CN103772426B - Organic silicon resin with high refractive index, preparation method and application thereof - Google Patents
Organic silicon resin with high refractive index, preparation method and application thereof Download PDFInfo
- Publication number
- CN103772426B CN103772426B CN201410027779.6A CN201410027779A CN103772426B CN 103772426 B CN103772426 B CN 103772426B CN 201410027779 A CN201410027779 A CN 201410027779A CN 103772426 B CN103772426 B CN 103772426B
- Authority
- CN
- China
- Prior art keywords
- organosilicon material
- methyl
- organic siliconresin
- phenyl
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention relates to organic silicon resin with high refractive index, a preparation method and an application thereof. Particularly, in the manufacturing process of the organic silicon resin, the organic silicon resin with high refractive index can be obtained by adding monomers shown in a formula I into a reaction system; in the formula, R1 and R2 are defined as the description in the specification. The organic silicon resin prepared by the invention is high in refractive index and can be used as an organic silicon adhesive in the field of LED (Light Emitting Diode) package.
Description
Technical field
The invention belongs to high-performance polymer and manufacture field, in particular it relates to a kind of double-component containing alkoxyl phenyl
High refractive index organic silicon resin material, and its preparation method and application.
Background technology
Light emitting diode (LED) is the light-emitting component that a class can directly convert electrical energy into luminous energy, used as a kind of new height
Effect solid light source, with remarkable advantages such as long-life, energy-conservation, environmental protections.In recent years, with the fast development of LED technology, send out
Light efficiency is stepped up, and the application market of LED is more extensive, and especially the worry in the shortage of current global energy is increasingly sharpened
Under background, LED more gets most of the attention in the prospect of illumination market, will be the tradition such as following replacement incandescent lamp, tengsten lamp and fluorescent lamp
One of light source high-tech sector most with prospects.
During manufacture LED component, the performance of LED encapsulation material is to its luminous efficiency, brightness and service life
Also significant impact will be produced.Using resistance to ultraviolet, heat-proof aging, high index of refraction, low stress encapsulating material, photograph can be significantly improved
The optical output power and service life of funerary objects part.Epoxy resin is to use most encapsulating materials, and epoxy resin has excellent
Electrical insulation capability, dielectric properties, transparent, caking property are good, and solidification does not produce small-molecule substance, and shrinkage factor is low, excellent storage stability,
Formula is flexible, the advantages of easy to operate.But crosslink density is high after it solidifies, and internal stress is big, and fragility is big, and poor impact resistance is used
Temperature is usually no more than 150 DEG C, therefore its application is subject to a definite limitation.Practical application shows, traditional epoxy resin, PC, PMMA
During as lens material, in addition to ageing-resistant performance substantially deficiency, the problem incompatible with interior encapsulating material interface is there is also,
Cause LED component after high/low temperature circulation experiment, luminous efficiency is drastically reduced.Research finds 150 DEG C or so epoxy resin
Transparency reduce, LED light output weaken, resin serious degradation can be also caused in the range of 135～145 DEG C, LED life is had
Important impact.In the case of high current, encapsulating material even can be carbonized, and in device surface conductive channel is formed, and lose device
Effect.
Organosilicon material has the performances such as excellent heat resistance, weatherability, moisture-proof, cold-resistant thermal shock, existing both at home and abroad
Related patent report by the use of organosilicon material as LED encapsulation material, such as Chinese patent literature CN101544881A and
CN101935455A, american documentation literature US6815520B2, US7294682B2, US2004/0116640A1 and US2009/
0221783A1.At present the organosilicon material of the LED encapsulation of patent report is broadly divided into two classes, and a class is methyl silicon resin, this
Class material has good gluing, but generally existing temperature tolerance is general, and the defect of refractive index low (about 1.43) belongs to LED
A more low-grade class in encapsulation organosilicon material, and another kind of is methyl phenyl silicone resin, although this kind of material has higher folding
Rate (about 1.50) is penetrated, and temperature tolerance is excellent, but with the raising of phenyl content, the rigidity of material also strengthens accordingly, so as to
Gluing is caused to decline.
In sum, this area still lacks a kind of refractive index height, and temperature tolerance is excellent, and with preferable close-burning LED
Encapsulation organosilicon material.
The content of the invention
It is an object of the invention to provide a kind of refractive index is high, temperature tolerance is excellent, and encapsulates with preferably close-burning LED
Organosilicon material.
