CN102391529A - 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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CN102391529A
CN102391529A CN2011101964068A CN201110196406A CN102391529A CN 102391529 A CN102391529 A CN 102391529A CN 2011101964068 A CN2011101964068 A CN 2011101964068A CN 201110196406 A CN201110196406 A CN 201110196406A CN 102391529 A CN102391529 A CN 102391529A
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acid
consumption
mixture
zinc
organosilane
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CN102391529B (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 Ltd 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 is with 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 that a kind of LED encapsulation is with 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 a 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, are prone to 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 receives investigator's favor because of having good thermotolerance, weathering resistance, moisture resistance, cold-resistant thermal shocking property etc.
Organosilicon material has advantages such as high-low temperature resistant, ageing-resistant, UV resistant, radiation hardness, is ideal 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%.U.S. Pat 20050212008 (its equating patent EP1424363) has been reported employing silicon hydrogen addition vulcanization technology; With ethenyl blocking Zylox 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.U.S. Pat 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 have excellent mechanical property and non-viscosity can, can stand the cold cycling impact between 1000 times-50 ℃ to 150 ℃ and 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 through 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), be 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 deficiency of 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 of the present invention is with silicone resin type organic-inorganic hybrid material preparation method, as follows:
1) cohydrolysis reaction: the mixture of an organosilane monomer, metallic compound and partial solvent is added drop-wise in 0 ℃ ~ 80 ℃ the still material of forming 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, extremely neutral with deionized water wash, when catalyzer is acidic cation-exchange resin, then with catalyst filtration; Each reactant consumption accounts for 0.05 ~ 80wt% of product quality by the metal atom content, and the mol ratio of R/Si is 1.2 ~ 2.2, and the mol% of Vi/R is 0.05 ~ 35%, and the mol% of Ph/R 5 ~ 75% regulates; The consumption of solvent is 0.1-10 times (preferable consumption is 0.5-5 times) of an organosilane monomer and metallic compound total mass; The consumption of water so that react fully be as the criterion (be generally 5 ~ 60% of an organosilane monomer quality, be preferably 20% ~ 40%);
Described an organosilane monomer is selected from one or both mixture of trifunctional an organosilane monomer, four sense an organosilane monomers; Perhaps be selected from the mixture of trifunctional an organosilane monomer and two sense an organosilane monomers; The mixture of four sense an organosilane monomers and two sense an organosilane monomers, the mixture of two sense an organosilane monomers and trifunctional an organosilane monomer and four sense an 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 an 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 2Among the ViSiOEt several kinds or all; Preferred an 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 a 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, YLENE, THF, the sherwood oil for one or more mixture in toluene, YLENE, di-toluene, THF, N-BUTYL ACETATE, Virahol, propyl carbinol, the sherwood oil etc.; Preferred solvent is a 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 reaction: 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, spend deionised water to neutral after stirring 0.5h ~ 5h; Then product is concentrated under 0.8MPa ~ 0.96MPa; And except that the water that desolvates and polycondensation reaction generates; By the degree that the relative viscosity and the gelation time of measurement polycondensation product solution are controlled polycondensation reaction, acquisition has the organic inorganic hybridization silicones 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, SWS-F 221 (Me 3SiOSiMe 3), decamethyl tetrasiloxane, 1,3-dimethyl--1,1; 3,3-tetraphenyl-sily oxide, α, ω-divinyl ZGK 5, α; ω-three silicon methyl polysiloxane, α, the silica-based ZGK 5 of ω-3,5-dimethylphenyl, α, one or more in the ω-three silicon phenyl polysiloxane; The solvent-free prepolymer of every 1000g ~ 500000g is used the 1mol end-capping reagent;
