula of the alkenyl alcohol is shown as a formula (4):

R₁is a straight chain alkyl and/or branched alkyl.

9. A method for producing a high refractive resin according to any one of claims 1 to 8, comprising:

and (3) reacting hydroxyl-terminated silicone oil with alkyl alcohol hafnium in a solvent, adding hydroxyl acrylate for reaction, and drying to obtain the high-refractive-index resin.

10. Use of the high refractive resin according to any one of claims 1 to 8 for optical materials.

Technical Field

The invention relates to synthesis of resin, in particular to high-refraction resin and a preparation method and application thereof.

Background

With the development of science and technology, polymer optical materials are applied more and more widely to materials such as optical disks, optical fibers, building materials, resin lenses, precision lenses, antireflection coatings and the like. High refractive index optical resins are an important research direction for optical materials, and can further reduce the curvature and thickness of elements, reduce the weight without affecting the refractive power thereof, and enable miniaturization and weight reduction of optical instruments.

When the high-refractive-index coating is coated on the surface of the high-refractive-index optical resin, various defects of poor wear resistance, solvent resistance, moisture absorption resistance and the like can be made up, and meanwhile, the loss of light transmittance can be avoided. However, the main optical resin at present is acrylate resin, and the cured coating film has a high refractive index, so that a new optical resin needs to be developed.

Disclosure of Invention

In order to solve the above problems, the first aspect of the present invention provides a high refractive resin having a structural formula represented by formula (1):

R₁is a linear alkylene group and/or a branched alkylene group, R₂Is alkyl or an alkyl derivative, R₃One or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl;

x is 5 to 50, and y is 10 to 50.

As a preferred embodiment of the present invention, R₁Is C1-C10 straight chain alkylene and/or C1-C10 branched chain alkylene.

As a preferable technical scheme of the invention, x is 10-30, and y is 15-30.

In a preferred embodiment of the present invention, the hydrogen atom in the alkyl group of the alkyl derivative is substituted with a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group.

As a preferable technical scheme of the invention, the preparation raw materials of the resin comprise hydroxyl-terminated silicone oil, hafnium alkyl alcohol and a hydroxyl compound, and the molar ratio is 1: (2-2.5): (6-6.5).

As a preferable technical scheme, the structural formula of the hydroxyl-terminated silicone oil is shown as a formula (2):

R₁is a linear and/or branched alkyl radical, R₃One or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl;

x is 5 to 50, and y is 10 to 50.

As a preferable technical scheme of the invention, the structural formula of the hydroxyl compound is R₂OH，R₂Is an alkyl group or an alkyl derivative.

As a preferable technical scheme of the invention, the preparation raw materials of the hydroxyl-terminated silicone oil comprise hydrogen-terminated silicone oil and alkenyl alcohol, and the structural formula of the hydrogen-terminated silicone oil is shown as the formula (3):

R₃one or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl; x is 5-50, y is 10-50;

the structural formula of the alkenyl alcohol is shown as a formula (4):

R₁is a straight chain alkyl and/or branched alkyl.

The second aspect of the present invention provides a method for preparing the high refractive resin, comprising:

and (3) reacting hydroxyl-terminated silicone oil with alkyl alcohol hafnium in a solvent, adding hydroxyl acrylate for reaction, and drying to obtain the high-refractive-index resin.

The third aspect of the invention provides a use of the high refractive resin for optical materials.

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

(1) the present invention provides a resin having organohafnium, silicone oil and R₂The inventor finds that the resin can be endowed with high refractive index by modifying the silicone oil, particularly the aryl-containing silicone oil, through hafnium, is used for preparing a transparent film with high refractive index, is expected to be used as a main component for preparing various high-refractive-index materials, and is applied to optical materials such as various optical lenses, optical communication devices, optoelectronic devices, electronic display screens, LED light-emitting element packaging, OLED device refractive index matching and the like.

(2) In addition, the invention discovers that the monomer number of the silicone oil in the resin and the alkyl number between the silicone oil and Hf also have influence on the refractive index of the resin and the dispersion compatibility between the resin and other resins, such as acrylic resin and polyurethane resin, and the structure of the resin provided by the invention is used for promoting the improvement of the refractive index and simultaneously being beneficial to the mixing and compatibility between the resin and other resins.