A kind of a first aspect of the present invention, there is provided alkoxyl phenyl triethoxysilane shown in formula I：
Wherein,
R1For the alkyl of substituted or unsubstituted C1-C18；
R2For the alkyl of substituted or unsubstituted C1-C4.
In another preference, described " replacement " refers to that one or more substituents for being selected from the following group replace：Halogen is former
Son, amido, hydroxyl, carboxyl, sulfydryl, C1～C10 alkyl, C1～C10 alkoxyls, C2～C10 ester groups, amide groups, C6～C30 are fragrant
Base, C1～C30 heteroaryls, C2～C10 acyl groups, C7～C30 alkyl-Fang Ji ﹑ C2～C30 alkyl-heteroaryls.
A kind of a second aspect of the present invention, there is provided preparation method of compound of formula I as described in the first aspect of the invention,
Methods described includes step：
In atent solvent, reacted with Formulas I a compound and Formulas I b compound, obtain compound of formula I.
In another preference, described atent solvent is selected from the group：Toluene, tetrahydrofuran, ether, or its combination.
In another preference, the reaction is carried out in the presence of metalating reagent；It is preferred that described metalating reagent
It is selected from the group：Mg, n-BuLi, or its combination.
In another preference, described reaction is carried out under an inert atmosphere；It is preferred that described reaction is protected in argon gas
Under carry out.
In another preference, described reaction is carried out in the presence of initiator, it is preferred that described initiator is iodine list
Matter.
In another preference, the mol ratio of described Formulas I a compound, Formulas I b compound and metallic catalyst is 1：
0.5-3：0.6-3.1.
A kind of a third aspect of the present invention, there is provided organosilicon material, the organosilicon material is included such as the present invention first
Compound of formula I described in aspect, or the organosilicon material is prepared with compound of formula I as described in the first aspect of the invention
's.
In another preference, described organosilicon material is with compound of formula I and one or more change being selected from the group
Compound is hydrolyzed to be polymerized and prepares：Phenyl alkoxysilane, alkyl silane, alkylalkenyl silane.
In another preference, described alkyl is the alkyl of C1-C20.
In another preference, described thiazolinyl is the thiazolinyl of C1-C20.
In another preference, described alkoxyl is the alkoxyl of C1-C20.
In another preference, described organosilicon material is with compound of formula I and one or more group for being selected from the group
The polymerization that is hydrolyzed is divided to prepare：Phenyltrimethoxysila,e, dimethoxydiphenylsilane, and methyl ethylene dimethoxy
Base silane；It is preferred that described organosilicon material is to be hydrolyzed to be polymerized with compound of formula I and following components to prepare：Benzene
Base trimethoxy silane, methylvinyldimethoxysilane, and optional dimethoxydiphenylsilane.
In another preference, described compound of formula I and phenyltrimethoxysila,e, dimethoxydiphenylsilane,
The mol ratio of methylvinyldimethoxysilane is 2～16：0～14：0～16：0～15, preferably 2～16：0～14：8：
7.5, more preferably 2：14：8：7.5 or 16:0:8:7.5.
In another preference, described hydrolytic polymerization is carried out in acid condition.
A kind of a fourth aspect of the present invention, there is provided organic siliconresin, described organic siliconresin is included such as the present invention the
Organosilicon material described in three aspects, or the organic siliconresin is with the organosilicon material system as described in third aspect present invention
Standby.
In another preference, described organic siliconresin is to carry out reaction with following components to prepare：Such as the present invention
Organosilicon material, methyl phenyl vinyl polysiloxane described in the third aspect, methyl and phenyl hydrogen-containing silicon oil, and platinum catalyst.
In another preference, in described organic siliconresin, the weight ratio of each component is：Described in third aspect present invention
Organosilicon material：Methyl phenyl vinyl polysiloxane：Methyl and phenyl hydrogen-containing silicon oil：Platinum catalyst=0～100:0～100:0～
100:0～10, preferably 100:100:100:2.5.
In another preference, described methyl phenyl vinyl polysiloxane is with one or more component being selected from the group
Carry out reaction preparation：Tetraethyl orthosilicate, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methyl ethylene diformazan
TMOS, and VTES；Preferably, described methyl phenyl vinyl polysiloxane is entered with following components
It is prepared by row reaction：Phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, and the optional component being selected from the group：Positive silicon
Acetoacetic ester, methylvinyldimethoxysilane, VTES, or its combination.
In another preference, the mol ratio of each component is：Tetraethyl orthosilicate：Phenyltrimethoxysila,e：Methyl
Phenyidimethoxysilane：Methylvinyldimethoxysilane：VTES=0～10：40～60：20～
40：0～20：0～20, preferably 5:50:30:10:10.
