CN103848990A - High-refractive index vinyl phenyl silicon resin for light-emitting diode (LED) package - Google Patents
High-refractive index vinyl phenyl silicon resin for light-emitting diode (LED) package Download PDFInfo
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Abstract
The invention provides a high-refractive index vinyl phenyl silicon resin for light-emitting diode (LED) package. The preparation process is simple and easy to operate, and the prepared vinyl phenyl silicon resin is high in light transmittance and reasonable in refractive index and vinyl content and suitable for LED package.
Description
Technical field
The present invention relates to a kind of packaging of photoelectric device silicone resin, especially relate to a kind of LED encapsulation high refractive index ethenylphenyl silicone resin.
Background technology
From late 1990s, along with the breakthrough of third generation semiconductor material gan technology and the appearance of blue, green and white light emitting diode, semiconductor technology is after causing microelectronic revolution, breed again new Industrial Revolution-illumination revolution, its mark is progressively replace incandescent and luminescent lamp of semiconductor lamp, is the quantum leap that the mankind are thrown light in history.Manufacturing in power-type LED device process, do not there is the effects such as moisture-resistant gas, anti-oxidation, anti-short circuit, protection chip due to LED itself, therefore need the processing procedure such as assembling routing, colloid encapsulation through different types.Packaged material can not only provide protection for LED chip, and can also play and determine that light distributes, reduces between chip and air refringence apart to increase the effects such as light output, and the reliability on LED and light output efficiency have absoluteness impact.The optical output power and the work-ing life that use high heat conduction, high refractive index, high resistance to ultraviolet and ageing-resistant ability and transparent packaged material can obviously improve LED device.
Organosilicon material main chain is made up of Si-O-Si key, side group is connected with different functional groups, gives the performance of the many excellences of material itself, as high transmission rate, high-weatherability and ageing resistance etc., can be at 200-250 DEG C of life-time service, or in the short period of time, reach 300-350 DEG C qualitative change can not occur.The appearance of organosilicon material efficiently solves the easy xanthochromia of conventional epoxies packaged material, to thermal shock bad adaptability, the problem such as cannot dispel the heat.Therefore, organosilicon material becomes the first-selection of current high-power LED encapsulation.
Organosilicon is exactly that mechanical property is poor as a shortcoming of packaged material.The present invention, from improving its mechanical property, by the controllable adjustment of silicone resin medium vinyl content being regulated and controled to the cross-linking density of silicon hydrogen addition, thereby realizes the comprehensive regulation to packaging plastic mechanical property.In the time that the contents of ethylene in vinyl polysiloxane is too low, the cross-linking density of packaging plastic is little; Otherwise cross-linking density is excessive, packaging plastic becomes fragile, and elongation, ageing-resistant performance are bad, therefore need controllable adjustment contents of ethylene, and it is changed within the specific limits.
Mostly existing patent is to adopt the method for hydrolyzing chlorosilane-polycondensation about the preparation of ethenylphenyl silicone resin, as patent CN101343365A, CN101979427A and US2002006794(Al), in reaction process, there are a large amount of HCl to produce, need to carry out aftertreatment, not only increase labour intensity, and to environment.It is that reaction raw materials is prepared methyl phenyl vinyl polysiloxane that CN101475689A adopts siloxanes, siloxanes used is vinyltrimethoxy silane, vinyltriethoxysilane, dimethyl vinyl methoxy silane, Vinyldimethylethoxysilane etc., the contents of ethylene of the standby ethenylphenyl silicone resin of this patent system is can modification scope very little, can only save at molecular chain-end keynote, it is adjustable that this patent does not explicitly point out contents of ethylene simultaneously, and the method for adjusting is not described yet.
The problem that patent of the present invention exists mainly for prior art, controlled introducing vinyl in silicone resin main chain, and carry out end-blocking by the two encapsulation header of vinyl, reach the controlled of contents of ethylene, a kind of novel organosilicon packaging plastic is provided, especially be applied in the high refractive index ethenylphenyl silicone resin that LED encapsulation field is used, and the preparation side of this resin is provided.
