CN102391529B - Preparation method of silicone resin type organic/inorganic hybrid material for packaging - Google Patents

Preparation method of silicone resin type organic/inorganic hybrid material for packaging Download PDF

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CN102391529B
CN102391529B CN 201110196406 CN201110196406A CN102391529B CN 102391529 B CN102391529 B CN 102391529B CN 201110196406 CN201110196406 CN 201110196406 CN 201110196406 A CN201110196406 A CN 201110196406A CN 102391529 B CN102391529 B CN 102391529B
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silicone resin
necked flask
deionized water
water wash
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CN102391529A (en
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来国桥
杨雄发
曹建
邵倩
杨琳琳
华西林
蒋剑雄
罗蒙贤
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Hebei thick and rich organosilicon products Limited by Share Ltd.
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Hangzhou Normal University
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Abstract

The invention relates to a preparation method of a silicone resin type organic/inorganic hybrid material for packaging. The invention aims to overcome the defects in the prior art, and provides a preparation method of a high-refractive-index high-light-transmittance silicone resin type organic/inorganic hybrid material for packaging. The method comprises the following steps: 1) cohydrolysis reaction; 2) prepolymer polycondensation reaction; and 3) packaging material preparation and vulcanization.

Description

A kind of encapsulation silicone resin type organic-inorganic hybrid material preparation method
Technical field
The present invention relates to mainly contain the high refractive index of aminomethyl phenyl silica chain link, transparent methyl phenyl vinyl polysiloxane LED packaged material, specifically is a kind of LED encapsulation silicone resin type organic-inorganic hybrid material preparation method.
Background technology
Power type light-emitting diode (Light Emitting Diode, LED) have energy-saving and environmental protection, safety, life-span length, less energy-consumption, etc. advantage, development through decades, be widely used in the big area picture and text and show that full-color screen, state indication, sign illumination, signal show, Backlight For Liquid Crystal Display Panels, aspects such as automobile combined tail lamp and room light, be expected to become after incandescent light, luminescent lamp, high-intensity gas discharge lamp the 4th generation light source.
The packaged material of cold-resistant thermal shocking, no xanthochromia, high transmission rate, high refractive index is technology crucial during LED makes.At present, be used for the LED encapsulation and be mostly some thermoplastic resins such as polymethylmethacrylate, polycarbonate, optics nylon and thermosetting epoxy resin etc.Yet along with the raising of LED brightness and the increasing of power, these materials are bad because of thermotolerance, easily produce look and become, and cause light decay, so that have a strong impact on the use properties of LED, and reduce the work-ing life of product greatly.Therefore, need seek new equivalent material.Organosilicon material is subjected to investigator's favor because having good thermotolerance, weathering resistance, moisture resistance, cold-resistant thermal shocking etc.
Organosilicon material has advantages such as high-low temperature resistant, ageing-resistant, UV resistant, radiation hardness, is desirable LED packaged material.WO2004107458 is reported under the platinum catalyst effect, the crosslinked method for preparing the LED packaged material of ethenyl blocking silicone resin and containing hydrogen silicone oil, and behind the packaged material sulfidization molding, shrinking percentage is low, and fast light Good Heat-resistance does not ftracture and transmittance reaches 95%.US Patent No. 20050212008 (its equating patent EP1424363) has been reported employing silicon hydrogen addition vulcanization technology, with ethenyl blocking silicon rubber and the crosslinked preparation power-type LED of containing hydrogen silicone oil packaged material, the refractive index of packaged material reaches 1.51 behind the sulfidization molding, behind 400nm light source irradiation 100h, transmittance drops to 92% from initial 95%, still is 92% behind the irradiation 500h.US Patent No. 20050006794 has been reported employing silicon hydrogen additive process, organo-silicone rubber and the crosslinked method for preparing the LED packaged material of containing hydrogen silicone oil with ethenyl blocking, packaged material behind the sulfidization molding has excellent mechanical property and non-viscosity energy, can stand the cold cycling impact between 1000 times-50 ℃ to 150 ℃ and does not ftracture.
