CN101935455B - Organosilicon material for packaging LED and preparation method thereof - Google Patents

Organosilicon material for packaging LED and preparation method thereof Download PDF

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CN101935455B
CN101935455B CN201010239022A CN201010239022A CN101935455B CN 101935455 B CN101935455 B CN 101935455B CN 201010239022 A CN201010239022 A CN 201010239022A CN 201010239022 A CN201010239022 A CN 201010239022A CN 101935455 B CN101935455 B CN 101935455B
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sio
hydrogen
platinum complex
mixture
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CN101935455A (en
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来国桥
杨雄发
蒋剑雄
华西林
邵倩
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NANTONG JINGYU MACHINE Co.,Ltd.
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Hangzhou Normal University
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Abstract

The invention relates to an organosilicon material for packaging an LED and a preparation method thereof, which needs to solve the technical problem of greatly improving the optical property, the mechanical property and the binding power with a bracket of the product. The organosilicon material of the invention is characterized by being prepared by mixing a component A and a component B at the mass ratio of 0.3:1-1:30, wherein the component A is vinyl polysiloxane, and the component B is hydrogen-containing polysiloxane; then adding D component, E component and component C, wherein the D component is vinyl MQ resin, the E component is one or more of vinyltrimethoxysilane, tetrabutyl titanate and KH-560, and the component C is a catalyst; and evenly mixing. The invention needs to solve the other technical problem of enabling the preparation method to be clean and pollution-free. The preparation method of the invention comprises the following steps: evenly mixing the components in proportion; carrying out vacuum deaeration at room temperature for 5-30 min; and carrying out vulcanization shaping at the vulcanizing temperature of 20-150 DEG C.

Description

A kind of LED encapsulation is with organosilicon material and preparation method thereof
Technical field
The present invention relates to a kind of compsn of macromolecular compound, specifically is that a kind of LED encapsulation is with organosilicon material and preparation method thereof.
Background technology
The electric energy that photodiode (LED) illumination consumes only is 1/10 of a conventional light source; Have characteristics such as the mercury, the volume that do not use serious environment pollution are little, the life-span is long, at first get into special lighting fields such as industrial equipments, instrument, traffic lights, automobile, backlight.Along with the improvement of LED performance, LED be expected to replace conventional light source such as incandescent light, luminescent lamp and become the 4th generation lighting source.
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.Be engaged in this respect research abroad early, successfully developed a series of products.
And the domestic research work of having only a few peoples to be engaged in this type material at present; Mainly be through modifying epoxy resin by organosilicon (seeing Chinese patent document CN1978526, CN101085855, CN101525466 and CN101525467); Though performance makes moderate progress; But compare with external product, have a long way to go.And, also be in the starting stage for the research of pure organosilicon product, also there is not the like product listing.What patent report was arranged at present is that (the Chinese invention patent CN101619170A) such as Liu Bailing of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences prepares the vinyl base polymer with containing vinyl silanes and chlorine-containing silane cohydrolysis; Prepare hydrogeneous linking agent with silane containing hydrogen and chlorine-containing silane cohydrolysis then; To measure component then and mix according to a certain percentage, material is used in the LED encapsulation that under platinum complex catalyst catalysis, obtains colourless, transparent, heat-resisting, low water absorption, colourless change through silicon hydrogen additive process sulfuration.This method need through the washing-in and operation, can produce a large amount of spent acid, contaminate environment, etching apparatus, labour intensity is bigger.(CN 101544881A) such as the Xiong Ting of Chengdu Guibao Technology Co., Ltd uses α, and alpha, omega-dihydroxy polydimethyl siloxane is a main raw material, under catalysis such as titanic acid ester complex compound, dibutyl tin laurate, prepared condensed type LED packaged material.Usually, condensed type Zylox shrinking percentage is bigger, produces bubble because of condensation reaction discharges micromolecular compound easily.
In general, the LED of present domestic use encapsulation is mainly leaned on import with organosilicon material, costs an arm and a leg, and produces and receives the foreign patent restriction, and this has seriously restricted the development of LED industry.
Summary of the invention
The technical issues that need to address of the present invention are, make optics, the mechanical mechanics property of product, improve a lot with the cohesive force of support.
Another technical problem that the present invention need solve is to make preparing method's cleanliness without any pollution.
