High-performance organic silicon resin packaging adhesive for LED packaging and preparation method of high-performance organic silicon resin packaging adhesive

Abstract

The invention relates to the technical field of electronic packaging, and particularly discloses a high-performance organic silicon resin packaging adhesive for LED packaging and a preparation method of the high-performance organic silicon resin packaging adhesive. The high-performance organic silicon resin packaging adhesive is prepared from a component A and a component B, wherein the weight ratio of the component A to the component B is 1: (0.5-2); the component A is mainly prepared from the following raw materials in parts by weight: 40-60 parts of vinyl-containing methyl phenyl silicon titanium resin, 0.05-0.2 part of a platinum catalyst and 1-3 parts of a boron-containing tackifier; and the component B is mainly prepared from the following raw materials in parts by weight: 40-60 parts of methyl phenyl silicone resin containing hydrogen groups and 0.1-0.3 part of an alkynyl-containing inhibitor. The high-performance organic silicon resin packaging adhesive has the characteristics of high light transmittance, high refractive index, high hardness, high bonding strength, high tensile strength and good heat aging resistance, shows excellent comprehensive performance, and meets the requirements of LED packaging.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of electronic packaging, in particular to a high-performance silicone resin packaging glue for LED packaging and a preparation method thereof. BACKGROUND

[0002] With the concept of sustainable development being deeply rooted in people's minds, lighting sources are also developing in the direction of green energy saving. Compared with traditional incandescent lamps and fluorescent lamps, lighting sources based on LED technology have the advantages of long service life, low power consumption and high luminous efficiency, and have been widely used in people's daily life. The wide application of LED lamps puts forward higher requirements for packaging materials.

[0003] LED packaging materials are mainly divided into epoxy resin packaging glue, polyurethane packaging glue and silicone resin packaging glue according to the base material. The epoxy resin packaging glue mainly has the problems of high brittleness, easy yellowing under light and poor heat resistance; the polyurethane packaging glue mainly has the problems of low mechanical strength, poor heat resistance and poor water resistance. Compared with the former two kinds of packaging materials, the silicone resin packaging glue has many advantages such as excellent solvent resistance, high and low temperature resistance, light resistance and so on, and is recognized as the most promising electronic industry packaging material. At present, the patent application CN110229339A provides a phenyl vinyl siloxane resin and a high refractive index LED packaging silicone resin composition. The refractive index of the phenyl vinyl siloxane resin is less than 1.6, and the tensile strength is less than 5 MPa. The refractive index and tensile strength are not good enough and need to be further improved. SUMMARY

[0004] In order to improve the refractive index and tensile strength of the silicone resin packaging glue, the application provides a high-performance silicone resin packaging glue for LED packaging and a preparation method thereof.

[0005] In the first aspect, the application provides a high-performance silicone resin packaging glue for LED packaging, which adopts the following technical scheme: A high-performance silicone resin packaging glue for LED packaging is prepared from component A and component B, and the weight ratio of the component A to the component B is 1:(0.5-2). The component A is mainly prepared from the following raw materials in parts by weight: vinyl-containing methylphenylsilicon titanium resin 40-60 parts, platinum catalyst 0.05-0.2 parts, and boron-containing tackifier 1-3 parts; and the component B is mainly prepared from the following raw materials in parts by weight: hydrogen-containing methylphenylsilicon resin 40-60 parts, and alkyne-containing inhibitor 0.1-0.3 parts.

[0006] The high-performance silicone resin encapsulating glue for LED packaging of the application has the characteristics of high light transmittance, high refractive index, high hardness, high adhesive strength, high tensile strength, and good heat aging resistance, and shows excellent comprehensive performance, meeting the needs of LED packaging.

[0007] The high-performance silicone resin encapsulating glue of the application has excellent light transmittance, hardness, and tensile strength after the silicon-hydrogen addition reaction of the vinyl-containing methylphenyl silicon titanium resin and the hydrogen-containing methylphenyl silicon resin. The introduction of phenyl can increase the refractive index and heat aging resistance. The titanium element is introduced into the vinyl-containing methylphenyl silicon titanium resin, further increasing the refractive index, light transmittance, tensile strength, and heat aging resistance. The boron-containing adhesion promoter is added to the A component, which has excellent compatibility with the vinyl-containing methylphenyl silicon titanium resin and the hydrogen-containing methylphenyl silicon resin, significantly improving the adhesive strength, further increasing the refractive index and transmittance, and making the high-performance silicone resin encapsulating glue show better comprehensive performance.

[0008] Optionally, the vinyl-containing methylphenyl silicon titanium resin is composed of methylphenyl structural units, diphenyl structural units, titanium oxygen structural units, and dimethyl vinyl structural units, and the structure formula of the vinyl-containing methylphenyl silicon titanium resin is as follows: (MePhSiO)m1(Ph2SiO)n1(TiO2)x1(Me2ViSiO 0.5 )y1, wherein m1:n1:x1:y1=(0.15-0.45):(0.3-0.6):(0.1-0.4):(0.1-0.3); The hydrogen-containing methylphenyl silicon resin is composed of methylphenyl structural units, diphenyl structural units, phenyl structural units, and dimethyl hydrogen structural units, and the structure formula of the hydrogen-containing methylphenyl silicon resin is as follows: (MePhSiO)m2(Ph2SiO)n2(PhSiO 1.5 )x2(Me2HSiO 0.5 )y2, wherein m2:n2:x2:y2=(0.15-0.4):(0.3-0.5):(0.2-0.4):(0.2-0.35).

[0009] By optimizing the structure formula of the vinyl-containing methylphenyl silicon titanium resin and the hydrogen-containing methylphenyl silicon resin, the stability of the A component and the B component is ensured.

[0010] Optionally, the raw material of the vinyl-containing methylphenyl silicon-titanium resin comprises a structural unit monomer, the structural unit monomer is one or both of a methylphenyl-containing siloxane monomer, a diphenyl-containing siloxane monomer, a titanate monomer, and a dimethyl vinyl-containing siloxane monomer; The methylphenyl-containing siloxane monomer is one or both of methylphenyl dimethoxysilane and methylphenyl diethoxysilane, and / or the diphenyl-containing siloxane monomer is one or both of diphenyl dimethoxysilane and diphenyl diethoxysilane, and / or the titanate monomer is one or more of tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisobutyl titanate, and / or the dimethyl vinyl-containing siloxane monomer is one or more of dimethyl vinyl methoxysilane, dimethyl vinyl ethoxysilane, and tetramethyl divinyl disiloxane.

[0011] By using the above technical solution, the monomers used in the raw material of the vinyl-containing methylphenyl silicon-titanium resin are optimized, which facilitates the preparation of the vinyl-containing methylphenyl silicon-titanium resin.

[0012] Optionally, the vinyl-containing methylphenyl silicon-titanium resin is prepared by the following method: mixing an organic solvent, a methylphenyl-containing siloxane monomer, a diphenyl-containing siloxane monomer, a titanate monomer, and a dimethyl vinyl-containing siloxane monomer, heating to 40-45℃, adding an acid catalyst, and heat-treating for 2-3h, heating to 80-85℃, heat-treating for 4-6h, cooling to room temperature, and obtaining a mixed solution; The mixed solution is extracted to obtain an organic phase; the organic phase is heated to 110-120℃, heat-treated for 30-60min, an alkali catalyst is added, heat-treated for 2-4h, cooled to room temperature, washed with water until neutral, and vacuum-removed low-boiling substances to obtain the vinyl-containing methylphenyl silicon-titanium resin.

[0013] Optionally, in the preparation of the vinyl-containing methylphenyl silicon-titanium resin, the amount of the organic solvent used is 15-20wt% of the total weight of the structural unit monomers, the amount of the acid catalyst used is 3-5wt% of the total weight of the structural unit monomers, and the amount of the alkali catalyst used is 0.1-0.3wt% of the total weight of the structural unit monomers.

[0014] Optionally, in the preparation of the vinyl-containing methylphenyl silicon-titanium resin, the organic solvent is one or more of methanol, ethanol, ethyl acetate, and butyl acetate. The acid catalyst is a hydrochloric acid solution, and the mass concentration of the hydrochloric acid solution is 15-20%. The extractant is one or more of toluene, xylene, and petroleum ether. The volume ratio of the extractant to the mixed solution is 1:(0.5-3). The alkali catalyst is one or both of sodium hydroxide and potassium hydroxide.