But above-mentioned LED packaged material refractive index is between 1.41-1.56, and its refractive index still differs greatly with the chip refractive index, and the light extraction efficiency of LED still has very big room for promotion.And the high refractive index aminomethyl phenyl organosilicon encapsulating material of non-modified after use for some time, still is difficult to avoid xanthochromia, causes light decay.In recent years, the modification by the high refractive index inorganic oxide prepares nano composite organosilicon LED packaged material, has characteristics such as specific refractory power height, anti-ultraviolet radiation performance are strong, high comprehensive performance, obtains countries in the world scholar's concern.ZnO, TiO 2And ZrO 2Deng having higher specific refractory power (2.0-2.4), it is the ideal material of inorganic nano phase in the preparation matrix material.But directly carry out nano combinedly, nano particle is easy to reunite, and the products obtained therefrom transmittance is low, is difficult to satisfy the demand of LED encapsulation; Prepare ZnO, TiO with sol-gel method 2And ZrO 2Deng with the organic-inorganic material of organosilicon material, long reaction time, gel easily, remove solvent after the product transmittance not high.
Summary of the invention
The present invention need solve the deficiencies in the prior art, and a kind of preparation method of high refractive index high transmission rate silicone resin type organic-inorganic hybrid material is provided.
A kind of LED encapsulation silicone resin type organic-inorganic hybrid material preparation method of the present invention, as follows:
1) cohydrolysis reaction: the mixture of organosilane monomer, metallic compound and partial solvent is added drop-wise in 0 ℃ ~ 80 ℃ the still material of being formed by water, residual solvent and catalyzer, stirs, after dropwising, continue reaction 0.5h ~ 10h, leave standstill, supernatant liquid is got in layering; When catalyzer is acid,,, when being acidic cation-exchange resin, then catalyzer is filtered by catalyzer to neutral with deionized water wash; Each reactant consumption accounts for 0.05 ~ 80wt% of product quality by the metal atom content, and the mol ratio of R/Si is that the mol% of 1.2 ~ 2.2, Vi/R is that the mol% of 0.05 ~ 35%, Ph/R 5 ~ 75% regulates; The consumption of solvent is 0.1-10 times (preferable consumption is 0.5-5 times) of organosilane monomer and metallic compound total mass; The consumption of water so that react fully be as the criterion (be generally 5 ~ 60% of organosilane monomer quality, be preferably 20% ~ 40%);
Described organosilane monomer is selected from one or both mixture of trifunctional organosilane monomer, four sense organosilane monomers, perhaps be selected from the mixture of trifunctional organosilane monomer and two sense organosilane monomers, the mixture of four sense organosilane monomers and two sense organosilane monomers, the mixture of two sense organosilane monomers and trifunctional organosilane monomer and four sense organosilane monomers; Wherein, two functional organosilanes are dichloromethyl phenylsilane, aminomethyl phenyl dimethoxy silane (MePhSi (OMe) 2), aminomethyl phenyl diethoxy silane (MePhSi (OEt) 2), diphenyl dichlorosilane, dimethyldichlorosilane(DMCS) (Me 2SiCl 2), methyl ethylene dichlorosilane (MeViSiCl 2), dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenylbenzene dipropoxy TMOS, phenylbenzene diisopropoxy TMOS, dimethyldimethoxysil,ne (Me 2Si (OMe) 2), dimethyldiethoxysilane (Me 2Si (OEt) 2) in one or more; Trifunctional organosilicon silane is phenyl-trichloro-silicane (PhSiCl 3), phenyltrimethoxysila,e (PhSi (OMe) 3), phenyl triethoxysilane (PhSi (OEt) 3), methyltrimethoxy silane (MeSi (OMe) 3), Union carbide A-162 (MeSi (OEt) 3), vinyltriethoxysilane (ViSi (OEt) 3), vinyltrimethoxy silane (ViSi (OMe) 3) in one or more; Four functional organosilanes are that (preferred organosilane monomer is MePhSi (OMe) in tetrachloro silicane, methyl silicate, tetraethoxy, positive silicic acid propyl ester, positive isopropyl silicate, the butyl silicate one or more 2, PhSi (OMe) 3, Me 2Si (OMe) 2, MeSi (OMe) 3, MePhSi (OEt) 2, Me 2Si (OEt) 2, PhSi (OEt) 3, MeSi (OEt) 3, MePh 2SiOEt, ViSi (OMe) 3, ViSi (OEt) 3And Me 2Several or whole among the ViSiOEt; Preferred organosilane monomer is MePhSi (OEt) 2, Me 2Si (OEt) 2, PhSi (OEt) 3, MeSi (OEt) 3, ViSi (OEt) 3And Me 2ViSiOEt);