Summary of the invention
The object of the present invention is to provide a kind of LED encapsulation high refractive index ethenylphenyl silicone resin and preparation method thereof.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of high refractive index ethenylphenyl silicone resin for LED encapsulation, is characterized in that having following general structure (I):
（SiO
2）
a1（PhSiO
1.5）
a2（Ph
2SiO）
b1（ViMeSiO）
b2(Me
2ViSiO
0.5)
c1 （I）
Wherein: 0≤a1<1,0<a2<1,0<b1<1,0<b2<1,0<c1<1, and a1+a2+b1+b2+c1=1; Described ethenylphenyl silicone resin has tridimensional network.
In said structure general formula (I): siloxane unit SiO
2represent four sense chain links, PhSiO
1.5siloxane unit represents tri functional chain, Ph
2siO and Vi MeSiO siloxane unit represent difunctionality chain link, Me
2viSiO
0.5siloxane unit represents simple function chain link, and wherein Ph is that phenyl, Vi are that vinyl, Me are methyl.The shared mole number in each silica unit when whole siloxane units that a1, a2, b1, b2, c1 represent to form silicone resin are 1mol, wherein 0≤a1<1(does not comprise 1), (not comprising 0), 0<a2<1(did not comprise 1), (not comprising 0), 0<b1<1(did not comprise 1), (not comprising 0), 0<b2<1(did not comprise 1), (not comprising 0), 0<c1<1(did not comprise 1).
The method of preparing LED encapsulation high refractive index ethenylphenyl silicone resin provided by the invention, comprises the following steps:
(1) in reactor, add the mixed solvent of deionized water and organic solvent composition, add organoalkoxysilane, controls 20～50 DEG C of temperature, organoalkoxysilane is hydrolyzed react 2～8h,
The general structure of described organoalkoxysilane is R
1 nsi (OR
2)
4-n, wherein: R
1be selected from methyl, ethyl, phenyl or aryl, R
2for methyl or ethyl, (not comprising 0), 0<n<3(did not comprise 3),
Described organic solvent is selected from one, more than two or three combination in toluene, dimethylbenzene, tetrahydrofuran (THF), Virahol and propyl carbinol;
(2) after hydrolysis reaction finishes, add catalyzer, condensation reaction is carried out in rising temperature to 65～125 DEG C, and the 2～16h that refluxes, is then cooled to 40～50 DEG C, adds end-capping reagent to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.02～0.95Mpa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 145～185 DEG C, obtains target product after organic solvent washing.
In above-mentioned steps (1), the organoalkoxysilane of use is two kinds, three kinds in phenyltrimethoxysila,e, methyl ethylene dimethoxy silane, dimethyldimethoxysil,ne, aminomethyl phenyl methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, hexamethyldisiloxane, tetraethoxy, methyl silicate and dimethyl vinylsiloxane or multiple combination preferably; In organoalkoxysilane, Ph/Me mol ratio is preferably 0.25～0.75, Vi/Me mol ratio and is preferably 0.01～0.5; The mass ratio of deionized water and organoalkoxysilane is preferably 1.8～4.5:1, and the mass ratio of described organic solvent and organoalkoxysilane is 1.6～5:1, is preferably 2.1～5:1.
Above-mentioned end-capping reagent is preferably dimethyl vinylsiloxane or tetramethyl divinyl disiloxane; The mass ratio of end-capping reagent and organoalkoxysilane is preferably 0.6%～5.2%:1, more preferably 0.8%～4.5%:1.
Above-mentioned catalyzer is preferably potassium hydroxide, sodium hydroxide, ammoniacal liquor, sodium ethylate, potassium tert.-butoxide, sulfuric acid or tetramethyl-oxyammonia; The mass ratio of catalyzer and organoalkoxysilane is preferably 0.1%～2%:1.
In above-mentioned steps (3), vacuum distillation temperature is preferably 140～160 DEG C.
In above-mentioned steps (4), washing is preferably toluene or dimethylbenzene with organic solvent, and the mass ratio of organic solvent and product is preferably 5%～25%:1.
LED encapsulation prepared by the present invention is used high refractive index ethenylphenyl silicone resin and preparation method thereof compared to existing technology, has following advantage:
(1) in building-up process, use siloxanes as reaction raw materials, avoid conventional hydrolyzing chlorosilane and the hydrochloric acid pollution on the environment that produces;
(2) in backbone structure, introduce vinyl, make the contents of ethylene of product resin adjustable, be beneficial to the mechanical property of regulation and control packaging plastic;
(3) preparation technology is simple, easy handling.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described, but do not limit the invention in these specific embodiments.One skilled in the art would recognize that the present invention contained all alternativess, improvement project and the equivalents that within the scope of claims, may comprise.