Organosilicon material is used in LED encapsulation of the present invention, it is characterized in that being mixed in 0.3: 1 ~ 1: 30 according to mass ratio by A component and B component, adds D component, E component and catalyzer C component then, is prepared from after mixing; Described A component is the vinyl ZGK 5; Described B component is a hydrogen containing siloxane; Described C component is the mixture of platinum complex and suppressor factor; The consumption of C component is that platinum element quality is that 1 ~ 60ppm of all components (is preferably 1 ~ 30ppm, more preferably 2 ~ 10ppm), and the mol ratio of suppressor factor and pt atom is (to be preferably 15 ~ 50:1) at 2 ~ 150: 1 by the consumption of platinum complex.The intensity of organosilicon material of the present invention and hardness can be regulated through adding D component (being used to increase the physical strength and the hardness of packaged material) and E component (being used to increase the cohesive force of packaged material and LED package support).
Described D component is that structural formula is (Me 3SiO) e(MeViSiO) fSiO 2Vinyl MQ resin, (e+f)=0.55 ~ 1.65 in the formula (being preferably 0.75 ~ 1.25), f/ (e+f)=0.0005 ~ 0.45 (being preferably 0.005 ~ 0.25), its consumption for except that the E component 0 ~ 60wt% of all components (be preferably 5 ~ 40wt%).
Described E component is one or several the mixture among tetraethoxy, vinyltrimethoxy silane, the positive butyl ester of boric acid, boric acid isopropyl ester, isocaprylic acid titanium, zirconium iso-octoate, tetrabutyl titanate, isopropyl titanate, KH-171, KH-560 and the KH-570; Perhaps one or more hydrolyzate (is preferably one or several the mixture among vinyltrimethoxy silane, boric acid isopropyl ester, isocaprylic acid titanium, tetrabutyl titanate, KH-560 and the KH-570; Perhaps one or more hydrolyzate; Optimum is one or more mixture among vinyltrimethoxy silane, tetrabutyl titanate, the KH-560, perhaps their hydrolyzate); The E amounts of components (is preferably 0.05 ~ 2.0wt%) for 0 ~ 8.0wt% of all other components;
Described A component vinyl silicone oil; Be that octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and closure agent are according to mol ratio 3 ~ 550:0 ~ 90:1; Under catalyst action; In 70 ~ 150 ℃ of following polymerase 10 .5 ~ 12h, the polymerization back that finishes is removed catalyzer and is got, and the vinyl silicone oil molecular structural formula is Me 2R 1SiO (Me 2SiO) a(MeViSiO) bSiR 1Me 2, the positive number of a=12 in the formula ~ 2200, the positive number of b=0 ~ 360, R 1For-CH 3Or-CH=CH 2
Catalyst system therefor is one or more the mixture (being preferably the TMAH silicon alkoxide) among TMAH, TMAH silicon alkoxide, NaOH, the KOH; Used closure agent is 1,1,3; 3 ,-tetramethyl--1,3-divinyl disiloxane (being the vinyl double-seal head), dimethyl-vinylsiloxane (being vinyl list end socket), SWS-F 221, decamethyl tetrasiloxane, 1; 3-dimethyl--1; 1,3, the mixture of one or more in 3-tetraphenyl-sily oxide (being preferably the vinyl double-seal head); When catalyzer is TMAH, TMAH silicon alkoxide; Need be heated to 135 ~ 180 ℃ of decomposition catalysts and be neutrality until tail gas; When catalyzer is NaOH, KOH, need to use that neutralizing agent---dilute sulphuric acid, dilute phosphoric acid or Hydrogen chloride are neutralized to neutrality.
