CN104744704A - Tackifying and reinforcing modified polysiloxane and preparation method and application thereof - Google Patents
Tackifying and reinforcing modified polysiloxane and preparation method and application thereof Download PDFInfo
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- CN104744704A CN104744704A CN201510096068.9A CN201510096068A CN104744704A CN 104744704 A CN104744704 A CN 104744704A CN 201510096068 A CN201510096068 A CN 201510096068A CN 104744704 A CN104744704 A CN 104744704A
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Abstract
The invention discloses a tackifying and reinforcing modified polysiloxane and a preparation method and application thereof. The modified polysiloxane is prepared from an intermediate polysiloxane product and an organic compound containing a tackifying group and a vinyl group through hydrosilylation reaction in the presence of a hydrosilylation reaction catalyst, wherein the intermediate polysiloxane product is prepared by terminating methyl vinyl polysiloxane by using a terminator and the tackifying group refers to an organic group capable of increasing adhesion to a substrate. The adhesive strength of a packaging adhesive prepared from the tackifying and reinforcing modified polysiloxane is improved greatly; in addition, other properties such as cured material hardness, light transmittance and tensile strength, are excellent.
Description
Technical field
The present invention relates to substrate packaging plastic technical field, particularly relate to LED glue technical field, particularly a kind of thickening reinforcement modified polyorganosiloxane and its preparation method and application.
Background technology
In recent years, the advantages such as LED (Light Emitting Diode, photodiode) is energy-conservation because of it as a kind of light emitting semiconductor device, extra long life, environmental protection, specular removal, are used widely in fields such as illumination, backlight, display screens rapidly.The electric energy of LED illumination consumption is only 1/10 of conventional light source, if use LED light source to replace conventional light source, will greatly reduce the spending rate of world energy sources.
At present, polysiloxane has replaced traditional epoxy resin, become the mainstay material of LED, polysiloxane has good high-low temperature resistant, ultraviolet aging resistance, insulation, the good characteristic such as hydrophobic, and there is very high transparency, these advantages make polysiloxane have the unrivaled advantage of epoxy resin as LED encapsulation material.Simultaneously LED is as a kind of electronic component, require polysiloxane have certain intensity, toughness, support viscosifying power destroy to avoid extraneous physics and chemistry, meet the protection of LED chip, and by the reliability testing of LED.
Now domestic LED is often because packaged material bonding force is not enough, need additionally to add tackifier, publication number is CN103184031A, name is called in the patent of " a kind of polysiloxane adhesion promoters and preparation method thereof ", owing to additionally using tackifier in LED glue, cause LED glue transmittance to decline, the problem such as to be clamminess in solidification rear surface.
Summary of the invention
The invention provides and a kind ofly there is high light transmittance and adhesive capacity and there is the thickening reinforcement modified polyorganosiloxane of good toughness and intensity, can provide LED reliability in use, and the present invention also provides the preparation method and application of this modified polyorganosiloxane.
According to a first aspect of the invention, the invention provides a kind of thickening reinforcement modified polyorganosiloxane, this modified polyorganosiloxane is through blocking agent the process middle silicone product obtained and the organic compound containing adhesion promoting groups and vinyl by methylvinyl-polysiloxane, under the effect of hydrosilylation catalyst, generated by addition reaction of silicon with hydrogen, wherein above-mentioned adhesion promoting groups refers to the organic group strengthened with the cementability of substrate.
As preferred version of the present invention, above-mentioned methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 0.8 ~ 1.2, and contents of ethylene is 3.5 ~ 5.5%; More preferably, above-mentioned methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 1.0, and contents of ethylene is 4.0%.
As preferred version of the present invention, there is one or two vinyl in the above-mentioned organic compound containing adhesion promoting groups and vinyl;
Preferably, the above-mentioned organic compound containing adhesion promoting groups and vinyl is selected from the combination of a kind of in glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate or at least two kinds.
According to a second aspect of the invention, the invention provides a kind of method preparing thickening reinforcement modified polyorganosiloxane, comprising: under catalyst action, use end-capping reagent to carry out termination process to methylvinyl-polysiloxane and obtain middle silicone product; Then above-mentioned middle silicone product is made to contact with the organic compound of vinyl with containing adhesion promoting groups, under the effect of hydrosilylation catalyst, generate above-mentioned thickening reinforcement modified polyorganosiloxane by addition reaction of silicon with hydrogen, wherein above-mentioned adhesion promoting groups refers to the organic group strengthened with the cementability of substrate.