Embodiment 1
(1) by dimethoxydiphenylsilane 30.76g, dimethyldimethoxysil,ne 42.29g, phenyltrimethoxysila,e 8.75g, the alkoxysilane mixture of vinyl methyl dimethoxysilane 2.36g and tetraethoxysilance 1.43g splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 186.91g deionized water, 229.38g dimethylbenzene and 67.94g Virahol of 30 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.82g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 96%, and refractive index is 1.5124, and contents of ethylene is 1.07mmol/g.
Embodiment 2
(1) by dimethoxydiphenylsilane 30.76g, dimethyldimethoxysil,ne 42.29g, phenyltrimethoxysila,e 8.75g, the mixture of vinyl methyl dimethoxysilane 2.36g and tetraethoxysilance 1.43g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 186.91g deionized water, 229.38g dimethylbenzene and 67.94g Virahol of 40 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.82g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 98%, and refractive index is 1.5176, and contents of ethylene is 1.22mmol/g.
Embodiment 3
(1) by dimethoxydiphenylsilane 30.76g, dimethyldimethoxysil,ne 42.29g, phenyltrimethoxysila,e 8.75g, the mixture of vinyl methyl dimethoxysilane 2.36g and tetraethoxysilance 1.43g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 186.91g deionized water, 229.38g dimethylbenzene and 67.94g Virahol of 45 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.82g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 99%, and refractive index is 1.5158, and contents of ethylene is 1.09mmol/g.
Embodiment 4
(1) by dimethoxydiphenylsilane 30.76g, dimethyldimethoxysil,ne 42.29g, phenyltrimethoxysila,e 8.75g, the mixture of vinyl methyl dimethoxysilane 2.36g and tetraethoxysilance 1.43g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 186.91g deionized water, 229.38g dimethylbenzene and 67.94g Virahol of 50 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.82g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 97%, and refractive index is 1.5124, and contents of ethylene is 1.22mmol/g.
Embodiment 5
(1) by dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 5.67g and tetraethoxy 2.06g organoalkoxysilane splashes into the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of the 45 DEG C reaction that is hydrolyzed, and the reaction times is 4.5h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91, rising temperature to 125 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 6.96g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 99%, and refractive index is 1.5174, and contents of ethylene is 2.36mmol/g.
Embodiment 6
(1) by dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 7.45g and tetraethoxy 2.06g organoalkoxysilane splashes into the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of the 45 DEG C reaction that is hydrolyzed, and the reaction times is 5h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 125 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 6.96g tetramethyl divinyl disiloxane to carry out end-blocking, and the reaction times is 4 hours;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 97%, and refractive index is 1.5201, and contents of ethylene is 3.47mmol/g.
Embodiment 7
(1) by dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 9.02g and tetraethoxy 2.06g organoalkoxysilane splashes into the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of the 55 DEG C reaction that is hydrolyzed, and the reaction times is 5.4h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 125 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 60 DEG C, adds 6.96g tetramethyl divinyl disiloxane to carry out end-blocking.
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin.
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 99%, and refractive index is 1.5207, and contents of ethylene is 4.73mmol/g.
Embodiment 8
(1) dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 12.71g and tetraethoxy 2.06g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of 50 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin;
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 98%, and refractive index is 1.5187, and contents of ethylene is 6.75mmol/g.
Embodiment 9
(1) dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 14.64g and tetraethoxy 2.06g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of 50 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin;
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 99%, and refractive index is 1.5214, and contents of ethylene is 7.03mmol/g.
Embodiment 10
(1) dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 14.64g and tetraethoxy 3.24g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of 50 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin;
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 98%, and refractive index is 1.5214, and contents of ethylene is 6.75mmol/g.
Embodiment 11
(1) dimethoxydiphenylsilane 43.26g, dimethyldimethoxysil,ne 54.19g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 14.64g and tetraethoxy 2.06g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of 50 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin;
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 99%, and refractive index is 1.5274, and contents of ethylene is 6.87mmol/g.