Described metallic compound is selected from titanium tetrachloride, tetramethyl alcohol titanium, titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, the isocaprylic acid titanium, the neodecanoic acid titanium, zirconium tetrachloride, tetramethyl alcohol zirconium, the tetraethoxide zirconium, four zirconium iso-propoxides, four butanols zirconiums, zirconium iso-octoate, the neodecanoic acid zirconium, zinc dichloride, dimethanol zinc, di-alcohol zinc, diisopropanol zinc, two butanols zinc, (preferred metallic compound is titanium tetraethoxide to the mixture of one or more in isocaprylic acid zinc or the zinc neodecanoate, titanium tetraisopropylate, the isocaprylic acid titanium, the neodecanoic acid titanium, the tetraethoxide zirconium, four zirconium iso-propoxides, zirconium iso-octoate, the neodecanoic acid zirconium, di-alcohol zinc, diisopropanol zinc, two butanols zinc, isocaprylic acid zinc, in the zinc neodecanoate etc. one or more; Most preferred metallic compound monomer is one or more in titanium tetraisopropylate, isocaprylic acid titanium, four zirconium iso-propoxides, zirconium iso-octoate, diisopropanol zinc, the isocaprylic acid zinc);
Described solvent is that (preferred solvent is one or more in toluene, dimethylbenzene, tetrahydrofuran (THF), the sherwood oil for one or more mixture in toluene, dimethylbenzene, di-toluene, tetrahydrofuran (THF), N-BUTYL ACETATE, Virahol, propyl carbinol, the sherwood oil etc.; Preferred solvent is toluene);
If muriate is arranged in the reaction raw materials, then need not add catalyzer, if chloride not then need add catalyzer, described catalyzer be acid or is acidic cation-exchange resin; Wherein, acid is selected from one or more the mixture (preferred acid for hydrochloric acid, phosphoric acid, acetic acid one or more) in hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, the acid of fluoroform semi-annular jade pendant or three hexafluorophosphoric acid; It is resin, weak acid acrylic resin, weak acid metha crylic resin that acidic cation-exchange resin is selected from superacicd styrene;
2) prepolymer polycondensation: it is 5 ~ 80% solution that the pre-polymer solution that obtains in the step 1) is made into solid content with solvent identical in the step 1), add polycondensation catalyst, backflow 0.5h ~ 12h, stop heating, add end-capping reagent, polycondensation catalyst after being cooled to room temperature, extremely neutral with deionized water wash behind stirring 0.5h ~ 5h; Then product is concentrated under 0.8MPa ~ 0.96MPa, and the water of desolventizing and polycondensation generation, by the degree that relative viscosity and the gelation time of measurement polycondensation product solution are controlled polycondensation, acquisition has the organic inorganic hybridization silicone resin of the high refractive index of vinyl;
Described end-capping reagent is selected from: trimethylchlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl vinyl methoxy silane (Me 2ViSiOMe), dimethyl vinyl Ethoxysilane (Me 2ViSiOEt), 1,1,3,3-tetramethyl--1,3-divinyl disiloxane (Me 2ViSiOSiOMe 2Vi), α, ω-divinyl silicone oil, α, ω-three silicon methyl ethylene silicone oil, α, the silica-based vinyl silicone oil of ω-3,5-dimethylphenyl, α, ω-three silicon phenyl vinyl silicone oil, hexamethyldisiloxane (Me 3SiOSiMe 3), decamethyl tetrasiloxane, 1,3-dimethyl-1,1,3,3-tetraphenyl-sily oxide, α, ω-divinyl polysiloxane, α, ω-three silicon methyl polysiloxane, α, the silica-based polysiloxane of ω-3,5-dimethylphenyl, α, one or more in the ω-three silicon phenyl polysiloxane; The solvent-free prepolymer of every 1000g ~ 500000g 1mol end-capping reagent;