(3) The inventor finds that the operation is complicated because the hydrogen-terminated silicone oil and the alkenyl alcohol are reacted under the action of the catalyst in the solvent environment, and the subsequent problems of solvent removal and the like exist, but the inventor finds that the hydroxyl-terminated silicone oil can be directly reacted at a proper temperature by controlling the polymerization degree of the silicone oil and the chain length of the alkenyl alcohol, the preparation method is simplified, and the obtained hydroxyl-terminated silicone oil has high yield and purity.

(4) In addition, the inventor finds that in the preparation process of the resin, after the hydroxyl-terminated silicone oil is firstly reacted with the hafnium alkyl alcohol, the two ends of the silicone oil are connected with the hafnium alkyl, then the hydroxyl compound containing the reaction groups such as vinyl, propenyl, isocyanate and the like is added, so that the reaction groups can be connected into the resin, the resin is convenient to cure, and the resin is used for optical materials.

Drawings

FIG. 1 is an infrared image of the resin and HEA (hydroxyethyl acrylate) provided in examples 2 and 3.

FIG. 2 shows the refractive indexes of examples 4 to 7 and comparative example 1 under different monochromatic lights.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.

The first aspect of the present invention provides a high refractive resin having a structural formula represented by formula (1):

R₁is a linear alkylene group and/or a branched alkylene group, preferably a C1-C10 linear alkylene group and/or a C1-C10 branched alkylene group, more preferably a C1-C5 linear alkylene group and/or a C1-C5 branched alkylene group, and there may be mentioned methylene, ethylene, butylene and isobutyl.

R₂Is an alkyl group or an alkyl derivative, preferably, hydrogen atoms in the alkyl group of the alkyl derivative are substituted by a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group, more preferably, 1-10 hydrogen atoms in the alkyl group of the alkyl derivative are substituted by a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group, more preferably, 1-5 hydrogen atoms in the alkyl group of the alkyl derivative are substituted by a vinyl group, an acrylate group (CH)₃CH₂COO-), methacrylate group (CH)₃CHCH₃COO-), or an isocyanate group, more preferably, R₂Is a C1-C20 alkyl or C1-C20 alkyl derivative, more preferably, R₂Is a C1-C10 alkyl or C1-C10 alkyl derivative, more preferably R₂C1-C5 alkyl or C1-C5 alkyl derivatives, which may be mentioned, methyl, ethyl, isopropyl, dodecyl, propyl, vinylmethyl, terminal acrylate ethyl,Terminal methacrylate ethyl groups, terminal isocyanatoethyl groups, isocyanatomethyl groups, and the like.

R₃One or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl; preferably, R₃One or more selected from C1-C5 alkyl, C1-C5 alkoxy and aryl, R₄One or more selected from C1-C5 alkyl, C1-C5 alkoxy and aryl, such as methyl, ethyl, phenyl, methoxy, ethoxy, naphthyl and phenyl, preferably R₃Is aryl, R₄Is an alkyl and/or alkoxy group.

x is 5 to 50, and there may be mentioned 10, 12, 15, 17, 19, 20, 25, 30, 35, 40, 45 and 50, preferably, x is 10 to 30, more preferably, x is 15 to 20.

y is 10 to 50, and there may be mentioned 10, 15, 17, 20, 21, 23, 24, 25, 30, 35, 40, 45 and 50, preferably, y is 15 to 30, more preferably, y is 15 to 20.

In a preferred embodiment, the resin of the present invention is prepared from raw materials comprising hydroxyl-terminated silicone oil, hafnium alkyl alcohol and hydroxyl compound, wherein the molar ratio is 1: (2-2.5): (6 to 6.5) examples of the solvent include, 1: 2: 6. 1: 2.1: 6.2, 1: 2.2: 6.4, 1: 2.5: 6.5, preferably, 1: (2-2.2): (6-6.5).