Embodiment 12
(1) dimethoxydiphenylsilane 48.26g, dimethyldimethoxysil,ne 59.51g, phenyltrimethoxysila,e 12.99g, the mixture of vinyl methyl dimethoxysilane 14.64g and tetraethoxy 2.06g organoalkoxysilane splashes into the reaction that is hydrolyzed in the mixed solvent being made up of 264.76g deionized water, 329.11g dimethylbenzene and 96.18g Virahol of 50 DEG C, and the reaction times is 3h;
(2) after hydrolysis reaction finishes, add tetramethyl-oxyammonia 0.91g, rising temperature to 122 DEG C is carried out condensation reaction, and then backflow 4h is cooled to 50 DEG C, adds 3.98g tetramethyl divinyl disiloxane to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.05MPa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 160 DEG C, then adds 37.81g dimethylbenzene to wash, then at 155 DEG C of temperature, carries out after underpressure distillation removes small molecules obtaining ethenylphenyl silicone resin;
After tested, the transmittance of the ethenylphenyl silicone resin of preparation is 99%, and refractive index is 1.5307, and contents of ethylene is 7.06mmol/g.
Claims (10)
1. a high refractive index ethenylphenyl silicone resin for LED encapsulation, is characterized in that having following general structure (I):
（SiO
2）
a1（PhSiO
1.5）
a2（Ph
2SiO）
b1（Vi MeSiO）
b2(Me
2ViSiO
0.5)
c1 （I）
Wherein: 0≤a1<1,0<a2<1,0<b1<1,0<b2<1,0<c1<1, and a1+a2+b1+b2+c1=1; Described ethenylphenyl silicone resin has tridimensional network.
2. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 1, is characterized in that comprising the following steps:
(1) in reactor, add the mixed solvent of deionized water and organic solvent composition, add organoalkoxysilane, controls 20～50 DEG C of temperature, organoalkoxysilane is hydrolyzed react 2～8h,
The general structure of described organoalkoxysilane is R
1 nsi (OR
2)
4-n, wherein: R
1be selected from methyl, ethyl, phenyl or aryl, R
2for methyl or ethyl, 0<n<3,
Described organic solvent is selected from one, more than two or three combination in toluene, dimethylbenzene, tetrahydrofuran (THF), Virahol and propyl carbinol;
(2) after hydrolysis reaction finishes, add catalyzer, condensation reaction is carried out in rising temperature to 65～125 DEG C, and the 2～16h that refluxes, is then cooled to 40～50 DEG C, adds end-capping reagent to carry out end-blocking;
(3) product step (2) being obtained carries out underpressure distillation under 0.02～0.95Mpa pressure, obtains product of distillation;
(4) product of distillation step (3) being obtained carries out slaking reaction at 145～185 DEG C, obtains target product after organic solvent washing.
3. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 2, is characterized in that described organoalkoxysilane is selected from two kinds, three kinds or multiple combination in phenyltrimethoxysila,e, methyl ethylene dimethoxy silane, dimethyldimethoxysil,ne, aminomethyl phenyl methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, hexamethyldisiloxane, tetraethoxy, methyl silicate and dimethyl vinylsiloxane.
4. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 2, is characterized in that in described organoalkoxysilane, Ph/Me mol ratio is that 0.25～0.75, Vi/Me mol ratio is 0.01～0.5.
5. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 2, it is characterized in that described end-capping reagent is dimethyl vinylsiloxane or tetramethyl divinyl disiloxane, the mass ratio of end-capping reagent and organoalkoxysilane is 0.6%～5.2%:1, described catalyzer is potassium hydroxide, sodium hydroxide, ammoniacal liquor, sodium ethylate, potassium tert.-butoxide, sulfuric acid or tetramethyl-oxyammonia, and the mass ratio of catalyzer and organoalkoxysilane is 0.1%～2%:1.
6. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 5, the mass ratio that it is characterized in that described end-capping reagent and organoalkoxysilane is 0.8%～4.5%:1.
7. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 2, the mass ratio that it is characterized in that described deionized water and organoalkoxysilane is 1.8～4.5:1, and the mass ratio of described organic solvent and organoalkoxysilane is 1.6～5:1.
8. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 7, the mass ratio that it is characterized in that described organic solvent and organoalkoxysilane is 2.1～5:1.
9. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 2, is characterized in that in described step (3), vacuum distillation temperature is 140～160 DEG C.