Described polycondensation catalyst is selected from silicon alkoxide, the lithium hydroxide of silicon alkoxide, potassium hydroxide, the potassium hydroxide of silicon alkoxide, sodium hydroxide, the sodium hydroxide of silicon alkoxide, the TBAH of Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, the silicon alkoxide of lithium hydroxide; Its consumption is 0.005 ~ 1.5wt% of solvent-free prepolymer quality;
Cohydrolysis-polycondensation temperature is 0 ℃ ~ 78 ℃ (are preferably room temperature ~ 78 ℃), and the reaction times is that 0.5 ~ 10h(is preferably 1 ~ 6h);
3) packaged material preparation and sulfuration: with step 2) in gained have the organic inorganic hybridization silicone resin of high refractive index of vinyl and the mixture of containing hydrogen silicone oil linking agent, platinum catalyst and inhibitor mixes according to silicon hydrogen and silico ethylene mol ratio 0.7 ~ 3:1, (after being preferably 5 ~ 30min), curing time 0.5 ~ 24h moulding gets product in room temperature ~ 150 ℃ through vacuum defoamation 5 ~ 40min;
Described containing hydrogen silicone oil linking agent structure is Me 2R 2SiO (Me 2SiO) d(MeHSiO) e(MePhSiO) fSiR 2Me 2, d is 3 ~ 900 positive integer in the formula, the positive integer of e=3 ~ 600, and f is 0 or 0 ~ 900 positive integer, 0≤f/ (d+e+f)≤0.99, R 2Be Me or H; Consumption is according to silicon hydrogen and silico ethylene mol ratio 0.7 ~ 3:1;
The mixture of described platinum catalyst and inhibitor, wherein platinum catalyst (being platinum complex) is selected from Platinic chloride, H 2PtCl 6Aqueous isopropanol, H 2PtCl 6Tetrahydrofuran solution, Pt (PPh 3) 4, Cp 2PtCl 2, the coordination of ethylene methacrylic radical siloxane the platinum complex of platinum complex, dichloro two (triphenylphosphine) of platinum complex, diethyl phthalate coordination in one or more mixture (be preferably Platinic chloride, H 2PtCl 6Aqueous isopropanol, H 2PtCl 6The platinum complex of tetrahydrofuran solution, the coordination of ethylene methacrylic radical siloxane in one or more, the platinum complex of ethylene methacrylic radical siloxane coordination more preferably), inhibitor is selected from one or more the mixture (be preferably one or both the mixture in propiolic alcohol, the tetramethyl-butynol, most preferably be the tetramethyl-butynol) in quinoline, pyridine, tertbutyl peroxide, propiolic alcohol, the tetramethyl-butynol; The consumption of platinum catalyst is that platinum element quality is that 1 ~ 150ppm(of all components weight is preferably 1 ~ 30ppm), and the mol ratio of inhibitor and pt atom is 2 ~ 150: 1(is preferably 15 ~ 50:1).
As preferably, when organic silicon monomer is selected from MePhSi (OEt) 2, PhSi (OMe) 3, Me 2Si (OEt) 2, Me 2During several or whole among the ViSiOEt, when metallic compound is selected from titanium tetraisopropylate, isocaprylic acid titanium, four zirconium iso-propoxides, zirconium iso-octoate, diisopropanol zinc, the isocaprylic acid zinc one or more, the reactant consumption accounts for 0.5 ~ 58wt% of product quality by the metal atom content, the mol ratio of R/Si is 1.1 ~ 2.0, the mol% of Vi/R is that the mol% of 0.05 ~ 35%, Ph/R is 5 ~ 75% adjustings.
As preferably, described step 1) reactant consumption accounts for 0 ~ 58wt% of product quality by the metal atom content, and the mol ratio of R/Si is that the mol% of 1.3 ~ 2.0, Vi/R is that the mol% of 3% ~ 10%, Ph/R 30 ~ 65% regulates.
As preferably, when catalyzer is selected from one or more mixture in hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, the acid of fluoroform semi-annular jade pendant or three hexafluorophosphoric acid, 10 ~ 200ppm that corresponding acid molecule content is organosilane monomer and metallic compound in the catalyzer; When catalyzer was Zeo-karb, the Zeo-karb consumption was 2 ~ 5% of organosilane monomer consumption.