In another preference, described reaction is hydrolytic polymerization.
In another preference, described reaction is carried out in acid condition.
In another preference, described platinum catalyst is selected from the group：Chloroplatinic acid, chloroplatinic acid-aqueous isopropanol, methyl second
Alkenyl siloxane platinum complex, or its combination.
In another preference, described methyl and phenyl hydrogen-containing silicon oil is prepared with following components reaction：Diphenyl diformazan
TMOS, tetramethyl tetrahydrochysene cyclotetrasiloxane (D4 H), and HMDO.
In another preference, described dimethoxydiphenylsilane, tetramethyl tetrahydrochysene cyclotetrasiloxane (D4 H), and six
The mol ratio of tetramethyldisiloxane is 0～200:0～50:0～8, preferably 100:25:4.
In another preference, described reaction is carried out in acid condition.
In another preference, described reaction is equilibrium polymerization.
In another preference, described organic siliconresin is to carry out reaction with following components A and component B to prepare：
Described component A includes：Organosilicon material, methyl phenyl vinyl silicon tree as described in third aspect present invention
Fat, and platinum catalyst；
Described component B includes：Methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil.
In another preference, described reaction includes：After A, B component are well mixed, vacuum outgas bubble 20～
30min, 80～140 DEG C of curing moldings.
In another preference, the weight ratio of component A and component B is 1-100：1-100, preferably 1-10：1-10.
In another preference, in described component A, the weight ratio of each component is：Having described in third aspect present invention
Machine silicon materials：Methyl phenyl vinyl polysiloxane：Platinum catalyst=0～100:0～50:0～10, preferably 100:50:2.5.
In another preference, in described component B, the weight ratio of each component is：Methyl phenyl vinyl polysiloxane:First
Base phenyl hydrogen-containing silicon oil=0～50:0～100, preferably 50：100.
A fifth aspect of the present invention, there is provided a kind of organic siliconresin feedstock composition, described composition includes：Such as this
Organosilicon material, methyl phenyl vinyl polysiloxane described in the invention third aspect, methyl and phenyl hydrogen-containing silicon oil, and platinum catalysis
Agent.
In another preference, described composition includes component A and component B, and
Described component A includes：Organosilicon material, methyl phenyl vinyl silicon tree as described in third aspect present invention
Fat, and platinum catalyst；
Described component B includes：Methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil.
In another preference, described feedstock composition is used to be polymerized so as to prepare such as fourth aspect present invention institute
The organic siliconresin stated.
A sixth aspect of the present invention, there is provided a kind of product, the product contains having as described in fourth aspect present invention
Machine silicones, or described product is prepared with the organic siliconresin as described in fourth aspect present invention.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and have in below (eg embodiment)
Can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Specific embodiment
The present inventor is through in-depth study for a long time, it has unexpectedly been found that, flexible oxygen-ether linkage is incorporated into into aminomethyl phenyl
In the middle of silicon resin system, the rigidity of methyl phenyl silicone resin can be effectively reduced, so keep material thermal resistance and high refraction
The gluing of organosilicon encapsulating material and resin base material is improve while rate.Such alkoxyl phenyl organic siliconresin can conduct
The new organosilicon material of one class is used in LED Packaging Industries.
Term
As used herein, term " hydrolytic polymerization " refers to that silane monomer sloughs alkane under alkalescence or acid condition with water reaction
Epoxide forms the process of silica silicon long-chain molecule.
Term " equilibrium polymerization " refers to that annular siloxane (generally four-membered ring) forms chain under acid or alkalescence condition
The process of silica silicon, this process is reversible process, as the membership that adds of end-capping reagent reaches linear siloxanes and annular siloxanes
Balance.
Term " methyl silicon resin " refers to that side base is entirely the silicones of methyl.
Term " methyl phenyl silicone resin " refers to that side base has the silicones of methyl and phenyl.
As used herein, term " C1-C18 alkyl " refers to the straight or branched alkyl with 1-18 carbon atom or cycloalkanes
Base, such as methyl, methylene, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclopropyl, cyclobutyl,
Cyclopenta, cyclohexyl, suberyl, or similar group.