10. the preparation method with high refractive index ethenylphenyl silicone resin according to LED encapsulation claimed in claim 2, is characterized in that in described step (4), washing organic solvent is toluene or dimethylbenzene, and the mass ratio of organic solvent and product is 5%～25%:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210524061.9A CN103848990B (en) | 2012-12-04 | 2012-12-04 | High index of refraction Vinylphenyl silicon resin is used in a kind of LED encapsulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210524061.9A CN103848990B (en) | 2012-12-04 | 2012-12-04 | High index of refraction Vinylphenyl silicon resin is used in a kind of LED encapsulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103848990A true CN103848990A (en) | 2014-06-11 |
| CN103848990B CN103848990B (en) | 2016-12-21 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151558A (en) * | 2014-08-08 | 2014-11-19 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method for MDTQ type methyl phenyl vinyl silicone resin |
| CN104231273A (en) * | 2014-09-16 | 2014-12-24 | 上海应用技术学院 | High-viscosity self-crosslinking LED package gum resin and preparation method thereof |
| CN104262630A (en) * | 2014-09-16 | 2015-01-07 | 上海应用技术学院 | Low-viscosity self-crosslinking LED packaging adhesive resin and preparation method thereof |
| CN104448318A (en) * | 2014-11-27 | 2015-03-25 | 深圳市森日有机硅材料有限公司 | MDQ phenyl vinyl silicone resin and preparation method thereof |
| CN105175728A (en) * | 2015-10-27 | 2015-12-23 | 江苏麒祥高新材料有限公司 | Preparation method of phenyl silicone resin packaging material used for electronic components |
| CN108644639A (en) * | 2018-05-21 | 2018-10-12 | 广东恒润光电有限公司 | A kind of Waterproof LED light source and preparation method thereof |
| CN110256676A (en) * | 2019-05-24 | 2019-09-20 | 中山大学 | A kind of phenyl hydrogen-containing siloxane resin, high refractive index LED encapsulation silicon resin composition and preparation method thereof |
| CN111253575A (en) * | 2020-03-03 | 2020-06-09 | 东莞市溢美材料科技有限公司 | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin |
| CN115678013A (en) * | 2022-11-18 | 2023-02-03 | 东莞市贝特利新材料有限公司 | Phenyl vinyl siloxane resin and preparation method thereof |
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| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151558A (en) * | 2014-08-08 | 2014-11-19 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method for MDTQ type methyl phenyl vinyl silicone resin |
| CN104151558B (en) * | 2014-08-08 | 2017-02-01 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method for MDTQ type methyl phenyl vinyl silicone resin |
| CN104231273A (en) * | 2014-09-16 | 2014-12-24 | 上海应用技术学院 | High-viscosity self-crosslinking LED package gum resin and preparation method thereof |
| CN104262630A (en) * | 2014-09-16 | 2015-01-07 | 上海应用技术学院 | Low-viscosity self-crosslinking LED packaging adhesive resin and preparation method thereof |
| CN104262630B (en) * | 2014-09-16 | 2017-06-23 | 上海应用技术学院 | A kind of low-viscosity self-cross linking type LED encapsulation gum resin and preparation method thereof |
| CN104448318A (en) * | 2014-11-27 | 2015-03-25 | 深圳市森日有机硅材料有限公司 | MDQ phenyl vinyl silicone resin and preparation method thereof |
| CN105175728A (en) * | 2015-10-27 | 2015-12-23 | 江苏麒祥高新材料有限公司 | Preparation method of phenyl silicone resin packaging material used for electronic components |
| CN108644639A (en) * | 2018-05-21 | 2018-10-12 | 广东恒润光电有限公司 | A kind of Waterproof LED light source and preparation method thereof |
| CN110256676A (en) * | 2019-05-24 | 2019-09-20 | 中山大学 | A kind of phenyl hydrogen-containing siloxane resin, high refractive index LED encapsulation silicon resin composition and preparation method thereof |
| CN110256676B (en) * | 2019-05-24 | 2022-03-08 | 中山大学 | Phenyl hydrogen-containing siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof |
| CN111253575A (en) * | 2020-03-03 | 2020-06-09 | 东莞市溢美材料科技有限公司 | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin |
| CN115678013A (en) * | 2022-11-18 | 2023-02-03 | 东莞市贝特利新材料有限公司 | Phenyl vinyl siloxane resin and preparation method thereof |
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Denomination of invention: A high refractive index vinyl phenyl silicone resin for LED packaging Effective date of registration: 20211011 Granted publication date: 20161221 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2021330001830 |
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