Compared with prior art, the inventive method adopts cohydrolysis-polycondensation legal, in-situ preparing LED encapsulation silicone resin type organic-inorganic hybrid material, and the reaction times is shorter, gained organic-inorganic hybrid material transmittance height.The silicone resin type organic-inorganic hybrid material transmittance that the inventive method obtains〉98%, refractive index 1.41-1.70, have radiation hardness, high-low temperature resistant, characteristic such as weather-proof, can be used as packaged materials such as LED embedding, SMD encapsulation, lens, also be expected for organosilicon materials such as seal gum, joint sealant and tackiness agent.
Embodiment
The present invention can further specify by following embodiment, but embodiment is not limiting the scope of the invention.
Embodiment 1
1) in the 1L there-necked flask that 46ml dimethylbenzene and 360ml water are housed, under 40 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 11ml TiCl 4, the mixing solutions of 88ml dimethylbenzene continues to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add the solvent that 50g dimethylbenzene is used,, 0.15gKOH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds 1.5g end-capping reagent MeSiCl 3, stirring 1h, deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue dimethylbenzene and polycondensation generation, obtain the clear silicone resin.
3) with the dimethyl containing hydrogen silicone oil of gained vinyl polysiloxane and hydrogen content 0.7wt% according to Si-H:Si-Vi=1.5:1, platinum complex catalyst H 2PtCl 6Tetrahydrofuran solution 10ppm, pyridine 10ppm after mixing, through vacuum defoamation 15min, in 150 ℃ of following sulfuration 1h, obtains the material of refractive index 1.44.
Embodiment2
1) in the 1L there-necked flask that 46ml toluene and 360ml water are housed, under 60 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 9ml isocaprylic acid zinc, 88ml toluene mixing solutions, continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add 50g toluene, 0.15g tetrabutylammonium hydroxide amine, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds 4.5g end-capping reagent α, the silica-based vinyl silicone oil of ω-3,5-dimethylphenyl stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual toluene and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.08wt% according to Si-H:Si-Vi=1.5:1, platinum complex catalyst H 2PtCl 6Aqueous isopropanol 10ppm, tertbutyl peroxide 50ppm after mixing, through vacuum defoamation 15min, in 150 ℃ of following sulfuration 1h, obtains the material of refractive index 1.48.
Embodiment 3
1) in the 1L there-necked flask that 46ml toluene and 360ml water are housed, under 60 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 9ml MePhSiCl 2, the 15ml zirconium iso-octoate, the mixing solutions of 88ml toluene continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add 50g toluene, 0.15gKOH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 6.0g decamethyl tetrasiloxane, stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual toluene and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.10wt% according to Si-H:Si-Vi=1.5:1, Pt (PPh 3) 410ppm after mixing, through vacuum defoamation 15min, vulcanizes 1h under 150 ℃, obtain the material of refractive index 1.53.
Embodiment 4
1) in the 1L there-necked flask that 46ml Virahol and 360ml water are housed, under 60 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 9ml MePhSiCl 2, the 35ml titanium isopropylate, the mixing solutions of 88ml Virahol continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add the 50g Virahol, the 0.15g strong aqua, 80 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 1.5g 3,5-dimethylphenyl chlorosilane, stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue Virahol and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and the hydrogen content 0.50wt% platinum complex 10ppm according to Si-H:Si-Vi=1.5:1, the coordination of ethylene methacrylic radical siloxane, propiolic alcohol 100ppm, after mixing, through vacuum defoamation 15min, under 150 ℃, vulcanize 2h, obtain the material of refractive index 1.55.
Embodiment 5
1) in the 1L there-necked flask that 46ml tetrahydrofuran (THF) and 360ml water are housed, under 60 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 9ml MePhSiCl 2, the 40ml zinc chloride, the mixing solutions of 88ml tetrahydrofuran (THF) continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add the 50g tetrahydrofuran (THF), 0.15gKOH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 4.5g 1,1,3,3-tetramethyl--1, the 3-divinyl disiloxane stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue tetrahydrofuran (THF) and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.50wt% according to Si-H:Si-Vi=3:1, Pt (PPh 3) 410ppm after tetramethyl-butynol 10ppm mixes, through vacuum defoamation 15min, vulcanizes 1h under 150 ℃, obtain the material of refractive index 1.51.