[0015] Optionally, the raw material of the methyl phenyl silicon resin containing hydrogen group comprises a structural unit monomer, the structural unit monomer is one or both of a methyl phenyl siloxane monomer, a diphenyl siloxane monomer, a phenyl siloxane monomer, and a dimethyl hydrogen siloxane monomer; The methyl phenyl siloxane monomer is one or both of methyl phenyl dimethoxysilane and methyl phenyl diethoxysilane, and / or the diphenyl siloxane monomer is one or both of diphenyl dimethoxysilane and diphenyl diethoxysilane, and / or the phenyl siloxane monomer is one or both of phenyl trimethoxysilane and phenyl triethoxysilane, and / or the dimethyl hydrogen siloxane monomer is one or more of dimethyl methoxysilane, dimethyl ethoxysilane, and tetramethyl disiloxane.

[0016] By using the above technical solution, the monomers used in the raw material of the methyl phenyl silicon resin containing hydrogen group are optimized, which facilitates the preparation of the methyl phenyl silicon resin containing vinyl group.

[0017] Optionally, the methyl phenyl silicon resin containing hydrogen group is prepared by the following method: mixing an organic solvent, a methyl phenyl siloxane monomer, a diphenyl siloxane monomer, a phenyl siloxane monomer, and a dimethyl hydrogen siloxane monomer, heating to 40-50°C, adding an acid catalyst X, and heat-treating for 3-5h, heating to 80-85°C, heat-treating for 4-6h, cooling to room temperature, and obtaining a mixed solution; The mixed solution is extracted to obtain an organic phase; an acid catalyst Y is added to the organic phase, heat-treating for 4-6h, washing with water until neutral, removing low-boiling substances under vacuum, and obtaining the methyl phenyl silicon resin containing hydrogen group.

[0018] Optionally, in the preparation of the methyl phenyl silicon resin containing hydrogen group, the amount of the organic solvent used is 10-15wt% of the total weight of the structural unit monomers, the amount of the acid catalyst X used is 3-6wt% of the total weight of the structural unit monomers, and the amount of the acid catalyst Y used is 3-6wt% of the total weight of the structural unit monomers.

[0019] Optionally, in the preparation of the methyl phenyl silicon resin containing hydrogen group, the organic solvent is one or more of methanol, ethanol, ethyl acetate, and butyl acetate. The acid catalyst X is a hydrochloric acid solution, and the mass concentration of the hydrochloric acid solution is 10-15%. The extractant is one or more of toluene, xylene, and petroleum ether. The volume ratio of the extractant to the mixed solution is 1:(0.5-3). The acid catalyst Y is concentrated sulfuric acid.

[0020] Optionally, the boron-containing adhesion promoter is prepared from a methyl vinyl siloxane monomer, a methyl phenyl siloxane monomer, an epoxy group-containing siloxane monomer, and a boron-containing monomer, and the structural formula of the boron-containing adhesion promoter is:

[0021] By adopting the technical scheme, the boron-containing tackifier is limited to ensure the stability of the boron-containing tackifier and the performance of the high-performance silicone resin encapsulating adhesive.

[0022] Optionally, the boron-containing tackifier is prepared from the methyl vinyl-containing raw materials including a methyl vinyl-containing siloxane monomer, a methyl phenyl-containing siloxane monomer, an epoxy group-containing siloxane monomer and a boron-containing monomer. The methyl vinyl-containing siloxane monomer is one or both of methyl vinyl dimethoxysilane and methyl vinyl diethoxysilane, and / or the methyl phenyl-containing siloxane monomer is one or both of methyl phenyl dimethoxysilane and methyl phenyl diethoxysilane, and / or the epoxy group-containing siloxane monomer is one or both of 3-(2,3-epoxypropoxy)propyl trimethoxysilane and 3-(2,3-epoxypropoxy)propyl triethoxysilane, and / or the boron-containing monomer is one or more of boric acid, methyl boric acid and phenyl boric acid.

[0023] Optionally, the boron-containing tackifier is prepared by mixing the organic solvent, the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer and the boron-containing monomer, heating to 70-75°C, adding a resin catalyst, holding for 4-6 h, filtering, and removing low-boiling substances under vacuum to obtain the boron-containing tackifier.

[0024] Optionally, in the preparation of the boron-containing tackifier, the molar ratio of the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer and the boron-containing monomer is (0.2-0.3):(0.4-0.5):(0.1-0.2):(0.3-0.4).

[0025] Optionally, in the preparation of the boron-containing tackifier, the amount of the organic solvent is 10-15 wt% of the total weight, and the amount of the resin catalyst is 5-10 wt% of the total weight, based on the total weight of the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer and the boron-containing monomer. The organic solvent is one or both of methanol and ethanol. The resin catalyst is an anion exchange resin.

[0026] Optionally, in the A component, the platinum catalyst is chloroplatinic acid-isopropyl alcohol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropyl alcohol solution is 0.05-0.2 mol / L. In the B component, the alkynyl-containing inhibitor is one or more of 1-ethynylcyclohexanol, 3,5-dimethyl-3-hexyn-1-ol and 3-methyl-1-butyne-3-ol.

[0027] In a second aspect, the application provides a preparation method of the high-performance silicone resin encapsulating adhesive for LED packaging, which adopts the following technical scheme: The application discloses a preparation method of the high-performance silicone resin encapsulating glue for LED packaging. The vinyl-containing methyl phenyl silicon titanium resin, a platinum catalyst and a boron-containing tackifier are mixed to obtain component A; The hydrogen-containing methyl phenyl silicon resin and the alkyne group-containing inhibitor are mixed to obtain component B; The components A and B are mixed and vacuum defoamed to obtain the high-performance silicone resin encapsulating glue.

[0028] In summary, the application has at least the following beneficial effects: 1. The high-performance silicone resin encapsulating glue for LED packaging has the following characteristics: Shore hardness > 70D, refractive index >= 1.7, light transmittance >= 90%, bonding strength > 5.MPa, tensile strength > 8MPa, no yellowing after 200 DEG C * 1h heat aging treatment, high light transmittance, high refractive index, high hardness, high bonding strength, high tensile strength and good heat aging resistance, and excellent comprehensive performance, and meets the requirements of LED packaging.

[0029] 2. The high-performance silicone resin encapsulating glue is mainly prepared from the vinyl-containing methyl phenyl silicon titanium resin and the hydrogen-containing methyl phenyl silicon resin, and has excellent light transmittance, hardness and tensile strength after the silicon hydrogen addition reaction. The phenyl and titanium elements are introduced, and the refractive index, light transmittance, tensile strength and heat aging resistance are further increased. Meanwhile, the boron-containing tackifier is added to component A, has excellent compatibility, significantly improves the bonding strength, further increases the refractive index and transmittance, and makes the high-performance silicone resin encapsulating glue have better comprehensive performance. DETAILED DESCRIPTION

[0030] The application is further described in detail in combination with the following examples. EXAMPLES

[0031] Example 1 The high-performance silicone resin encapsulating glue for LED packaging is prepared from component A and component B, and the weight ratio of the components A and B is 1:1. The component A is mainly prepared from the following raw materials: 50g of the vinyl-containing methyl phenyl silicon titanium resin, 0.1g of a platinum catalyst and 2g of a boron-containing tackifier. The component B is mainly prepared from the following raw materials: 50g of the hydrogen-containing methyl phenyl silicon resin and 0.2g of the alkyne group-containing inhibitor.

[0032] The application discloses a preparation method of the high-performance silicone resin encapsulating glue for LED packaging. S1, preparing raw materials of component A SA1, vinyl-containing methyl phenyl silicon titanium resin: the raw materials of the vinyl-containing methyl phenyl silicon titanium resin include structural unit monomers, and the structural unit monomers are methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, titanate monomers and dimethyl vinyl-containing siloxane monomers. The methyl phenyl-containing siloxane monomers are methyl phenyl dimethoxysilane; the diphenyl-containing siloxane monomers are diphenyl dimethoxysilane; the titanate monomers are tetrapropyl titanate; and the dimethyl vinyl-containing siloxane monomers are dimethyl vinyl methoxysilane.