Unless stated otherwise, herein described each group includes substituted or unsubstituted situation, and described takes
In generation, refers to that one or more substituents for being selected from the following group replace：Halogen atom, amido, hydroxyl, carboxyl, sulfydryl, C1～C10 alkane
Base, C1～C10 alkoxyls, C2～C10 ester groups, amide groups, C6～C30 aryl, C1～C30 heteroaryls, C2～C10 acyl groups, C7
～C30 alkyl-Fang Ji ﹑ C2～C30 alkyl-heteroaryls.
Methyl phenyl silicone resin with flexible oxygen-ether linkage
The invention provides a kind of alkoxyl phenyl triethoxysilane shown in formula I：
Wherein,
R1For the alkyl of substituted or unsubstituted C1-C18；
R2For the alkyl of substituted or unsubstituted C1-C4.
Described alkoxyl phenyl triethoxysilane can be prepared by the following method：
In atent solvent, reacted with Formulas I a compound and Formulas I b compound, obtain compound of formula I.
Described atent solvent is not particularly limited, and preferably may be selected from the following group：Toluene, tetrahydrofuran, ether, or its group
Close.
The reaction is preferably carried out in the presence of metallic catalyst；More preferably, described metalating reagent is selected from the group：
Mg, n-BuLi, or its combination.
In another preference, described reaction is carried out under an inert atmosphere；It is preferred that described reaction is protected in argon gas
Under carry out.
In another preference, described reaction is carried out in the presence of elemental iodine.
In another preference, the mol ratio of described Formulas I a compound, Formulas I b compound and metallic catalyst is 1：
0.5-3：0.6-3.1.
Described compound of formula I can be used to prepare organosilicon material, and then prepare organic siliconresin.In the present invention, one
It is to be hydrolyzed to be polymerized with one or more compound being selected from the group with compound of formula I to plant preferred described organosilicon material
Prepare：Phenyl alkoxysilane, alkyl silane, alkylalkenyl silane.
In another preference, described alkyl is the alkyl of C1-C20.
In another preference, described thiazolinyl is the thiazolinyl of C1-C20.
In another preference, described alkoxyl is the alkoxyl of C1-C20.
In another preference, described organosilicon material is with compound of formula I and one or more group for being selected from the group
The polymerization that is hydrolyzed is divided to prepare：Phenyl triethoxysilane, dimethoxydiphenylsilane, and methyl ethylene dimethoxy
Base silane；It is preferred that described organosilicon material is to be hydrolyzed to be polymerized with compound of formula I and following components to prepare：Benzene
Ethyl triethoxy silicane alkane, methylvinyldimethoxysilane, and optional dimethoxydiphenylsilane.
The proportioning of the various components is not particularly limited, and can determine according to actual needs.One in the present invention is excellent
In selecting example, described compound of formula I and phenyl triethoxysilane, dimethoxydiphenylsilane, methyl ethylene dimethoxy
The mol ratio of base silane is 2～16；0～14；0～16；0～15.
In another preference, described hydrolytic polymerization is carried out in acid condition.
Present invention also offers a kind of organic siliconresin, described organic siliconresin includes described organosilicon material, or
The organic siliconresin is prepared with described organosilicon material.
A kind of preferred described organic siliconresin is to carry out reaction with following components to prepare：Described organosilicon material
Material, methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil, and platinum catalyst.
Wherein, described methyl phenyl vinyl polysiloxane can be prepared with common method, for example, with the one kind being selected from the group
Or various ingredients carry out reaction preparation：Tetraethyl orthosilicate, phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, methyl
Vinyl dimethoxysilane, and VTES；Preferably, described methyl phenyl vinyl polysiloxane is to use
Following components carries out reaction preparation：Phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane, and optional be selected from the group
Component：Tetraethyl orthosilicate, methylvinyldimethoxysilane, VTES, or its combination.
In another preference, the mol ratio of each component is：Tetraethyl orthosilicate：Phenyltrimethoxysila,e：Methyl
Phenyidimethoxysilane：Methylvinyldimethoxysilane：VTES=0～10：40～60：20～
40：0～20：0～20.
In another preference, described reaction is hydrolytic polymerization.
In another preference, described reaction is carried out in acid condition.
In another preference, described platinum catalyst is selected from the group：Chloroplatinic acid, chloroplatinic acid-aqueous isopropanol, methyl second
Alkenyl siloxane platinum complex, or its combination.
In another preference, described methyl and phenyl hydrogen-containing silicon oil is prepared with following components reaction：Diphenyl diformazan
TMOS, tetramethyl tetrahydrochysene cyclotetrasiloxane (D4 H), and HMDO.