As preferred version of the present invention, above-mentioned methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 1.0, and contents of ethylene is 4%;
Preferably, above-mentioned end-capping reagent is selected from the combination of a kind of in tetramethyl disiloxane of hexamethyldisiloxane, tetramethyl disiloxane, dimethyl methoxy silane and 1,3-two (3-glycidylpropyl)-1,1,3,3-or at least two kinds;
Preferably, the mass ratio of above-mentioned methylvinyl-polysiloxane and above-mentioned end-capping reagent is that every 100 mass parts methylvinyl-polysiloxane add 1-10 mass parts end-capping reagent, is more preferably every 100 mass parts methylvinyl-polysiloxane and adds 2-5 mass parts end-capping reagent;
Preferably, above-mentioned termination process is carried out in organic solvent; More preferably, above-mentioned organic solvent is the non-polar solvent of the combination being selected from a kind of in toluene, p-Xylol, m-xylene, hexamethyldisiloxane, normal hexane, hexanaphthene, sherwood oil, tetracol phenixin, Skellysolve A and iso-pentane or at least two kinds;
Preferably, above-mentioned termination process is carried out at 80 DEG C-100 DEG C;
Preferably, the consumption of the catalyzer used in above-mentioned termination process to add 0.01-0.5 mass parts of catalyst in 100 mass parts methylvinyl-polysiloxane, more preferably to add 0.05-0.1 mass parts of catalyst in 100 mass parts methylvinyl-polysiloxane;
Preferably, the catalyzer that above-mentioned termination process uses is selected from
solid super-strong acid,
the combination of a kind of in super acids, acidic white earth, phosphonitrilic chloride, trifluoromethanesulfonic acid and p-methyl benzenesulfonic acid or at least two kinds.
As preferred version of the present invention, there is one or two vinyl in the above-mentioned organic compound containing adhesion promoting groups and vinyl;
Preferably, the above-mentioned organic compound containing adhesion promoting groups and vinyl is selected from the combination of a kind of in glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate or at least two kinds;
Preferably, the above-mentioned add-on containing the organic compound of adhesion promoting groups and vinyl is the methylvinyl-polysiloxane initial relative to 100 mass parts, adds the organic compound that 5-25 mass parts contains adhesion promoting groups and vinyl;
Preferably, in above-mentioned middle silicone product, Si-H molar weight and the described ratio containing the molar weight of the organic compound medium vinyl of adhesion promoting groups and vinyl are 0.1 ~ 1.0, are more preferably 0.5;
Preferably, above-mentioned hydrosilylation catalyst is selected from the combination of a kind of in platinum powder, platinum black, Platinic chloride, the aqueous isopropanol of Platinic chloride and the diolefine complex compound of Platinic chloride or at least two kinds;
Preferably, the add-on of above-mentioned hydrosilylation catalyst is the methylvinyl-polysiloxane initial relative to 100 mass parts, add 0.01-0.5 mass parts hydrosilylation catalyst, be more preferably the methylvinyl-polysiloxane initial relative to 100 mass parts, add 0.02-0.1 mass parts hydrosilylation catalyst.
As preferred version of the present invention, above-mentioned addition reaction of silicon with hydrogen carries out in organic solvent; More preferably, above-mentioned organic solvent is the non-polar solvent of the combination being selected from a kind of in toluene, p-Xylol, m-xylene, hexamethyldisiloxane, normal hexane, hexanaphthene, sherwood oil, tetracol phenixin, Skellysolve A and iso-pentane or at least two kinds;
Preferably, above-mentioned middle silicone product is made to carry out in the mode organic solution of above-mentioned middle silicone product being added dropwise to the organic compound of above-mentioned vinyl with contacting with the organic compound of vinyl containing adhesion promoting groups;
Preferably, the organic compound that the organic solution of above-mentioned middle silicone product is added dropwise to above-mentioned vinyl is carried out at 20-50 DEG C, and continue after completing above-mentioned dropping to react 2-6h;
Preferably, after above-mentioned continuation reaction 2-6h, temperature is increased to 90-110 DEG C, then continues reaction 2-5h, removing low-boiling-point substance and solvent, obtain modified polyorganosiloxane.
As preferred version of the present invention, aforesaid method comprises:
(1) be in the methylvinyl-polysiloxane of 100 parts, add the end-capping reagent that organic solvent that mass parts is 60-100 part and mass parts are 2-5 part to mass parts, after treating that above-mentioned methylvinyl-polysiloxane is dissolved, be warming up to 80 DEG C-100 DEG C, and add the catalyzer that mass parts is 0.05-0.1 part, reacting after 1-8 hour stops heating and stirring to obtain the organic solvent solution of middle silicone product, be cooled to room temperature, use washed with de-ionized water 3-5 time to pH value close to neutrality, siccative is put in the solution of above-mentioned middle silicone product, to remove the moisture in solution, preferably, above-mentioned siccative is selected from the combination of a kind of in anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous and calcium oxide or at least two kinds, with
(2) after solution clarification, filter out above-mentioned siccative, add 100-200 mass parts organic solvent, middle silicone product solution being added drop-wise at 20-50 DEG C 5-25 mass parts contains in the organic compound of adhesion promoting groups and vinyl and the mixing solutions of 0.02-0.1 mass parts hydrosilylation catalyst, after reaction 2-6h, temperature is increased to 90-110 DEG C, continues reaction 2-5h, reaction terminates rear removing low-boiling-point substance and solvent, obtains above-mentioned modified polyorganosiloxane.