Described polycondensation catalyst is selected from silicon alkoxide, the Lithium Hydroxide MonoHydrate of silicon alkoxide, Pottasium Hydroxide, the Pottasium Hydroxide of silicon alkoxide, sodium hydroxide, the sodium hydroxide of silicon alkoxide, the TBAH of TMAH, TMAH, the silicon alkoxide of Lithium Hydroxide MonoHydrate; 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 the gained organic inorganic hybridization silicone resin and the mixture of containing hydrogen silicone oil linking agent, platinum catalyst and suppressor factor that have a high refractive index of vinyl mix 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 suppressor factor, 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, ethylene methacrylic radical siloxane coordinate platinum complex, diethyl phthalate coordinate platinum complex, dichloro two (triphenylphosphine) platinum complex in one or more mixture (be preferably Platinic chloride, H 2PtCl 6Aqueous isopropanol, H 2PtCl 6Tetrahydrofuran solution, in the ethylene methacrylic radical siloxane coordinate platinum complex one or more; Ethylene methacrylic radical siloxane coordinate platinum complex more preferably); Suppressor factor 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 (be preferably 1 ~ 30ppm), and the mol ratio of suppressor factor and pt atom is (to be preferably 15 ~ 50:1) at 2 ~ 150: 1.
As preferably, when organic silicon monomer is selected from MePhSi (OEt) 2, PhSi (OMe) 3, Me 2Si (OEt) 2, Me 2Among the ViSiOEt several kinds or all the time; 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, and the mol% of Vi/R is 0.05 ~ 35%, and the mol% of 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 1.3 ~ 2.0, and the mol% of Vi/R is 3% ~ 10%, and the mol% of Ph/R 30 ~ 65% regulates.
As preferably, when catalyzer is selected from one or more the 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 pairing acid molecule content is an organosilane monomer and metallic compound in the catalyzer; When catalyzer was Zeo-karb, the Zeo-karb consumption was 2 ~ 5% of an an organosilane monomer consumption.
Compared with prior art, the inventive method adopts cohydrolysis-polycondensation legal, and in-situ preparing LED encapsulates with silicone resin type organic-inorganic hybrid material, and the reaction times is shorter, and gained organic-inorganic hybrid material transmittance is high.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 to be used for organosilicon materials such as sealer, joint sealant and tackiness agent.
Embodiment
The present invention can further specify through following embodiment, but embodiment is not the restriction to protection domain of the present invention.
Embodiment 1
1) in the 1L there-necked flask that 46ml YLENE 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 YLENE continues to stir 1h.Leave standstill, layering, remove 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 YLENE is used,, 0.15gKOH, 100 ℃ of refluxed 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 YLENE 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, remove 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 refluxed 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, remove 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 refluxed 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, remove 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 refluxed 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 hydrogen content 0.50wt% according to Si-H:Si-Vi=1.5:1, ethylene methacrylic radical siloxane coordinate platinum complex 10ppm; 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 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 THF continue to stir 1h.Leave standstill, layering, remove the sub-cloud acid solution.Extremely neutral with 40 ℃ ~ 50 ℃ deionized water wash.
2) get gained pre-polymer solution 50g, add the 50g THF, 0.15gKOH, 100 ℃ of refluxed 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 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, remove 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 refluxed 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% according to Si-H:Si-Vi=2:1, ethylene methacrylic radical siloxane coordinate platinum complex 4 ppm; 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, remove 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 refluxed 5h in the 250ml there-necked flask, cooling adds end-capping reagent 1.5g SWS-F 221, 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 hydrogen content 0.50wt% according to Si-H:Si-Vi=0.8:1, diethyl phthalate coordinate platinum complex; 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, remove 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 TMAH; 100 ℃ of refluxed 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 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, remove the sub-cloud acid solution.
2) get gained pre-polymer solution 50g, add the 50g propyl carbinol, 0.15gKOH, 100 ℃ of refluxed 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,,, obtain the material of refractive index 1.68 in 150 ℃ of following sulfuration 2h through vacuum defoamation 15min.
Embodiment 10
1) in the 1L there-necked flask that 23ml toluene and 23ml YLENE, 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 YLENE continue to stir 1h.Leave standstill, layering, remove 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 YLENE, the 0.15g TBAH; 100 ℃ of refluxed 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,,, obtain the material of refractive index 1.60 in 150 ℃ of following sulfuration 2h through vacuum defoamation 15min.
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, remove 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 refluxed 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 (8)

