CN110229339B - Phenyl vinyl siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof - Google Patents

Phenyl vinyl siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof Download PDF

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CN110229339B
CN110229339B CN201910442167.6A CN201910442167A CN110229339B CN 110229339 B CN110229339 B CN 110229339B CN 201910442167 A CN201910442167 A CN 201910442167A CN 110229339 B CN110229339 B CN 110229339B
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容敏智
张泽平
章明秋
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to phenyl vinyl siloxane resin, a high-refractive-index LED packaging silicon resin composition and a preparation method thereof. The phenyl vinyl siloxane resin is prepared by the following method: s1: mixing monomers, adding an organic solvent to obtain a mixed solution, and adding a hydrolysis catalyst; s2: dripping water at 0-60 ℃ for hydrolysis reaction, washing, performing suction filtration, adding an alkali catalyst for condensation reaction at 120-160 ℃, washing, and performing suction filtration to obtain the phenyl vinyl siloxane resin. The phenyl vinyl siloxane resin provided by the invention has high refractive index, excellent flexibility and yellowing resistance; when the silicon resin is used for preparing LED packaging silicon resin, the silicon resin has high refractive index, excellent tensile strength, bonding strength, light transmittance and yellowing resistance, and partial properties of the silicon resin reach or are higher than the level of similar imported products abroad, so that the basic requirements of LED packaging can be met; the packaged surface-mounted LED device has excellent air tightness.

Description

Phenyl vinyl siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic packaging, and particularly relates to phenyl vinyl siloxane resin, a high-refractive-index LED packaging silicon resin composition and a preparation method thereof.
Background
A Light Emitting Diode (LED) is a semiconductor device that can directly convert electrical energy into optical energy. Compared with the illumination mode of an incandescent lamp or a fluorescent lamp, the LED lamp has the advantages of energy conservation, low consumption, long service life, environmental protection, controllable color, small volume and the like, and is expected to be used as a new generation of illumination light source to replace the traditional light source. The encapsulating materials used for the LED lighting device are mainly epoxy resin and silicone resin. Compared to epoxy resins, silicones have numerous advantages: such as excellent ultraviolet aging resistance, weather resistance, thermal stability, high light transmittance, high refractive index, insulativity and the like, and is an ideal choice for high-power LED packaging materials.
With the continuous improvement of LED manufacturing technology, such as the maturity of high-power white-light LED and lead-free reflow soldering technology, the packaging technology of high-power LED has gradually become the technical key of power-type LED development. At present, high-performance organic silicon resin for packaging power type LED basically depends on import, the main core technology is monopolized by a few foreign companies such as Dow Corning, Xinyue and the like, and the high cost limits the popularization of high-power LED devices. Therefore, the need for a high refractive index transparent silicon material for LED package is more and more urgent. At present, domestic research still belongs to a starting stage, a lot of blanks exist, and the domestic produced organic silicon packaging material can only be used for middle and low-end products with low performance requirements. The high-performance LED packaging silicone resin must have the performances of high refractive index, high light transmittance, ultraviolet resistance, thermal aging resistance, low stress and the like, wherein the key point of the problem is to improve the refractive index.
The refractive index of the LED chip is usually greater than 2.5, while the refractive index of the encapsulant is much smaller, and if the difference between the refractive indexes of the LED chip and the encapsulant is too large, the light emitted by the LED chip may not be completely extracted due to total reflection, which reduces the optical efficiency of the LED device. Therefore, the refractive index of the packaging material is improved, the difference between the refractive index of the packaging material and the refractive index of the LED chip is reduced, and the light extraction efficiency of the LED can be obviously improved. In polysiloxanes, the benzene ring has a relatively high molar refractive index (Si-Ph bond refractive index of 27.39, whereas in silicone polymers, Si-CH3Only 7.57 and more only 1.75 Si-O bonds), thus increasing the phenyl content and well increasing the refractive index of the polysiloxane. However, an increase in the phenyl content will affect the brittleness of the polysiloxane and make the material more susceptible to yellowing.
In view of this, the development of an organosilicon encapsulating material with high refractive index and unaffected other properties has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defect and the defect of low refractive index of the packaging material in the prior art and provides a preparation method of phenyl vinyl siloxane resin. According to the invention, through selection and dosage optimization of specific monomers, the content of phenyl in the prepared phenyl vinyl siloxane resin is greatly increased, and the refractive index is improved; in addition, the content of vinyl is reasonable, which is beneficial to curing reaction; meanwhile, due to the addition of octamethylcyclotetrasiloxane, a methylsiloxane chain segment is introduced into the phenyl vinyl siloxane resin, so that the flexibility of the phenyl vinyl siloxane resin is greatly increased, and the finally obtained phenyl vinyl siloxane resin is high in refractive index and excellent in flexibility and yellowing resistance; when the silicon resin is used for preparing LED packaging silicon resin, the silicon resin has high refractive index, excellent tensile strength, bonding strength, light transmittance and yellowing resistance, and partial properties of the silicon resin reach or are higher than the level of similar imported products abroad, so that the basic requirements of LED packaging can be met; the packaged surface-mounted LED device has excellent air tightness.
The invention also aims to provide application of the phenyl vinyl siloxane resin in preparing LED packaging silicone resin.
Another object of the present invention is to provide a high refractive index LED encapsulation silicone resin composition.
The invention also aims to provide a preparation method of the high-refractive-index LED packaging silicone resin composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
a phenyl vinyl siloxane resin is prepared by the following method:
s1: mixing the following monomers: mixing diphenyldimethoxysilane, methylvinyldimethoxysilane, octamethylcyclotetrasiloxane and tetramethyldivinyldisiloxane, adding an organic solvent to obtain a mixed solution, and adding a hydrolysis catalyst; the mass ratio of the diphenyldimethoxysilane to the methylvinyldimethoxysilane to the octamethylcyclotetrasiloxane to the tetramethyldivinyldisiloxane is 50-70: 10-20: 10-30: 5-15;
s2: adding water dropwise at 30-60 ℃ for hydrolysis reaction, washing, distilling under reduced pressure, adding an alkali catalyst to adjust the pH to 11-14, carrying out condensation reaction at 120-160 ℃, washing, and distilling under reduced pressure to obtain the phenyl vinyl siloxane resin.
The invention adopts diphenyldimethoxysilane, methyl vinyl dimethoxysilane, octamethylcyclotetrasiloxane and tetramethyl divinyl disiloxane as monomers, can improve the phenyl content of phenyl vinyl siloxane resin and obtain proper vinyl content, and further improves the refractive index and the curing effect; meanwhile, by selecting octamethylcyclotetrasiloxane and introducing a methylsiloxane chain segment into a resin molecular chain, the flexibility is greatly increased, and the finally obtained phenyl vinyl siloxane resin is high in refractive index and excellent in flexibility and yellowing resistance. When the prepared LED packaging silicone resin is used for preparing LED packaging silicone resin, the prepared LED packaging silicone resin has high refractive index, excellent tensile strength, bonding strength, light transmittance and yellowing resistance, and part of the properties of the LED packaging silicone resin reach or are higher than the level of similar imported products abroad, so that the basic requirements of LED packaging can be met; the packaged surface-mounted LED device has excellent air tightness.