According to a third aspect of the invention we, the invention provides a kind of LED composition, comprise the thickening reinforcement modified polyorganosiloxane that the method for the thickening reinforcement modified polyorganosiloxane of first aspect or second aspect is obtained, and methyl vinyl silicon oil, inhibitor, solidifying agent and containing hydrogen silicone oil;
Preferably, the Average molecular formula of above-mentioned methyl vinyl silicon oil is as follows:
ViMe
2siO (Me
2siO)
100siMeVi, wherein Me represents methyl, and Vi represents vinyl;
Preferably, above-mentioned containing hydrogen silicone oil is tetramethyl-ring tetrasiloxane;
Preferably, described inhibitor is the combination of a kind of in ethynylcyclohexanol, 3-Phenyl-1-butyn-3-ol, 3-propyl group-ethyl acetylene-3-alcohol and 3-octyl group-ethyl acetylene-3-alcohol or at least two kinds, is more preferably ethynylcyclohexanol;
Preferably, above-mentioned solidifying agent is the aqueous isopropanol of Platinic chloride, and more preferably, in the aqueous isopropanol of above-mentioned Platinic chloride, the mass content of Pt is at 1000ppm-100000ppm, more preferably 10000ppm;
Preferably, in above-mentioned composition, the content of each component is as follows, above-mentioned thickening reinforcement modified polyorganosiloxane is 15-35 mass parts, above-mentioned methyl vinyl silicon oil is 60-90 mass parts, above-mentioned containing hydrogen silicone oil is amount required when SiH/Vi is 1.2 ~ 1.4 in above-mentioned composition, above-mentioned inhibitor is 0.01% ~ 0.5% of above-mentioned composition total mass, and above-mentioned solidifying agent is the 1-50ppm of above-mentioned composition by the gauge of Pt;
Further preferably, in above-mentioned composition, the content of each component is as follows, above-mentioned thickening reinforcement modified polyorganosiloxane is 25 mass parts, above-mentioned methyl vinyl silicon oil is 75 mass parts, above-mentioned containing hydrogen silicone oil is amount required when SiH/Vi is 1.3 in above-mentioned composition, above-mentioned inhibitor is 0.05 of above-mentioned composition total mass, and above-mentioned solidifying agent is the 5ppm of above-mentioned composition by the gauge of Pt.
According to a forth aspect of the invention, the invention provides the application of thickening reinforcement modified polyorganosiloxane in preparation LED composition as the thickening reinforcement modified polyorganosiloxane of first aspect or the method for second aspect obtain.
Thickening reinforcement modified polyorganosiloxane of the present invention, owing to wherein introducing the organic group that can strengthen with the cementability of substrate, therefore its bond strength promotes greatly.Compare this polysiloxanes existing, the bond strength of the packaging plastic using thickening reinforcement modified polyorganosiloxane of the present invention to be re-dubbed improves more than 6 times.In addition, other performance, as cured article hardness, transmittance and tensile strength keep good, the problem especially not causing transmittance to decline because introducing thickening reinforcement modified polyorganosiloxane of the present invention.
Accompanying drawing explanation
Fig. 1 is the principle schematic of the bond strength test method of cured body in the embodiment of the present invention.
Embodiment
Below by embodiment and specific embodiment, the present invention is described in further detail.
Key point of the present invention is, methylvinyl-polysiloxane and the organic compound containing adhesion promoting groups and vinyl are passed through addition reaction of silicon with hydrogen by contriver, generate a kind of thickening reinforcement modified polyorganosiloxane that can significantly improve itself and substrate adhesive intensity, and a kind of LED composition using thickening reinforcement modified polyorganosiloxane of the present invention to be re-dubbed is provided on this basis.Thickening reinforcement modified polyorganosiloxane of the present invention and above-mentioned LED composition in non-limiting manner in LED, can improve its package strength.The invention provides the detailed preparation technology of thickening reinforcement modified polyorganosiloxane and above-mentioned LED composition.Should be understood that, thickening reinforcement modified polyorganosiloxane of the present invention and LED composition are not limited to the material prepared by the inventive method.
Thickening reinforcement modified polyorganosiloxane of the present invention, can by methylvinyl-polysiloxane through blocking agent the process middle silicone product obtained and the organic compound containing adhesion promoting groups and vinyl, under the effect of hydrosilylation catalyst, generated by addition reaction of silicon with hydrogen, wherein above-mentioned adhesion promoting groups refers to the organic group strengthened with the cementability of substrate.
In a scheme of the present invention, methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 1.0, and contents of ethylene is 4%.The silicone resin of MQ type is a kind of silicone resin be made up of with four-functional group Si-O unit (SiQZ is called for short Q unit) simple function group Si-O unit (M unit), has the tight globe of bilayer structure.