[0033] A preparation method of the vinyl-containing methyl phenyl silicon titanium resin: the methyl phenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the titanate monomers and the dimethyl vinyl-containing siloxane monomers are mixed, and 15 wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is increased to 40 ℃, 3 wt% of an acid catalyst based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 2 h. The temperature is increased to 80 ℃, the mixture is treated at the temperature for 4 h, and the mixture is cooled to 25 ℃ to obtain a mixed solution.

[0034] The mixed solution is mixed with an extractant, and the mixture is allowed to stand and separate into layers to obtain an organic phase. The organic phase is heated to 110 ℃, and the mixture is treated at the temperature for 60 min. 0.1 wt% of a base catalyst based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 2 h. The mixture is cooled to 25 ℃, washed to neutral, and vacuumed to remove low-boiling substances to obtain the vinyl-containing methyl phenyl silicon titanium resin.

[0035] In the preparation method, the molar ratio of the methyl phenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the titanate monomers and the dimethyl vinyl-containing siloxane monomers is 0.36:0.57:0.22:0.18; the organic solvent is ethanol; the acid catalyst is a hydrochloric acid solution with a mass concentration of 20%; the extractant is dimethylbenzene; the volume ratio of the extractant to the mixed solution is 1:1; the base catalyst is sodium hydroxide; and the washing liquid used in the washing to neutral is a hydrochloric acid-ethanol solution, and the mass concentration of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%.

[0036] SA2, boron-containing adhesion promoter: the raw materials of the boron-containing adhesion promoter include methyl vinyl-containing siloxane monomers, methyl phenyl-containing siloxane monomers, epoxy group-containing siloxane monomers and boron-containing monomers. The methyl vinyl-containing siloxane monomers are methyl vinyl dimethoxysilane; the methyl phenyl-containing siloxane monomers are methyl phenyl dimethoxysilane; the epoxy group-containing siloxane monomers are 3-(2,3-epoxypropoxy) propyl trimethoxysilane; and the boron-containing monomers are boric acid.

[0037] The preparation method of the boron-containing adhesion promoter: the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer are mixed, and 15wt% of the total weight of the reaction monomers of the organic solvent is added. The temperature is raised to 70℃, 5wt% of the total weight of the reaction monomers of the resin catalyst is added, and the mixture is treated for 4h, filtered, and vacuumed to remove low-boiling substances to obtain the boron-containing adhesion promoter.

[0038] The molar ratio of the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer is 0.2:0.4:0.1:0.3; the organic solvent is methanol; and the resin catalyst is anion exchange resin D201.

[0039] SA3, platinum catalyst: the platinum catalyst is chloroplatinic acid-isopropanol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropanol solution is 0.1mol / L.

[0040] S2, preparation of component A: the vinyl-containing methyl phenyl silicon titanium resin, the platinum catalyst, and the boron-containing adhesion promoter are mixed to obtain component A.

[0041] S3, preparation of B component raw materials SB1, vinyl-containing methyl phenyl silicon titanium resin: the raw materials of the vinyl-containing methyl phenyl silicon titanium resin include structural unit monomers, and the structural unit monomers are methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, phenyl-containing siloxane monomers, and dimethyl hydrogen-containing siloxane monomers. The methyl phenyl-containing siloxane monomer is methyl phenyl dimethoxysilane; the diphenyl-containing siloxane monomer is diphenyl dimethoxysilane; the phenyl-containing siloxane monomer is phenyl trimethoxysilane; and the dimethyl hydrogen-containing siloxane monomer is dimethyl methoxysilane.

[0042] The preparation method of the vinyl-containing methyl phenyl silicon titanium resin: the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the phenyl-containing siloxane monomer, and the dimethyl hydrogen-containing siloxane monomer are mixed, and 15wt% of the total weight of the structural unit monomers of the organic solvent is added. The temperature is raised to 40℃, 4wt% of the total weight of the structural unit monomers of the acid catalyst X is added, and the mixture is treated for 3h, the temperature is raised to 80℃, and the mixture is treated for 4h, and then the mixture is cooled to room temperature to obtain a mixed solution.

[0043] The extractant is added to the mixed solution, and the mixture is allowed to stand and separate into layers to obtain an organic phase. 4wt% of the total weight of the structural unit monomers of the acid catalyst Y is added to the organic phase, and the mixture is treated for 6h, washed with water until neutral, and vacuumed to remove low-boiling substances to obtain a hydrogen-containing methyl phenyl silicon resin.

[0044] The molar ratio of the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the phenyl-containing siloxane monomer, and the dimethyl hydrogen-containing siloxane monomer is 0.3:0.45:0.34:0.18; the organic solvent is ethanol; the acid catalyst X is a hydrochloric acid solution with a mass concentration of 10%; the extractant is xylene; the volume ratio of the extractant to the mixed solution is 1:1; and the acid catalyst Y is concentrated sulfuric acid.

[0045] SB2, acetylenic group-containing inhibitor: the acetylenic group-containing inhibitor is 1-ethynylcyclohexanol.

[0046] S4, preparation of component B: the methylphenyl-containing siloxane monomer and the acetylenic group-containing inhibitor are mixed to obtain component B.

[0047] S5, preparation of high-performance silicone resin encapsulating adhesive: components A and B are mixed, and vacuum defoaming is performed for 30 minutes to obtain the high-performance silicone resin encapsulating adhesive.

[0048] Example 2 A high-performance silicone resin encapsulating adhesive for LED packaging, which is different from example 1 in that the preparation method of the high-performance silicone resin encapsulating adhesive is different.

[0049] A preparation method of a high-performance silicone resin encapsulating adhesive for LED packaging, comprising the following steps: S1, preparation of raw materials of component A SA1, methylphenyl-containing siloxane monomer: the raw materials of the methylphenyl-containing siloxane monomer include structural unit monomers, and the structural unit monomers are a methylphenyl-containing siloxane monomer, a diphenyl-containing siloxane monomer, a titanium ester monomer, and a dimethyl vinyl-containing siloxane monomer. The methylphenyl-containing siloxane monomer is methylphenyl diethoxysilane; the diphenyl-containing siloxane monomer is diphenyl diethoxysilane; the titanium ester monomer is tetrabutyl titanate; and the dimethyl vinyl-containing siloxane monomer is dimethyl vinyl ethoxysilane.

[0050] A preparation method of the methylphenyl-containing siloxane monomer: the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanium ester monomer, and the dimethyl vinyl-containing siloxane monomer are mixed, and 15wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is increased to 40℃, 3wt% of an acid catalyst based on the total weight of the structural unit monomers is added, and heat treatment is performed for 2.5 hours. The temperature is increased to 80℃, heat treatment is performed for 4.5 hours, and the temperature is cooled to 25℃ to obtain a mixed solution.

[0051] The extractant is added to the mixed solution, mixed, and allowed to separate into layers to obtain an organic phase. The organic phase is warmed to 110°C, and held for 30 min. 0.1wt% of an alkali catalyst based on the total weight of the structural unit monomers is added, and held for 2h. The temperature is cooled to 25°C, and washed until neutral. The low boiling point material is removed under vacuum to obtain the vinyl-containing methylphenyl silicon-titanium resin.

[0052] The molar ratio of the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer, and the dimethyl vinyl-containing siloxane monomer is 0.32:0.5:0.18:0.2; the organic solvent is ethanol; the acid catalyst is a 20% hydrochloric acid solution by mass concentration. The extractant is xylene, and the volume ratio of the extractant to the mixed solution is 1:1. The alkali catalyst is sodium hydroxide. In the neutralization process, a hydrochloric acid-ethanol solution is used as the washing liquid, and the mass concentration of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%.

[0053] SA2, boron-containing adhesion promoter: The raw materials of the boron-containing adhesion promoter include methyl vinyl-containing siloxane monomers, methylphenyl-containing siloxane monomers, epoxy-containing siloxane monomers, and boron-containing monomers. The methyl vinyl-containing siloxane monomer is methyl vinyl diethoxysilane; the methylphenyl-containing siloxane monomer is methylphenyl diethoxysilane; the epoxy-containing siloxane monomer is 3-(2,3-epoxypropoxy) propyl triethoxysilane; and the boron-containing monomer is boric acid.

[0054] Method for preparing the boron-containing adhesion promoter: The methyl vinyl-containing siloxane monomers, the methylphenyl-containing siloxane monomers, the epoxy-containing siloxane monomers, and the boron-containing monomers are mixed, and 15wt% of an organic solvent based on the total weight of the reaction monomers is added. The temperature is raised to 70°C, 6wt% of a resin catalyst based on the total weight of the reaction monomers is added, and held for 4.5h. The mixture is filtered, and the low boiling point material is removed under vacuum to obtain the boron-containing adhesion promoter.