Embodiment 6
1) in the 1L there-necked flask that 46ml toluene and 360ml water are housed, under 60 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 9ml MePhSiCl 2, 70ml isocaprylic acid titanium, the mixing solutions of 88ml toluene continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add 50g toluene, 0.15g Na 2CO 3, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 1.5g MeSiCl 3, stirring 1h, deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual toluene and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.50wt% platinum complex 4 ppm according to Si-H:Si-Vi=2:1, the coordination of ethylene methacrylic radical siloxane, after tetramethyl-butynol 10ppm mixes, through vacuum defoamation 15min, under 150 ℃, vulcanize 1h, obtain the material of refractive index 1.52.
Embodiment 7
1) in the 1L there-necked flask that 46ml sherwood oil and 360ml water are housed, under 60 ℃ of stirrings, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 18ml Me 2SiCl 2, 9ml MePhSiCl 2, 70ml isocaprylic acid titanium, 25ml n-propyl titanium, the mixing solutions of 88ml sherwood oil continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add the 50g sherwood oil, 0.15gNaOH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 1.5g hexamethyldisiloxane, stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual petroleum ether and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and the hydrogen content 0.50wt% platinum complex according to Si-H:Si-Vi=0.8:1, diethyl phthalate coordination, after pyridine 10ppm mixes, through vacuum defoamation 15min, under 150 ℃, vulcanize 1h, obtain the material of refractive index 1.54.
Embodiment 8
1) in the 1L there-necked flask that 46ml N-BUTYL ACETATE, 360ml water and catalyzer 0.1g concentrated hydrochloric acid (36.5%) are housed, under 40 ℃ of stirrings, drips 62.2ml PhSi (OMe) in the 2h 3, 31.8ml MeViSi (OEt) 2, 36.7ml Me 2Si (OEt) 2, 47 ml MePhSi (OEt) 2, the 40ml tetrabutyl titanate, the 88ml N-BUTYL ACETATE
Mixing solutions, continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add the 50g N-BUTYL ACETATE, the 0.15g Tetramethylammonium hydroxide, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 5.0g α, ω-three silicon methyl ethylene silicone oil stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue N-BUTYL ACETATE and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and the hydrogen content 0.50wt% platinum complex 8ppm according to Si-H:Si-Vi=1:1, dichloro two (triphenylphosphine), after propiolic alcohol 10ppm mixes, through vacuum defoamation 15min, under 150 ℃, vulcanize 2h, obtain the material of refractive index 1.63.
Embodiment 9
1) in the 1L there-necked flask that 46ml propyl carbinol, 360ml water and catalyzer 11g acidic cation-exchange resin are housed, under 40 ℃ of stirrings, drips 62.2ml PhSi (OMe) in the 2h 3, 31.8ml MeViSi (OEt) 2, 36.7ml Me 2Si (OEt) 2, 56.8 ml Ph 2Si (OEt) 2, the 40ml tetrabutyl titanate, the mixing solutions of 88ml propyl carbinol continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.
2) get gained pre-polymer solution 50g, add the 50g propyl carbinol, 0.15gKOH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 1.5g dimethyl vinyl Ethoxysilane, stirs 1h, and deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue propyl carbinol and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.50wt% according to Si-H:Si-Vi=1.8:1, H 2PtCl 6Tetrahydrofuran solution 8ppm, after tertbutyl peroxide 10ppm mixes, through vacuum defoamation 15min, in 150 ℃ of following sulfuration 2h, obtain the material of refractive index 1.68.
Embodiment 10
1) in the 1L there-necked flask that 23ml toluene and 23ml dimethylbenzene, 360ml water and catalyzer 0.1g concentrated hydrochloric acid (36.5%) are housed, under 40 ℃ of stirrings, drips 62.2ml PhSi (OMe) in the 2h 3, 31.8ml MeViSi (OEt) 2, 18.4ml Me 2Si (OEt) 2, 23.5 ml MePhSi (OEt) 2, the 40ml tetrabutyl titanate, the mixing solutions of 44ml toluene and 44ml dimethylbenzene continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add 25g toluene and 25g dimethylbenzene, the 0.15g TBAH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 3.0g dimethyl vinyl methoxy silane, stir 1h, deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual solvent and polycondensation generation, obtain the clear silicone resin.