In a scheme of the present invention, there is one or two vinyl in the above-mentioned organic compound containing adhesion promoting groups and vinyl, does not exceed two vinyl.Preferably, the above-mentioned organic compound containing adhesion promoting groups and vinyl is selected from the combination of a kind of in glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate or at least two kinds.Described combination typical case but the example of indefiniteness be such as: the combination of glycidyl allyl ether and vinyltrimethoxy silane, the combination of glycidyl allyl ether and vinyltriethoxysilane, the combination of vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane, the combination of γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate, the combination of diallyl p phthalate and vinyltriethoxysilane, glycidyl allyl ether, the combination of vinyltrimethoxy silane and vinyltriethoxysilane, vinyltrimethoxy silane, the combination of vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane, glycidyl allyl ether, vinyltrimethoxy silane, the combination of vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane, etc..
The above-mentioned selection containing the organic compound of adhesion promoting groups and vinyl needs according to different base materials (base material as LED support), uses different organic compound.For the plastics such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), acrylonitrile-butadiene-styrene copolymer (ABS), nylon66 fiber and PC polycarbonate (PC), polyether-ether-ketone (PEEK), polyester (PES), polyethers (acyl) imines (PEI), preferably use diallyl p phthalate; For stainless steel, copper, nickel, aluminium, glass fiber reinforced epoxy resin veneer sheet, phenolic sheet, polyphtalamide resin (PPA) etc., preferably use glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane.For meeting the bonding demand to composite base plate, two or more above-mentioned organic compound can be used simultaneously.
In a scheme of the present invention, the method preparing thickening reinforcement modified polyorganosiloxane comprises: under catalyst action, uses end-capping reagent to carry out termination process to methylvinyl-polysiloxane and obtains middle silicone product; Then middle silicone product is made to contact with the organic compound of vinyl with containing adhesion promoting groups, under the effect of hydrosilylation catalyst, generate thickening reinforcement modified polyorganosiloxane by addition reaction of silicon with hydrogen, wherein adhesion promoting groups refers to the organic group strengthened with the cementability of substrate.
Wherein, above-mentioned methylvinyl-polysiloxane is as defined above, and the range of choice of the above-mentioned organic compound containing adhesion promoting groups and vinyl is as defined above.
In such scheme, end-capping reagent can be selected from the combination of a kind of in tetramethyl disiloxane of hexamethyldisiloxane, tetramethyl disiloxane, dimethyl methoxy silane and 1,3-two (3-glycidylpropyl)-1,1,3,3-or at least two kinds.Described combination typical case but the example of indefiniteness be such as: the combination of hexamethyldisiloxane and tetramethyl disiloxane, the combination of hexamethyldisiloxane and dimethyl methoxy silane, tetramethyldisiloxane and 1, two (the 3-glycidylpropyl)-1 of 3-, 1, 3, the combination of 3-tetramethyl disiloxane, the combination of tetramethyl disiloxane and dimethyl methoxy silane, tetramethyl disiloxane and 1, two (the 3-glycidylpropyl)-1 of 3-, 1, 3, the combination of 3-tetramethyl disiloxane, dimethyl methoxy silane and 1, two (the 3-glycidylpropyl)-1 of 3-, 1, 3, the combination of 3-tetramethyl disiloxane, tetramethyldisiloxane, the combination of tetramethyl disiloxane and dimethyl methoxy silane, tetramethyl disiloxane, dimethyl methoxy silane and 1, two (the 3-glycidylpropyl)-1 of 3-, 1, 3, the combination of 3-tetramethyl disiloxane, tetramethyldisiloxane, tetramethyl disiloxane, dimethyl methoxy silane and 1, two (the 3-glycidylpropyl)-1 of 3-, 1, 3, the combination of 3-tetramethyl disiloxane, etc..
In such scheme, the mass ratio of methylvinyl-polysiloxane and end-capping reagent can add 1-10 mass parts end-capping reagent for every 100 mass parts methylvinyl-polysiloxane, be more preferably every 100 mass parts methylvinyl-polysiloxane and add 2-5 mass parts end-capping reagent, such as every 100 mass parts methylvinyl-polysiloxane add 1.5,2.5,3.5,5,5.8,6.0,7.8,8.2,9.0,9.5 mass parts end-capping reagents.
In such scheme, termination process needs to carry out in organic solvent.More preferably, organic solvent is the non-polar solvent of the combination being selected from a kind of in toluene, p-Xylol, m-xylene, hexamethyldisiloxane, normal hexane, hexanaphthene, sherwood oil, tetracol phenixin, Skellysolve A and iso-pentane or at least two kinds.Described combination typical case but the example of indefiniteness be such as: the combination of toluene and p-Xylol, the combination of toluene and m-xylene, the combination of toluene and hexamethyldisiloxane, the combination of p-Xylol and m-xylene, the combination of p-Xylol and hexamethyldisiloxane, the combination of m-xylene and hexamethyldisiloxane, toluene, the combination of p-Xylol and m-xylene, p-Xylol, m-xylene, the combination of hexamethyldisiloxane, toluene, p-Xylol, m-xylene, the combination of hexamethyldisiloxane, the combination of normal hexane and hexanaphthene, the combination of normal hexane and sherwood oil, the combination of normal hexane and tetracol phenixin, the combination of hexanaphthene and sherwood oil, the combination of normal hexane and tetracol phenixin, normal hexane, the combination of hexanaphthene and sherwood oil, normal hexane, hexanaphthene, the combination of sherwood oil and tetracol phenixin, etc..