In addition, the preparation method has simple process and easy post-treatment, and does not generate corrosive substances.
Preferably, the mass ratio of diphenyldimethoxysilane, methylvinyldimethoxysilane, octamethylcyclotetrasiloxane and tetramethyldivinyldisiloxane in S1 is 50:15:20: 5.
Under the mass ratio, the phenyl vinyl siloxane resin has more excellent refraction, flexibility and yellowing resistance.
Preferably, the mass fraction of the monomers in the S1 mixed solution is 25-75%.
More preferably, the mass fraction of the monomer in the S1 mixed solution is 50%.
Preferably, the organic solvent in S1 is one or more of toluene, xylene or benzene.
Preferably, the hydrolysis catalyst in S1 is trifluoromethanesulfonic acid.
More preferably, trifluoromethanesulfonic acid is added to S1 to bring the pH of the mixed solution to less than 1.
The amounts of water and alkaline catalyst used in S2 can be controlled according to the requirements of the existing hydrolysis and condensation reactions, respectively.
Preferably, the molar ratio of S2 between water and the alkoxy group of the reactive group is 1-1.4: 1.
In general, a preferred hydrolysis reaction is achieved when water is used in a molar ratio of the alkoxy groups of the reactive functional groups of 1: 1.
The dropping speed of water can be adjusted according to the intensity of hydrolysis reaction, generally, the dropping speed of one drop of 30-70 s is proper, and annular byproducts are easy to appear too fast, so that the transparency of the product is affected.
Preferably, the base catalyst in S2 is one or more of sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide.
A high-refractive-index LED packaging silicone resin composition comprises the following components in parts by weight:
Figure BDA0002072347020000021
Figure BDA0002072347020000031
the invention takes phenyl vinyl siloxane resin and phenyl hydrogen-containing siloxane resin as curing monomers to be cured under the action of Karstedt catalyst; and the hyperbranched phenyl siloxane reinforcing agent with better compatibility is selected, so that the crosslinking points of the cured silicone resin are more concentrated, the stress can be effectively dispersed, and even a sea-island structure is formed, thereby playing the roles of toughening and reinforcing; the organic silicon tackifier is selected to improve the adhesive property and the adhesive force of the silicon resin condensate and the LED substrate, and block water and the like in the air, so that the obtained LED packaging silicon resin composition has higher phenyl content and proper vinyl content, high refractive index, better flexibility and yellowing resistance, partial performance reaching or higher than the level of similar imported products abroad, and can meet the basic requirements of LED packaging; the packaged surface-mounted LED device has excellent air tightness. Specifically, the method comprises the following steps: the tensile strength can reach 1.4-4.1 MPa, the bonding strength can reach 0.3-1.2 MPa, the light transmittance at 450nm is close to 90%, the Shore hardness can reach 60-85A, and the refractive index can reach 1.56.
It is understood that Karstedt's catalyst is added in an amount of 10-20 ppm per unit mass (g) of the high refractive index LED encapsulation silicone composition.
Preferably, the high-refractive-index LED encapsulation silicone resin composition consists of the following components in parts by weight:
Figure BDA0002072347020000032
preferably, the phenyl hydrogen-containing siloxane resin is prepared by the following preparation method: mixing the following monomers: mixing phenyl trimethoxy silane, diphenyl dimethoxy silane, tetramethyl cyclotetrasiloxane and tetramethyl disiloxane, water and a hydrolysis reaction catalyst, adding an organic solvent to obtain a mixed solution, heating to 30-60 ℃, carrying out hydrolysis reaction for 1-5 h, heating to 110-140 ℃, carrying out water diversion reaction for 2-11 h, washing, and carrying out reduced pressure distillation to obtain the phenyl hydrogen-containing siloxane resin; the mass ratio of the phenyltrimethoxysilane to the diphenyldimethoxysilane to the tetramethylcyclotetrasiloxane to the tetramethyldisiloxane is 15-25: 45-55: 10-20: 1.5-15.
The invention provides a preparation method of phenyl hydrogen-containing siloxane resin, which is characterized in that phenyl trimethoxy silane, diphenyl dimethoxy silane, tetramethyl cyclotetrasiloxane and tetramethyl disiloxane are selected as monomers, so that the obtained phenyl hydrogen-containing siloxane resin has high phenyl content and high refractive index; meanwhile, the tetramethylcyclotetrasiloxane is selected, so that an Si-H bond and a methylsiloxane chain segment are simultaneously introduced into a molecular chain of the phenyl hydrogen-containing siloxane resin, the phenyl hydrogen-containing siloxane resin not only can be effectively used as a cross-linking agent, but also the flexibility is greatly increased.
The refractive indexes of the phenyl vinyl siloxane resin and the phenyl hydrogen-containing siloxane resin prepared by the specific method are close to each other, so that the problem that the optical performance of the obtained packaging material is poor due to the fact that the vinyl siloxane resin and the hydrogen-containing siloxane resin have different refractive indexes in the conventional technology is further solved; in addition, the refractive indexes of the LED packaging silicone resin composition and the LED packaging silicone resin composition are both high, and the refractive index of the LED packaging silicone resin composition is further improved through the cooperation effect of the two, so that the LED packaging silicone resin composition has more excellent comprehensive performance.
Preferably, the mass ratio of the phenyltrimethoxysilane, the diphenyldimethoxysilane, the tetramethylcyclotetrasiloxane and the tetramethyldisiloxane is 20:40:25: 5.
Under the mass ratio, the phenyl hydrogen-containing siloxane resin has proper molecular weight, viscosity and content of silicon hydroxyl, and more excellent refractive index and molecular chain flexibility.
Preferably, the mass concentration of the monomer in the mixed solution is 25-75%.
More preferably, the mass concentration of the monomer in the mixed solution is 50%.
Preferably, the organic solvent is one or more of toluene, xylene or benzene.
Preferably, the hydrolysis reaction catalyst is one or more of concentrated hydrochloric acid, glacial acetic acid or AMBERLYST-15WET strong acid type cation exchange resin.
Preferably, the molar ratio of the water to the alkoxy groups of the hydrolysis reaction group is 1-1.4: 1.
Preferably, the mass ratio of the phenyltrimethoxysilane to the hydrolysis reaction catalyst is 15-25: 1.2-5.8.