In another preference, described dimethoxydiphenylsilane, tetramethyl tetrahydrochysene cyclotetrasiloxane (D4 H), and six
The mol ratio of tetramethyldisiloxane is 0～200:0～50:0～8.
In another preference, described reaction is carried out in acid condition.
In another preference, described reaction is equilibrium polymerization.
In the present invention, a kind of more preferred described organic siliconresin is reacted with following components A and component B
Prepare：
Described component A includes：Described organosilicon material, methyl phenyl vinyl polysiloxane, and platinum catalyst；
Described component B includes：Methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil.
In another preference, described reaction includes：After A, B component are well mixed, vacuum outgas bubble 20～
30min, 80～140 DEG C of curing moldings.
Main advantages of the present invention include：
(1) the invention provides a kind of organo-silicon compound with flexible oxygen-ether linkage, described compound can be made
For the component of organic siliconresin, for reducing the rigidity of organic siliconresin, strengthen cohesiveness.
(2) the invention provides a kind of organosilicon material, described material can be used for preparing answering with excellent properties
Charge-coupled point of organic siliconresin.
(2) present invention also offers a kind of double-component high refractive index organic silicon resin containing alkoxyl phenyl, and its system
Method is made, the organic siliconresin for being obtained has high index of refraction, high light transmittance, excellent temperature tolerance and gluing, can meet LED
The requirement of Packaging Industry.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number are calculated by weight.
The preparation of the p-methoxyphenyl triethoxysilane of embodiment 1
Under argon gas protection, add in 250 milliliters of dry there-necked flasks 1.44 grams of (0.06mol) magnesium rods, 20.8 grams
(0.1mol) tetraethyl orthosilicate, a small amount of iodine and 100 milliliters of dried toluene, stir and are slowly added to 9.35 grams
(0.05mol) 4- bromoanisoles and 20 milliliters of dried tetrahydrofuran compounds, low-grade fever after system color fade, ice
Water-bath 24h, diatomite removes solvent after filtering, 7.34 grams of the cut of 80 DEG C/10mba, yield 54% are collected in vacuum distillation.1H NMR(400MHz,CDCl3,δin ppm):7.58～7.60 (d, 2H), 6.89～6.91 (d, 2H), 3.79～3.86 (m,
9H), 1.20～1.24 (t, 9H).
The preparation of the methyl vinyl silicone of embodiment 2
50 milliliters of water, 50 milliliters of concentrated hydrochloric acids and 30 milliliters of toluene are added in 500 milliliters of clean there-necked flasks, is stirred vigorously
Down 5.2 grams of (0.025mol) tetraethyl orthosilicates, 50.0 grams of (0.25mol) phenyl trimethoxy silicon are added dropwise by constant pressure funnel
Alkane, 27.3 grams of (0.15mol) aminomethyl phenyl dimethoxysilanes, 6.61 grams of (0.05mol) methylvinyldimethoxysilanes,
The mixed solution of 9.5 grams of (0.05mol) VTESs and 20 milliliters of toluene, reaction temperature control 20 DEG C with
Under, continue to react 3h after completion of dropping, it is subsequently heated to 80 DEG C and continues to react 3h, room temperature is cooled to, it is washed to neutrality, organic layer
With anhydrous sodium sulfate drying, toluene is removed after filtration, decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound, obtains
25.5 grams of methyl phenyl vinyl polysiloxanes, refractive index 1.544.
The preparation of the p-methoxyphenyl methyl phenyl vinyl polysiloxane of embodiment 3
25 milliliters of water, 25 milliliters of concentrated hydrochloric acids and 15 milliliters of toluene are added in 250 milliliters of clean there-necked flasks, is stirred vigorously
Down 5.4 grams of (0.02mol) p-methoxyphenyl triethoxysilanes, 27.7 grams (0.14mol) are added dropwise by constant pressure funnel
Phenyl triethoxysilane, 19.5 grams of (0.08mol) dimethoxydiphenylsilanes, 10.0 grams of (0.075mol) methyl ethylenes
The mixed solution of dimethoxysilane and 10 milliliters of toluene, reaction temperature is controlled below 20 DEG C, continues to react after completion of dropping
3h, is subsequently heated to 80 DEG C and continues to react 3h, is cooled to room temperature, is washed to neutrality, and organic layer anhydrous sodium sulfate drying is filtered
After remove toluene, decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound, obtains 12.2 grams of p-methoxyphenyl methylbenzenes
Base vinyl polysiloxane, refractive index 1.552.