In such scheme, termination process is preferably carried out at 80 DEG C-100 DEG C, such as, carry out at 82 DEG C, 85 DEG C, 87 DEG C, 89 DEG C, 91 DEG C, 93 DEG C, 95 DEG C, 97 DEG C or 99 DEG C.
In such scheme, the consumption of the catalyzer used in termination process is to add 0.01-0.5 mass parts of catalyst in 100 mass parts methylvinyl-polysiloxane, more preferably to add 0.05-0.1 mass parts of catalyst in 100 mass parts methylvinyl-polysiloxane, such as 100 mass parts methylvinyl-polysiloxane add 0.012 mass parts, 0.02 mass parts, 0.03 mass parts, 0.05 mass parts, 0.08 mass parts, 0.12 mass parts, 0.15 mass parts, 0.3 mass parts or 0.5 mass parts of catalyst.
In such scheme, the catalyzer that termination process uses can be selected from
solid super-strong acid,
the combination of a kind of in super acids, acidic white earth, phosphonitrilic chloride, trifluoromethanesulfonic acid and p-methyl benzenesulfonic acid or at least two kinds.Described combination typical case but the example of indefiniteness be such as:
solid super-strong acid and
the combination of super acids,
the combination of super acids and acidic white earth, the combination of acidic white earth and phosphonitrilic chloride, the combination of phosphonitrilic chloride and trifluoromethanesulfonic acid, the combination of trifluoromethanesulfonic acid and p-methyl benzenesulfonic acid,
solid super-strong acid,
the combination of super acids and acidic white earth,
the combination of super acids, acidic white earth and phosphonitrilic chloride, the combination of acidic white earth, phosphonitrilic chloride and trifluoromethanesulfonic acid, etc.
In such scheme, there is one or two vinyl in the organic compound containing adhesion promoting groups and vinyl; Preferably, the organic compound containing adhesion promoting groups and vinyl can be selected from the combination of a kind of in glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate or at least two kinds.
In such scheme, the add-on of the organic compound containing adhesion promoting groups and vinyl is the methylvinyl-polysiloxane initial relative to 100 mass parts, adds the organic compound that 5-25 mass parts contains adhesion promoting groups and vinyl.Such as initial relative to 100 mass parts methylvinyl-polysiloxane, adds the organic compound that 6 mass parts, 7.2 mass parts, 9.7 mass parts, 10.5 mass parts, 15.4 mass parts, 16.8 mass parts, 18 mass parts, 22.5 mass parts or 24.8 mass parts contain adhesion promoting groups and vinyl.
In such scheme, the ratio of Si-H molar weight and the molar weight of the organic compound medium vinyl containing adhesion promoting groups and vinyl preferably 0.5 in middle silicone product.
In such scheme, hydrosilylation catalyst can be selected from the combination of a kind of in platinum powder, platinum black, Platinic chloride, the aqueous isopropanol of Platinic chloride and the diolefine complex compound of Platinic chloride or at least two kinds.Described combination typical case but the example of indefiniteness be such as: the combination of platinum powder and platinum black, the combination of platinum powder and Platinic chloride, the combination of platinum powder and isopropyl alcohol solution of chloroplatinic acid, the combination of the diolefine complex compound of isopropyl alcohol solution of chloroplatinic acid and Platinic chloride, the combination of platinum black and Platinic chloride, the combination of Platinic chloride and isopropyl alcohol solution of chloroplatinic acid, the combination of the diolefine complex compound of platinum black and Platinic chloride, the combination of platinum powder, platinum black and Platinic chloride, the combination of the diolefine complex compound of platinum powder, platinum black, Platinic chloride and Platinic chloride, etc.
In such scheme, the add-on of hydrosilylation catalyst can be the methylvinyl-polysiloxane initial relative to 100 mass parts, add 0.01-0.5 mass parts hydrosilylation catalyst, be more preferably the methylvinyl-polysiloxane initial relative to 100 mass parts, add 0.02-0.1 mass parts hydrosilylation catalyst.Such as, the methylvinyl-polysiloxane initial relative to 100 mass parts, adds 0.012 mass parts, 0.02 mass parts, 0.03 mass parts, 0.05 mass parts, 0.08 mass parts, 0.12 mass parts, 0.15 mass parts, 0.3 mass parts or 0.5 mass parts hydrosilylation catalyst.
In such scheme, addition reaction of silicon with hydrogen needs to carry out in organic solvent; More preferably, organic solvent is the non-polar solvent of the combination being selected from a kind of in toluene, p-Xylol, m-xylene, hexamethyldisiloxane, normal hexane, hexanaphthene, sherwood oil, tetracol phenixin, Skellysolve A and iso-pentane or at least two kinds.