Described B component containing hydrogen silicone oil is octamethylcyclotetrasiloxane D4, tetramethyl-tetrahydrochysene cyclotetrasiloxane D 4 HWith closure agent according to mol ratio 1.25 ~ 212.5: 0.75 ~ 100: 1, under catalyst action,, remove catalyzer after polymerization finishes and get at 20 ~ 100 ℃ of following polymerase 10 .5 ~ 24h, its molecular structure is Me 2R 2SiO (Me 2SiO) c(MeHSiO) dSiR 2Me 2, the positive number of c=5 in the formula ~ 850, the positive number of d=3 ~ 400, R 2For-CH 3Or H;
Catalyst system therefor is wide aperture Zeo-karb, SO 4 2-/ M xO yType solid super-strong acid, SO 4 2-/ M xO y/ Ln 3+The mixture of one or more in type rare-earth solid superacid, acidic white earth, 98% vitriol oil, 70% vitriol oil, 50% vitriol oil etc. is preferably wide aperture Zeo-karb or rare-earth solid superacid; End-capping reagent is 1,1,3,3-tetramethyl--1,3-dihydro sily oxide, α; ω-two silicon hydrogen base containing hydrogen silicone oil, α, ω-three silicon Methyl Hydrogen Polysiloxane Fluid, α, the silica-based containing hydrogen silicone oil of ω-3,5-dimethylphenyl, α, ω-three silicon phenyl hydrogen-containing silicon oil, SWS-F 221, decamethyl tetrasiloxane, 1; 3-dimethyl--1,1,3,3-tetraphenyl-sily oxide, α; ω-two silicon hydrogen based polysiloxane, α, ω-three silicon methyl polysiloxane, α, the silica-based ZGK 5 of ω-3,5-dimethylphenyl, α, the mixture of one or more in the ω-three silicon phenyl polysiloxane (is preferably 1; 1,3,3-tetramethyl--1,3-dihydro sily oxide); When catalyzer is wide aperture Zeo-karb, SO 4 2-/ M xO yType solid super-strong acid, SO 4 2-/ M xO y/ Ln 3+During in type rare-earth solid superacid, the acidic white earth one or more; Only need to filter to remove catalyzer; When catalyzer is 98% vitriol oil, 70% vitriol oil, 50% vitriol oil; Water is washed till neutrality, or uses neutralizing agent---and yellow soda ash, sodium hydrogencarbonate, sodium hydrogen phosphate or SODIUM PHOSPHATE, MONOBASIC are neutralized to neutrality.
Platinum complex in the described C component is 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, NSC 7352 platinum dichloride, dichloro two (triphenylphosphine) platinum complex in one or more mixture, platinum complex is 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 in the C component is one or more the mixture in quinoline, pyridine, tertbutyl peroxide, propiolic alcohol, the tetramethyl-butynol, and suppressor factor is preferably one or both the mixture in propiolic alcohol, the tetramethyl-butynol; Optimum is the tetramethyl-butynol.
Preparing method of the present invention, after proportionally each component being mixed, the vacuum defoamation time is 5 ~ 30min, curing temperature is 20 ~ 150 ℃.
Compared with prior art, beneficial effect of the present invention is following:
(1) the present invention adopts the method for cyclosiloxane ring-opening copolymerization to prepare vinyl ZGK 5 and hydrogen containing siloxane, cleanliness without any pollution, and labour intensity is low, is convenient to industrialization;
(2) through adding D component reinforced filling MQ resin, when improving the mechanical mechanics property of product, help improving the cohesive force of packaged material and support;
(3) add the E component, under the prerequisite of the transmittance that does not influence product, vulcanization rate and storage time, improved the cohesive force of packaged material and support.
The organosilicon material that the inventive method obtains; Refractive index can reach 1.41, hardness 0-80 shore A, transmittance>98%; Operable time>24h; Curing temperature is 20 ~ 150 ℃, is very suitable for the embedding of LED, SMD encapsulation etc., can also be applied to fields such as optical lens, solar cell substrate, touch-screen.
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 clean there-necked flask of 250ml, adds 150g D4,5.16g D 4 ViUnder-0.096MPa/35 ~ 40 ℃, remove moisture; Add 2.79g vinyl double-seal head and 3.16g TMAH silicon alkoxide then; At 100 ℃ of polyase 13 h; Be warming up to the about 3h of decomposition catalyst between 145 ~ 160 ℃ then, under-0.096MPa/180 ℃, take off low molecular compound then, obtain 120g A component Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2
2) in the clean there-necked flask of 250ml, add 150g D4 and under-0.096MPa/35 ~ 40 ℃, remove moisture, add 4.32g D then 4 H, hydrogeneous double-seal head of 1.98g and 7.82 g wide aperture Zeo-karbs at 70 ℃ of polymerization 5h, filter then, and clear liquid is taken off low molecular compound under-0.096MPa/180 ℃, obtain 125g B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2
3) get above-mentioned gained A component and each 10g of B component, add the platinum complex catalyst of 0.030g (about 8ppm), after mixing; Through vacuum defoamation 15min, sulfuration 2h gets product refractive index 1.41 under 100 ℃; Hardness is 0, records transmittance 96.5% with ultraviolet spectrophotometer.