Preferably, the hyperbranched phenyl siloxane reinforcing agent is prepared by the following method: mixing the following monomers: mixing hexamethyldisiloxane and tetramethyldivinyldisiloxane, water and an acid catalyst, adding an organic solvent to obtain a mixed solution, dropwise adding phenyltrimethoxysilane, performing hydrolysis reaction at 30-50 ℃ for 0.5-4 h, heating to 50-120 ℃, continuing to react for 1-3 h, washing, and performing reduced pressure distillation to obtain the hyperbranched phenylsiloxane reinforcing agent; the mass ratio of the hexamethyldisiloxane to the tetramethyldivinyldisiloxane to the phenyltrimethoxysilane is 5-15: 10-20: 15-25.
The invention provides a preparation method of a specific hyperbranched phenyl siloxane reinforcing agent.
The hyperbranched phenyl siloxane prepared by the specific method has the advantages of simple reaction process, easy adjustment of molecular weight and good compatibility with high-refractive-index packaging silicone resin, and can further improve the toughness and strength of a cured silicone resin when used for LED packaging silicone resin compositions.
Preferably, the hyperbranched phenylsiloxane reinforcing agent has the following structural formula:
Figure BDA0002072347020000041
the hyperbranched phenyl siloxane reinforcing agent prepared by the method has basically similar structure, and the difference is only the difference of the substitution number of hyperbranched and the position and the content of terminal functional group vinyl.
Preferably, the mass ratio of hexamethyldisiloxane, tetramethyldivinyldisiloxane and phenyltrimethoxysilane is 12.5:12.5: 25.
Preferably, the organic solvent is one or more of toluene, xylene or benzene.
Preferably, the mass concentration of the monomer in the mixed solution is 25-75%.
More preferably, the mass concentration of the monomer in the mixed solution is 50%.
Preferably, the molar ratio of the water to the alkoxy groups of the hydrolysable groups is 0.4 to 0.75: 1.
Preferably, the mass ratio of the hexamethyldisiloxane to the acid catalyst is 5-15: 2-6.
Preferably, the silicone tackifier is prepared by the following method: mixing the following monomers: mixing phenyltrimethoxysilane, diphenyldimethoxysilane, methylvinyldimethoxysilane and tetramethyldivinyldisiloxane, adding an organic solvent to obtain a mixed solution, adding a hydrolysis reaction catalyst, carrying out hydrolysis reaction at 30-50 ℃, washing, carrying out rotary evaporation, adding a silane coupling agent and a condensation reaction catalyst, heating to 80-140 ℃, and reacting for 1-7 hours; washing and filtering to obtain the organic silicon tackifier; the mass ratio of the phenyltrimethoxysilane to the diphenyldimethyloxysilane to the methylvinyldimethoxysilane to the tetramethyldivinyldisiloxane to the silane coupling agent is 15-25: 25-35: 10-20: 2-15: 10-20.
Preferably, the mass ratio of the phenyltrimethoxysilane, the diphenyldimethoxysilane, the methylvinyldimethoxysilane, the tetramethyldivinyldisiloxane and the silane coupling agent is 20:30:15:5: 15.
Preferably, the organic solvent is one or more of toluene, xylene or benzene.
Preferably, the mass concentration of the monomer in the mixed solution is 25-75%.
More preferably, the mass concentration of the monomer in the mixed solution is 50%.
Preferably, the hydrolysis catalyst is trifluoromethanesulfonic acid.
More preferably, trifluoromethanesulfonic acid is added to a pH of less than 1.
Preferably, the silane coupling agent is one or more of KH-550, KH-560 or KH-570.
Preferably, the mass ratio of the phenyltrimethoxysilane to the silane coupling agent is 15-25: 2-7.
Preferably, the condensation reaction catalyst is one or more of potassium hydroxide, sodium hydroxide or tetramethyl ammonium hydroxide.
The preparation method of the high-refractive-index LED packaging silicone resin composition comprises the following steps: and mixing phenyl vinyl siloxane and phenyl hydrogen-containing siloxane, adding hyperbranched phenyl siloxane, a silicon resin tackifier and a Karstedt catalyst, stirring, removing bubbles, gradually heating and curing to obtain the high-refractive-index LED packaging silicon resin composition.
Preferably, de-bubbling is performed using vacuum.
Preferably, the curing process is to heat the mixture to 100-150 ℃ at a heating rate of 5-20 ℃/min.
Specifically, heating to 100 ℃ at a heating rate of 10-20 ℃/min for curing for 1h, then continuously heating to 130 ℃ for curing for 2h, and continuously heating to 150 ℃ for curing for 3 h.
The application of the high-refractive-index LED packaging silicone resin composition as a packaging material in LED packaging is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through selection and dosage optimization of specific monomers, the content of phenyl in the prepared phenyl vinyl siloxane resin is greatly increased, and the refractive index is improved; in addition, the content of vinyl is reasonable, which is beneficial to obtaining moderate crosslinking degree by curing reaction; meanwhile, due to the addition of octamethylcyclotetrasiloxane, a methylsiloxane chain segment is introduced into the phenyl vinyl siloxane resin, so that the flexibility of the phenyl vinyl siloxane resin is greatly increased; the hyperbranched phenyl siloxane reinforcing agent and the organic silicon tackifier can further improve the mechanical strength and the cohesiveness of a final material, and when the hyperbranched phenyl siloxane reinforcing agent and the organic silicon tackifier are used for preparing LED packaging silicone resin, the hyperbranched phenyl siloxane reinforcing agent has good heat resistance and yellowing resistance, the tensile strength can reach 1.4-4.1 MPa, the cohesional strength can reach 0.3-1.2 MPa, the light transmittance of 450nm is close to 90%, the Shore hardness can reach 60-85A, the refractive index can reach 1.56, partial performances can reach or are higher than partial products such as a Meiji chart, Dow Corning and the like, the hyperbranched phenyl siloxane reinforcing agent has the advantages of low price, simple process and the like, can meet the basic requirements of LED packaging, and has the potential of industrial production; the packaged surface-mounted LED device has excellent air tightness.
Drawings
FIG. 1 is an infrared spectrum of a phenyl vinyl siloxane resin provided in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a phenyl vinyl siloxane resin provided in example 1;
FIG. 3 is an IR spectrum of a phenyl hydrosiloxane resin provided in example 17;
FIG. 4 is a nuclear magnetic hydrogen spectrum of phenyl hydrosiloxane resin provided in example 17;
FIG. 5 is an IR spectrum of a hyperbranched phenylsiloxane reinforcing agent provided in example 33;
FIG. 6 is a nuclear magnetic hydrogen spectrum of a hyperbranched phenylsiloxane reinforcing agent provided in example 33;
FIG. 7 is an infrared spectrum of a silicone adhesion promoter provided in example 45;
FIG. 8 is a nuclear magnetic hydrogen spectrum of the silicone adhesion promoter provided in example 45;
fig. 9 is a photograph showing the results of the red ink test of the surface-mount LED package devices of example 56 and comparative examples 1 and 2.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The tensile property of the cured product is tested by a universal tester, dumbbell type tensile sample strips are cast according to the method specified by the national standard GB/T16421-.