[0055] The molar ratio of the methyl vinyl-containing siloxane monomers, the methylphenyl-containing siloxane monomers, the epoxy-containing siloxane monomers, and the boron-containing monomers is 0.2:0.4:0.1:0.3; the organic solvent is methanol; and the resin catalyst is anion exchange resin D201.

[0056] SA3, platinum catalyst: The platinum catalyst is chloroplatinic acid-isopropyl alcohol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropyl alcohol solution is 0.1mol / L.

[0057] S2, preparation of component A: The vinyl-containing methylphenyl silicon-titanium resin, the platinum catalyst, and the boron-containing adhesion promoter are mixed to obtain component A.

[0058] S3, preparation of raw materials for component B SB1, vinyl-containing methylphenyl silicon-titanium resin: the raw materials of the vinyl-containing methylphenyl silicon-titanium resin include structural unit monomers, and the structural unit monomers are methylphenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, phenyl-containing siloxane monomers, and dimethyl hydrogen-containing siloxane monomers. The methylphenyl-containing siloxane monomers are methylphenyl diethoxysilane; the diphenyl-containing siloxane monomers are diphenyl diethoxysilane; the phenyl-containing siloxane monomers are phenyl triethoxysilane; and the dimethyl hydrogen-containing siloxane monomers are dimethyl ethoxysilane.

[0059] A preparation method of the vinyl-containing methylphenyl silicon-titanium resin: the methylphenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the phenyl-containing siloxane monomers, and the dimethyl hydrogen-containing siloxane monomers are mixed, and 15 wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is increased to 40℃, 5 wt% of an acid catalyst X based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 3 h. The temperature is increased to 80℃, the mixture is treated at the temperature for 5 h, and the mixture is cooled to room temperature to obtain a mixed solution.

[0060] An extractant is added to the mixed solution, the mixture is allowed to stand and separate into layers, and an organic phase is obtained. 5 wt% of an acid catalyst Y based on the total weight of the structural unit monomers is added to the organic phase, and the mixture is treated at the temperature for 6 h. The mixture is washed with water until neutral, and low-boiling substances are removed from the mixture under vacuum to obtain a methylphenyl silicon resin containing hydrogen.

[0061] In the preparation method, the molar ratio of the methylphenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the phenyl-containing siloxane monomers, and the dimethyl hydrogen-containing siloxane monomers is 0.32:0.4:0.36:0.16; the organic solvent is ethanol; the acid catalyst X is a hydrochloric acid solution with a mass concentration of 10%; the extractant is dimethylbenzene; the volume ratio of the extractant to the mixed solution is 1:1; and the acid catalyst Y is concentrated sulfuric acid. In the washing until neutral treatment, ethanol is used as the washing liquid.

[0062] SB2, acetylenyl-containing inhibitor: the acetylenyl-containing inhibitor is 1-ethynylcyclohexanol.

[0063] S4, preparation of the B component: the methylphenyl silicon resin containing hydrogen and the acetylenyl-containing inhibitor are mixed to obtain the B component.

[0064] S5, preparation of the high-performance silicone resin encapsulating adhesive: the A component and the B component are mixed, and the mixture is vacuum-deaerated for 30 min to obtain the high-performance silicone resin encapsulating adhesive.

[0065] Example 3 A high-performance silicone resin encapsulating adhesive for LED packaging, which is different from the high-performance silicone resin encapsulating adhesive of Example 1 in that the preparation method of the high-performance silicone resin encapsulating adhesive is different.

[0066] A preparation method of a high-performance silicone resin encapsulating adhesive for LED packaging, which comprises the following steps: S1, preparing A group of raw materials SA1, vinyl-containing methyl phenyl silicon titanium resin: the raw materials of the vinyl-containing methyl phenyl silicon titanium resin include structural unit monomers, the structural unit monomers are methyl phenyl-containing siloxane monomer, diphenyl-containing siloxane monomer, titanate monomer, dimethyl vinyl-containing siloxane monomer. The methyl phenyl-containing siloxane monomer is methyl phenyl dimethoxysilane; the diphenyl-containing siloxane monomer is diphenyl diethoxysilane; the titanate monomer is tetrapropyl titanate; and the dimethyl vinyl-containing siloxane monomer is tetramethyl divinyl disiloxane.

[0067] The preparation method of the vinyl-containing methyl phenyl silicon titanium resin: the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer and the dimethyl vinyl-containing siloxane monomer are mixed, and 15wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is raised to 45℃, 4wt% of an acid catalyst based on the total weight of the structural unit monomers is added, and the mixture is treated at 85℃ for 5h, and then cooled to 25℃ to obtain a mixed solution.

[0068] The mixed solution is mixed with an extractant, and then allowed to stand and separate into layers to obtain an organic phase. The organic phase is heated to 115℃, treated at 115℃ for 30min, 0.2wt% of an alkali catalyst based on the total weight of the structural unit monomers is added, and the mixture is treated at 115℃ for 2.5h, and then cooled to 25℃. The mixture is washed to neutral, and low-boiling substances are removed under vacuum to obtain the vinyl-containing methyl phenyl silicon titanium resin.

[0069] The molar ratio of the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer and the dimethyl vinyl-containing siloxane monomer is 0.3:0.56:0.2:0.18; the organic solvent is ethanol; the acid catalyst is a hydrochloric acid solution with a mass concentration of 15%; the extractant is dimethylbenzene, and the volume ratio of the extractant to the mixed solution is 1:1; the alkali catalyst is sodium hydroxide; and the washing to neutral treatment uses a hydrochloric acid-ethanol solution, and the mass concentration of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%.

[0070] SA2, boron-containing adhesion promoter: the raw materials of the boron-containing adhesion promoter include methyl vinyl-containing siloxane monomer, methyl phenyl-containing siloxane monomer, epoxy-containing siloxane monomer and boron-containing monomer. The methyl vinyl-containing siloxane monomer is methyl vinyl dimethoxysilane; the methyl phenyl-containing siloxane monomer is methyl phenyl diethoxysilane; the epoxy-containing siloxane monomer is 3-(2,3-epoxypropoxy) propyl trimethoxysilane; and the boron-containing monomer is phenyl boronic acid.

[0071] The preparation method of the boron-containing adhesion promoter: the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer are mixed, and 15wt% of the total weight of the reaction monomers of the organic solvent is added. The temperature is raised to 70℃, 7wt% of the total weight of the reaction monomers of the resin catalyst is added, and the temperature is maintained for 5h, filtered, and vacuum removed to obtain the boron-containing adhesion promoter.

[0072] The molar ratio of the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer is 0.2:0.45:0.15:0.3; the organic solvent is methanol; and the resin catalyst is anion exchange resin D201.

[0073] SA3, platinum catalyst: the platinum catalyst is chloroplatinic acid-isopropanol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropanol solution is 0.2mol / L.

[0074] S2, preparation of component A: the vinyl-containing methyl phenyl silicon titanium resin, the platinum catalyst, and the boron-containing adhesion promoter are mixed to obtain component A.

[0075] S3, preparation of B component raw materials SB1, vinyl-containing methyl phenyl silicon titanium resin: the raw materials of the vinyl-containing methyl phenyl silicon titanium resin include structural unit monomers, and the structural unit monomers are methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, phenyl-containing siloxane monomers, and dimethyl hydrogen-containing siloxane monomers. The methyl phenyl-containing siloxane monomer is methyl phenyl dimethoxysilane; the diphenyl-containing siloxane monomer is diphenyl diethoxysilane; the phenyl-containing siloxane monomer is phenyl trimethoxysilane; and the dimethyl hydrogen-containing siloxane monomer is dimethyl ethoxysilane.

[0076] The preparation method of the vinyl-containing methyl phenyl silicon titanium resin: the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the phenyl-containing siloxane monomer, and the dimethyl hydrogen-containing siloxane monomer are mixed, and 15wt% of the total weight of the structural unit monomers of the organic solvent is added. The temperature is raised to 45℃, 4wt% of the total weight of the structural unit monomers of the acid catalyst X is added, and the temperature is maintained for 2.5h, the temperature is raised to 80℃, and the temperature is maintained for 4h, and the temperature is cooled to room temperature to obtain a mixed solution.