The preparation of the p-methoxyphenyl methyl phenyl vinyl polysiloxane of embodiment 4
25 milliliters of water, 25 milliliters of concentrated hydrochloric acids and 15 milliliters of toluene are added in 250 milliliters of clean there-necked flasks, is stirred vigorously
Down 43.2 grams of (0.16mol) p-methoxyphenyl triethoxysilanes, 19.5 grams (0.08mol) are added dropwise by constant pressure funnel
The mixing of dimethoxydiphenylsilane, 10.0 grams of (0.075mol) methylvinyldimethoxysilanes and 10 milliliters of toluene is molten
Liquid, reaction temperature is controlled below 20 DEG C, continues to react 3h after completion of dropping, is subsequently heated to 80 DEG C and is continued to react 3h, cooling
To room temperature, neutrality is washed to, organic layer anhydrous sodium sulfate drying removes toluene after filtration, decompression is warmed up to 150 DEG C/10mba
Micromolecular compound is sloughed, 17.2 grams of p-methoxyphenyl methyl phenyl vinyl polysiloxanes, refractive index 1.560 is obtained.
The preparation of the methyl and phenyl hydrogen-containing silicon oil of embodiment 5
Add in 100 milliliters of clean there-necked flasks 48.87 grams of (0.2mol) dimethoxydiphenylsilanes, 12.0 grams
(0.05mol) tetramethyl tetrahydrochysene cyclotetrasiloxane (D4 H), 1.29 grams of (0.008mol) HMDOs (MM) and 2.4 grams it is dense
Sulfuric acid, after being stirred vigorously reaction 0.5h, adds 3.6 grams of water, continues to react 6h, is subsequently adding 3.0 grams of water and 20 milliliters of toluene, stirs
After mixing 1h, addition is washed to neutrality, organic layer anhydrous sodium sulfate drying, removes toluene after filtration, decompression be warmed up to 120 DEG C/
10mba sloughs micromolecular compound, obtains 19.2 grams of methyl and phenyl hydrogen-containing silicon oils, refractive index 1.543.
The preparation of double-component silicones of the embodiment 6 containing alkoxyl phenyl
Take p-methoxyphenyl prepared by the methyl vinyl silicone and 4.0 grams of embodiments 3 of 2.0 grams of preparations of embodiments 2
Methyl phenyl vinyl polysiloxane is well mixed, 120 DEG C of heat treatment 1h, and vacuum outgas bubble 30min is subsequently adding 0.1 gram of methyl
Vinylsiloxane platinum complex, is well mixed, and in vacuum defoamation 30min, obtains component A.
Take aminomethyl phenyl prepared by methyl vinyl silicone prepared by 2.0 grams of embodiments 2 and 4.0 grams of embodiments 5 hydrogeneous
Silicone oil is well mixed, 120 DEG C of heat treatment 1h, and vacuum outgas bubble 30min obtains component B.
By A, B component according to mass ratio 1:1 is well mixed, refractive index 1.544, vacuum outgas bubble 20min, then consolidates for 80 DEG C
Change 1h, 140 DEG C of solidify afterwards 3h.
Concrete data are as shown in the table：
In upper table, light transmittance is tested by UV, visible light near infrared spectrometer；Refractive index is surveyed by Abbe refractometer
Examination.
Heat endurance is tested using TGA (thermogravimetric analysis), and carrier gas used is argon gas, and heating rate is 10 DEG C/min.
Gluing passes through red ink experiment test.Support after will encapsulating is soaked in red ink under the conditions of 25 ± 2 DEG C
In, examine under a microscope after 24h and whether there is infiltration.
The preparation of the aminomethyl phenyl double-component silicones of embodiment 7
Take methyl vinyl silicone and 4.0 grams of commercially available methyl phenyl vinyl polysiloxanes prepared by 2.0 grams of embodiments 2
(refractive index 1.540) is well mixed, 120 DEG C of heat treatment 1h, and vacuum outgas bubble 30min is subsequently adding 0.1 gram of methyl ethylene silicon
Oxygen alkane platinum complex, is well mixed, and in vacuum defoamation 30min, obtains component A '.
Take aminomethyl phenyl prepared by methyl vinyl silicone prepared by 2.0 grams of embodiments 2 and 4.0 grams of embodiments 5 hydrogeneous
Silicone oil is well mixed, 120 DEG C of heat treatment 1h, and vacuum outgas bubble 30min obtains component B.
By A, B component according to mass ratio 1:1 is well mixed, vacuum outgas bubble 20min, then 80 DEG C of solidification 1h, after 140 DEG C
Solidification 3h.