Embodiment 2
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 211.8 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 4.36g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.033g (about 10ppm) again is after mixing, through vacuum defoamation 20 min; Sulfuration 2.5h under 100 ℃, refractive index 1.41, hardness is 40 shore A components; Tensile strength 2.39MPa, elongation 75% records transmittance 94.8% with ultraviolet spectrophotometer.
Embodiment 3
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 211.8 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 4.36g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.033g (about 10ppm) again is after 0.2616g vinyltrimethoxy silane (1.0 wt%) mixes, through vacuum defoamation 20 min; Sulfuration 2.5h under 100 ℃, refractive index 1.41, hardness is 40 shore A; Tensile strength 2.89MPa, elongation 88% records transmittance 95.0% with ultraviolet spectrophotometer.
Embodiment 4
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 211.8 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 4.36g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators, add the platinum complex catalyst of 0.033g (about 10ppm) again; 0.1308g vinyltrimethoxy silane (0.5wt%) and 0.1308g (0.5wt%) tetrabutyl titanate are after mixing, through vacuum defoamation 20 min; Sulfuration 2 h under 100 ℃, refractive index 1.41, hardness is 42 shore A; Tensile strength 2.95 MPa, elongation 95 % record transmittance 94.5% with ultraviolet spectrophotometer.
Embodiment 5
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 211.8 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 4.36g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators, add the platinum complex catalyst of 0.033g (about 10ppm) again.0.0872g vinyltrimethoxy silane (0.33wt%), 0.0872g (0.33wt%) tetrabutyl titanate and 0.0872g KH-560 at 80 ℃ of following cohydrolysis 5h, are joined in the sizing material after removing moisture and by product, after mixing; Through vacuum defoamation 20 min, vulcanize 2 h, refractive index 1.41 down in 100 ℃; Hardness is 38 shore A; Tensile strength 3.25 MPa, elongation 110 % record transmittance 98.0% with ultraviolet spectrophotometer.
Embodiment 6
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 211.0 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 2.1g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0144g (about 5ppm) again is after mixing, through vacuum defoamation 20 min; Sulfuration 3 h under 100 ℃, refractive index 1.41, hardness is 25 shore A; Tensile strength 1.26 MPa, elongation 125 % record transmittance 98.5 % with ultraviolet spectrophotometer.
Embodiment 7
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 211.36 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 3.20 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0092g (about 3ppm) again is after mixing, through vacuum defoamation 20 min; Sulfuration 4 h under 100 ℃, refractive index 1.41, hardness is 31 shore A; Tensile strength 1.85 MPa, elongation 118 % record transmittance 96.2 % with ultraviolet spectrophotometer.
Embodiment 8
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 212.2 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D 5.55 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0092g (about 3ppm) again is after mixing, through vacuum defoamation 20 min; Sulfuration 4 h under 100 ℃, refractive index 1.41, hardness is 45 shore A; Tensile strength 2.45 MPa, elongation 70 % record transmittance 94.2 % with ultraviolet spectrophotometer.
Embodiment 9
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 212.67 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 6.80 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0221 g (about 6ppm) again is after mixing, through vacuum defoamation 30 min; Sulfuration 1.5 h under 100 ℃, refractive index 1.41, hardness is 52 shore A; Tensile strength 2.30 MPa, elongation 55 % record transmittance 93.0 % with ultraviolet spectrophotometer.
Embodiment 10
Get gained A component Me among the embodiment 1 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 210g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 213.64 g, the adding structural formula is (Me 3SiO) 0.97(MeViSiO) 0.03SiO 2D component 9.46 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.012 g (about 3ppm) again is after mixing, through vacuum defoamation 30 min; Sulfuration 1.5 h under 100 ℃, refractive index 1.41, hardness is 64 shore A; Tensile strength 1.85 MPa, elongation 24 % record transmittance 91.0 % with ultraviolet spectrophotometer.