The adhesive property of the cured material is tested by a universal tester, the tensile shear strength of the aluminum sheet by the silicone resin is determined and evaluated by referring to the national standard GB/T13936-92, and at least 5 parallel samples are tested and the average value is taken.
The hardness of the cured product is tested by a Shore A hardness tester, and at least 5 parallel samples are tested and averaged.
The transmittance of the cured product was measured by using a UV-3150 type UV-visible-near infrared spectrophotometer, manufactured by Shimadzu corporation, Japan. In addition, the light transmittance was measured for the cured products with different aging times, and the yellowing index was calculated according to the method described in ASTM E313D 1925.
The refractive indices of the liquid silicone resin and the cured product (thickness 1mm) were measured using a 2WE-T digital Abbe refractometer from Shanghai optical precision instruments Ltd, with bromonaphthalene as the correction medium.
The air tightness of the surface-mounted LED packaging device is checked by adopting a red ink penetration experiment, if the air tightness is not good, the red ink can penetrate into the device after the experiment, and an optical microscope is adopted to observe the device before and after the experiment.
Example 1
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The IR and NMR spectra are shown in FIGS. 1 and 2, respectively, and the molecular weight, appearance and refractive index data are shown in Table 1.
1260cm in FIG. 1-1Is classified into Si-CH3Symmetric bending vibration of (2); 1406cm-1C-C shear mode bending vibration attributed to Si-Vi; 1429. 1473, 1457 and 1592cm-1C ═ C stretching vibration attributed to Si-Ph; 2959cm-1Is attributed to CH3The stretching vibration of (2); 3050 and 3070cm-1C-H stretching vibration attributed to benzene ring, and the success of preparing phenyl vinyl siloxane prepolymer at 860cm-1And 3700--1No Si-OH peak appears between the two points, which indicates that the condensation reaction is carried out more thoroughly.
The chemical shift assignments in fig. 2 are as follows: 6.99-7.74 ppm belongs to Si-Ph; 0 to 0.27ppm of Si-CH3. No peak around 1.59ppm was observed indicating the absence of Si-OH, indicating that the preparation process allowed the condensation reaction to proceed relatively completely.
Example 2
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% of potassium hydroxide to adjust the pH, carrying out condensation reaction for 0.5h at 150 ℃, moving to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 3
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 5h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 4
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 120 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 5
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 160 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 6
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% of sodium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 7
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 2% tetramethylammonium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 8
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.5% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 9
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 10
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 60 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 11
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 6g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, toluene was added to prepare a mixed solution having a monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid was added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 12
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 8g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, toluene was added to prepare a mixed solution having a monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid was added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 13
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 10g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, toluene was added to prepare a mixed solution having a monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid was added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 14
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
50g of diphenyldimethoxysilane, 5g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, toluene was added to prepare a mixed solution having a monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid was added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 15
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
30g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 5g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 16
This example provides a phenyl vinyl siloxane resin, which was prepared as follows.
60g of diphenyldimethoxysilane, 15g of methylvinyldimethoxysilane, 20g of octamethylcyclotetrasiloxane and 10g of tetramethyldivinyldisiloxane are mixed and placed in a round-bottomed flask, toluene is added to prepare a mixed solution with the monomer mass ratio of 50%, and 0.1g of trifluoromethanesulfonic acid is added dropwise to make the solution acidic. Slowly dropwise adding pure water with the same molar ratio with the reaction functional group within 3h at 40 ℃ for hydrolysis reaction, and hydrolyzing for 1h after dropwise adding. The solution was transferred to a separatory funnel and washed with water until the solution was neutral. And (3) decompressing by using a rotary evaporator at 55 ℃ to remove the solvent and water, adding 0.1% potassium hydroxide to adjust the pH, carrying out condensation reaction for 2h at 150 ℃, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin. The molecular weight, appearance and refractive index data are shown in table 1.
Example 17
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 11 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. The solvent and water were removed under reduced pressure at 150 c,the obtained product is phenyl hydrogen-containing siloxane resin. The IR and NMR spectra are shown in FIGS. 3 and 4, respectively, and the molecular weight, appearance and refractive index data are shown in Table 2.
In FIG. 3, the infrared absorption peaks are assigned as follows: 1260cm-1Is classified into Si-CH3Symmetric bending vibration of (2); 1430 and 1593cm-1C ═ C stretching vibration attributed to Si-Ph; 2166cm-1Stretching vibration attributed to Si-H; 2963cm-1Is attributed to CH3The stretching vibration of (2); 3072cm-1The C-H stretching vibration of the benzene ring preliminarily proves that the hydrogen-containing siloxane prepolymer is successfully prepared at 860cm-1And 3700--1No Si-OH peak appears between the two points, which indicates that the condensation reaction is carried out more thoroughly.
The chemical shift assignments in fig. 4 are as follows: 6.99-7.74 ppm belongs to Si-Ph; 5.17-6.13 ppm of Si-H; 0 to 0.22ppm of Si-CH3。
Example 18
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 120 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 19
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 110 ℃, connecting with a water separator,and (5) carrying out water diversion reaction for 4 hours. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 20
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 140 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 21
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 19.5g of 19.5g H were weighed out2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 22
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2O and 3.5g of concentrated hydrochloric acid are placed in a round-bottom flask, toluene with the same mass is added, the temperature is raised to 50 DEG CAnd (4) carrying out hydrolysis reaction for 4 hours, then heating to 130 ℃, connecting with a water separator, and carrying out water separation reaction for 4 hours. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 23
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 2g of AMBERLYST-15WET strong acid type cation exchange resin in a round bottom flask, adding toluene with equal mass, heating to 50 ℃, performing hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and performing water separation reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 24
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 2 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 25
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 3 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 26
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 6 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 27
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 1.2g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 28
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane and 15g of tetramethylring were weighed outTetrasiloxane, 5g of tetramethyldisiloxane, 13g H2Placing O and 4.8g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 29
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 1.5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 30
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxysilane, 50g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 10g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 130 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 31
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
20g of phenyltrimethoxy were weighedSilane, 50g diphenyldimethoxysilane, 5g tetramethylcyclotetrasiloxane, 5g tetramethyldisiloxane, 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 140 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 32
This example provides a phenyl hydrogen siloxane resin, which is prepared as follows.
30g of phenyltrimethoxysilane, 40g of diphenyldimethoxysilane, 15g of tetramethylcyclotetrasiloxane, 5g of tetramethyldisiloxane and 13g H2Placing O and 3.5g of glacial acetic acid into a round-bottom flask, adding toluene with equal mass, heating to 50 ℃, carrying out hydrolysis reaction for 4h, heating to 140 ℃, connecting a water separator, and carrying out water diversion reaction for 4 h. The solution was transferred to a 500ml separatory funnel and washed with water until the solution appeared neutral. And (3) decompressing at 150 ℃ to remove the solvent and the water, thus obtaining the product, namely the phenyl hydrogen-containing siloxane resin. The molecular weight, appearance and refractive index data are shown in table 2.