Concrete data are as shown in the table：
As can be seen that after the alkoxyl phenyl triethoxysilane for adding the present invention, obtaining from above-described embodiment
Organic siliconresin has the optical properties such as excellent refractive index, light transmittance.
The all documents referred in the present invention are all incorporated as in this application reference, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content for having read the present invention, those skilled in the art can
To make various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (12)
1. a kind of organosilicon material, it is characterised in that described organosilicon material is with compound of formula I and (a) being selected from the group
(b) it is prepared by the polymerization that is hydrolyzed：(a) phenyl alkoxysilane and (b) alkylalkenyl silane and/or alkyl silane；Wherein,
Alkyl, described thiazolinyl be the thiazolinyl of C1-C20, described alkoxyl be C1-C20 alcoxyl of the described alkyl for C1-C20
Base；
Described compound of formula I is shown below：
Wherein,
R1For the alkyl of substituted or unsubstituted C1-C18；
R2For the alkyl of substituted or unsubstituted C1-C4；
Wherein, described replacement refers to that one or more substituents for being selected from the following group replace：Halogen atom, amido, hydroxyl, carboxylic
Base, sulfydryl, C1～C10 alkyl, C1～C10 alkoxyls, C2～C10 ester groups, amide groups, C6～C30 aryl, C1～C30 heteroaryls
Base, C2～C10 acyl groups, C7～C30 alkyl-Fang Ji ﹑ C2～C30 alkyl-heteroaryls.
2. organosilicon material as claimed in claim 1, it is characterised in that described organosilicon material be with compound of formula I with
One or more component being selected from the group polymerization that is hydrolyzed is prepared：Phenyltrimethoxysila,e, diphenyl dimethoxy
Silane, and methylvinyldimethoxysilane.
3. organosilicon material as claimed in claim 1, it is characterised in that described organosilicon material be with compound of formula I with
The following components polymerization that is hydrolyzed is prepared：Phenyltrimethoxysila,e, methylvinyldimethoxysilane, and it is optional
Dimethoxydiphenylsilane.
4. organosilicon material as claimed in claim 1, it is characterised in that described compound of formula I and phenyl trimethoxy silicon
Alkane, dimethoxydiphenylsilane, the mol ratio of methylvinyldimethoxysilane are 2～16：0～14：0～16：0～
15。
5. organosilicon material as claimed in claim 1, it is characterised in that described compound of formula I and phenyl trimethoxy silicon
Alkane, dimethoxydiphenylsilane, the mol ratio of methylvinyldimethoxysilane are 2～16：0～14：8：7.5.
6. organosilicon material as claimed in claim 1, it is characterised in that described compound of formula I and phenyl trimethoxy silicon
Alkane, dimethoxydiphenylsilane, the mol ratio of methylvinyldimethoxysilane are 2：14：8：7.5 or 16:0:8:7.5.
7. a kind of organic siliconresin, it is characterised in that described organic siliconresin includes organosilicon material as claimed in claim 1
Expect, or the organic siliconresin is prepared with organosilicon material as claimed in claim 1.
8. organic siliconresin as claimed in claim 7, it is characterised in that described organic siliconresin is carried out with following components
Reaction is prepared：Organosilicon material, methyl phenyl vinyl polysiloxane, aminomethyl phenyl Silicon Containing Hydrogen as claimed in claim 1
Oil, and platinum catalyst.
9. organic siliconresin as claimed in claim 7, it is characterised in that described organic siliconresin be with following components A and
Component B carries out reaction and prepares：
Described component A includes：Organosilicon material, methyl phenyl vinyl polysiloxane as claimed in claim 1, and platinum catalysis
Agent；
Described component B includes：Methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil.
10. a kind of organic siliconresin feedstock composition, it is characterised in that described composition includes：As claimed in claim 1
Organosilicon material, methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil, and platinum catalyst.
11. organic siliconresin feedstock compositions as claimed in claim 10, it is characterised in that described composition includes component
A and component B, and
Described component A includes：Organosilicon material, methyl phenyl vinyl polysiloxane as claimed in claim 1, and platinum catalysis
Agent；
Described component B includes：Methyl phenyl vinyl polysiloxane, methyl and phenyl hydrogen-containing silicon oil.