Hydroxyl-terminated silicone oil

In one embodiment, the hydroxyl-terminated silicone oil of the present invention has a structural formula as shown in formula (2):

R₁is a linear and/or branched alkyl radical, R₃One or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl;

x is 5 to 50, and y is 10 to 50.

Preferably, the raw materials for preparing the hydroxyl-terminated silicone oil comprise hydrogen-terminated silicone oil and alkenyl alcohol, and the structural formula of the hydrogen-terminated silicone oil is shown as formula (3):

R₃one or more selected from alkyl, alkoxy and aryl, R₄One or more selected from alkyl, alkoxy and aryl; x is 5-50, y is 10-50;

the structural formula of the alkenyl alcohol is shown as a formula (4):

R₁are straight chain and/or branched alkyl groups, examples of which include, but are not limited to, propenol, butenol, isobutenol, pentenol, isopentenol.

More preferably, the molar ratio of hydrogen-terminated silicone oil to alkenyl alcohol is 1: (2 to 2.5) examples of the solvent include, 1: 2. 1: 2.1, 1: 2.2, 1: 2.3, 1: 2.4, 1: 2.5, preferably 1: (2-2.2), more preferably 1: (2-2.1).

Further preferably, the preparation method of the hydroxyl-terminated silicone oil comprises the following steps: and (3) reacting the hydrogen-terminated silicone oil with the alkenyl alcohol under the action of a catalyst to obtain the hydroxyl-terminated silicone oil. More preferably, the reaction temperature of the present invention is 90-120 ℃, and can be enumerated by 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃. The reaction time of the hydroxyl-terminated silicone oil can be determined according to a sodium hydroxide titration mode, and is not particularly limited, and in one embodiment, the reaction time is 8-12 hours, and can be enumerated by 8 hours, 9 hours, 10 hours, 11 hours and 12 hours.

The sodium hydroxide titration method comprises the following steps: taking a mixture of hydrogen-terminated silicone oil and alkenyl alcohol which react under a catalyst, adding the mixture into an acetone solution, titrating by using a 1N sodium hydroxide solution, and finishing the reaction when the taken reaction solution has no bubbles (hydrogen is released because a silicon-hydrogen bond can react with the sodium hydroxide solution).

In a preferred embodiment, the preparation method of the hydroxyl-terminated silicone oil comprises the following steps: heating hydrogen-terminated silicone oil to 90-120 ℃, dropwise adding a catalyst and mixing with alkene alcohol, and reacting to obtain the hydroxyl-terminated silicone oil. The catalyst of the present invention is not specifically limited, and is a resin catalyst in the art, and chloroplatinic acid, Karstedt platinum catalyst, Speier catalyst, RhCl (PPh) catalyst are exemplified₃)₃In one embodiment, the catalyst comprises 5 to 50ppm, by weight, of the combined weight of hydrogen-terminated silicone oil and alkenyl alcohol, such as 5ppm, 8ppm, 10ppm, 15ppm, 20ppm, 25ppm、30ppm、35ppm、40ppm、45ppm、50ppm。

Alkyl alcohol hafnium

In the present invention, specific types of the hafnium alkyl alcohol are not limited, and there may be mentioned hafnium ethoxide, hafnium tert-butoxide, hafnium isopropoxide, hafnium n-propoxide and hafnium n-butoxide.

Hydroxy compounds

In one embodiment, the hydroxy compound of the present invention has the formula R₂OH，R₂Is an alkyl group or an alkyl derivative. Preferably, hydrogen atoms in the alkyl group of the alkyl derivative are substituted by a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group, more preferably, 1 to 10 hydrogen atoms in the alkyl group of the alkyl derivative are substituted by a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group, and more preferably, 1 to 5 hydrogen atoms in the alkyl group of the alkyl derivative are substituted by a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group.

As examples of the hydroxyl compound, there may be mentioned hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1, 2-propanediol 2-methyl-2- (meth) acrylate, 2-hydroxy-1, 3-propanediol 2- (meth) acrylate or 2, 3-dihydroxypropane (meth) acrylate, pentaerythritol tri (meth) acrylate, methanol, ethanol, propanol, vinyl methanol, vinyl propanol, isocyanato methanol, isocyanato butanol.

The second aspect of the present invention provides a method for producing the high refractive resin as described above, comprising:

and (3) reacting hydroxyl-terminated silicone oil with alkyl alcohol hafnium in a solvent, adding hydroxyl acrylate for reaction, and drying to obtain the high-refractive-index resin. In the preparation method of the high refractive resin, the reaction temperature is 60-90 ℃, preferably 60-80 ℃, and can be enumerated as 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃.

In one embodiment, the method for preparing a high refractive resin according to the present invention comprises: and (3) reacting the hydroxyl-terminated silicone oil and the alkyl alcohol hafnium in the solvent for 3-8 hours, adding hydroxyl acrylate for reaction for 2-4 hours, and drying to obtain the high-refraction resin. Preferably, the method for preparing the high refractive resin according to the present invention comprises: and (3) reacting the hydroxyl-terminated silicone oil and the alkyl alcohol hafnium in the solvent for 4-6 hours, adding hydroxyl acrylate for reaction for 2-4 hours, and drying to obtain the high-refraction resin.

More preferably, the method for preparing the high refractive resin of the present invention comprises:

and (3) reacting hydroxyl-terminated silicone oil and alkyl alcohol hafnium in a solvent, adding hydroxyl acrylate and a polymerization inhibitor for reaction, and drying to obtain the high-refraction resin.

The solvent is not particularly limited, and toluene, xylene, tetrahydrofuran, ethyl acetate, and the like can be mentioned. The polymerization inhibitor is not particularly limited, and examples thereof include p-hydroxyanisole, methylhydroquinone, phenothiazine and dibutylhydroxytoluene. In one embodiment, the polymerization inhibitor is 0.1 to 1% by weight, for example, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, and preferably 0.1 to 0.5% by weight, based on the total weight of the hydroxyl-terminated silicone oil, the hafnium alkyl alcohol, and the hydroxy acrylate.

In the present invention, drying is carried out after the reaction in order to remove the solvent and the alkyl alcohol produced, and examples of the drying include distillation under reduced pressure, spray drying, vacuum drying and the like. The inventors have found that the reaction is also proceeding during the removal of the solvent and the alkyl alcohol formed, and that the reaction is terminated when no liquid comes out.

The third aspect of the present invention provides a use of the high refractive resin as described above for an optical material. Such as various optical lenses, optical communication devices, optoelectronic devices, electronic display screens, LED light-emitting element packages, OLED devices, and the like.

Examples

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

Example 1 provides a hydroxyl-terminated silicone oil

This example provides a hydroxyl terminated silicone oil A₁The structural formula is as follows:

x average 18, y average 22.

The embodiment also provides a preparation method of the hydroxyl terminated silicone oil, which comprises the following steps: adding 550g of hydrogen-terminated silicone oil (x average value 18 and y average value 22) into a 1L four-neck round-bottom flask, heating to 100 ℃, keeping the temperature at 100 ℃, dropwise adding allyl alcohol (0.005 g of Karstedt Pt catalyst and 12.54g of allyl alcohol) premixed with Karstedt Pt catalyst, after dropwise adding, enabling the reaction liquid to be in a turbid state, keeping the temperature at 90 ℃ for continuing to react for 3 hours, gradually enabling the reaction liquid to become clear and transparent, putting 5g of the reaction liquid into an acetone solution, titrating with a 1N sodium hydroxide solution, when the taken-out reaction liquid has no bubbles (hydrogen is released due to the fact that silicon-hydrogen bonds can react with the sodium hydroxide solution), and obtaining hydroxyl-terminated silicone oil A after the reaction is finished₁。

The structural formula of the hydrogen-terminated silicone oil is shown as follows:

x average 18, y average 22.

Examples 2 to 3 provide an organohafnium-modified resin

Example 2

This example provides an organohafnium modified bis-phenyl silicone acrylate resin, whose structural formula is M₁Shown in the figure:

x average 18, y average 22.

This example also provides a method for preparing the above-mentioned organohafnium-modified bis-phenyl silicone oil acrylate resin, comprising: hydroxyl-terminated silicone oil A1550 g was placed in A1L four-necked round-bottomed flask, 100g of toluene solution was added, stirring was carried out, 88.80g of hafnium isopropoxide was added, after reaction at 80 ℃ for 5 hours, 73.86g of hydroxyethyl acrylate and 0.10g of p-hydroxyanisole were added, stirring was carried out at 80 ℃ for 3 hours, vacuum distillation was carried out after that, vacuum distillation was carried out while reaction was carried out to evaporate off the isopropanol and the solution toluene produced by the reaction, when no liquid flowed out from the receiving flask at the tail, the reaction was terminated, and discharging was carried out to obtain a clear and transparent organohafnium-modified bis-phenyl silicone oil acrylate resin M1 (as can be seen from FIG. 1, in infrared spectroscopy, there was no peak at a wavelength of 3450cm-1 indicating that the hydroxyl-terminated bis-phenyl silicone oil and hydroxyethyl acrylate were successfully bonded to the organohafnium), viscosity at 30 ℃ was 3000cps, and refractive index was 1.605.

Example 3

This example provides an organohafnium modified bis-phenyl silicone acrylate resin, whose structural formula is M₁Shown in the figure:

the average values of x 18, y 22,

this example also provides a method for preparing the above-mentioned organohafnium-modified bis-phenyl silicone oil acrylate resin, comprising: hydroxyl-terminated silicone oil A1550 g was placed in A1L four-necked round-bottomed flask, 100g of toluene solution was added, stirring was carried out, 99.84g of hafnium tert-butoxide was added, the mixture was placed at 80 ℃ for reaction for 5 hours, 189.75g of pentaerythritol triacrylate and 0.30g of p-hydroxyanisole were added, the mixture was placed at 80 ℃ for stirring for 3 hours, then distillation under reduced pressure was carried out, distillation under reduced pressure was carried out while reaction was carried out, the isopropanol and the solution toluene produced by the reaction were distilled off, when no liquid flowed out from the tail receiver, the reaction was terminated, and discharging was carried out, thus obtaining a clear and transparent organohafnium-modified bis-phenyl silicone oil acrylate resin M2 (as can be seen from FIG. 1, in infrared spectroscopy, there was no peak at wavelength of 3450cm-1, indicating that the hydroxyl-terminated bis-phenyl silicone oil and hydroxyethyl acrylate were successfully bonded to organohafnium), viscosity at 30 ℃ was 12000cps, and refractive index was 1.621.

Examples 4 to 7 and comparative example 1 provide an optical material

The raw materials for preparing the optical materials provided in examples 4 to 7 and comparative example 1 and the weight ratio thereof are shown in table 1. Wherein TPO (2,4, 6-trimethylbenzoyl-diphenylphosphine oxide) is used as a photoinitiator, and polyurethane acrylate resin CN 989NS (marked as B-605) is from Saedoma chemical Co.

TABLE 1

	Preparation of the starting Material
		Example 4	Resin M1: TPO ═ 1: 0.03
Example 5	Resin M2: TPO ═ 1: 0.03
		Example 6	Resin M1: urethane acrylate resin CN 989 NS: TPO ═ 0.5: 0.5: 0.03
Example 7	Resin M2: urethane acrylate resin CN 989 NS: TPO ═ 0.5: 0.5: 0.03
		Comparative example 1	Urethane acrylate resin CN 989 NS: TPO ═ 1: 0.03

For examples 4-7 and comparative example 1, the intensity of light passing through the optical fiber was 3000 mJ-cm^-2After the medium-pressure mercury lamp is irradiated and cured to form a film, the refractive indexes of different films under 400nm, 600nm, 800nm and 1600nm monochromatic light are measured by a Michelson interferometer, and the obtained result is shown in figure 2.

From FIG. 2, it is found that M₁、M₂The refractive indexes of the resins under different wavelength monochromatic light after being respectively cured into films or matched with CN 989NS for curing into films are all higher than that of the resins after being independently cured into films by CN 989NS, which shows that the organic hafnium modified resin can be used as a formula for curing into films and is expected to be applied to preparing transparent films with high refractive indexes.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.