1. an encapsulation is characterized in that as follows with silicone resin type organic-inorganic hybrid material preparation method:
1) cohydrolysis reaction: the mixture of an organosilane monomer, metallic compound and partial solvent is added drop-wise in 0 ℃ ~ 80 ℃ the still material of forming 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, extremely neutral with deionized water wash, when catalyzer is acidic cation-exchange resin, then with catalyst filtration; Each reactant consumption accounts for 0.05 ~ 80wt% of product quality by the metal atom content, and the mol ratio of R/Si is 1.2 ~ 2.2, and the mol% of Vi/R is 0.05 ~ 35%, and the mol% of Ph/R 5 ~ 75% regulates; The consumption of solvent is an organosilane monomer and metallic compound total mass 0.1-10 a times; The consumption of water is so that react to such an extent that fully be as the criterion;
Described an organosilane monomer is selected from one or both mixture of trifunctional an organosilane monomer, four sense an organosilane monomers; Perhaps be selected from the mixture of trifunctional an organosilane monomer and two sense an organosilane monomers; The mixture of four sense an organosilane monomers and two sense an organosilane monomers, the mixture of two sense an organosilane monomers, trifunctional an organosilane monomer and four sense an organosilane monomers; Wherein, two functional organosilanes are one or more in dichloromethyl phenylsilane, aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, diphenyl dichlorosilane, dimethyldichlorosilane(DMCS), methyl ethylene dichlorosilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenylbenzene dipropoxy TMOS, phenylbenzene diisopropoxy TMOS, dimethyldimethoxysil,ne, the dimethyldiethoxysilane; Trifunctional organosilicon silane is one or more in phenyl-trichloro-silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, vinyltriethoxysilane, the vinyltrimethoxy silane; Four functional organosilanes are one or more in tetrachloro silicane, methyl silicate, tetraethoxy, positive silicic acid propyl ester, positive isopropyl silicate, the butyl silicate;
Described metallic compound is selected from one or more the mixture in titanium tetrachloride, tetramethyl alcohol titanium, titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, isocaprylic acid titanium, neodecanoic acid titanium, zirconium tetrachloride, tetramethyl alcohol zirconium, tetraethoxide zirconium, four zirconium iso-propoxides, four butanols zirconiums, zirconium iso-octoate, neodecanoic acid zirconium, zinc dichloride, dimethanol zinc, di-alcohol zinc, diisopropanol zinc, two butanols zinc, isocaprylic acid zinc or the zinc neodecanoate;
Described solvent is one or more the mixture in toluene, YLENE, di-toluene, THF, N-BUTYL ACETATE, Virahol, propyl carbinol, the sherwood oil etc.;
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 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: with the prepolymer that obtains in the step 1) use with step 1) in identical solvent to be made into solid content be 5 ~ 80% solution; Add polycondensation catalyst; Backflow 0.5h ~ 12h; Stop heating, add end-capping reagent after being cooled to room temperature, stir behind 0.5h ~ 5h with deionized water wash to neutral; Then product is concentrated under 0.8MPa ~ 0.96MPa; And except that the water that desolvates and polycondensation generates; Through the degree that the 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, dimethyl-vinyl Ethoxysilane, 1,1,3; 3-tetramethyl--1,3-divinyl disiloxane, 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, SWS-F 221, decamethyl tetrasiloxane, 1; 3-dimethyl--1,1,3; 3-tetraphenyl-sily oxide, α, ω-divinyl ZGK 5, α, ω-three silicon methyl polysiloxane, α; The silica-based ZGK 5 of ω-3,5-dimethylphenyl, α, one or more in the ω-three silicon phenyl polysiloxane; Its consumption is that the solvent-free prepolymer of every 1000g ~ 500000g is used the 1mol end-capping reagent;
Described polycondensation catalyst is selected from silicon alkoxide, the Lithium Hydroxide MonoHydrate of silicon alkoxide, Pottasium Hydroxide, the Pottasium Hydroxide of silicon alkoxide, sodium hydroxide, the sodium hydroxide of silicon alkoxide, the TBAH of TMAH, TMAH, the silicon alkoxide of Lithium Hydroxide MonoHydrate; Its consumption is 0.005 ~ 1.5wt% of solvent-free prepolymer quality;
Cohydrolysis-polycondensation temperature is 0 ℃ ~ 78 ℃, and the reaction times is 0.5 ~ 10h;
3) packaged material preparation and sulfuration: with step 2) in the gained organic inorganic hybridization silicone resin and the mixture of containing hydrogen silicone oil linking agent, platinum catalyst and suppressor factor that have a high refractive index of vinyl mix according to silicon hydrogen and silico ethylene mol ratio 0.7 ~ 3:1; Behind vacuum defoamation 5 ~ 40min, curing time 0.5 ~ 24h moulding gets product in room temperature ~ 150 ℃;
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 suppressor factor, wherein platinum catalyst is selected from Platinic chloride, H 2PtCl 6Aqueous isopropanol, H 2PtCl 6Tetrahydrofuran solution, Pt (PPh 3) 4, Cp 2PtCl 2, ethylene methacrylic radical siloxane coordinate platinum complex, diethyl phthalate coordinate platinum complex, dichloro two (triphenylphosphine) platinum complex in one or more mixture, suppressor factor is selected from one or more the mixture in quinoline, pyridine, tertbutyl peroxide, propiolic alcohol, the tetramethyl-butynol; The consumption of platinum catalyst is that platinum element quality is 1 ~ 150ppm of all components, and the mol ratio of suppressor factor and pt atom is 2 ~ 150: 1.
2. preparation method according to claim 1 is characterized in that in the step 1), when organic silicon monomer is selected from MePhSi (OEt) 2, PhSi (OMe) 3, Me 2Si (OEt) 2, Me 2Among the ViSiOEt several kinds or all the time; 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, and the mol% of Vi/R is 0.05 ~ 35%, and the mol% of Ph/R is 5 ~ 75% adjustings.
3. preparation method according to claim 2; It is characterized in that described step 1) reactant consumption accounts for 0 ~ 58wt% of product quality by the metal atom content; The mol ratio of R/Si is 1.3 ~ 2.0, and the mol% of Vi/R is 3% ~ 10%, and the mol% of Ph/R is 30 ~ 65% adjustings.
4. according to claim 1 or 2 or 3 described preparing methods; In the step 1) that it is characterized in that; When catalyzer is selected from one or more the 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 pairing acid molecule content is an organosilane monomer and metallic compound in the catalyzer; When catalyzer was Zeo-karb, the Zeo-karb consumption was 2 ~ 5% of an an organosilane monomer consumption.
5. according to claim 1 and 2 or 3 described preparing methods, the consumption that it is characterized in that step 1) water is 20% ~ 40% of an an organosilane monomer quality.
6. preparation method according to claim 4, the consumption that it is characterized in that step 1) water is 20% ~ 40% of an organosilane monomer and a metallic compound total mass.
7. according to claim 1 or 2 or 3 described preparing methods, the consumption that it is characterized in that the described platinum complex of step 3) is that platinum element quality is 1 ~ 30ppm of all components, and the mol ratio of suppressor factor and pt atom is for being 15 ~ 50:1.
8. preparation method according to claim 4, the consumption that it is characterized in that the described platinum complex of step 3) is that platinum element quality is 1 ~ 30ppm of all components, and the mol ratio of suppressor factor and pt atom is for being 15 ~ 50:1.
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Inventor after: Jiang Jianxiong

Inventor after: Luo Mengxian

Inventor after: Xu Jinchang

Inventor before: Laiguoqiao

Inventor before: Yang Xiongfa

Inventor before: Cao Jian

Inventor before: Shao Qian

Inventor before: Yang Linlin

Inventor before: Hua Xilin

Inventor before: Jiang Jianxiong

Inventor before: Luo Mengxian

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Effective date of registration: 20211223

Address after: 065800 Xinqiao Economic Development Zone, Wen'an County, Langfang City, Hebei Province

Patentee after: Hebei thick and rich organosilicon products Limited by Share Ltd.

Address before: 065800 pengerwan Industrial Zone, Zhaogezhuang Town, Wen'an County, Langfang City, Hebei Province

Patentee before: Wen'an Huawei Chemical Co., Ltd

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