In such scheme, middle silicone product is preferably carried out with contacting with the organic compound of vinyl containing adhesion promoting groups in the mode of the organic compound organic solution of middle silicone product being added dropwise to vinyl.Although directly the disposable mode adding reaction system of a large amount of middle silicone product also can be realized object of the present invention, adopt dropping mode can make sluggish, evenly, fully carry out, produce the product of high-quality.
In such scheme, the organic compound organic solution of middle silicone product being added dropwise to vinyl carries out under 20-50 DEG C (such as 22 DEG C, 28 DEG C, 35 DEG C, 40 DEG C, 46 DEG C, 47 DEG C, 48 DEG C or 47 DEG C), and continues reaction 2-6h (such as 2.5h, 2.8h, 3.2h, 3.5h, 4.5h, 5.0h, 5.2h, 5.7h or 5.9h) after completing dropping.
In such scheme, after continuing reaction 2-6h, temperature can be increased to 90-110 DEG C (such as 92 DEG C, 97 DEG C, 98 DEG C, 102 DEG C, 105 DEG C, 107 DEG C or 109 DEG C), continue reaction 2-5h (such as 2.5h, 2.8h, 3.2h, 3.5h, 4.5h or 5.0h) again, then remove low-boiling-point substance and solvent, obtain modified polyorganosiloxane.
In the present invention's the most preferred embodiment, described method comprises:
(1) be in the methylvinyl-polysiloxane of 100 parts, add the end-capping reagent that organic solvent that mass parts is 60-100 part and mass parts are 2-5 part to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 80 DEG C-100 DEG C, and add the catalyzer that mass parts is 0.05-0.1 part, reacting after 1-8 hour stops heating and stirring to obtain the organic solvent solution of middle silicone product, be cooled to room temperature, use washed with de-ionized water 3-5 time to pH value close to neutrality, siccative is put in the solution of middle silicone product, to remove the moisture in solution, preferably, siccative is selected from the combination of a kind of in anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous and calcium oxide or at least two kinds, with
(2) after solution clarification, filter out siccative, add 100-200 mass parts organic solvent, middle silicone product solution being added drop-wise at 20-50 DEG C 5-25 mass parts contains in the organic compound of adhesion promoting groups and vinyl and the mixing solutions of 0.02-0.1 mass parts hydrosilylation catalyst, after reaction 2-6h, temperature is increased to 90-110 DEG C, continues reaction 2-5h, reaction terminates rear removing low-boiling-point substance and solvent, obtains modified polyorganosiloxane.
The present invention also provides a kind of LED composition, and said composition comprises thickening reinforcement modified polyorganosiloxane of the present invention, and methyl vinyl silicon oil, inhibitor, solidifying agent and containing hydrogen silicone oil.
Should be noted that thickening reinforcement modified polyorganosiloxane of the present invention is as thickening reinforced additive, may be used in the packaging plastic of various different components formula, because based on thickening reinforcement modified polyorganosiloxane of the present invention and the large feature of substrate adhesive intensity, known it is with a wide range of applications.
In a preferred embodiment of the invention, the Average molecular formula of methyl vinyl silicon oil is as follows:
ViMe
2siO (Me
2siO)
100siMeVi, wherein Me represents methyl, and Vi represents vinyl.
In a preferred embodiment of the invention, containing hydrogen silicone oil is tetramethyl-ring tetrasiloxane.
In a preferred embodiment of the invention, inhibitor is the combination of a kind of in ethynylcyclohexanol, 3-Phenyl-1-butyn-3-ol, 3-propyl group-ethyl acetylene-3-alcohol and 3-octyl group-ethyl acetylene-3-alcohol or at least two kinds, is preferably ethynylcyclohexanol.
In a preferred embodiment of the invention, solidifying agent is the aqueous isopropanol of Platinic chloride, and more preferably, in the aqueous isopropanol of above-mentioned Platinic chloride, the mass content of Pt is at 1000ppm-100000ppm, more preferably 10000ppm.In fact namely this solidifying agent plays the effect of catalyzer, for the carrying out of catalytic curing reaction.
In a preferred embodiment of the invention, in composition, the content of each component is as follows, thickening reinforcement modified polyorganosiloxane is 15-35 mass parts, methyl vinyl silicon oil is 60-90 mass parts, containing hydrogen silicone oil is amount required when SiH/Vi is 1.2 ~ 1.4 in composition, inhibitor is 0.01% ~ 0.5% of composition total mass, and solidifying agent is the 1-50ppm of composition by the gauge of Pt;
In a more preferred of the present invention, in composition, the content of each component is as follows, thickening reinforcement modified polyorganosiloxane is 25 mass parts, methyl vinyl silicon oil is 75 mass parts, containing hydrogen silicone oil is amount required when SiH/Vi is 1.3 in composition, inhibitor is 0.05 of composition total mass, and solidifying agent is the 5ppm of composition by the gauge of Pt.