[0077] The extractant is added to the mixed solution, and the organic phase is obtained by standing and layering. 5wt% of the total weight of the structural unit monomers of the acid catalyst Y is added to the organic phase, and the temperature is maintained for 6h, and then washed with water until neutral, and the low boiling point substances are removed under vacuum to obtain the hydrogen-containing methyl phenyl silicon resin.

[0078] The molar ratio of the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the phenyl-containing siloxane monomer, and the dimethyl hydrogen-containing siloxane monomer is 0.35:0.42:0.3:0.16; the organic solvent is ethanol; the acid catalyst X is a hydrochloric acid solution with a mass concentration of 10%; the extractant is xylene; the volume ratio of the extractant to the mixed solution is 1:1; and the acid catalyst Y is concentrated sulfuric acid.

[0079] SB2, acetylenic group-containing inhibitor: the acetylenic group-containing inhibitor is 3,5-dimethyl-3-hexyn-1-ol.

[0080] S4, preparation of component B: the hydrogen-containing methylphenyl-containing silicone resin and the acetylenic group-containing inhibitor are mixed to obtain component B.

[0081] S5, preparation of high-performance silicone resin encapsulant: components A and B are mixed, vacuum degassing is performed for 30 min, and a high-performance silicone resin encapsulant is obtained.

[0082] Example 4 A high-performance silicone resin encapsulant for LED packaging, which is different from example 1 in that the preparation method of the high-performance silicone resin encapsulant is different.

[0083] A preparation method of a high-performance silicone resin encapsulant for LED packaging, comprising the following steps: S1, preparation of raw materials of component A SA1, vinyl-containing methylphenyl-containing silicone titanium resin: the raw materials of the vinyl-containing methylphenyl-containing silicone titanium resin include structural unit monomers, and the structural unit monomers are a methylphenyl-containing siloxane monomer, a diphenyl-containing siloxane monomer, a titanate monomer, and a dimethyl vinyl-containing siloxane monomer. The methylphenyl-containing siloxane monomer is methylphenyl diethoxysilane; the diphenyl-containing siloxane monomer is diphenyl dimethoxysilane; the titanate monomer is tetrapropyl titanate; and the dimethyl vinyl-containing siloxane monomer is dimethyl vinyl methoxysilane.

[0084] A preparation method of the vinyl-containing methylphenyl-containing silicone titanium resin: the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer, and the dimethyl vinyl-containing siloxane monomer are mixed, and 15 wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is increased to 40°C, 4 wt% of an acid catalyst based on the total weight of the structural unit monomers is added, and heat treatment is performed for 2 h. The temperature is increased to 85°C, heat treatment is performed for 5 h, the temperature is cooled to 25°C, and a mixed solution is obtained.

[0085] The extractant is added into the mixed solution, mixed, and then allowed to separate into layers to obtain an organic phase. The organic phase is heated to 115℃, and then treated for 60 min. 0.3wt% of an alkali catalyst based on the total weight of the structural unit monomers is added, and then treated for 2.5 h. The temperature is cooled to 25℃, and then washed until neutral. Low boiling point substances are removed under vacuum to obtain a methyl phenyl silicon titanium resin containing a vinyl group.

[0086] The molar ratio of the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer, and the dimethyl vinyl-containing siloxane monomer is 0.32:0.5:0.23:0.2; the organic solvent is ethanol; the acid catalyst is a hydrochloric acid solution with a mass concentration of 15%; the extractant is xylene; the volume ratio of the extractant to the mixed solution is 1:1; the alkali catalyst is sodium hydroxide; and the washing solution used in the neutralization treatment is a hydrochloric acid-ethanol solution with a mass concentration of 5% of hydrochloric acid.

[0087] SA2, boron-containing adhesion promoter: The raw materials of the boron-containing adhesion promoter include a methyl vinyl-containing siloxane monomer, a methyl phenyl-containing siloxane monomer, an epoxy group-containing siloxane monomer, and a boron-containing monomer. The methyl vinyl-containing siloxane monomer is methyl vinyl diethoxysilane; the methyl phenyl-containing siloxane monomer is methyl phenyl dimethoxysilane; the epoxy group-containing siloxane monomer is 3-(2,3-epoxypropoxy) propyl trimethoxysilane; and the boron-containing monomer is phenyl boronic acid.

[0088] Method for preparing the boron-containing adhesion promoter: The methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer are mixed, and 15wt% of an organic solvent based on the total weight of the reaction monomers is added. The temperature is raised to 70℃, 8wt% of a resin catalyst based on the total weight of the reaction monomers is added, and then treated for 4.5 h. Filtration is performed, and low boiling point substances are removed under vacuum to obtain the boron-containing adhesion promoter.

[0089] The molar ratio of the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer is 0.2:0.45:0.15:0.3; the organic solvent is methanol; and the resin catalyst is anion exchange resin D201.

[0090] SA3, platinum catalyst: The platinum catalyst is a chloroplatinic acid-isopropyl alcohol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropyl alcohol solution is 0.2mol / L.

[0091] S2, preparation of component A: The methyl phenyl silicon titanium resin containing a vinyl group, the platinum catalyst, and the boron-containing adhesion promoter are mixed to obtain component A.

[0092] S3, preparation of raw materials for component B SB1, vinyl-containing methylphenyl silicon-titanium resin: the raw materials of the vinyl-containing methylphenyl silicon-titanium resin include structural unit monomers, and the structural unit monomers are methylphenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, phenyl-containing siloxane monomers, and dimethyl hydrogen-containing siloxane monomers. The methylphenyl-containing siloxane monomers are methylphenyl diethoxysilane; the diphenyl-containing siloxane monomers are diphenyl dimethoxysilane; the phenyl-containing siloxane monomers are phenyl triethoxysilane; and the dimethyl hydrogen-containing siloxane monomers are dimethyl methoxysilane.

[0093] A preparation method of the vinyl-containing methylphenyl silicon-titanium resin: the methylphenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the phenyl-containing siloxane monomers, and the dimethyl hydrogen-containing siloxane monomers are mixed, and 15 wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is increased to 45 ℃, 5 wt% of an acid catalyst X based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 3 h. The temperature is increased to 85 ℃, and the mixture is treated at the temperature for 4.5 h. The mixture is cooled to room temperature, and a mixed solution is obtained.

[0094] An extractant is added to the mixed solution, and the mixture is allowed to stand and separate into layers, so that an organic phase is obtained. 5 wt% of an acid catalyst Y based on the total weight of the structural unit monomers is added to the organic phase, and the mixture is treated at the temperature for 5 h. The mixture is washed with water until neutral, and low-boiling substances are removed from the mixture under vacuum, so that a methylphenyl silicon resin containing hydrogen groups is obtained.

[0095] In the formula, the molar ratio of the methylphenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the phenyl-containing siloxane monomers, and the dimethyl hydrogen-containing siloxane monomers is 0.3:0.45:0.34:0.17; the organic solvent is ethanol; the acid catalyst X is a hydrochloric acid solution with a mass concentration of 15%; the extractant is dimethylbenzene; the volume ratio of the extractant to the mixed solution is 1:1; the acid catalyst Y is concentrated sulfuric acid; and the washing liquid used in the neutralization treatment is ethanol.

[0096] SB2, acetylenyl-containing inhibitor: the acetylenyl-containing inhibitor is 3,5-dimethyl-3-hexyn-1-ol.

[0097] S4, preparation of the B component: the methylphenyl silicon resin containing hydrogen groups and the acetylenyl-containing inhibitor are mixed, so that the B component is obtained.

[0098] S5, preparation of the high-performance silicone resin encapsulating adhesive: the A component and the B component are mixed, and the mixture is vacuum degassed for 30 min, so that the high-performance silicone resin encapsulating adhesive is obtained.

[0099] Example 5 A high-performance silicone resin encapsulating adhesive for LED packaging, which is different from the high-performance silicone resin encapsulating adhesive of Example 1 in that the preparation method of the high-performance silicone resin encapsulating adhesive is different.