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.50wt% according to Si-H:Si-Vi=1.5:1, H 2PtCl 6Aqueous isopropanol 8ppm, after quinoline 10ppm mixes, through vacuum defoamation 15min, in 150 ℃ of following sulfuration 2h, obtain the material of refractive index 1.60.
Comparative Examples:
1) cohydrolysis reaction: in the 1L there-necked flask that 46ml toluene and 360ml water are housed, under 0 ℃ of stirring, Dropwise 5 0ml PhSiCl in the 2h 3, 22ml MeViSiCl 2, 30ml Me 2SiCl 2, 88ml toluene mixing solutions, continue to stir 1h.Leave standstill, layering, except the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) prepolymer polycondensation: get gained pre-polymer solution 50g, add 50g toluene, be made into the solution of solid content 25%, add 0.15gKOH, 100 ℃ of following backflow 5h in the 250ml there-necked flask, cooling adds end-capping reagent 1.5g MeSiCl 3, stirring 1h, deionized water wash is to neutral.Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual toluene and polycondensation generation, obtain the clear silicone resin.
3) packaged material preparation and sulfuration: with the dimethyl containing hydrogen silicone oil of gained vinyl polysiloxane and hydrogen content 1.2wt% according to Si-H:Si-Vi=1.2:1, platinum catalyst H 2PtCl 6Aqueous isopropanol 10ppm, quinoline 20ppm after mixing, through vacuum defoamation 15min, in 150 ℃ of following sulfuration 1h, obtains the material of refractive index 1.41.

Claims (6)

1. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) in the 1L there-necked flask that 46mL dimethylbenzene and 360mL water are housed, under 40 ℃ of stirrings, Dropwise 5 0mLPhSiCl in the 2h 3, 22mL MeViSiCl 2, 18mLMe 2SiCl 2, 11mL TiCl 4, the mixing solutions of 88mL dimethylbenzene continues to stir 1h; Leave standstill, layering, except the sub-cloud acid solution; Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash;
2) get gained pre-polymer solution 50g, add 50g dimethylbenzene, 0.15gKOH, 100 ℃ of following backflow 5h in the 250mL there-necked flask, cooling adds 1.5g end-capping reagent MeSiCl 3, stirring 1h, deionized water wash is to neutral; Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue dimethylbenzene and polycondensation generation, obtain the clear silicone resin;
3) with the dimethyl containing hydrogen silicone oil of gained vinyl polysiloxane and hydrogen content 0.7wt% according to Si-H:Si-Vi=1.5:1, platinum complex catalyst H 2PtCl 6Tetrahydrofuran solution 10ppm, pyridine 10ppm after mixing, through vacuum defoamation 15min, in 150 ℃ of following sulfuration 1h, obtains the material of refractive index 1.44.
2. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) in the 1L there-necked flask that 46mL toluene and 360mL water are housed, under 60 ℃ of stirrings, Dropwise 5 0mL PhSiCl in the 2h 3, 22mLMeViSiCl 2, 18mL Me 2SiCl 2, 9mLMePhSiCl 2, the 15mL zirconium iso-octoate, the mixing solutions of 88mL toluene continue to stir 1h; Leave standstill, layering, except the sub-cloud acid solution; Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash;
2) get gained pre-polymer solution 50g, add 50g toluene, 0.15gKOH, 100 ℃ of following backflow 5h in the 250mL there-necked flask, cooling adds end-capping reagent 6.0g decamethyl tetrasiloxane, stirs 1h, and deionized water wash is to neutral; Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual toluene and polycondensation generation, obtain the clear silicone resin;
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.10wt% according to Si-H:Si-Vi=1.5:1, Pt (PPh 3) 410ppm after mixing, through vacuum defoamation 15min, vulcanizes 1h under 150 ℃, obtain the material of refractive index 1.53.
3. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) in the 1L there-necked flask that 46mL Virahol and 360mL water are housed, under 60 ℃ of stirrings, Dropwise 5 0mLPhSiCl in the 2h 3, 22mLMeViSiCl 2, 18mLMe 2SiCl 2, 9mL MePhSiCl 2, the 35mL titanium isopropylate, the mixing solutions of 88mL Virahol continue to stir 1h; Leave standstill, layering, except the sub-cloud acid solution; Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash;
2) get gained pre-polymer solution 50g, add the 50g Virahol, the 0.15g strong aqua, 80 ℃ of following backflow 5h in the 250mL there-necked flask, cooling adds end-capping reagent 1.5g 3,5-dimethylphenyl chlorosilane, stirs 1h, and deionized water wash is to neutral; Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue Virahol and polycondensation generation, obtain the clear silicone resin;
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and the hydrogen content 0.50wt% platinum complex 10ppm according to Si-H:Si-Vi=1.5:1, the coordination of ethylene methacrylic radical siloxane, propiolic alcohol 100ppm, after mixing, through vacuum defoamation 15min, under 150 ℃, vulcanize 2h, obtain the material of refractive index 1.55.
4. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) in the 1L there-necked flask that 46mL tetrahydrofuran (THF) and 360mL water are housed, under 60 ℃ of stirrings, Dropwise 5 0mLPhSiCl in the 2h 3, 22mLMeViSiCl 2, 18mLMe 2SiCl 2, 9mL MePhSiCl 2, the 40mL zinc chloride, the mixing solutions of 88mL tetrahydrofuran (THF) continue to stir 1h; Leave standstill, layering, except the sub-cloud acid solution; Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash;
2) get gained pre-polymer solution 50g, add the 50g tetrahydrofuran (THF), 0.15gKOH, 100 ℃ of following backflow 5h in the 250mL there-necked flask, cooling adds end-capping reagent 4.5g 1,1,3,3-tetramethyl--1, the 3-divinyl disiloxane stirs 1h, and deionized water wash is to neutral; Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residue tetrahydrofuran (THF) and polycondensation generation, obtain the clear silicone resin;
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.50wt% according to Si-H:Si-Vi=3:1, Pt (PPh 3) 410ppm after tetramethyl-butynol 10ppm mixes, through vacuum defoamation 15min, vulcanizes 1h under 150 ℃, obtain the material of refractive index 1.51.
5. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) in the 1L there-necked flask that 46mL toluene and 360mL water are housed, under 60 ℃ of stirrings, Dropwise 5 0mLPhSiCl in the 2h 3, 22mLMeViSiCl 2, 18mLMe 2SiCl 2, 9ml MePhSiCl 2, 70mL isocaprylic acid titanium, the mixing solutions of 88mL toluene continue to stir 1h; Leave standstill, layering, except the sub-cloud acid solution; Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash;
2) get gained pre-polymer solution 50g, add 50g toluene, 0.15g Na 2CO 3, 100 ℃ of following backflow 5h in the 250mL there-necked flask, cooling adds end-capping reagent 1.5g MeSiCl 3, stirring 1h, deionized water wash is to neutral; Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual toluene and polycondensation generation, obtain the clear silicone resin;
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and hydrogen content 0.50wt% platinum complex 4 ppm according to Si-H:Si-Vi=2:1, the coordination of ethylene methacrylic radical siloxane, after tetramethyl-butynol 10ppm mixes, through vacuum defoamation 15min, under 150 ℃, vulcanize 1h, obtain the material of refractive index 1.52.
6. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) in the 1L there-necked flask that 46mL sherwood oil and 360mL water are housed, under 60 ℃ of stirrings, Dropwise 5 0mL PhSiCl in the 2h 3, 22mLMeViSiCl 2, 18mLMe 2SiCl 2, 9mLMePhSiCl 2, 70mL isocaprylic acid titanium, 25mL n-propyl titanium, the mixing solutions of 88mL sherwood oil continue to stir 1h; Leave standstill, layering, except the sub-cloud acid solution; Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash;
2) get gained pre-polymer solution 50g, add the 50g sherwood oil, 0.15gNaOH, 100 ℃ of following backflow 5h in the 250mL there-necked flask, cooling adds end-capping reagent 1.5g hexamethyldisiloxane, stirs 1h, and deionized water wash is to neutral; Under 0.8 ~ 0.96MPa, concentrate, and remove the water of residual petroleum ether and polycondensation generation, obtain the clear silicone resin;
3) with the methyl and phenyl hydrogen-containing silicon oil of gained vinyl polysiloxane and the hydrogen content 0.50wt% platinum complex according to Si-H:Si-Vi=0.8:1, diethyl phthalate coordination, after pyridine 10ppm mixes, through vacuum defoamation 15min, under 150 ℃, vulcanize 1h, obtain the material of refractive index 1.54.
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