Above-mentioned composition can be composite by following process: the inhibitor of thickening reinforcement modified polyorganosiloxane 25 mass parts of synthesizing in the present invention, above-mentioned methyl vinyl silicon oil 75 mass parts, specified amount and solidifying agent are stirred 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, in planetary stirrer, continue stirring 10 minutes, finally in vacuum defoamation machine, carry out deaeration.
In embodiment below and comparative example, we use the thickening reinforcement modified polyorganosiloxane synthesized in following material and the embodiment of the present invention to carry out composite, obtain the composition that can encapsulate LED.
1. the Average molecular formula of methyl vinyl silicon oil is as follows:
ViMe
2siO (Me
2siO)
100siMeVi, wherein Me represents methyl, and Vi represents vinyl.
2. containing hydrogen silicone oil is tetramethyl-ring tetrasiloxane.
3. inhibitor uses ethynylcyclohexanol, and consumption is 0.05% of composition total mass;
4. solidifying agent uses the aqueous isopropanol of Platinic chloride, and the content of Pt is at 10000ppm, and solidifying agent usage quantity is carried out calculating with the Pt of the 5ppm of composition total mass amount and added.
Composite process: the inhibitor of thickening reinforcement modified polyorganosiloxane 25 mass parts of synthesizing in embodiment, above-mentioned methyl vinyl silicon oil 75 mass parts, specified amount and solidifying agent are stirred 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, in planetary stirrer, continue stirring 10 minutes, finally in vacuum defoamation machine, carry out deaeration.
The condition of cure of composition is 80 DEG C of reaction 1h, then 150 DEG C of reaction 3h.
Performance test methods is as follows:
[hardness of cured body]
Above-mentioned composition is formed as the plates solidified, and according to GB/T531-2008, utilizes A type hardness tester meter to measure the hardness of these plates.
In addition, sheet cured body is kept 1000 hours in the baking oven of 150 DEG C, then measure the hardness after oven test by method same as described above.
[light transmission of composition]
Curable above-mentioned composition is clipped between two sheet glass.Measured the light transmission of obtained composition by the automatic recording spectrophotometer (light path: 0.1cm) of the visible ray (wavelength region of 400nm to 800nm) can measuring any wavelength at 25 DEG C.By from through the Transmission light deducting the Transmission light extending only through glass in the Transmission light of glass and composition and determine through composition.
[light transmission of cured body]
Curable organosilicon resin composition is clipped between two sheet glass, and it is solidified under these conditions.Measured the light transmission of obtained cured body by the automatic recording spectrophotometer (light path: 0.1cm) of the visible ray (wavelength region of 400nm to 700nm) can measuring any wavelength at 25 DEG C.By from through the Transmission light deducting the Transmission light extending only through glass in the Transmission light of glass and composition and determine through cured body.
In addition, aforementioned cured body is kept 1000 hours in the baking oven of 150 DEG C, then measure the transmittance after oven test by method same as described above.
[bond strength of cured body]
According to the testing method of GB/T13936-1992, at two silver-plated aluminium sheet (width: 25mm; Length: 50mm; Thickness: 1mm) between fill gaps curable organosilicon resin composition (as shown in Figure 1) of the present invention.In the hot air circulate formula baking oven of above-mentioned condition of cure, keep said composition to solidify.After being cooled to room temperature, in tensile testing machine, measured the bond strength of cured body by the obtained sample that stretches in horizontal direction relative to each other.
[cured body tensile strength]
By the recessed in-tank-solidification of cured body at rectangle tetrafluoroethylene, after completion of cure, use cut-off knife to be cut into dumbbell shaped the cured body of rectangle according to GB/T528-2009, tensilon is tested the tensile strength of cured body.
Describe the present invention in detail by the following examples, these embodiments are only exemplary, do not form limiting the scope of the invention.
Following examples Raw source is described as follows: methylvinyl-polysiloxane is purchased from Zhejiang profit standing grain chemical industry, and tetramethyl disiloxane is purchased from Quzhou Rui Lijie chemical industry, and toluene, ethanol are chemical purchased from Guangzhou, CaCl
2purchased from western Gansu Province chemical industry,
super acids is purchased from ShengQuan catalyst Application Science Co., Ltd., Qufu City, and other materials is purchased from Aladdin.
Embodiment 1
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 60 parts and the tetramethyl disiloxane of mass parts 2 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 80 DEG C, and add the p-methyl benzenesulfonic acid that mass parts is 0.05 part, stop heating after 8 hours and stir the toluene solution obtaining middle silicone product, be cooled to room temperature, deionization is used to wash 3 times to neutral, Calcium Chloride Powder Anhydrous is put in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, add 100 mass parts toluene, middle silicone product solution is slowly added drop-wise at 20 DEG C in the mixing solutions of 7 parts of glycidyl allyl ethers, 8 parts of vinyltrimethoxy silanes and 0.04 mass parts isopropyl alcohol solution of chloroplatinic acid (Pt content is 8000ppm), after reaction 6h, temperature is increased to 90 DEG C, continues reaction 5 hours, reaction terminates rear removing low-boiling-point substance and toluene, obtains modified polyorganosiloxane.