Example 33
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% concentrated hydrochloric acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The IR and NMR spectra are shown in FIGS. 5 and 6, respectively, and the molecular weight, appearance and refractive index data are shown in Table 3.
In FIG. 5, the infrared absorption peaks are assigned as follows: 1253cm-1Is classified into Si-CH3Symmetric bending vibration of (2); 1430. 1474 and 1594cm-1C ═ C stretching vibration attributed to Si-Ph; 2958cm-1Is attributed to CH3The stretching vibration of (2); 3051 and 3073cm-1Belongs to C-H stretching vibration of benzene ring, and preliminarily proves that the hyperbranched phenyl siloxane is successfully prepared at 860cm-1And 3700--1No Si-OH peak appears between the two points, which indicates that the condensation reaction is carried out more thoroughly.
The chemical shift assignments in fig. 6 are as follows: 6.70-8.00 ppm belongs to Si-Ph; 5.28-6.28 ppm belongs to Si-Vi; 3.17-3.80 ppm of O-CH3(ii) a 0 to 0.31ppm of Si-CH3。
Example 34
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% concentrated hydrochloric acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 50 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 35
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% concentrated hydrochloric acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 100 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 36
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% glacial acetic acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 37
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 1% concentrated sulfuric acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 38
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 1% concentrated hydrochloric acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. MoleculeThe amount, appearance and refractive index data are shown in table 3.
Example 39
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 5% concentrated hydrochloric acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 40
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 8g H2Mixing O and 2% glacial acetic acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
EXAMPLE 41
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g hexamethyldisiloxane, 10g tetramethyldivinyldisiloxane, 10g H2Mixing O and 2% glacial acetic acid, placing in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 0.5h, transferring the solution to a separating funnel, washing with water to neutrality, washing with 150 DEG CAnd (4) decompressing and pumping out the solvent and the water to obtain the hyperbranched phenyl siloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 42
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
3g hexamethyldisiloxane, 3g tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% glacial acetic acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 43
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
30g of hexamethyldisiloxane, 30g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% glacial acetic acid, placing the mixture into a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 20g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, continuing to react for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and water at 150 ℃ under reduced pressure to obtain the hyperbranched phenylsiloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 44
This example provides a hyperbranched phenylsiloxane reinforcing agent, and the preparation method thereof is as follows.
10g of hexamethyldisiloxane, 10g of tetramethyldivinyldisiloxane, 6g H were weighed out2Mixing O and 2% glacial acetic acid, placing in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with a monomer mass ratio of 50%, dropwise adding 30g of phenyltrimethoxysilane, performing hydrolysis reaction at 50 ℃ for 2h after dropwise adding, heating to 80 ℃, and continuing heatingAnd (3) reacting for 2h, transferring the solution to a separating funnel, washing with water to be neutral, and removing the solvent and the water at 150 ℃ under reduced pressure to obtain the hyperbranched phenyl siloxane reinforcing agent. The molecular weight, appearance and refractive index data are shown in table 3.
Example 45
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The IR and NMR spectra are shown in FIGS. 7 and 8, respectively, and the molecular weight, appearance and refractive index data are shown in Table 4.
The infrared absorption peaks in FIG. 7 are assigned as follows: 909cm-1Vibration attributed to an epoxy group; 1084cm-1Telescopic vibration attributed to C-O-C; 1408cm-1C-C shear mode bending vibration attributed to Si-Vi; 1430 and 1593cm-1C ═ C stretching vibration attributed to Si-Ph; 2941cm-1Is attributed to CH3The stretching vibration of (2); 3051cm-1Belongs to C-H stretching vibration of benzene ring, and the successful preparation of the organic silicon tackifier is proved in the first time, and the thickness of the organic silicon tackifier is 860cm-1And 3700--1No Si-OH peak appears between the two points, which indicates that the condensation reaction is carried out more thoroughly.
The chemical shift assignments in fig. 8 are as follows: 6.99-7.74 ppm belongs to Si-Ph; 5.54-6.19 ppm belongs to Si-Vi; 3.03-3.60 ppm of O-CH3(ii) a 2.48ppm are attributed to epoxide groups; 0 to 0.30ppm of Si-CH3。
Example 46
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 80 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 47
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 140 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 48
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 1 hour. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 49
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 3 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 50
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 15g of KH560 silane coupling agent and 0.1 wt% of potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and distilling the reaction solution at 150 ℃ under reduced pressure to remove the solvent and the water to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 51
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 15g of KH570 silane coupling agent and 0.1 wt% of potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 3 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and distilling the reaction solution at 150 ℃ under reduced pressure to remove the solvent and the water to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 52
This example provides a silicone adhesion promoter prepared as follows.
Weighing 25g of phenyltrimethoxysilane, 35g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 4.5g of tetramethyldivinyldisiloxane, mixing, placing in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 53
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 30g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 8g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 54
This example provides a silicone adhesion promoter prepared as follows.
Weighing 15g of phenyltrimethoxysilane, 25g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 55
This example provides a silicone adhesion promoter prepared as follows.
Weighing 20g of phenyltrimethoxysilane, 35g of diphenyldimethyloxysilane, 15g of methylvinyldimethoxysilane and 5g of tetramethyldivinyldisiloxane, mixing, placing the mixture in a round-bottom flask, adding toluene with equal mass to prepare a mixed solution with the monomer mass ratio of 50%, adding 8 drops of trifluoromethanesulfonic acid, carrying out hydrolysis reaction at 40 ℃, dropwise adding a certain amount of water within 2h, then hydrolyzing for 1h, transferring the solution to a 500ml separating funnel, and washing with water until the solution is neutral. Then, the solvent and water are removed by rotary evaporation at 95 ℃, 5g KH560 and 10g KH570 silane coupling agents and 0.1 wt% potassium hydroxide are added, and the temperature is raised to 100 ℃ for reaction for 5 hours. And transferring the reaction solution to a 500ml separating funnel, washing the reaction solution to be neutral by water, and removing the solvent and the water by reduced pressure distillation at 150 ℃ to obtain the organic silicon tackifier. The molecular weight, appearance and refractive index data are shown in table 4.
Example 56
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of the phenyl vinyl siloxane resin in example 1 and 50g of the phenyl hydrogen-containing siloxane resin in example 17 were mixed, 15g of the hyperbranched phenyl siloxane reinforcing agent in example 33, 1.5g of the organic silicon tackifier in example 45 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred and defoamed in vacuum until no air bubbles appeared, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, 130 ℃ for 2 hours and 150 ℃ for 3 hours to obtain a transparent silicon resin cured product. The properties are shown in Table 5. The components are packaged by using a surface mount package process, and the airtightness between the bracket and the silicone resin after the electronic components are packaged is detected by using a red ink experiment, as shown in fig. 9 a.