[0100] A preparation method of a high-performance silicone resin encapsulating glue for LED packaging, comprising the following steps: S1, preparing A component raw materials SA1, vinyl-containing methylphenyl silicon-titanium resin: the raw materials of the vinyl-containing methylphenyl silicon-titanium resin include structural unit monomers, and the structural unit monomers are methylphenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, titanate monomers and dimethyl vinyl-containing siloxane monomers. The methylphenyl-containing siloxane monomers are methylphenyl dimethoxysilane; the diphenyl-containing siloxane monomers are diphenyl dimethoxysilane; the titanate monomers are tetraisopropyl titanate; and the dimethyl vinyl-containing siloxane monomers are dimethyl vinyl diethoxysilane.

[0101] A preparation method of the vinyl-containing methylphenyl silicon-titanium resin: the methylphenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the titanate monomers and the dimethyl vinyl-containing siloxane monomers are mixed, and 20 wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is raised to 40℃, 5 wt% of an acid catalyst based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 2.5 h. The temperature is raised to 80℃, the mixture is treated at the temperature for 6 h, and the mixture is cooled to 25℃, so as to obtain a mixed solution.

[0102] The mixed solution is mixed with an extractant, and is allowed to stand and separate into layers, so as to obtain an organic phase. The organic phase is heated to 110℃, and is treated at the temperature for 30 min. 0.1 wt% of a base catalyst based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 2.5 h. The mixture is cooled to 25℃, is washed to neutral, and is vacuumed to remove low-boiling substances, so as to obtain the vinyl-containing methylphenyl silicon-titanium resin.

[0103] In the preparation method, the molar ratio of the methylphenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the titanate monomers and the dimethyl vinyl-containing siloxane monomers is 0.36:0.55:0.25:0.18; the organic solvent is ethanol; the acid catalyst is a hydrochloric acid solution with a mass concentration of 15%; the extractant is toluene, and the volume ratio of the extractant to the mixed solution is 1:1; the base catalyst is potassium hydroxide; and the washing liquid used in the treatment of washing to neutral is a hydrochloric acid-ethanol solution, and the mass concentration of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%.

[0104] SA2, boron-containing adhesion promoter: the raw materials of the boron-containing adhesion promoter include methyl vinyl-containing siloxane monomers, methylphenyl-containing siloxane monomers, epoxy group-containing siloxane monomers and boron-containing monomers. The methyl vinyl-containing siloxane monomers are methyl vinyl dimethoxysilane; the methylphenyl-containing siloxane monomers are methylphenyl dimethoxysilane; the epoxy group-containing siloxane monomers are 3-(2,3-epoxypropoxy) propyl triethoxysilane; and the boron-containing monomers are methyl borate.

[0105] The preparation method of the boron-containing adhesion promoter: the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer are mixed, and 20wt% of the total weight of the reaction monomers of the organic solvent is added. The temperature is raised to 75℃, 8wt% of the total weight of the reaction monomers of the resin catalyst is added, and the temperature is maintained for 5h, filtered, and vacuum removed to obtain the boron-containing adhesion promoter.

[0106] The molar ratio of the methyl vinyl-containing siloxane monomer, the methyl phenyl-containing siloxane monomer, the epoxy group-containing siloxane monomer, and the boron-containing monomer is 0.25:0.4:0.1:0.35; the organic solvent is ethanol; and the resin catalyst is anion exchange resin D201.

[0107] SA3, platinum catalyst: the platinum catalyst is chloroplatinic acid-isopropanol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropanol solution is 0.05mol / L.

[0108] S2, preparation of component A: the vinyl-containing methyl phenyl silicon titanium resin, the platinum catalyst, and the boron-containing adhesion promoter are mixed to obtain component A.

[0109] S3, preparation of B component raw materials SB1, vinyl-containing methyl phenyl silicon titanium resin: the raw materials of the vinyl-containing methyl phenyl silicon titanium resin include structural unit monomers, and the structural unit monomers are methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, phenyl-containing siloxane monomers, and dimethyl hydrogen-containing siloxane monomers. The methyl phenyl-containing siloxane monomer is methyl phenyl dimethoxysilane; the diphenyl-containing siloxane monomer is diphenyl dimethoxysilane; the phenyl-containing siloxane monomer is phenyl triethoxysilane; and the dimethyl hydrogen-containing siloxane monomer is tetramethyl disiloxane.

[0110] The preparation method of the vinyl-containing methyl phenyl silicon titanium resin: the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the phenyl-containing siloxane monomer, and the dimethyl hydrogen-containing siloxane monomer are mixed, and 10wt% of the total weight of the structural unit monomers of the organic solvent is added. The temperature is raised to 45℃, 3wt% of the total weight of the structural unit monomers of the acid catalyst X is added, and the temperature is maintained for 3h, the temperature is raised to 80℃, and the temperature is maintained for 4h, and then the temperature is cooled to room temperature to obtain a mixed solution.

[0111] The extractant is added to the mixed solution, and the organic phase is obtained by standing and layering. 5wt% of the total weight of the structural unit monomers of the acid catalyst Y is added to the organic phase, and the temperature is maintained for 5h, and then washed with water until neutral, and the low-boiling substances are removed under vacuum to obtain the hydrogen-containing methyl phenyl silicon resin.

[0112] The molar ratio of the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the phenyl-containing siloxane monomer, and the dimethyl hydrogen-containing siloxane monomer is 0.28:0.48:0.35:0.2; the organic solvent is ethanol; the acid catalyst X is a hydrochloric acid solution with a mass concentration of 15%; the extractant is xylene; the volume ratio of the extractant to the mixed solution is 1:1; and the acid catalyst Y is concentrated sulfuric acid.

[0113] SB2, acetylenic group-containing inhibitor: the acetylenic group-containing inhibitor is 3,5-dimethyl-3-hexyn-1-ol.

[0114] S4, preparation of component B: the hydrogen-containing methylphenyl-containing silicone resin and the acetylenic group-containing inhibitor are mixed to obtain component B.

[0115] S5, preparation of high-performance silicone resin encapsulant: components A and B are mixed, vacuum degassing is performed for 30 min, and a high-performance silicone resin encapsulant is obtained.

[0116] Example 6 A high-performance silicone resin encapsulant for LED packaging, which is different from example 1 in that the preparation method of the high-performance silicone resin encapsulant is different.

[0117] A preparation method of a high-performance silicone resin encapsulant for LED packaging, comprising the following steps: S1, preparation of raw materials of component A SA1, vinyl-containing methylphenyl-containing silicone titanium resin: the raw materials of the vinyl-containing methylphenyl-containing silicone titanium resin include structural unit monomers, and the structural unit monomers are a methylphenyl-containing siloxane monomer, a diphenyl-containing siloxane monomer, a titanate monomer, and a dimethyl vinyl-containing siloxane monomer. The methylphenyl-containing siloxane monomer is methylphenyl diethoxysilane; the diphenyl-containing siloxane monomer is diphenyl diethoxysilane; the titanate monomer is tetraisopropyl titanate; and the dimethyl vinyl-containing siloxane monomer is tetramethyl divinyl disiloxane.

[0118] Preparation method of the vinyl-containing methylphenyl-containing silicone titanium resin: the methylphenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer, and the dimethyl vinyl-containing siloxane monomer are mixed, and 15wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is raised to 45°C, 5wt% of an acid catalyst based on the total weight of the structural unit monomers is added, and the temperature is maintained for 3h. The temperature is raised to 80°C, the temperature is maintained for 5h, and the temperature is cooled to 25°C to obtain a mixed solution.

[0119] The extractant is added to the mixed solution, mixed, and allowed to separate into layers to obtain an organic phase. The organic phase is warmed to 115℃, and held for 30 min. 0.2wt% of an alkali catalyst based on the total weight of the structural unit monomers is added, and held for 3h. The temperature is cooled to 25℃, and washed until neutral. The low boiling point material is removed under vacuum to obtain a methyl phenyl silicon titanium resin containing a vinyl group.

[0120] The molar ratio of the methyl phenyl-containing siloxane monomer, the diphenyl-containing siloxane monomer, the titanate monomer, and the dimethyl vinyl-containing siloxane monomer is 0.3:0.53:0.23:0.2; the organic solvent is ethanol; the acid catalyst is a 15% hydrochloric acid solution by mass concentration. The extractant is toluene, and the volume ratio of the extractant to the mixed solution is 1:1. The alkali catalyst is potassium hydroxide. In the neutralization process, a hydrochloric acid-ethanol solution is used as the washing liquid, and the mass concentration of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%.