Embodiment 11
1) in the clean there-necked flask of 250ml, adds 150g D4 and under-0.096MPa/35 ~ 40 ℃, remove moisture; Add 2.79g vinyl double-seal head and 3.16g TMAH silicon alkoxide then; At 100 ℃ of polyase 13 h; Be warming up to the about 5h of decomposition catalyst between 145 ~ 160 ℃ then, under-0.096MPa/180 ℃, take off low molecular compound then, obtain 125g A component Me 2ViSiO (Me 2SiO) 135.1SiViMe 2
2) in the clean there-necked flask of 250ml, add 150g D4 and under-0.096MPa/35 ~ 40 ℃, remove moisture, add 4.32g D then 4 H, hydrogeneous double-seal head of 1.98g and 7.82 g wide aperture Zeo-karbs at 70 ℃ of polymerization 5h, filter then, and clear liquid is taken off low molecular compound under-0.096MPa/180 ℃, obtain 125g B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2
3) get above-mentioned gained A component Me 2ViSiO (Me 2SiO) 135.1SiViMe 29g and B component Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 24g, the platinum complex catalyst of adding 0.0163g (about 10ppm), after mixing, through vacuum defoamation 15min, sulfuration 3h under 100 ℃, refractive index 1.41, hardness is 0, records transmittance 97.2% with ultraviolet spectrophotometer.
Embodiment 12
1) in the clean there-necked flask of 250ml, adds 150g D4 and under-0.096MPa/35 ~ 40 ℃, remove moisture; Add 0.558g vinyl double-seal head and 3.16g TMAH silicon alkoxide then; At 100 ℃ of polyase 13 h; Be warming up to the about 5h of decomposition catalyst between 145 ~ 160 ℃ then, under-0.096MPa/180 ℃, take off low molecular compound then, obtain 122g A component Me 2ViSiO (Me 2SiO) 675.7SiViMe 2
2) in the clean there-necked flask of 250ml, add 15g D4 and under-0.096MPa/35 ~ 40 ℃, remove moisture, add 145 g D then 4 H, hydrogeneous double-seal head of 1.98g and 7.82 g wide aperture Zeo-karbs at 70 ℃ of polymerization 2 h, filter then, and clear liquid is taken off low molecular compound under-0.096MPa/180 ℃, obtain 115 g B component Me 2HSiO (Me 2SiO) 13.7(MeHSiO) 163.5SiHMe 2
3) get above-mentioned gained A 28.5 g and B 1.0g, add the platinum complex catalyst of 0.011g (about 3ppm), after mixing; Through vacuum defoamation 15min; Sulfuration 0.5 h under 150 ℃, refractive index 1.41, hardness is 25 shore A; Elongation 320% records transmittance 98.0% with ultraviolet spectrophotometer.
Embodiment 13
Get gained A component Me among the embodiment 12 2ViSiO (Me 2SiO) 675.7SiViMe 228.5g with B component Me 2HSiO (Me 2SiO) 13.7(MeHSiO) 163.5SiHMe 21.0 g, the adding structural formula is (Me 3SiO) 0.87(MeViSiO) 0.03SiO 2D component 5.9 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0178g (about 4ppm) again is after the E component vinyltrimethoxy silane (1.0 wt%) of 0.2616g mixes, through vacuum defoamation 20 min; Sulfuration 4 h under 80 ℃, refractive index 1.41, hardness is 48 shore A; Tensile strength 3.52 MPa, elongation 86% records transmittance 95.5% with ultraviolet spectrophotometer.
Embodiment 14
Get gained A component Me among the embodiment 12 2ViSiO (Me 2SiO) 675.7SiViMe 228.5g with B component Me 2HSiO (Me 2SiO) 13.7(MeHSiO) 163.5SiHMe 21.0 g, the adding structural formula is (Me 3SiO) 1.0(MeViSiO) 0.10SiO 2D component 5.9 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0178g (about 4ppm) again is after the E component vinyltrimethoxy silane (1.0 wt%) of 0.3540g mixes, through vacuum defoamation 20 min; Sulfuration 4 h under 80 ℃, refractive index 1.41, hardness is 55 shore A; Tensile strength 3.86 MPa, elongation 65% records transmittance 93.5% with ultraviolet spectrophotometer.
Embodiment 15
Get gained A component Me among the embodiment 12 2ViSiO (Me 2SiO) 675.7SiViMe 228.5g with B component Me 2HSiO (Me 2SiO) 13.7(MeHSiO) 163.5SiHMe 21.2 g, the adding structural formula is (Me 3SiO) 0.8(MeViSiO) 0.30SiO 2D 6.0 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators; The platinum complex catalyst that adds 0.0178g (about 4ppm) again, 0.118g vinyltrimethoxy silane (0.33wt%), 0.118g isopropyl titanate (0.33wt%) and 0.118g KH-560 (0.33wt%); After mixing,, vulcanize 6h down in 60 ℃ through vacuum defoamation 30 min; Refractive index 1.41, hardness are 65 shore A, tensile strength 3.92 MPa; Elongation 40% records transmittance 91.5% with ultraviolet spectrophotometer.
Embodiment 16
1) in the clean there-necked flask of 250ml, adds 135g D4 and 15g D 4 ViUnder-0.096MPa/35 ~ 40 ℃, remove moisture; Add 0.78g vinyl double-seal head and 3.16g TMAH silicon alkoxide then; At 100 ℃ of polyase 13 h; Be warming up to the about 5h of decomposition catalyst between 145 ~ 160 ℃ then, under-0.096MPa/180 ℃, take off low molecular compound then, obtain 124g A component Me 2ViSiO (Me 2SiO) 435.4(MeViSiO) 41.6SiViMe 2
2) in the clean there-necked flask of 250ml, add 35g D4 and under-0.096MPa/35 ~ 40 ℃, remove moisture, add 115 g D then 4 H, hydrogeneous double-seal head of 0.96g and 7.82 g wide aperture Zeo-karbs at 70 ℃ of polymerization 2 h, filter then, and clear liquid is taken off low molecular compound under-0.096MPa/180 ℃, obtain 115 g B component Me 2HSiO (Me 2SiO) 65.1(MeHSiO) 263.6SiHMe 2
3) get above-mentioned gained A component 10.5 g and B component 1.1g, the adding structural formula is (Me 3SiO) 0.65(MeViSiO) 0.45SiO 2D component 2.1 g, add after the dissolving of 10ml toluene finishes, remove toluene with Rotary Evaporators, add the platinum complex catalyst of 0.0086g (about 5ppm) again; 0.137g vinyltrimethoxy silane (1.0wt%) is after mixing, through vacuum defoamation 30 min; Sulfuration 24 h under 25 ℃, refractive index 1.41, hardness is 76 shore A; Tensile strength 2.95 MPa, elongation 80% records transmittance 92.5% with ultraviolet spectrophotometer.

Claims (3)

1. organosilicon material is used in a LED encapsulation, it is characterized in that being mixed in 0.3: 1 ~ 1: 30 according to mass ratio by A component and B component, adds D component, E component and catalyzer C component then, is prepared from after mixing;
Described A component is the vinyl ZGK 5; Described B component is a hydrogen containing siloxane; Described C component is the mixture of platinum complex and suppressor factor; The consumption of C component is that platinum element quality is 1 ~ 60ppm of all components by the consumption of platinum complex, and the mol ratio of suppressor factor and pt atom is 2 ~ 150: 1;
Described A component vinyl ZGK 5; Be octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and closure agent according to mol ratio 3 ~ 550: 0 ~ 90: 1; Under catalyst action; In 70 ~ 150 ℃ of following polymerase 10 .5 ~ 12h, to remove catalyzer after polymerization finishes and obtain vinyl silicone oil, its molecular structural formula is Me 2R 1SiO (Me 2SiO) a(MeViSiO) bSiR 1Me 2, the positive number of a=12 in the formula ~ 2200, the positive number of b=0 ~ 360, R 1For-CH 3Or-CH=CH 2
Catalyst system therefor is one or more the mixture among TMAH, TMAH silicon alkoxide, NaOH, the KOH; Used closure agent is 1,1,3,3;-tetramethyl--1,3-divinyl disiloxane, dimethyl-vinylsiloxane, SWS-F 221, decamethyl tetrasiloxane, 1,3-dimethyl--1; 1,3, the mixture of one or more in 3-tetraphenyl-sily oxide; When catalyzer is TMAH, TMAH silicon alkoxide; Need be heated to 135 ~ 180 ℃ of decomposition catalysts and be neutrality until tail gas; When catalyzer is NaOH, KOH, need to use that neutralizing agent---dilute sulphuric acid, dilute phosphoric acid or Hydrogen chloride are neutralized to neutrality;
Described B component hydrogen containing siloxane; Be octamethylcyclotetrasiloxane, tetramethyl-tetrahydrochysene cyclotetrasiloxane and closure agent according to mol ratio 1.25 ~ 212.5: 0.75 ~ 100: 1; Under catalyst action; At 20 ~ 100 ℃ of following polymerase 10 .5 ~ 24h, after finishing, polymerization removes the catalyzer gained, and its molecular structure is Me 2R 2SiO (Me 2SiO) c(MeHSiO) dSiR 2Me 2, the positive number of c=5 in the formula ~ 850, the positive number of d=3 ~ 400, R 2For-CH 3Or H;
Catalyst system therefor is wide aperture Zeo-karb, SO 4 2-/ M xO yType solid super-strong acid, SO 4 2-/ M xO y/ Ln 3+The mixture of one or more in type rare-earth solid superacid, acidic white earth, 98% vitriol oil, 70% vitriol oil, 50% vitriol oil; End-capping reagent is 1,1,3,3-tetramethyl--1; 3-dihydro sily oxide, α, ω-two silicon hydrogen base containing hydrogen silicone oil, α, ω-three silicon Methyl Hydrogen Polysiloxane Fluid, α, the silica-based containing hydrogen silicone oil of ω-3,5-dimethylphenyl, α; ω-three silicon phenyl hydrogen-containing silicon oil, SWS-F 221, decamethyl tetrasiloxane, 1,3-dimethyl--1,1; 3,3-tetraphenyl-sily oxide, α, ω-two silicon hydrogen based polysiloxane, α; ω-three silicon methyl polysiloxane, α, the silica-based ZGK 5 of ω-3,5-dimethylphenyl, α, the mixture of one or more in the ω-three silicon phenyl polysiloxane; When catalyzer is wide aperture Zeo-karb, SO 4 2-/ M xO yType solid super-strong acid, SO 4 2-/ M xO y/ Ln 3+During in type rare-earth solid superacid, the acidic white earth one or more; Only need to filter to remove catalyzer; When catalyzer is 98% vitriol oil, 70% vitriol oil, 50% vitriol oil; Water is washed till neutrality, or uses neutralizing agent---and yellow soda ash, sodium hydrogencarbonate, sodium hydrogen phosphate or SODIUM PHOSPHATE, MONOBASIC are neutralized to neutrality;
Platinum complex in the described C component is 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, NSC 7352 platinum dichloride, dichloro two (triphenylphosphine) platinum complex in one or more mixture; Suppressor factor in the C component is one or more the mixture in quinoline, pyridine, tertbutyl peroxide, propiolic alcohol, the tetramethyl-butynol;
Described D component is that structural formula is (Me 3SiO) e(MeViSiO) fSiO 2Vinyl MQ resin, (e+f)=0.55 ~ 1.65 in the formula, f/ (e+f)=0.0005 ~ 0.45, its consumption are 0 ~ 60wt% of all components except that the E component;
Described E component is one or several the mixture among tetraethoxy, vinyltrimethoxy silane, the positive butyl ester of boric acid, boric acid isopropyl ester, isocaprylic acid titanium, zirconium iso-octoate, tetrabutyl titanate, isopropyl titanate, KH-171, KH-560 and the KH-570; Perhaps one or more hydrolyzate, its consumption is 0 ~ 8.0wt% of all other components.
2. organosilicon material is used in LED according to claim 1 encapsulation, and the consumption that it is characterized in that described C component is that platinum element quality is 1 ~ 30ppm of all components by the consumption of platinum complex, and the mol ratio of suppressor factor and pt atom is 15 ~ 50:1; (e+f)=0.75 ~ 1.25 in the described D component structure formula, f/ (e+f)=0.005 ~ 0.25, its consumption are 5 ~ 40wt% of all components except that the E component; Described E amounts of components is 0.05 ~ 2.0wt% of all other components.
3. a LED according to claim 1 or claim 2 encapsulates the preparation method with organosilicon material, it is characterized in that after proportionally each component being mixed, through room temperature vacuum defoamation 5 ~ 30min, curing temperature is 20 ~ 150 ℃ of following sulfidization moldings.
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