Example 57
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of phenyl vinyl siloxane resin in example 1 and 50g of phenyl hydrogen-containing siloxane resin in example 17 were mixed, 10g of hyperbranched phenyl siloxane reinforcing agent in example 33, 1.5g of organic silicon tackifier in example 45 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred and defoamed in vacuum until no bubbles appear, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, at 130 ℃ for 2 hours and at 150 ℃ for 3 hours to obtain a transparent cured product of silicone resin. The properties are shown in Table 5.
Example 58
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
40g of the phenyl vinyl siloxane resin in example 1 and 40g of the phenyl hydrogen-containing siloxane resin in example 17 were mixed, 15g of the hyperbranched phenyl siloxane reinforcing agent in example 33, 1.5g of the organic silicon tackifier in example 45 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred and defoamed in vacuum until no air bubbles appeared, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, 130 ℃ for 2 hours and 150 ℃ for 3 hours to obtain a transparent silicon resin cured product. The properties are shown in Table 5.
Example 59
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of the phenyl vinyl siloxane resin in example 14 and 50g of the phenyl hydrogen-containing siloxane resin in example 27 were mixed, 15g of the hyperbranched phenyl siloxane reinforcing agent in example 38, 1.5g of the organosilicon tackifier in example 51 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred, vacuum defoamed until no bubbles appeared, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, 130 ℃ for 2 hours and 150 ℃ for 3 hours to obtain a transparent cured silicone resin product. The properties are shown in Table 5.
Example 60
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of the phenyl vinyl siloxane resin in example 11 and 50g of the phenyl hydrogen-containing siloxane resin in example 31 were mixed, 15g of the hyperbranched phenyl siloxane reinforcing agent in example 36, 1.5g of the organosilicon tackifier in example 47 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred and defoamed in vacuum until no air bubbles appeared, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, 130 ℃ for 2 hours and 150 ℃ for 3 hours to obtain a transparent cured silicone resin product. The properties are shown in Table 5.
Example 61
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of phenyl vinyl siloxane resin in example 1 and 50g of phenyl hydrogen-containing siloxane resin in example 26 were mixed, 15g of hyperbranched phenyl siloxane reinforcing agent in example 44, 1.5g of organic silicon tackifier in example 52 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred and defoamed in vacuum until no bubbles appear, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, at 130 ℃ for 2 hours and at 150 ℃ for 3 hours to obtain a transparent silicon resin cured product. The properties are shown in Table 5.
Comparative example 1
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of phenyl vinyl siloxane resin in example 1 and 50g of phenyl hydrogen-containing siloxane resin in example 17 were mixed, 10ppm of Karstedt catalyst was added, the mixture was stirred uniformly, vacuum defoamed until no bubbles appeared, and the mixture was cured in an oven at 100 ℃ for 1 hour, at 130 ℃ for 2 hours and at 150 ℃ for 3 hours to obtain a transparent cured silicone resin product. The properties are shown in Table 5. And (3) packaging the component by using a surface-mount packaging process, and detecting the airtightness between the bracket and the silicone resin after the electronic component is packaged by adopting a red ink experiment, as shown in fig. 9 b.
Comparative example 2
This example provides a high refractive index LED encapsulating silicone composition, which is prepared as follows.
50g of the phenyl vinyl siloxane resin in example 1 and 50g of the phenyl hydrogen-containing siloxane resin in example 17 were mixed, 15g of the hyperbranched phenyl MT siloxane in example 33 and 10ppm of Karstedt catalyst were added, the mixture was uniformly stirred, vacuum defoamed until no bubbles appeared, and the mixture was placed in an oven to be cured at 100 ℃ for 1 hour, 130 ℃ for 2 hours and 150 ℃ for 3 hours to obtain a transparent cured silicone resin product. The properties are shown in Table 5. And (3) packaging the component by using a surface-mount packaging process, and detecting the airtightness between the bracket and the silicone resin after the electronic component is packaged by using a red ink experiment, as shown in fig. 9 c.
TABLE 1 comparison of Properties of phenyl vinyl siloxane resins prepared under different conditions
Figure BDA0002072347020000201
As shown in table 1, the phenyl vinyl siloxane resins prepared under different conditions in examples 1 to 16 all have higher refractive index, and the molecular weight and the fluidity of the phenyl vinyl siloxane resin can be adjusted by changing the preparation conditions, which are specifically as follows: examples 1-3 show that when the condensation reaction time is short, oligomers with low molecular weight are mainly generated, and the fluidity is good; with the extension of the condensation reaction, the fluidity of the product is reduced, and the subsequent curing operation is inconvenient. Examples 1, 4 and 5 show that the influence of temperature on the polymer is complex, the ring-opening reaction rate can be increased by increasing the temperature, the molecular weight of the polymer is increased, but the depolymerization reverse reaction is accelerated by excessively high temperature, and the content of phenyl groups is reduced, so that the refractive index is reduced. Examples 1, 6 and 7 show that the molecular weights of the products obtained by the three catalysts are very close to each other, but the appearance of the product obtained by the NaOH catalytic polymerization is milky (CH)3)4The appearance of the product obtained by NOH catalytic polymerization is milky light yellow, the appearance of the product obtained by KOH catalytic polymerization is colorless and transparent, and the molecular weight and the refractive index both meet the requirements, so the KOH is a better condensation reaction catalyst. Examples 1, 8 and 9 show that when the amount of the catalyst is too large, the polymerization rate is too fast and the system is not easily controlled, resulting in a decrease in light transmittance of the product. Examples 1, 10 show that the hydrolysis temperature directly affects the rate of hydrolysis of the monomers and the appearance of the final polymer, and that excessive temperatures can even lead to gels and difficulties in obtaining a clear, homogeneous liquid. Examples 1, 11, 12, 13 and 14 show that the content of the endcapping agent tetramethyldivinyldisiloxane is effective in controlling the molar mass of the polymer, the molecular weight of the polymer gradually decreases with increasing amount of the endcapping agent, and the molecular weight of the product without the endcapping agent decreasesThe amount is difficult to control, and gelation is easy to occur; the addition of the end-capping agent can enable the product to be capped by a dimethyl vinyl silicon base, and in the process of curing with hydrogen-containing siloxane, the hydrosilylation reaction can prolong the molecular chain and improve the performance of the cured product; the methylvinyldimethoxysilane content can also serve to adjust the vinyl content of the product. Examples 1, 15, 16 show that the diphenyldimethoxysilane content is effective in adjusting the phenyl content and refractive index, but an increase in the content also results in a decrease in flowability.