12. a kind of products, it is characterised in that the product contains organic siliconresin as claimed in claim 7, or described system
Product are prepared with organic siliconresin as claimed in claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410027779.6A CN103772426B (en) | 2014-01-21 | 2014-01-21 | Organic silicon resin with high refractive index, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410027779.6A CN103772426B (en) | 2014-01-21 | 2014-01-21 | Organic silicon resin with high refractive index, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103772426A CN103772426A (en) | 2014-05-07 |
| CN103772426B true CN103772426B (en) | 2017-05-10 |
Family
ID=50565240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410027779.6A Active CN103772426B (en) | 2014-01-21 | 2014-01-21 | Organic silicon resin with high refractive index, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772426B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104448320B (en) * | 2014-11-20 | 2017-11-07 | 中国科学院上海有机化学研究所 | A kind of manufacture method of silicones of phenyl containing trifluoro-ethylene and application |
| CN104531054B (en) * | 2014-12-19 | 2016-06-22 | 苏州佳亿达电器有限公司 | A kind of preparation method of high performance lED encapsulation glue |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532900A (en) * | 2010-12-20 | 2012-07-04 | 常州化学研究所 | Organosilicon lens material for power type light-emitting diode (LED) packaging |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4009067B2 (en) * | 2001-03-06 | 2007-11-14 | 信越化学工業株式会社 | Addition-curing silicone resin composition |
-
2014
- 2014-01-21 CN CN201410027779.6A patent/CN103772426B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532900A (en) * | 2010-12-20 | 2012-07-04 | 常州化学研究所 | Organosilicon lens material for power type light-emitting diode (LED) packaging |
Non-Patent Citations (2)
| Title |
|---|
| A facile and efficient synthesis of aryltriethoxysilanes via sonochemical Barbier-type reaction;Adam Shih-Yuan Lee et al.;《Tetrahedron Letters》;20060814;第7085-7087页 * |
| Improved Synthesis of Aryltrialkoxysilanes via Treatment of Aryl Grignard or Lithium Reagents with Tetraalkyl Orthosilicates;Amy S. Manoso et al.;《J. Org. Chem.》;20041026;第8305-8314页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772426A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103627178B (en) | A kind of LED encapsulation liquid silicon rubber composition and preparation method thereof | |
| CN103122149B (en) | Optical package high refractive index High-transparency silicon rubber and its preparation method | |
| CN102181159B (en) | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof | |
| CN102391529B (en) | Preparation method of silicone resin type organic/inorganic hybrid material for packaging | |
| CN102977554B (en) | Epoxy/organosilicon co-curing composite material for LED packaging and preparation method | |
| CN103937257B (en) | Organic silicone thixotropic agent and thixotropy addition type liquid silicone rubber | |
| CN101899159B (en) | Silicone resin for one-component LED packaging materials and preparation method thereof | |
| CN103805128A (en) | Adhesive for high-refractive index LED (Light Emitting Diode) package glue and adhesive synthesizing method | |
| CN104861168A (en) | Phenyl hydrogen silicone oil for LED (Light Emitting Diode) encapsulation adhesive and preparation method thereof | |
| CN103665879A (en) | Organic silicon gel composition for high-power LED (light-emitting diode) packaging | |
| CN103772426B (en) | Organic silicon resin with high refractive index, preparation method and application thereof | |
| CN102433005B (en) | Liquid phenyl silica gel for LED and preparation method thereof | |
| CN102876282A (en) | Preparation method of transparent organic silica glue for encapsulating nano SiO2 modified COB-LEDs | |
| CN103613766A (en) | Preparation method of phenyl hydrogen-containing silicone oil for power type LED (Light-Emitting Diode) packaging | |
| CN103289096A (en) | Preparation method and application of polyhedral oligomeric silsesquioxane skeleton containing vinyl silicone oil | |
| CN104098905A (en) | Strong elastic phenyl organic silicone resin for LED lens and preparation method thereof | |
| JP2009102297A (en) | (thio)phenoxyphenyl silane composition and method for producing the same | |
| CN101619170A (en) | Preparation and application of silica gel for LED packaging | |
| CN101665572A (en) | Organic silicon resin for encapsulating LED and preparation method thereof | |
| CN103834178B (en) | Organic silicon resin as well as preparation method and application thereof | |
| JP2014076924A (en) | Surface modified composite metal oxide fine particles | |
| WO2014061517A1 (en) | Curable composition containing silica particles, cured product thereof, and semiconductor sealing material using same | |
| CN109705352A (en) | A kind of vinyl polysiloxane and its preparation method and application | |
| CN109679350A (en) | A kind of optical grade silica gel for optical device | |
| CN104004362B (en) | A kind of penylene phenylate support organosilicon material of power type LED encapsulation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |