CN101899159A - Silicone resin for one-component LED packaging materials and preparation method thereof - Google Patents
Silicone resin for one-component LED packaging materials and preparation method thereof Download PDFInfo
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Abstract
The invention relates to organic polysiloxane for one-component LED packaging materials, having the following general structure of (SiO2) a1(R1SiO3/2) a2(R2R3SiO) b1(R4R5SiO) c1(R4R62SiO1/2) c2(R7R82SiO1/2) d1(HR9SiO)e1(HR102SiO1/2)e2. In the formula, R1, R2, R3, R5, R6, R7, R8, R9 and R10 represent monovalent alkyl of unsaturated bonds without containing fatty group, R4 expresses alkenyl with 2-10 carbon atoms, a1, a2, c1, c2, e1 and e2 respectively represent a number not less than 0 and less than 1, a1+ a2 is more than 0 and less than 1, b1 is more than 0 and less than 1, c1+c2 is more than 0 and less than 1, d1 is more than 0 and less than 1, e1+e2 is more than 0 and less than 1, and a1+ a2+ b1+ c1+c2+d1+ e1+e2 is equal to 1. The preparation method thereof comprises the following steps of adding a terminating agent, a catalyst, hydrogen group siloxane, alkenyl siloxane and the like into a mixture of alkoxy silane and solvent to carry out polycondensation after hydrolyzation and obtaining a target product through vacuum distillation. The organic polysiloxane is added into the catalyst and an inhibitor to prepare a one-component LED sealing combination.
Description
Technical field
The present invention relates to be used for the sealed light emitting diode organosilicon encapsulating material of (being called for short LED), relate more specifically to single component used for packing material silicone resin of a kind of sealing LED and preparation method thereof.
Background technology
Current LED Application Areas is quite extensive, and electronic product, household appliances, automobile, traffic sign, billboard etc. need pointolite or area source occasion such as, all are the LED application markets.Great power LED as the 4th generation electric light source, possesses the title of " green illumination light source ", having little, the safe low voltage of volume, good characteristics such as the life-span is long, electro-optical efficiency is high, response speed is fast, energy-saving and environmental protection, is the light source of new generation of tool potentiality of 21 century.
The structure and the complex process of LED encapsulation, and directly have influence on use properties and the life-span of LED, the packaged material of its use is a hot research in recent years always.Characteristics such as transmittance height, refractive index are big because silicone resin has, Heat stability is good, stress is little, water absorbability is low, obviously be better than traditional Resins, epoxy, in high-power LED encapsulation, be used widely, silicone resin heatproof in addition, can cross Reflow Soldering, therefore often be directly used in packaging LED chips, silicone resin is progressively substituting traditional packaged material.
About the silicone resin packaged material, all carried out a large amount of research both at home and abroad, but this research work all concentrates on the exploitation of the organopolysiloxane and the composition thereof of two-pack.For example publication number is the Chinese patent application of CN101016446A, discloses a kind of organosilicon electronic encapsulation material, comprises as the vinyl polysiloxane of base resin with as the poly-methyl hydrogen phenyl siloxane of solidifying agent.Document WO 2005/062080 discloses a kind of organopolysiloxane composition of addition-curable, comprise the organopolysiloxane resins that is bonded directly to alkenyl, hydroxyl and phenyl on the Siliciumatom as containing of A component, and as the organic hydrogen polysiloxanes of B component.This class packaged material need in use will comprise respectively two kinds of compositions of base resin and solidifying agent be cured after mixing, and must be when each the use, to mix, and will promptly mix i.e. usefulness that it should use very inconvenient.In addition, mostly the method for preparing this organosiloxane resins of birdsing of the same feather flock together at present is to adopt chlorosilane as raw material, produces a large amount of hydrochloric acid in the production process, needs recovery technology.Also have report to adopt the alkylsiloxane ring body to prepare silicone resin, but some but is not allow facilely in this class ring body, cost is also high.
Summary of the invention
In order to overcome the above-mentioned deficiency of prior art, the organopolysiloxane that one aspect of the present invention provides a kind of one-component LED packaging materials to use can make the one-component LED sealing compositions after this organopolysiloxane and catalyzer and the inhibitor mixed.The preparation method of this organopolysiloxane also is provided on the other hand.
One-component LED packaging materials organopolysiloxane of the present invention is an alkenyl hydrogen base Difunctional Modified Polysiloxane, has following general structural formula:
(SiO
2)
a1(R
1SiO
3/2)
a2(R
2R
3SiO)
b1(R
4R
5SiO)
c1(R
4R
6 2SiO
1/2)
c2(R
7R
8 2SiO
1/2)
d1(HR
9SiO)
e1(HR
10 2SiO
1/2)
e2 (I)
In the formula (I), R
1, R
2, R
3, R
5, R
6, R
7, R
8, R
9, R
10The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), R
4Expression has the alkenyl of 2～10 carbon atoms, and a1, a2, c1, c2, e1, e2 represent respectively more than or equal to 0 and less than 1 number, 0＜a1+a2＜1,0＜b1＜1,0＜c1+c2＜1,0＜d1＜1,0＜e1+e2＜1, a1+a2+b1+c1+c2+d1+e1+e2=1.
Preferably, in the formula (I), 0.45≤a1+a2≤0.75,0.01≤b1≤0.10,0.10≤c1+c2≤0.25,0.02≤d1≤0.20,0.10≤e1+e2≤0.25.
Preferably, in the formula (I), R
1, R
2, R
3Be phenyl and/or methyl, R
7, R
8Be all phenyl and/or be all methyl, R
4Be vinyl, R
5, R
6, R
9, R
10Be methyl, and a1=0.
The one-component LED packaging materials of the present invention preparation method of organopolysiloxane comprises following step of carrying out successively:
A, with organoalkoxysilane, end-capping reagent, solvent and catalyst mix, under 0 ℃～40 ℃ temperature, stir and drip the water reaction, after dripping, be heated to 45 ℃～50 ℃ and continue reaction 1～3 hour;
Wherein said organoalkoxysilane comprises: is selected from the organic radical dialkoxy silicane of general formula (II) expression, and is selected from the organic radical trialkoxy silane of general formula (III) expression and/or is selected from the tetraalkoxysilane that general formula (IV) is represented,
Described end-capping reagent is selected from organic radical sily oxide, the organic radical disilazane of general formula (VI) expression or the silanol of general formula (VII) expression that logical formula V is represented,
R
2R
3Si(OR
11)
2 (II)
R
1Si(OR
12)
3 (III)
Si(OR
13)
4 (IV)
(R
7R
8 2Si)
2O (V)
(R
7R
8 2Si)
2NH (VI)
R
7R
8 2SiOH (VII)
R among formula (II), (III), (IV), (V), (VI), (VII)
1, R
2, R
3, R
7, R
8The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), R
11, R
12, R
13Represent identical or different alkyl;
B, adding hydrogen base organoalkoxysilane and/or hydrogen radical siloxane stir adding alkenyl organoalkoxysilane and/or alkenyl siloxanes down, and drip acetate, and after dripping off, being warming up to 50 ℃～100 ℃ carried out the polycondensation polyreaction 1～3 hour;
Wherein said hydrogen base organoalkoxysilane is selected from the hydrogen base organic radical dialkoxy silicane of general formula (VIII) expression, described hydrogen radical siloxane is selected from the hydrogen base organic radical sily oxide of general formula (IX) expression, described alkenyl organoalkoxysilane is selected from the alkenyl organic radical organoalkoxysilane of general formula (X) expression, described alkenyl siloxanes is selected from the alkenyl organic radical sily oxide of general formula (XI) expression
HR
9Si(OR
14)
2 (VII)
(HR
10 2Si)
2O (IX)
R
4R
5Si(OR
15)
2 (X)
(R
4R
6 2Si)
2O (XI)
R among formula (VIII), (IX), (X), (XI)
5, R
6, R
9, R
10The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), R
4Expression has the alkenyl of 2～10 carbon atoms, R
14, R
15Represent identical or different alkyl;
C, add solvent and water and also mix, leave standstill then and separate organic layer and water layer, described organic layer is washed to neutral after drying repeatedly, underpressure distillation removes low molecule again.
Preferably, in the A step: described organoalkoxysilane is selected from one or more in dimethoxydiphenylsilane, dimethyldimethoxysil,ne, aminomethyl phenyl diethoxy silane, the dimethyldiethoxysilane,
And be selected from phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, the Union carbide A-162 one or more and/or be selected from tetraethoxy, the methyl silicate one or both,
Described end-capping reagent is selected from one or more in hexamethyldisiloxane, hexamethyldisilazane, hexaphenyl sily oxide, the triphenyl silanol;
In the B step: described hydrogen base organoalkoxysilane is selected from one or both in methyl hydrogen dimethoxy silane, the methyl hydrogen diethoxy silane, and described hydrogen radical siloxane is selected tetramethyl disiloxane for use,
Described alkenyl organoalkoxysilane is selected from one or both in methyl ethylene diethoxy silane, the methyl ethylene dimethoxy silane, and described alkenyl siloxanes selects 1 for use, 3-divinyl-1,1,3,3-tetramethyl disiloxane.
Among the preparation method of the present invention, the catalyzer in the described A step is preferably trifluoromethayl sulfonic acid, hydrochloric acid or strong acidic ion resin.
Wherein, the solvent in described A step and the C step is preferably toluene, dimethylbenzene or hexanaphthene.
Wherein, the vacuum distillation temperature in the described C step is preferably 140 ℃～160 ℃.
The invention has the beneficial effects as follows: one-component LED packaging materials organopolysiloxane of the present invention, contain with the alkenyl and the hydrogen base bifunctional of Si direct bonding and have the structure of above-mentioned general formula (I), under catalyst action, promptly carry out silicon-addition reaction of hydrogen and crosslinking curing; After itself and catalyzer, the inhibitor mixed packing can prepare one-component LED packaging materials, take out i.e. usefulness, very convenient when being used for the LED encapsulation.Preparation method of the present invention does not use chlorosilane to make raw material, and adopts organoalkoxysilane and/or siloxanes hydrolytic condensation, does not produce hydrogenchloride, and is environment friendly and pollution-free; And by changing the organopolysiloxane that the raw material amount ratio can obtain different viscosity; The organopolysiloxane transparency that makes is good, refractive index is high and ageing-resistant.
Description of drawings
Fig. 1 is the one-component LED sealing compositions encapsulated LED light flux curve over time that adopts organopolysiloxane preparation of the present invention
Embodiment
Organopolysiloxane of the present invention is the polysiloxane that Direct Bonding has alkenyl, hydrogen base bifunctional on a kind of Siliciumatom, has following general structural formula:
(SiO
2)
a1(R
1SiO
3/2)
a2(R
2R
3SiO)
b1(R
4R
5SiO)
c1(R
4R
6 2SiO
1/2)
c2(R
7R
8 2SiO
1/2)
d1(HR
9SiO)
e1(HR
10 2SiO
1/2)
e2 (I)
In the formula (I), R
1, R
2, R
3, R
5, R
6, R
7, R
8, R
9, R
10Represent the univalence hydrocarbyl of one or more not fatty family unsaturated link(age)s independently of one another, they can be identical or different groups.This group can be enumerated methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl; Cyclopentyl, cyclohexyl or similar cycloalkyl; Phenyl, tolyl, xylyl or similar aryl; Benzyl, styroyl, hydrocinnamyl or similar aralkyl; 3,3,3-trifluoro propyl, 3-chloropropyl or similar haloalkyl; Below most preferably alkyl and aryl, especially methyl and phenyl.R
4Expression has the alkenyl of 2～10 carbon atoms, for example vinyl, allyl group, butenyl, pentenyl etc., wherein preferred vinyl.The shared mole number of each siloxane unit when whole siloxane units that a1, a2, b1, c1, c2, d1, e1, e2 represent to constitute organopolysiloxane resins respectively are 1mol.In addition, a1, a2, c1, c2, e1, e2 represent respectively more than or equal to 0 and less than 1 number, 0＜a1+a2＜1,0＜b1＜1,0＜c1+c2＜1,0＜d1＜1,0＜e1+e2＜1, a1+a2+b1+c1+c2+d1+e1+e2=1.Preferred 0.45≤a1+a2≤0.75,0.01≤b1≤0.10,0.10≤c1+c2≤0.25,0.02≤d1≤0.20,0.10≤e1+e2≤0.25.
Work as R
1, R
2, R
3Be phenyl and/or methyl, R
7, R
8Be all phenyl and/or be all methyl, R
4Be vinyl, R
5, R
6, R
9, R
10Be methyl, and during a1=0, organopolysiloxane of the present invention can be with following general structural formula (I ') expression (wherein Ph represents phenyl, and Me represents methyl, and Vi represents vinyl):
(PhSiO
3/2)
a21(MeSiO
3/2)
a22(Me
2SiO)
b11(Ph
2SiO)
b12(MePhSiO)
b13(ViMeSiO)
c11(ViMe
2SiO
1/2)
c21(Me
3SiO
1/2)
d11(Ph
3SiO
1/2)
d12(HMeSiO)
e11(HMe
2SiO
1/2)
e21 (I′)
In the formula (I '), a21, a22, b11, b12, b13, c11, c21, d11, d12, e11, e21 represent respectively more than or equal to 0 and less than 1 number, 0＜a21+a22＜1,0＜b11+b12+b13＜1,0＜c11+c21＜1,0＜d11+d12＜1,0＜e11+e21＜1, a21+a22+b11+b12+b13+c11+c21+d11+d12+e11+e21=1.Wherein preferably: 0.45≤a21+a22≤0.75,0.01≤b11+b12+b13≤0.10,0.10≤c11+c21≤0.25,0.02≤d11+d12≤0.20,0.10≤e11+e21≤0.25.Further preferably: a21, b12, b13, d12's and greater than 0, just contain phenyl at least, more preferably phenyl accounts for the ratio of phenyl and methyl total mole number greater than 25%.For example, get a21=0.59, a22=0, b11=b13=0, b12=0.03, c11=0, c21=0.13, d11=0.11, d12=0, e11=0, during e21=0.14, the composition structural formula of this organopolysiloxane is:
(PhSiO
3/2)
0.59(Ph
2SiO)
0.03(ViMe
2SiO
1/2)
0.13(Me
3SiO
1/2)
0.11(HMe
2SiO
1/2)
0.14。
The one-component LED packaging materials of the present invention preparation method of organopolysiloxane comprises following step of carrying out successively:
A, with organoalkoxysilane, end-capping reagent, solvent and catalyst mix, under 0 ℃～40 ℃ temperature, stir and drip the water reaction, after dripping, be heated to 45 ℃～50 ℃ and continue reaction 1～3 hour;
B, adding hydrogen base organoalkoxysilane and/or hydrogen radical siloxane stir adding alkenyl organoalkoxysilane and/or alkenyl siloxanes down, and drip acetate, and after dripping off, being warming up to 50 ℃～100 ℃ carried out the polycondensation polyreaction 1～3 hour;
C, add solvent and water and also mix, leave standstill then and separate organic layer and water layer, the organic layer after separating is washed to neutral after drying repeatedly, underpressure distillation removes low molecule again.
In the A step, organoalkoxysilane comprises: be selected from the organic radical dialkoxy silicane of general formula (II) expression, and be selected from the organic radical trialkoxy silane of general formula (III) expression and/or be selected from the tetraalkoxysilane that general formula (IV) is represented; End-capping reagent is selected from: the organic radical disilazane of the organic radical sily oxide that logical formula V is represented, general formula (VI) expression or the silanol of general formula (VII) expression.
In the B step, hydrogen base organoalkoxysilane is selected from the hydrogen base organic radical dialkoxy silicane of general formula (VIII) expression, and the hydrogen radical siloxane is selected from the hydrogen base organic radical sily oxide of general formula (IX) expression; The alkenyl organoalkoxysilane is selected from the alkenyl organic radical organoalkoxysilane of general formula (X) expression, and the alkenyl siloxanes is selected from the alkenyl organic radical sily oxide of general formula (XI) expression.
R
2R
3Si(OR
11)
2 (II)
R
1Si(OR
12)
3 (III)
Si(OR
13)
4 (IV)
(R
7R
8 2Si)
2O (V)
(R
7R
8 2Si)
2NH (VI)
R
7R
8 2SiOH (VII)
HR
9Si(OR
14)
2 (VIII)
(HR
10 2Si)
2O (IX)
R
4R
5Si(OR
15)
2 (X)
(R
4R
6 2Si)
2O (XI)
R among formula (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI)
1, R
2, R
3, R
5, R
6, R
7, R
8, R
9, R
10The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl; Cyclopentyl, cyclohexyl or similar cycloalkyl; Phenyl, tolyl, xylyl or similar aryl; Benzyl, styroyl, hydrocinnamyl or similar aralkyl; 3,3,3-trifluoro propyl, 3-chloropropyl or similar haloalkyl; Wherein most preferably alkyl and aryl, especially methyl and phenyl.R
4Expression has the alkenyl of 2～10 carbon atoms, for example vinyl, allyl group, butenyl, pentenyl etc., wherein preferred vinyl.R
11, R
12, R
13, R
14, R
15Represent identical or different alkyl, what can exemplify has methyl, ethyl, propyl group, butyl, amyl group, hexyl, preferable methyl and an ethyl.
Preferably raw materials used as preparation method of the present invention: in the A step, organoalkoxysilane is selected from one or more in dimethoxydiphenylsilane, dimethyldimethoxysil,ne, aminomethyl phenyl diethoxy silane, the dimethyldiethoxysilane, and
Be selected from phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, the Union carbide A-162 one or more and/or be selected from tetraethoxy, the methyl silicate one or both;
End-capping reagent wherein is selected from one or more in hexamethyldisiloxane, hexamethyldisilazane, hexaphenyl sily oxide, the triphenyl silanol.
In the B step, hydrogen base organoalkoxysilane is selected from one or both in methyl hydrogen dimethoxy silane, the methyl hydrogen diethoxy silane, and the hydrogen radical siloxane is selected tetramethyl disiloxane for use;
Alkenyl organoalkoxysilane wherein is selected from one or both in methyl ethylene diethoxy silane, the methyl ethylene dimethoxy silane, and the alkenyl siloxanes selects 1 for use, 3-divinyl-1,1,3,3-tetramethyl disiloxane.
More preferably: have a kind of phenyl that contains at least in used organoalkoxysilane or the end-capping reagent raw material in the A step.
Among the preparation method of the present invention, the catalyzer in the A step is preferably trifluoromethayl sulfonic acid, hydrochloric acid or strong acidic ion resin.Solvent is preferably toluene, dimethylbenzene or hexanaphthene.Vacuum distillation temperature in the C step is preferably 140 ℃～160 ℃, and the best is 150 ℃.
Mixture with a kind of organopolysiloxane of aforementioned formula (I) or (I ') expression or multiple such organopolysiloxane, with the catalyzer of catalytic amount, an amount of inhibitor mixed, be mixed with water white LED sealing compositions, be the LED packaged material of single component.Wherein the viscosity of organopolysiloxane or its mixture is advisable with 1000～20000mPas (25 ℃).Catalyzer is used to promote that thereby the silicon-addition reaction of hydrogen of organopolysiloxane makes its crosslinking curing, appropriate catalyst is platinum, rhodium, palladium or its compound, preferred platinum class catalyzer, as the alcoholic solution of platinum black, Platinic chloride, platinum-alkene complex compound, platinum-ketone complex compound, platinum-vinylsiloxane complex compound or the like, more preferably the microcapsule-type platinum catalyst of sealing with polyorganosiloxane resin or vibrin.Inhibitor is used to improve curing performance and period of storage, and it is the alkynol with 2～10 carbon atoms, for example methylbutynol, butynediol, propiolic alcohol, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexin-3-alcohol.The prescription of LED sealing compositions suggestion is: organopolysiloxane or its mixture 100 weight parts of aforementioned formula (I) or (I ') expression, platinum catalyst 0.05～1.0 weight part, alkynol inhibitor 0.05～1.0 weight part.
The measuring method of following embodiment medium viscosity adopts standard GB/T 2794-1995 " mensuration of tackiness agent viscosity ", and the measuring method of refractive index adopts standard GB/T 614-2006 " chemical reagent index determination universal method ".
Among the following embodiment, Ph represents phenyl, and Me represents methyl, and Vi represents vinyl.
Embodiment 1
Accurate weighing toluene 400g, hexamethyldisiloxane 32.2g, dimethoxydiphenylsilane 24.4g, phenyltrimethoxysila,e 409.86g and trifluoromethayl sulfonic acid 0.40g add in the 2L four-hole boiling flask, under 0 ℃, drip the water reaction while stirring, the dropping water yield is 37.26g, after dripping, be heated to 50 ℃ and continue reaction 1 hour, add tetramethyl disiloxane 32.16g then, stir down and add 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 40.17g, and drip acetate 100g, after dripping off, be warming up to 60 ℃ of reactions 3 hours, be chilled to room temperature, add toluene and water, mix standing separation, remove water layer, organic layer is washed to neutral after drying repeatedly, and underpressure distillation removes low molecules such as solvent under 140 ℃ of temperature again, gets (PhSiO
3/2)
0.59(Ph
2SiO)
0.03(ViMe
2SiO
1/2)
0.13(Me
3SiO
1/2)
0.11(HMe
2SiO
1/2)
0.14Phenyl vinyl hydrogen based polysiloxane (also claiming silicone resin) 326g, its viscosity is 17000mPas (25 ℃), refractive index is 1.528.
Embodiment 2
Accurate weighing toluene 400g, hexamethyldisiloxane 48.3g, dimethyldimethoxysil,ne 12g, phenyltrimethoxysila,e 400g and trifluoromethayl sulfonic acid 0.40g add in the 2L four-hole boiling flask, stir and drip the water reaction down at 20 ℃, the dropping water yield is 36.36g, after dripping, be heated to 45 ℃ and continue reaction 2 hours, add tetramethyl disiloxane 48.0g then, stir down and add 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 64.0g, and drip acetate 100g, after dripping off, be warming up to 50 ℃ of reactions 3 hours, be chilled to room temperature, add toluene and water, thorough mixing is even, standing separation, remove water layer, organic layer is washed to neutral after drying repeatedly, and underpressure distillation removes low molecules such as solvent under 150 ℃ of temperature again, obtains (PhSiO
3/2)
0.49(Me
2SiO)
0.02(ViMe
2SiO
1/2)
0.17(Me
3SiO
1/2)
0.15(HMe
2SiO
1/2)
0.17Phenyl vinyl based hydrogen-based silicone resin 330g, its viscosity is 1500mPas (25 ℃), refractive index is 1.513.
Embodiment 3
Accurate weighing toluene 400g, hexamethyldisiloxane 24.3g, dimethyldimethoxysil,ne 12g, phenyltrimethoxysila,e 400g and strong acidic ion resin 100g, add in the 2L four-hole boiling flask, stir and drip the water reaction down at 40 ℃, the dropping water yield is 36.36g, after dripping, be heated to 50 ℃ and continue reaction 3 hours, add methyl hydrogen dimethoxy silane 75.94g then, stir adding 1 down, 3-divinyl-1,1,3,3-tetramethyl disiloxane 64.0g, and dropping acetate 100g, after dripping off, be warming up to 80 ℃ of reactions 3 hours, be chilled to room temperature, remove by filter resin cation (R.C.), add toluene and water, mix standing separation, remove water layer, organic layer is washed to neutral after drying repeatedly, removes low molecules such as solvent 150 ℃ of following underpressure distillation again, get (PhSiO
3/2)
0.53(Me
2SiO)
0.03(ViMe
2SiO
1/2)
0.17(Me
3SiO
1/2)
0.08(HmeSiO)
0.19Phenyl vinyl based hydrogen-based silicone resin 352g, its viscosity is 2800mPas (25 ℃), refractive index is 1.518.
Embodiment 4
Accurate weighing toluene 400g, triphenyl silanol 27.6g, dimethyldimethoxysil,ne 12g, phenyltrimethoxysila,e 400g and trifluoromethayl sulfonic acid 0.40g add in the 2L four-hole boiling flask, stir and drip the water reaction down at 25 ℃, the dropping water yield is 36.36g, after dripping, be heated to 50 ℃ and continue reaction 1.5 hours, add tetramethyl disiloxane 48.0g then, stir down and add 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 64.0g, and drip acetate 100g, after dripping off, be warming up to 100 ℃ of reactions 1 hour, be chilled to room temperature, add toluene and water, mix standing separation, remove water layer, organic layer is washed to neutral after drying repeatedly, removes low molecules such as solvent 160 ℃ of following underpressure distillation again, get (PhSiO
3/2)
0.56(Me
2SiO)
0.03(ViMe
2SiO
1/2)
0.19(Ph
3SiO
1/2)
0.03(HMe
2SiO
1/2)
0.19Phenyl vinyl hydrogen based polysiloxane 310g, its viscosity is 7600mPas (25 ℃), refractive index is 1.521.
Embodiment 5
Accurate weighing toluene 400g, triphenyl silanol 55.2g, dimethoxydiphenylsilane 24.4g, phenyltrimethoxysila,e 400g and trifluoromethayl sulfonic acid 0.40g add in the 2L four-hole boiling flask, stir and drip the water reaction down at 30 ℃, the dropping water yield is 42.8g, after dripping, be heated to 45 ℃ and continue reaction 2 hours, add tetramethyl disiloxane 32.16g then, stir down and add 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 1.85g, and drip acetate 100g, after dripping off, be warming up to 50 ℃ of reactions 3 hours, be chilled to room temperature, add toluene and water, mix standing separation, remove water layer, organic layer is washed to neutral after drying repeatedly, and underpressure distillation removes low molecules such as solvent under 150 ℃ of temperature again, gets (PhSiO
3/2)
0.62(Ph
2SiO)
0.03(ViMe
2SiO
1/2)
0.14(Ph
3SiO
1/2)
0.06(HMe
2SiO
1/2)
0.15High phenyl vinyl hydrogen based polysiloxane 305g, its viscosity is 20000mPas (25 ℃), refractive index is 1.541.
Embodiment 6
Prepare water white one-component LED sealing compositions, its part by weight is:
100 parts of the phenyl vinyl hydrogen based polysiloxanes of embodiment 5 preparations
0.1 part of platinum catalyst
0.08 part in inhibitor
Adopt more general packaged type then, with the prepared water white one-component LED sealing compositions package power GaN chip that is 1W, promptly get the LED lamp after the curing, using next straight-through electroluminescence of electric current, use the photochromic electrical parameter comprehensive tester of SSP3112 type LED then, the measuring light flux over time, and paint curve as shown in Figure 1.As can be seen from Figure 1, the initial stage transmittance of material is switched on after 1000 hours more than 95%, and light decay is stabilized in 4%, thus institute's synthetic silicone resin transmittance height, ageing-resistant, the life-span is long, is applicable to the encapsulation of great power LED.
Should be noted that at last above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention.It will be understood by those of skill in the art that and to carry out some deductions or to be equal to replacement technical scheme of the present invention, and do not break away from the essence and the scope of technical solution of the present invention.
Claims (10)
1. one-component LED packaging materials organopolysiloxane, described organopolysiloxane is an alkenyl hydrogen base Difunctional Modified Polysiloxane, has following general structural formula:
(SiO
2)
a1(R
1SiO
3/2)
a2(R
2R
3SiO)
b1(R
4R
5SiO)
c1(R
4R
6 2SiO
1/2)
c2(R
7R
8 2SiO
1/2)
d1(HR
9SiO)
e1(HR
10 2SiO
1/2)
e2 (I)
In the formula (I), R
1, R
2, R
3, R
5, R
6, R
7, R
8, R
9, R
10The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), R
4Expression has the alkenyl of 2～10 carbon atoms, and a1, a2, c1, c2, e1, e2 represent respectively more than or equal to 0 and less than 1 number, 0＜a1+a2＜1,0＜b1＜1,0＜c1+c2＜1,0＜d1＜1,0＜e1+e2＜1, a1+a2+b1+c1+c2+d1+e1+e2=1.
2. one-component LED packaging materials organopolysiloxane according to claim 1 is characterized in that: in the formula (I), and 0.45≤a1+a2≤0.75,0.01≤b1≤0.10,0.10≤c1+c2≤0.25,0.02≤d1≤0.20,0.10≤e1+e2≤0.25.
3. one-component LED packaging materials organopolysiloxane according to claim 1 is characterized in that: in the formula (I), and R
1, R
2, R
3Be phenyl and/or methyl, R
7, R
8Be all phenyl and/or be all methyl, R
4Be vinyl, R
5, R
6, R
9, R
10Be methyl, and a1=0.
4. one-component LED sealing compositions, it includes claim 1,2 or 3 described one-component LED packaging materials organopolysiloxanes.
5. one kind with the described one-component LED sealing compositions of claim 4 encapsulated LED lamp.
6. an one-component LED packaging materials comprises following step of carrying out successively with the preparation method of organopolysiloxane:
A, with organoalkoxysilane, end-capping reagent, solvent and catalyst mix, under 0 ℃～40 ℃ temperature, stir and drip the water reaction, after dripping, be heated to 45 ℃～50 ℃ and continue reaction 1～3 hour;
Wherein said organoalkoxysilane comprises: is selected from the organic radical dialkoxy silicane of general formula (II) expression, and is selected from the organic radical trialkoxy silane of general formula (III) expression and/or is selected from the tetraalkoxysilane that general formula (IV) is represented,
Described end-capping reagent is selected from organic radical sily oxide, the organic radical disilazane of general formula (VI) expression or the silanol of general formula (VII) expression that logical formula V is represented,
R
2R
3Si(OR
11)
2 (II)
R
1Si(OR
12)
3 (III)
Si(OR
13)
4 (IV)
(R
7R
8 2Si)
2O (V)
(R
7R
8 2Si)
2NH (VI)
R
7R
8 2SiOH (VII)
R among formula (II), (III), (IV), (V), (VI), (VII)
1, R
2, R
3, R
7, R
8The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), R
11, R
12, R
13Represent identical or different alkyl;
B, adding hydrogen base organoalkoxysilane and/or hydrogen radical siloxane stir adding alkenyl organoalkoxysilane and/or alkenyl siloxanes down, and drip acetate, and after dripping, being warming up to 50 ℃～100 ℃ carried out the polycondensation polyreaction 1～3 hour;
Wherein said hydrogen base organoalkoxysilane is selected from the hydrogen base organic radical dialkoxy silicane of general formula (VIII) expression, described hydrogen radical siloxane is selected from the hydrogen base organic radical sily oxide of general formula (IX) expression, described alkenyl organoalkoxysilane is selected from the alkenyl organic radical organoalkoxysilane of general formula (X) expression, described alkenyl siloxanes is selected from the alkenyl organic radical sily oxide of general formula (XI) expression
HR
9Si(OR
14)
2 (VIII)
(HR
10 2Si)
2O (IX)
R
4R
5Si(OR
15)
2 (X)
(R
4R
6 2Si)
2O (XI)
R among formula (VIII), (IX), (X), (XI)
5, R
6, R
9, R
10The univalence hydrocarbyl of the not fatty family of expression unsaturated link(age), R
4Expression has the alkenyl of 2～10 carbon atoms, R
14, R
15Represent identical or different alkyl;
C, add solvent and water and also mix, leave standstill then and separate organic layer and water layer, described organic layer is washed to neutral after drying repeatedly, underpressure distillation removes low molecule again.
7. the one-component LED packaging materials according to claim 6 preparation method of organopolysiloxane, it is characterized in that: in the described A step: described organoalkoxysilane is selected from one or more in dimethoxydiphenylsilane, dimethyldimethoxysil,ne, aminomethyl phenyl diethoxy silane, the dimethyldiethoxysilane, and
Be selected from phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, the Union carbide A-162 one or more and/or be selected from tetraethoxy, the methyl silicate one or both,
Described end-capping reagent is selected from one or more in hexamethyldisiloxane, hexamethyldisilazane, hexaphenyl sily oxide, the triphenyl silanol;
In the described B step: described hydrogen base organoalkoxysilane is selected from one or both in methyl hydrogen dimethoxy silane, the methyl hydrogen diethoxy silane, and described hydrogen radical siloxane is selected tetramethyl disiloxane for use,
Described alkenyl organoalkoxysilane is selected from one or both in methyl ethylene diethoxy silane, the methyl ethylene dimethoxy silane, and described alkenyl siloxanes selects 1 for use, 3-divinyl-1,1,3,3-tetramethyl disiloxane.
8. according to the preparation method of claim 6 or 7 described one-component LED packaging materials usefulness organopolysiloxanes, it is characterized in that: the catalyzer in the described A step is trifluoromethayl sulfonic acid, hydrochloric acid or strong acidic ion resin.
9. according to the preparation method of claim 6 or 7 described one-component LED packaging materials usefulness organopolysiloxanes, it is characterized in that: the solvent in described A step and the C step is toluene, dimethylbenzene or hexanaphthene.
10. according to the preparation method of claim 6 or 7 described one-component LED packaging materials usefulness organopolysiloxanes, it is characterized in that: the vacuum distillation temperature in the described C step is 140 ℃～160 ℃.
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