TABLE 2 comparison of Properties of phenyl-hydrogenpolysiloxane resins prepared under different conditions
Figure BDA0002072347020000211
As shown in table 2, the phenyl hydrogen-containing polysiloxane resins prepared under different conditions in examples 17 to 32 all have higher refractive index, and the molecular weight and the fluidity of the phenyl hydrogen-containing polysiloxane resins can be adjusted by changing the preparation conditions, which are specifically as follows: examples 17, 21, 24, 25 and 26 show that the relative molecular weight increases and then decreases with the increase of the reaction time, and that unreacted silicon hydroxyl groups remain in the system when the condensation time is short, so that the degree of condensation is insufficient and the molecular weight is small; when the time exceeds 4 hours, the depolymerization rate of polymer molecules is greater than the polycondensation rate, the molecular weight is reduced by prolonging the condensation time, but the rearrangement of the polymer is more regular. Examples 18, 19, 20 and 21 show that at lower condensation temperatures, the silanol condensation is incomplete and the product appears milky; too high a temperature increases the rate of depolymerization of the polymer, resulting in a decrease in the molecular weight of the product; the condensation temperature of the prepolymer at 130 ℃ is colorless and transparent, the molecular weight of the prepolymer is proper, and the condensation temperature is more preferable. Examples 20, 21 show that the amount of water does not have a great effect on the refractive index of the product, but on the appearance of the system; as the water addition amount is increased, the hydrolysis rates of all monomers are inconsistent, so that the hydrolysis liquid is not uniform, and the silanol generated by hydrolysis is cyclized, and the product is milky white. Examples 20, 22 and 23 show that three different catalysts have certain catalytic effects, and the product prepared from concentrated hydrochloric acid has small molecular weight and is colored; the strong acid cation exchange resin has slightly low catalytic activity, so that the molecular weight of the product is not large enough, and the product can be removed by filtering after the reaction is finished, but the product can also be crushed during the stirring process to influence the transparency of the product; the prepolymer prepared by glacial acetic acid is colorless and transparent, and the molecular weight and the refractive index both meet the requirements, so that the catalyst is a better catalyst. Examples 20, 27, 28 show that the molecular weight gradually increases until it stabilizes as the amount of catalyst used increases. Examples 20, 29 and 30 show that the content of tetramethyldisiloxane as the end-capping agent is effective in controlling the molar mass of the polymer, and that the molecular weight of the polymer decreases gradually as the amount of the end-capping agent increases. Examples 20, 31, and 32 show that adjusting the raw material ratio can change the molecular weight and refractive index of the product, and that increasing the relative content of phenyltrimethoxysilane can increase the molecular weight and refractive index, but tends to result in a more brittle cured product.
TABLE 3 comparison of Properties of hyperbranched phenylsiloxane reinforcing Agents prepared under different conditions
Figure BDA0002072347020000212
Figure BDA0002072347020000221
As shown in table 3, the hyperbranched phenylsiloxane reinforcing agents prepared under different conditions in examples 33 to 44 all have higher refractive index, and the molecular weight and the fluidity of the hyperbranched phenylsiloxane reinforcing agent can be adjusted by changing the preparation conditions, which are specifically as follows: examples 33, 34, 35 show that when the condensation temperature is lower, the probability of collision between silicon hydroxyl groups is lower, effective collision is reduced, the reaction degree is reduced, the molecular weight of the generated polymer is smaller, and the fluidity is better; if the condensation temperature is too high, the molecular motion of the system is violent, the effective collision among silicon hydroxyl groups is accelerated, the condensation reaction is promoted, the molecular weight of the generated product is larger, the molecular chain motion becomes difficult, the viscosity of the polymer is obviously increased, and the polymer becomes gel when serious. Examples 33, 36 and 37 show that different catalysts have a greater effect on the hydrolytic condensation of siloxane, concentrated sulfuric acid has a higher catalytic activity, the product molecular weight is significantly higher than that of glacial acetic acid and concentrated hydrochloric acid, and glacial acetic acid and concentrated hydrochloric acid products are better under the same catalyst concentration. Examples 33, 38 and 39 show that the rate of hydrolysis and condensation of siloxanes increases with increasing catalyst usage in the experimental range, the extent of reaction increases, the molecular weight of the polymer formed increases, and the viscosity of the product increases. Examples 36, 40 and 41 show that the viscosity of the product can be obviously different with different water addition amounts, and when the water addition amount is more, the product has a large number of hydroxyl groups, and the viscosity of the product is increased due to intermolecular hydrogen bonding; when the amount of added water is small, the molecular weight of the condensed polymer is small, the viscosity is low, and the fluidity is good, but the molecular weight of the generated polymer is too low, and the reinforcing effect on the material is reduced, so that the proportion of water and the methoxyl functional group needs to be controlled to ensure that the product has a certain reinforcing effect and proper molecular weight. Examples 36, 42, 43 show that the ratio of hexamethyldisiloxane to tetramethyldivinyldisiloxane blocking agent has a large effect on the molecular weight of the product, and when the amount of the blocking agent is low, the molecular weight is large, the flowability is reduced, the number of reactive groups such as vinyl groups at the ends of the molecular chain is reduced, the number of reactive sites is reduced, and when the blocking agent is added to a substrate, the substrate cannot be effectively reinforced; when the amount of the end-capping agent is too large, the molecular weight is low, the viscosity of the product is low, but when the amount of the end-capping agent is too large, reaction sites are increased, and when the end-capping agent is used as a reinforcing filler, the mechanical properties such as toughness of the product are also poor when the end-capping agent is added into a matrix, and the material is easily brittle. When the ratio of the blocking agent was varied, which also means that the phenyltrimethoxysilane content was varied, in combination with example 44, it was also demonstrated that increasing the phenyltrimethoxysilane content increased the refractive index of the product.
Table 4 comparison of properties of silicone adhesion promoters prepared under different conditions
Figure BDA0002072347020000222
Figure BDA0002072347020000231
As shown in table 4, the organic silicon tackifiers prepared under different conditions in examples 45 to 55 all have higher refractive index, and the molecular weight and the fluidity of the organic silicon tackifier can be adjusted as follows by changing the preparation conditions: examples 45, 46, 47 show that the condensation temperature does not have a major effect on the refractive index of the product, but that the condensation molecular weight increases and then decreases with increasing reaction temperature. Examples 45, 48 and 49 show that as the condensation time is prolonged, the condensation reaches dynamic equilibrium, and the molecular weight of the product is larger, so that the fluidity of the product is reduced and the viscosity is increased; furthermore, as the condensation time is prolonged, the rearrangement of the siloxane produced by condensation is more sufficient, and the copolymer produced is further rearranged into a regular structure. Examples 45, 50, 51 show that KH560 gives a yellowish color to the product due to the presence of amino groups, while neither KH570 alone nor KH560 in smaller amounts affect the color of the product, and furthermore the coupling agent does not affect the molecular weight and refractive index of the product much. Examples 45, 52, 53 show that the number average molecular weight of the product gradually decreases with increasing amount of the end-capping reagent, indicating that the end-capping reagent can make a large adjustment to the molecular weight of the polymer; in addition, it can be seen that the amount of the end-capping agent has a large influence on the refractive index, and as the amount of the end-capping agent increases, the phenyl content relatively decreases, and the refractive index gradually decreases. Examples 45, 54, 55 show that the refractive index can be adjusted by controlling the addition of phenyltrimethoxysilane and diphenyldisiloxane, the higher the content of phenyl monomer, the larger the refractive index; however, if the refractive index is not as high as possible, and if the refractive index difference is large, the compatibility with other components is lowered, and the light transmittance of the final cured silicone resin for LED encapsulation is affected.
TABLE 5 comparison of the Properties of the cured Silicone resins
Figure BDA0002072347020000232
Examples 56, 57, 58, comparative example 1 and comparative example 2 show that an increase in the ratio of hyperbranched phenylsiloxane reinforcing agent to silicone tackifier has an important effect on improving the mechanical strength and adhesive strength of the product. Examples 56, 59, and 60 show that a higher overall performance can be achieved by appropriate selection of compositions under different conditions, and that the silicone prepared by the method has more excellent refractive index, tensile strength, and adhesive strength by comparison with several commercial silicones.
Fig. 9 is a photograph showing the results of red ink test of the surface mount LED package devices of example 56 (fig. 9-a), comparative example 1 (fig. 9-b) and comparative example 2 (fig. 9-c). As can be seen from the figure, the substrate packaged in example 56 was boiled in red ink at 80 ℃ for two hours, and no red ink penetrated into the chip, indicating that the prepared silicone material had good adhesion to the substrate, effectively blocked the penetration of moisture, oxygen, dust, and the like, and had sufficient airtightness. While the product without hyperbranched phenylsiloxane reinforcing agent and silicone tackifier (comparative example 1) and the product without tackifier (comparative example 2) had a small amount of red ink penetration at the edge.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.

Claims (4)

1. The high-refractive-index LED packaging silicone resin composition is characterized by comprising the following components in parts by weight:
40-60 parts of phenyl vinyl siloxane resin,
40-60 parts of phenyl hydrogen-containing siloxane resin,
10-20 parts of hyperbranched phenyl siloxane reinforcing agent,
0.5 to 2 parts of organic silicon tackifier,
10-20 ppm Karstedt catalyst;
the phenyl vinyl siloxane resin is prepared by the following method:
s1: mixing the following monomers: mixing diphenyldimethoxysilane, methylvinyldimethoxysilane, octamethylcyclotetrasiloxane and tetramethyldivinyldisiloxane, adding an organic solvent to obtain a mixed solution, and adding a hydrolysis catalyst; the mass ratio of the diphenyldimethoxysilane to the methylvinyldimethoxysilane to the octamethylcyclotetrasiloxane to the tetramethyldivinyldisiloxane is 50-70: 10-20: 10-30: 5-15;
s2: dripping water at 30-60 ℃ for hydrolysis reaction, washing, distilling under reduced pressure, adding an alkali catalyst to adjust the pH to 11-14, carrying out condensation reaction at 120-160 ℃, washing, and distilling under reduced pressure to obtain the phenyl vinyl siloxane resin;
the phenyl hydrogen-containing siloxane resin is prepared by the following preparation method: mixing the following monomers: mixing phenyl trimethoxy silane, diphenyl dimethoxy silane, tetramethyl cyclotetrasiloxane and tetramethyl disiloxane, water and a hydrolysis reaction catalyst, adding an organic solvent to obtain a mixed solution, heating to 30-60 ℃, carrying out hydrolysis reaction for 1-5 h, heating to 110-140 ℃, carrying out water diversion reaction for 2-11 h, washing, and carrying out reduced pressure distillation to obtain the phenyl hydrogen-containing siloxane resin; the mass ratio of the phenyltrimethoxysilane to the diphenyldimethoxysilane to the tetramethylcyclotetrasiloxane to the tetramethyldisiloxane is 15-25: 45-55: 10-20: 1.5-15
The hyperbranched phenyl siloxane reinforcing agent is prepared by the following method: mixing the following monomers: mixing hexamethyldisiloxane and tetramethyldivinyldisiloxane, water and an acid catalyst, adding an organic solvent to obtain a mixed solution, dropwise adding phenyltrimethoxysilane, performing hydrolysis reaction at 30-50 ℃ for 0.5-4 h, heating to 50-120 ℃, continuing to react for 1-3 h, washing, and performing reduced pressure distillation to obtain the hyperbranched phenylsiloxane reinforcing agent; the mass ratio of the hexamethyldisiloxane to the tetramethyldivinyldisiloxane to the phenyltrimethoxysilane is 5-15: 10-20: 15-25;
the organic silicon tackifier is prepared by the following method: mixing the following monomers: mixing phenyltrimethoxysilane, diphenyldimethoxysilane, methylvinyldimethoxysilane and tetramethyldivinyldisiloxane, adding an organic solvent to obtain a mixed solution, adding a hydrolysis catalyst, carrying out hydrolysis reaction washing at 30-50 ℃, adding a silane coupling agent and a condensation reaction catalyst after rotary evaporation, and heating to 80-140 ℃ for reaction for 1-7 hours; washing and filtering to obtain the organic silicon tackifier; the mass ratio of the phenyltrimethoxysilane to the diphenyldimethyloxysilane to the methylvinyldimethoxysilane to the tetramethyldivinyldisiloxane to the silane coupling agent is 15-25: 25-35: 10-20: 2-15: 10-20.
2. The high refractive index LED encapsulation silicone resin composition according to claim 1, wherein the mass ratio of diphenyldimethoxysilane, methylvinyldimethoxysilane, octamethylcyclotetrasiloxane and tetramethyldivinyldisiloxane in S1 is 50:15:20: 5.
3. The high-refractive-index LED encapsulation silicone resin composition as claimed in claim 1, which is prepared from the following components in parts by weight:
50 parts of phenyl vinyl siloxane resin,
50 parts of phenyl hydrogen-containing siloxane resin,
15 parts of hyperbranched phenyl siloxane reinforcing agent,
1.5 parts of organic silicon tackifier,
karstedt catalyst 10 ppm.
4. The preparation method of the high-refractive-index LED encapsulation silicone resin composition of any one of claims 1 to 3, characterized by comprising the following steps: and mixing phenyl vinyl siloxane resin and phenyl hydrogen-containing siloxane resin, adding hyperbranched phenyl siloxane reinforcing agent, organic silicon tackifier and Karstedt catalyst, stirring, defoaming and curing to obtain the high-refractive-index LED packaging silicon resin composition.
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