CN113667128B - High-refraction resin and preparation method and application thereof - Google Patents
High-refraction resin and preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to the synthesis of resins, and more particularly, to a high refractive resin and a method for preparing the sameAnd applications. The preparation raw materials of the resin comprise hydroxyl-terminated silicone oil, hafnium alkyl alcohol and hydroxyl compound. The invention provides a resin, which comprises organohafnium, silicone oil and R 2 The inventor finds that the silicon oil, especially the silicon oil containing aryl, can be endowed with high refractive index by modifying the silicon 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 packages, OLED device refractive index matching and the like.
Description
Technical Field
The invention relates to synthesis of resin, in particular to high refractive resin, and a preparation method and application thereof.
Background
With the development of science and technology, polymer optical materials are increasingly used in materials such as optical discs, optical fibers, building materials, resin lenses, precision lenses, antireflection coatings and the like. The high refractive index optical resin is an important research direction of optical materials, can further reduce the curvature and thickness of the element, lighten the weight without affecting the refractive power thereof, and can miniaturize and lighten the optical instrument.
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 overcome, and meanwhile, the loss of light transmittance can be avoided. However, the main optical resin is acrylate resin, and the coating film obtained by curing is difficult to reach high refractive index, so that new optical resin needs to be developed.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a high refractive resin having a structural formula shown in formula (1):
R 1 is a linear alkylene and/or a branched alkylene, R 2 Is alkyl or alkyl derivative, R 3 One or more selected from alkyl, alkoxy and aryl, R 4 One or more selected from alkyl, alkoxy and aryl;
x is 5-50, y is 10-50.
As a preferable technical scheme of the invention, R 1 Is a C1-C10 linear alkylene group and/or a C1-C10 branched alkylene group.
As a preferable technical scheme of the invention, x is 10-30, and y is 15-30.
As 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 hydroxyl compound, and the molar ratio is 1: (2-2.5): (6-6.5).
As a preferable technical scheme of the invention, the structural formula of the hydroxyl-terminated silicone oil is shown as the formula (2):
R 1 is a linear alkyl and/or a branched alkyl, R 3 One or more selected from alkyl, alkoxy and aryl, R 4 One or more selected from alkyl, alkoxy and aryl;
x is 5-50, y is 10-50.
As a preferable technical scheme of the invention, the structural formula of the hydroxyl compound is R 2 OH，R 2 Is alkyl or 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):
R 3 one or more selected from alkyl, alkoxy and aryl, R 4 One 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 formula (4):
R 1 is a straight chain alkyl group and/or a branched chain alkyl group.
The second aspect of the present invention provides a method for preparing the high refractive resin, comprising:
and (3) after the hydroxyl-terminated silicone oil and the hafnium alkyl alcohol react in a solvent, adding hydroxy acrylic ester for reaction, and drying to obtain the high refractive resin.
In a third aspect, the present invention provides the use of the high refractive resin for optical materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a resin, which comprises organohafnium, silicone oil and R 2 The inventor finds that the silicon oil, especially the silicon oil containing aryl, can be endowed with high refractive index by modifying the silicon 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 packages, OLED device refractive index matching and the like.
(2) In addition, the present invention has found that the number of monomers of silicone oil in the resin, and the number of alkyl groups between silicone oil and Hf also have an effect on the refractive properties of the resin, and the dispersion compatibility with other resins such as acrylic resins, polyurethane resins, and by using the structure of the resin provided by the present invention, the mixing and compatibility with other resins are facilitated while the improvement of refractive properties is promoted.
(3) The inventor finds that the general hydroxyl-terminated silicone oil is characterized in that the hydroxyl-terminated silicone oil and alkenyl alcohol react under the action of a catalyst in a solvent environment, the subsequent problems of solvent removal and the like exist, the operation is complex, and the inventor finds that the hydroxyl-terminated silicone oil can directly react at a proper temperature by controlling the polymerization degree of the silicone oil and the chain length of the alkenyl alcohol, so that 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, hydroxyl-terminated silicone oil reacts with hafnium alkyl firstly, so that after two ends of the silicone oil are connected with organic hafnium, hydroxyl compounds containing vinyl, propenyl, isocyanate groups and other reactive groups are added, the reactive groups can be connected into the resin, subsequent curing is facilitated, the resin is used for optical materials, one or more reactive groups can be introduced, the cured resin has high refractive index, and the obtained coating film has smooth surface and high attachment rate.
Drawings
FIG. 1 is an infrared plot of the resins and HEA (hydroxyethyl acrylate) provided in examples 2, 3.
FIG. 2 shows refractive indices of examples 4 to 7 and comparative example 1 under different monochromatic light.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included. 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, definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, 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, step, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list 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 ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
Approximating language, in the specification and claims, may be applied to modify an amount that would not limit the invention to the specific amount, but would include an acceptable portion that would be close to the amount without resulting in a change in the basic function involved. Accordingly, the modification of a numerical value with "about", "about" or the like means that the present invention is not limited to the precise numerical value. In some examples, the approximating language may correspond to the precision of an instrument for measuring the value. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
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 shown in formula (1):
R 1 the straight-chain alkylene and/or branched alkylene is preferably a C1-C10 straight-chain alkylene and/or a C1-C10 branched alkylene, more preferably a C1-C5 straight-chain alkylene and/or a C1-C5 branched alkylene, and examples thereof include methylene, ethylene, butylene and isobutyl.
R 2 Is an alkyl group or an alkyl derivative, preferably, hydrogen atoms in an alkyl group of the alkyl derivative are substituted with a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group, more preferably, 1 to 10 hydrogen atoms in an alkyl group of the alkyl derivative are substituted with a vinyl group, an acrylate group, a methacrylate group, or an isocyanate group, still more preferably, 1 to 5 hydrogen atoms in an alkyl group of the alkyl derivative are substituted with a vinyl group, an acrylate group (CH 3 CH 2 COO-), methacrylate group (CH) 3 CHCH 3 COO-), or isocyanate groups, more preferably R 2 Is C1-C20 alkyl or C1-C20 alkyl derivative, more preferably R 2 Is C1-C10 alkyl or C1-C10 alkyl derivative, more preferably R 2 Examples of the alkyl group include a C1-C5 alkyl group and a C1-C5 alkyl derivative, and examples of the alkyl group include methyl group and ethyl groupIsopropyl, dodecyl, propyl, vinyl methyl, terminal acrylate ethyl,
Terminal methacrylate ethyl, terminal isocyanate ethyl, isocyanate methyl, and the like.
R 3 One or more selected from alkyl, alkoxy and aryl, R 4 One or more selected from alkyl, alkoxy and aryl; preferably, R 3 One or more selected from C1-C5 alkyl, C1-C5 alkoxy and aryl, R 4 One or more selected from C1-C5 alkyl, C1-C5 alkoxy, and aryl, such as methyl, ethyl, phenyl, methoxy, ethoxy, naphthyl, and phenylthio, preferably R 3 Is aryl, R 4 Is alkyl and/or alkoxy.
Examples of x are 5 to 50, 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.
Examples of y are 10 to 50, 10, 15, 17, 20, 21, 23, 24, 25, 30, 35, 40, 45, and 50, preferably y is 15 to 30, and more preferably y is 15 to 20.
In a preferred embodiment, the resin of the present invention is prepared from the raw materials of hydroxyl-terminated silicone oil, hafnium alkyl alcohol and hydroxyl compound in a molar ratio of 1: (2-2.5): (6 to 6.5), there may be mentioned 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 structural formula of the hydroxyl-terminated silicone oil is shown as formula (2):
R 1 is a linear alkyl and/or a branched alkyl, R 3 Selected from alkyl, alkoxy, arylOne or more of R 4 One or more selected from alkyl, alkoxy and aryl;
x is 5-50, y is 10-50.
Preferably, the preparation raw materials of the hydroxyl-terminated silicone oil comprise hydrogen-terminated silicone oil and alkenyl alcohol, wherein the structural formula of the hydrogen-terminated silicone oil is shown as the formula (3):
R 3 one or more selected from alkyl, alkoxy and aryl, R 4 One 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 formula (4):
R 1 are straight chain alkyl groups and/or branched chain alkyl groups, and as examples of alkenyl alcohols include, but are not limited to, propenol, butenol, isobutenyl alcohol, pentenol, isopentenyl alcohol.
More preferably, the molar ratio of the hydrogen-terminated silicone oil to the alkenyl alcohol is 1: (2 to 2.5), there may be mentioned 1:2.1: 2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, preferably 1: (2 to 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 alkenyl alcohol under the action of a catalyst to obtain the hydroxyl-terminated silicone oil. Still more preferably, the reaction temperature of the present invention is 90 to 120℃and 90℃95℃100℃105℃110℃115℃120℃may be mentioned. The reaction time of the hydroxyl-terminated silicone oil may be determined by titration with sodium hydroxide, and is not particularly limited, and in one embodiment, the reaction time is 8 to 12 hours, and examples thereof include 8 hours, 9 hours, 10 hours, 11 hours, and 12 hours.
The method for titrating sodium hydroxide comprises the following steps: and (3) taking a mixture of the terminal hydrogen silicone oil and the alkenyl alcohol which react under the action of a catalyst, adding the mixture into an acetone solution, titrating the mixture by using a 1N sodium hydroxide solution, and ending the reaction when the taken reaction solution has no bubbles (because a silicon hydrogen bond can react with the sodium hydroxide solution to release hydrogen).
In a preferred embodiment, the preparation method of the hydroxyl-terminated silicone oil comprises the following steps: heating the hydrogen-terminated silicone oil to 90-120 ℃, dropwise adding a catalyst and mixing the olefin alcohol, and reacting to obtain the hydroxyl-terminated silicone oil. The catalyst is not particularly limited in the present invention, and examples of the catalyst used in the resin in the art include chloroplatinic acid, karstedt platinum catalyst, speier catalyst, rhCl (PPh) 3 ) 3 In one embodiment, the catalyst is 5 to 50ppm based on the total weight of the terminal hydrogen silicone oil and the alkenyl alcohol, and examples thereof include 5ppm, 8ppm, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, and 50ppm.
Hafnium alkyl alcohol
The present invention is not limited to a specific kind of hafnium alkyl alcohol, and examples thereof include hafnium ethoxide, hafnium tert-butoxide, hafnium isopropoxide, hafnium n-propoxide and hafnium n-butoxide.
Hydroxy compounds
In one embodiment, the hydroxy compounds of the present invention have the formula R 2 OH，R 2 Is alkyl or alkyl derivative. Preferably, the hydrogen atoms in the alkyl group of the alkyl derivative are substituted with vinyl groups, acrylate groups, methacrylate groups, or isocyanate groups, more preferably, 1 to 10 hydrogen atoms in the alkyl group of the alkyl derivative are substituted with vinyl groups, acrylate groups, methacrylate groups, or isocyanate groups, and even more preferably, 1 to 5 hydrogen atoms in the alkyl group of the alkyl derivative are substituted with vinyl groups, acrylate groups, methacrylate groups, or isocyanate groups.
Examples of the hydroxyl compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1, 2-methyl-2- (meth) acrylate, 2-hydroxy-1, 3-propanediol 2- (meth) acrylate, 2, 3-dihydroxypropane (meth) acrylate, pentaerythritol tri (meth) acrylate, methanol, ethanol, propanol, vinyl methanol, vinyl propanol, isocyanatomethanol, and isocyanatobutanol.
The second aspect of the present invention provides a method for producing a high refractive resin as described above, comprising:
and (3) after the hydroxyl-terminated silicone oil and the hafnium alkyl alcohol react in a solvent, adding hydroxy acrylic ester for reaction, and drying to obtain the high refractive resin. In the method for producing the high refractive resin, the reaction temperature is 60 to 90 ℃, preferably 60 to 80 ℃, and examples thereof include 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃.
In one embodiment, the method for preparing the high refractive resin of the present invention comprises: and (3) reacting hydroxyl-terminated silicone oil with hafnium alkyl alcohol in a solvent for 3-8 hours, adding hydroxyl acrylic ester for reacting for 2-4 hours, and drying to obtain the high refractive resin. Preferably, the preparation method of the high refractive resin of the present invention comprises: and (3) reacting hydroxyl-terminated silicone oil and hafnium alkyl alcohol in a solvent for 4-6 hours, adding hydroxyl acrylic ester for reacting for 2-4 hours, and drying to obtain the high refractive resin.
More preferably, the method for preparing the high refractive resin of the present invention comprises:
and (3) after the hydroxyl-terminated silicone oil and the hafnium alkyl alcohol react in a solvent, adding hydroxyl acrylic ester and a polymerization inhibitor for reaction, and drying to obtain the high refractive resin.
The solvent is not particularly limited, and toluene, xylene, tetrahydrofuran, ethyl acetate, and the like can be cited. The polymerization inhibitor is not particularly limited in the present invention, and p-hydroxyanisole, methylhydroquinone, phenothiazine, and dibutylhydroxytoluene may be mentioned. In one embodiment, the polymerization inhibitor is 0.1 to 1% by weight of the total weight of the hydroxyl-terminated silicone oil, the hafnium alkyl alcohol and the hydroxyl acrylate, and examples thereof include 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.
In order to remove the solvent and the produced alkyl alcohol, the present invention is dried after the reaction, and examples of the drying method include distillation under reduced pressure, spray drying, and vacuum drying. The inventors have found that the reaction also proceeds during the removal of the solvent and the alkyl alcohol formed, and that the reaction is terminated when no liquid comes out.
In a third aspect, the present invention provides the use of a 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 is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
Example 1 provides a hydroxyl terminated silicone oil
This example provides a hydroxyl-terminated silicone oil A 1 The structural formula is as follows:
x average 18, y average 22.
The example 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, y average value 22) into a 1L four-necked round bottom flask, heating to 100 ℃, dropwise adding allyl alcohol (0.005 g of KarstedtPt catalyst and 12.54g of allyl alcohol) premixed with KarstedtPt catalyst at a constant temperature of 100 ℃, after the completion of the dropwise adding, continuously reacting at a constant temperature of 90 ℃ for 3 hours, gradually clarifying and transparentizing the reaction solution, taking 5g of the reaction solution into an acetone solution, titrating with a 1N sodium hydroxide solution, and when the taken reaction solution has no bubbles (because a silicon hydrogen bond can react with the sodium hydroxide solution, releasing hydrogen), and ending the reaction to obtain the hydroxyl-terminated silicone oil A 1 。
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 bisphenyl silicone oil acrylate resin of the formula M 1 The following is shown:
x average 18, y average 22.
The example also provides a preparation method of the organohafnium modified diphenyl silicone oil acrylate resin, which comprises the following steps: 550g of hydroxyl-terminated silicone oil A is placed in A1L four-neck round bottom flask, 100g of toluene solution is added, stirring is uniform, 88.80g of hafnium isopropoxide is added, after the mixture is placed at 80 ℃ for reaction for 5 hours, 73.86g of hydroxyethyl acrylate and 0.10g of p-hydroxyanisole are added, the mixture is placed at 80 ℃ for stirring for 3 hours, then reduced pressure distillation is carried out while the reaction is carried out, isopropanol and solution toluene generated by the reaction are distilled off while reduced pressure distillation, when no liquid flows out from a tail receiving bottle, the reaction is stopped, discharging is carried out, and clear transparent organic hafnium modified diphenyl silicone oil acrylate resin M1 (as can be seen from figure 1, no peak exists at a wavelength of 3450cm < -1 > in an infrared spectrum, which indicates that the hydroxyl-terminated diphenyl silicone oil and the hydroxyethyl acrylate are successfully bonded to the organic hafnium) has a viscosity of 3000cps at 30 ℃ and a refractive index of 1.605.
Example 3
This example provides an organohafnium modified bisphenyl silicone oil acrylate resin of the formula M 1 The following is shown:
x average 18, y average 22,
the example also provides a preparation method of the organohafnium modified diphenyl silicone oil acrylate resin, which comprises the following steps: 550g of hydroxyl-terminated silicone oil A is placed in A1L four-neck round bottom flask, 100g of toluene solution is added, stirring is uniform, 99.84g of hafnium tert-butoxide is added, after the mixture is placed at 80 ℃ for reaction for 5 hours, 189.75g of pentaerythritol triacrylate and 0.30g of p-hydroxyanisole are added, the mixture is placed at 80 ℃ for stirring for 3 hours, then reduced pressure distillation is carried out while the reaction is carried out, isopropanol and solution toluene generated by the reaction are distilled off, when no liquid flows out from a tail receiving bottle, the reaction is stopped, discharging is carried out, and clear transparent organic hafnium modified diphenyl silicone oil acrylate resin M2 (as can be seen from figure 1, no peak exists at a wavelength of 3450cm < -1 > in an infrared spectrum, which indicates that the hydroxyl-terminated diphenyl silicone oil and hydroxyethyl acrylate are successfully bonded to the organic hafnium) has a viscosity of 12000cps at 30 ℃ and a refractive index of 1.621.
Examples 4 to 7 and comparative example 1 provide an optical material
The raw materials for preparing the optical materials and the weight ratio thereof provided in examples 4 to 7 and comparative example 1 are shown in table 1. Wherein TPO (2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide) is a photoinitiator, and urethane acrylate resin CN 989NS (designated as B-605) is from the company of sand-dammar chemical Co.
TABLE 1
| Preparation of raw materials | |
| Example 4 | Resin M1: tpo=1: 0.03 |
| Example 5 | Resin M2: tpo=1: 0.03 |
| Example 6 | Resin M1: polyurethane acrylate resin CN 989NS: TPO = 0.5:0.5:0.03 |
| Example 7 | Resin M2: polyurethane acrylate resin CN 989NS: TPO = 0.5:0.5:0.03 |
| Comparative example 1 | Polyurethane acrylate resin CN 989NS: tpo=1: 0.03 |
The light intensity of the comparative examples 4 to 7 and comparative example 1 was 3000 mJ.cm -2 After the medium-pressure mercury lamp is irradiated and cured to form a film, the refractive index of different films under 400nm, 600nm, 800nm and 1600nm monochromatic light is measured by a Michelson interferometer, and the obtained result is shown in figure 2.
From FIG. 2, M 1 、M 2 The refractive index of the resin after being respectively cured into a film or being matched with CN 989NS to be cured into a film is higher than that of the resin after being singly cured into a film of CN 989NS, which shows that the organohafnium modified resin can be used as the refractive index after being cured into a film according to the formula and is expected to be applied to preparing a transparent film with high refractive index.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (7)
1. A high refractive resin is characterized in that the structural formula of the resin is shown as a formula (1):
R 1 is a linear alkylene and/or a branched alkylene, R 2 Is alkyl or alkyl derivative, R 3 One or more selected from alkyl, alkoxy and aryl, R 4 One or more selected from alkyl, alkoxy and aryl;
x is 5-50, y is 10-50;
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;
the preparation raw materials of the resin comprise hydroxyl-terminated silicone oil, hafnium alkyl alcohol and hydroxyl compound, wherein the molar ratio is 1: (2-2.5): (6-6.5);
the structural formula of the hydroxyl-terminated silicone oil is shown as the formula (2):
R 1 is a linear alkylene and/or a branched alkylene, R 3 One or more selected from alkyl, alkoxy and aryl, R 4 One or more selected from alkyl, alkoxy and aryl;
x is 5 to 50, and y is 10 to 50.
2. The high refractive resin according to claim 1, wherein R in the formula (1) and the formula (2) 1 Is C1-C10 straightChain alkylene and/or C2-C10 branched alkylene.
3. The high refractive resin according to claim 1, wherein x is 10 to 30 and y is 15 to 30 in the formula (1) and the formula (2).
4. The high refractive resin according to claim 1, wherein the hydroxyl compound has the structural formula of R 2 OH，R 2 Is alkyl or alkyl derivative.
5. The high refractive resin according to claim 1, wherein 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 formula (3):
R 3 one or more selected from alkyl, alkoxy and aryl, R 4 One 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 formula (4):
R 1 is a straight chain alkyl group and/or a branched chain alkyl group.
6. A method for producing the high refractive resin according to any one of claims 1 to 5, comprising:
and (3) after the hydroxyl-terminated silicone oil and the hafnium alkyl alcohol react in a solvent, adding hydroxy acrylic ester for reaction, and drying to obtain the high refractive resin.
7. Use of a high refractive resin according to any one of claims 1 to 5, for optical materials.
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| TWI565732B (en) * | 2012-06-13 | 2017-01-11 | 財團法人工業技術研究院 | Organic-inorganic hybrid resin, method for forming the same, and transparent resin composition formed therefrom |
| KR101521227B1 (en) * | 2012-11-12 | 2015-05-18 | 주식회사 한솔케미칼 | Organometal polysiloxane and process for preparing them |
| CN103897194B (en) * | 2014-03-07 | 2016-03-30 | 浙江大学 | A kind of synthetic method of polysiloxane of tert-hydroxyl end-blocking |
| CN106633079B (en) * | 2016-12-31 | 2019-05-14 | 华南理工大学 | A kind of high refractive index silicon zirconium hybrid resin and preparation method thereof |
| CN111471178A (en) * | 2020-05-14 | 2020-07-31 | 哈尔滨工业大学 | High-temperature-resistant hybrid organic silicon resin with framework doped with hafnium and preparation method thereof |
| CN112608478A (en) * | 2020-12-02 | 2021-04-06 | 甘肃银光聚银化工有限公司 | Method for preparing hydroxyl-terminated silicone oil |
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