[0121] SA2, boron-containing adhesion promoter: The raw materials of the boron-containing adhesion promoter include methyl vinyl-containing siloxane monomers, methyl phenyl-containing siloxane monomers, epoxy group-containing siloxane monomers, and boron-containing monomers. The methyl vinyl-containing siloxane monomer is methyl vinyl diethoxysilane; the methyl phenyl-containing siloxane monomer is methyl phenyl dimethoxysilane; the epoxy group-containing siloxane monomer is 3-(2,3-epoxypropoxy) propyl trimethoxysilane; and the boron-containing monomer is methyl borate.

[0122] Method for preparing the boron-containing adhesion promoter: The methyl vinyl-containing siloxane monomers, the methyl phenyl-containing siloxane monomers, the epoxy group-containing siloxane monomers, and the boron-containing monomers are mixed, and 20wt% of an organic solvent based on the total weight of the reaction monomers is added. The temperature is raised to 75℃, 7wt% of a resin catalyst based on the total weight of the reaction monomers is added, and held for 5h. Filtration is performed, and the low boiling point material is removed under vacuum to obtain the boron-containing adhesion promoter.

[0123] The molar ratio of the methyl vinyl-containing siloxane monomers, the methyl phenyl-containing siloxane monomers, the epoxy group-containing siloxane monomers, and the boron-containing monomers is 0.25:0.4:0.1:0.35; the organic solvent is ethanol; and the resin catalyst is anion exchange resin D201.

[0124] SA3, platinum catalyst: The platinum catalyst is chloroplatinic acid-isopropyl alcohol solution, and the molar concentration of chloroplatinic acid in the chloroplatinic acid-isopropyl alcohol solution is 0.05mol / L.

[0125] S2, preparation of component A: The methyl phenyl silicon titanium resin containing a vinyl group, the platinum catalyst, and the boron-containing adhesion promoter are mixed to obtain component A.

[0126] S3, preparation of raw materials for component B SB1, vinyl-containing methyl phenyl silicon titanium resin: the raw materials of the vinyl-containing methyl phenyl silicon titanium resin include structural unit monomers, and the structural unit monomers are methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, phenyl-containing siloxane monomers, and dimethyl hydrogen-containing siloxane monomers. The methyl phenyl-containing siloxane monomers are methyl phenyl diethoxysilane; the diphenyl-containing siloxane monomers are diphenyl dimethoxysilane; the phenyl-containing siloxane monomers are phenyl trimethoxysilane; and the dimethyl hydrogen-containing siloxane monomers are tetramethyl disiloxane.

[0127] A preparation method of the vinyl-containing methyl phenyl silicon titanium resin: the methyl phenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the phenyl-containing siloxane monomers, and the dimethyl hydrogen-containing siloxane monomers are mixed, and 10 wt% of an organic solvent based on the total weight of the structural unit monomers is added. The temperature is increased to 40 ℃, 4 wt% of an acid catalyst X based on the total weight of the structural unit monomers is added, and the mixture is treated at the temperature for 2 h. The temperature is increased to 80 ℃, the mixture is treated at the temperature for 5 h, and the mixture is cooled to room temperature to obtain a mixed solution.

[0128] An extractant is added to the mixed solution, the mixture is allowed to stand and separate into layers, and an organic phase is obtained. 4 wt% of an acid catalyst Y based on the total weight of the structural unit monomers is added to the organic phase, and the mixture is treated at the temperature for 5 h. The mixture is washed with water until neutral, and low-boiling substances are removed under vacuum to obtain a methyl phenyl silicon resin containing hydrogen.

[0129] In the formula, the molar ratio of the methyl phenyl-containing siloxane monomers, the diphenyl-containing siloxane monomers, the phenyl-containing siloxane monomers, and the dimethyl hydrogen-containing siloxane monomers is 0.26:0.44:0.36:0.22; the organic solvent is ethanol; the acid catalyst X is a hydrochloric acid solution with a mass concentration of 10%; the extractant is dimethylbenzene; the volume ratio of the extractant to the mixed solution is 1:1; the acid catalyst Y is concentrated sulfuric acid; and the washing liquid used in the neutralization treatment is ethanol.

[0130] SB2, acetylenic group-containing inhibitor: the acetylenic group-containing inhibitor is 3-methyl-1-butyne-3-ol.

[0131] S4, preparation of the B component: the methyl phenyl silicon resin containing hydrogen and the acetylenic group-containing inhibitor are mixed to obtain the B component.

[0132] S5, preparation of the high-performance silicone resin encapsulating adhesive: the A component and the B component are mixed, and vacuum degassing is performed for 30 min to obtain the high-performance silicone resin encapsulating adhesive.

[0133] Example 7 A high-performance silicone resin encapsulant for LED packaging, which differs from Example 1 in that the raw material ratio of A component and B component is different, and the A component is mainly made of the following raw materials: vinyl-containing methyl phenyl silicone resin 40 g, platinum catalyst 0.05 g, boron-containing adhesion promoter 3 g. The B component is mainly made of the following raw materials: hydrogen-containing methyl phenyl silicone resin 60 g, alkyne group-containing inhibitor 0.1 g.

[0134] Example 8 A high-performance silicone resin encapsulant for LED packaging, which differs from Example 1 in that the raw material ratio of A component and B component is different, and the A component is mainly made of the following raw materials: vinyl-containing methyl phenyl silicone resin 60 g, platinum catalyst 0.2 g, boron-containing adhesion promoter 1 g. The B component is mainly made of the following raw materials: hydrogen-containing methyl phenyl silicone resin 40 g, alkyne group-containing inhibitor 0.3 g.

[0135] Comparative Example Comparative Example 1 A high-performance silicone resin encapsulant for LED packaging, which differs from Example 1 in that in the raw materials of A component, the preparation method of vinyl-containing methyl phenyl silicone resin uses an equal amount of methyl phenyl-containing siloxane monomer, diphenyl-containing siloxane monomer, and dimethyl vinyl-containing siloxane monomer to replace titanate monomer, and the molar ratio of methyl phenyl-containing siloxane monomer, diphenyl-containing siloxane monomer, titanate monomer, and dimethyl vinyl-containing siloxane monomer is 0.36:0.57:0.18.

[0136] Comparative Example 2 A high-performance silicone resin encapsulant for LED packaging, which differs from Example 1 in that in the raw materials of A component, no boron-containing adhesion promoter is added.

[0137] Comparative Example 3 A high-performance silicone resin encapsulant for LED packaging, which differs from Example 1 in that in the raw materials of A component, the preparation method of boron-containing adhesion promoter uses an equal amount of methyl vinyl-containing siloxane monomer, methyl phenyl-containing siloxane monomer, and epoxy-containing siloxane monomer to replace boron-containing monomer, and the molar ratio of methyl vinyl-containing siloxane monomer, methyl phenyl-containing siloxane monomer, and epoxy-containing siloxane monomer is 0.2:0.4:0.1.

[0138] Performance detection The high-performance silicone resin encapsulating glue obtained in each of Examples 1-8 and Comparative Examples 1-3 was filled into the LED to be encapsulated, and then the temperature was raised to 85°C, and the temperature was kept for 0.5 h, the temperature was raised to 150°C, and the temperature was kept for 2 h, and the temperature was reduced to 25°C, the high-performance silicone resin encapsulating glue was cured to form a glue layer, and a sample was obtained, and the surface glue layer of the sample was detected for the following properties, and the detection results are shown in Table 1.

[0139] In the hardness test, the hardness of the surface glue layer of the sample was detected by using a Shore D hardness tester. In the light transmittance test, the light transmittance of the surface glue layer of the sample was detected by using an ultraviolet-visible spectrophotometer. In the refractive index test, the refractive index of the surface glue layer of the sample was detected by using an Abbe refractometer.

[0140] In the adhesive strength test, the shear strength of the surface glue layer of the sample was detected according to GB / T 13936-92. In the mechanical strength test, the tensile strength of the surface glue layer of the sample was detected according to GB / T 16421-1996. In the heat aging resistance test, the sample was placed at a temperature of 200°C for 1 h, and the surface glue layer of the sample was observed for yellowing.

[0141] Table 1 detection results As can be seen from Table 1, the high-performance silicone resin encapsulating glue has high Shore hardness, refractive index, light transmittance, adhesive strength, and tensile strength, the Shore hardness is 71-77D, the refractive index is 1.70-1.77, the light transmittance is 90-92%, the adhesive strength is 5.16-5.43 MPa, and the tensile strength is 8.42-8.68 MPa, and the high-performance silicone resin encapsulating glue has no yellowing after heat aging treatment at 200°C for 1 h. The high-performance silicone resin encapsulating glue has high light transmittance, high refractive index, and high hardness, and also has excellent adhesive strength, tensile strength, and heat aging resistance, and has excellent comprehensive performance, and meets the market demand.

[0142] Comparing Example 1 with Comparative Example 1, it can be seen that the introduction of titanium element in the vinyl-containing methylphenylsilicon titanium resin significantly increases the hardness, refractive index, light transmittance, tensile strength, and heat aging resistance. Comparing Example 1 with Comparative Example 2, it can be seen that the addition of the boron-containing adhesion promoter in the raw material of component A improves the refractive index, light transmittance, and tensile strength to a certain extent, and significantly improves the adhesive strength. Comparing Example 1 with Comparative Example 3, it can be seen that the introduction of boron element in the boron-containing adhesion promoter improves the use effect of the boron-containing adhesion promoter, and increases the adhesive strength and tensile strength of the high-performance silicone resin encapsulating glue.

[0143] It should be noted that the foregoing examples have been provided merely for the purposes of explanation and are in no way to be construed as limiting. The examples have been described with reference to illustrative rather than limiting examples. Modifications can be made to the examples as well as equivalents to what have been described without departing from the scope and spirit of the disclosure. Although the disclosure has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can effect a wide variety of modifications to the preferred embodiments without departing from the scope and spirit of the disclosure.

Claims

1. A high-performance silicone resin encapsulant for LED encapsulation, characterized by: The high-performance silicone resin encapsulating adhesive is made of component A and component B, and the weight ratio of the component A to the component B is 1:(0.5-2); The component A is mainly made of raw materials in the following weight parts: vinyl-containing methyl phenyl silicon-titanium resin 40-60 parts, platinum catalyst 0.05-0.2 parts, boron-containing tackifier 1-3 parts; and the component B is mainly made of raw materials in the following weight parts: hydrogen-containing methyl phenyl silicon resin 40-60 parts, alkyne group-containing inhibitor 0.1-0.3 parts.

2. The high-performance silicone resin encapsulant for LED packaging according to claim 1, characterized in that: The vinyl-containing methyl phenyl silicon-titanium resin is composed of methyl phenyl structural units, diphenyl structural units, titanium oxide structural units and dimethyl vinyl structural units, and the structural formula of the vinyl-containing methyl phenyl silicon-titanium resin is: (MePhSiO)m1(Ph2SiO)n1(TiO2)x1(Me2ViSiO 0.5 )y1, wherein m1:n1:x1:y1=(0.15-0.45):(0.3-0.6):(0.1-0.4):(0.1-0.3). The hydrogen-containing methyl phenyl silicon resin is composed of methyl phenyl structural units, diphenyl structural units, phenyl structural units and dimethyl hydrogen structural units, and the structural formula of the hydrogen-containing methyl phenyl silicon resin is: (MePhSiO)m2(Ph2SiO)n2(PhSiO 1.5 )x2(Me2HSiO 0.5 )y2, wherein m2:n2:x2:y2=(0.15-0.4):(0.3-0.5):(0.2-0.4):(0.2-0.35).

3. The high-performance silicone resin encapsulant for LED package according to claim 1, characterized in that: The raw materials of the vinyl-containing methyl phenyl silicon-titanium resin include structural unit monomers, and the structural unit monomers are methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, titanate monomers and dimethyl vinyl-containing siloxane monomers. The methyl phenyl-containing siloxane monomers are one or both of methyl phenyl dimethoxysilane and methyl phenyl diethoxysilane, and / or, The diphenyl-containing siloxane monomers are one or both of diphenyl dimethoxysilane and diphenyl diethoxysilane, and / or, The titanate monomers are one or more of tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate and tetraisobutyl titanate, and / or, The dimethyl vinyl-containing siloxane monomers are one or more of dimethyl vinyl methoxysilane, dimethyl vinyl ethoxysilane and tetramethyl divinyl disiloxane.

4. The high-performance silicone resin encapsulant for LED package according to claim 3, characterized in that: The vinyl-containing methyl phenyl silicon-titanium resin is prepared by the following method: mixing organic solvent, methyl phenyl-containing siloxane monomers, diphenyl-containing siloxane monomers, titanate monomers and dimethyl vinyl-containing siloxane monomers, heating to 40-45 DEG C, adding acid catalyst, heat treatment for 2-3 h, heating to 80-85 DEG C, heat treatment for 4-6 h, cooling to room temperature to obtain a mixed solution; The mixed solution is extracted to obtain an organic phase; the organic phase is heated to 110-120 DEG C, heat treatment for 30-60 min, adding base catalyst, heat treatment for 2-4 h, cooling to room temperature, washing with water until neutral, vacuum removal of low boiling point substances to obtain the vinyl-containing methyl phenyl silicon-titanium resin.

5. The high-performance silicone resin encapsulant for LED package according to claim 4, characterized in that: In the preparation of the vinyl-containing methyl phenyl silicon-titanium resin, the use amount of the organic solvent is 15-20 wt% of the total weight of the structural unit monomers, the use amount of the acid catalyst is 3-5 wt% of the total weight of the structural unit monomers, and the use amount of the base catalyst is 0.1-0.3 wt% of the total weight of the structural unit monomers.

6. The high-performance silicone resin encapsulant for LED package according to claim 1, characterized in that: The raw material of the methyl phenyl silicon resin containing hydrogen group comprises structural unit monomers, the structural unit monomers are one or both of methyl phenyl siloxane monomers, diphenyl siloxane monomers, phenyl siloxane monomers, dimethyl hydrogen group siloxane monomers; The methyl phenyl siloxane monomers are one or both of methyl phenyl dimethoxysilane and methyl phenyl diethoxysilane, and / or, The diphenyl siloxane monomers are one or both of diphenyl dimethoxysilane and diphenyl diethoxysilane, and / or, The phenyl siloxane monomers are one or both of phenyl trimethoxysilane and phenyl triethoxysilane, and / or, The dimethyl hydrogen group siloxane monomers are one or more of dimethyl methoxysilane, dimethyl ethoxysilane and tetramethyl disiloxane.

7. The high-performance silicone resin encapsulant for LED packaging according to claim 6, characterized in that: The methyl phenyl silicon resin containing hydrogen group is prepared by the following method: mixing an organic solvent, methyl phenyl siloxane monomers, diphenyl siloxane monomers, phenyl siloxane monomers and dimethyl hydrogen group siloxane monomers, heating to 40-50℃, adding acid catalyst X, holding for 3-5h, heating to 80-85℃, holding for 4-6h, cooling to room temperature to obtain a mixed solution; extracting the mixed solution to obtain an organic phase; adding acid catalyst Y to the organic phase, holding for 4-6h, washing with water until neutral, removing low boiling point substances under vacuum to obtain the methyl phenyl silicon resin containing hydrogen group.

8. The high-performance silicone resin encapsulant for LED packaging according to claim 7, characterized in that: In the preparation of the methyl phenyl silicon resin containing hydrogen group, the amount of the organic solvent used is 10-15wt% of the total weight of the structural unit monomers, the amount of acid catalyst X used is 3-6wt% of the total weight of the structural unit monomers, and the amount of acid catalyst Y used is 3-6wt% of the total weight of the structural unit monomers.

9. The high-performance silicone resin encapsulant for LED package according to claim 1, characterized in that: The boron-containing adhesion promoter is prepared from methyl vinyl siloxane monomers, methyl phenyl siloxane monomers, epoxy group-containing siloxane monomers and boron-containing monomers, and the structural formula of the boron-containing adhesion promoter is:

10. A method of preparing a high performance silicone resin encapsulant for LED encapsulation according to any one of claims 1 to 9, characterized by: The method comprises the following steps: Mixing the methyl phenyl silicon titanium resin containing vinyl group, a platinum catalyst and the boron-containing adhesion promoter to obtain component A; Mixing the methyl phenyl silicon resin containing hydrogen group and the acetylene group-containing inhibitor to obtain component B; Mixing component A and component B and vacuum defoaming to obtain the high-performance silicone resin packaging adhesive.

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