Thickening reinforcement modified polyorganosiloxane 25 mass parts of the present embodiment synthesis, the methyl vinyl silicon oil of the above-mentioned of 75 mass parts, the inhibitor of specified amount and catalyzer are stirred 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Embodiment 2
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 80 parts and the tetramethyl disiloxane of mass parts 5 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 85 DEG C, and add the phosphonitrilic chloride that mass parts is 0.1 part, stop heating after 6 hours and stir the toluene solution obtaining middle silicone product, be cooled to room temperature, deionization is used to wash 5 times to neutral, Calcium Chloride Powder Anhydrous is put in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, add 200 mass parts toluene, middle silicone product solution is slowly added drop-wise at 50 DEG C in the mixing solutions of complex compound (Pt content is 8000ppm) of the tetramethyl divinyl disiloxane of the γ-methacryloxypropyl trimethoxy silane of 5 mass parts, the vinyltriethoxysilane of 10 mass parts and 0.04 mass parts Platinic chloride, after reaction 6h, temperature is increased to 110 DEG C, continue reaction 2 hours, reaction terminates rear removing low-boiling-point substance and toluene, obtains modified polyorganosiloxane.
Thickening reinforcement modified polyorganosiloxane 25 mass parts of the present embodiment synthesis, the methyl vinyl silicon oil of the above-mentioned of 75 mass parts, the inhibitor of specified amount and catalyzer are stirred 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Embodiment 3
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 100 parts and the tetramethyl disiloxane of mass parts 3 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 90 DEG C, and to add mass parts be 0.06 part
super acids, stops heating and stirs the toluene solution obtaining middle silicone product, being cooled to room temperature after 2 hours, use deionization to wash 4 times to neutral, put into by Calcium Chloride Powder Anhydrous in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, add 150 mass parts toluene, middle silicone product solution is slowly added drop-wise at 40 DEG C in the mixing solutions of the glycidyl allyl ether of 6 mass parts, the vinyltrimethoxy silane of 9 mass parts and 0.04 mass parts hydrosilylation catalyst (Pt content is 8000ppm), after reaction 4h, temperature is increased to 100 DEG C, continues reaction 3 hours, reaction terminates rear removing low-boiling-point substance and toluene, obtains modified polyorganosiloxane.
Thickening reinforcement modified polyorganosiloxane 25 mass parts of the present embodiment synthesis, the methyl vinyl silicon oil of the above-mentioned of 75 mass parts, the inhibitor of specified amount and catalyzer are stirred 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Embodiment 4
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 80 parts and the tetramethyl disiloxane of mass parts 4 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 85 DEG C, and add the trifluoromethayl sulfonic acid that mass parts is 0.08 part, stop heating after 8 hours and stir the toluene solution obtaining middle silicone product, be cooled to room temperature, deionization is used to wash 4 times to neutral, Calcium Chloride Powder Anhydrous is put in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, add 100 mass parts toluene, middle silicone product solution is slowly added drop-wise at 50 DEG C in the mixing solutions of para Toluic Acid's diallyl (molecular weight 246.26) of 3 mass parts, the vinyltrimethoxy silane of 12 mass parts and 0.04 mass parts hydrosilylation catalyst (Pt content is 8000ppm), after reaction 5h, temperature is increased to 100 DEG C, continue reaction 5 hours, reaction terminates rear removing low-boiling-point substance and toluene, obtains modified polyorganosiloxane.
Thickening reinforcement modified polyorganosiloxane 25 mass parts of the present embodiment synthesis, the methyl vinyl silicon oil of the above-mentioned of 75 mass parts, the inhibitor of specified amount and catalyzer are stirred 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Comparative example 1
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 60 parts and the tetramethyl disiloxane of mass parts 2 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 80 DEG C, and add the p-methyl benzenesulfonic acid that mass parts is 0.05 part, stop heating after 8 hours and stir the toluene solution obtaining middle silicone product, be cooled to room temperature, deionization is used to wash 3 times to neutral, Calcium Chloride Powder Anhydrous is put in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, removing low-boiling-point substance and toluene, obtain modified polyorganosiloxane.
The above-mentioned methyl vinyl silicon oil of thickening reinforcement modified polyorganosiloxane 25 mass parts of this comparative example being synthesized, 75 mass parts, the inhibitor of specified amount and catalyzer stir 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Comparative example 2
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 80 parts and the tetramethyl disiloxane of mass parts 5 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 85 DEG C, and add the phosphonitrilic chloride that mass parts is 0.1 part, stop heating after 6 hours and stir the toluene solution obtaining middle silicone product, be cooled to room temperature, deionization is used to wash 5 times to neutral, Calcium Chloride Powder Anhydrous is put in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, removing low-boiling-point substance and toluene, obtain modified polyorganosiloxane.
The above-mentioned methyl vinyl silicon oil of thickening reinforcement modified polyorganosiloxane 25 mass parts of this comparative example being synthesized, 75 mass parts, the inhibitor of specified amount and catalyzer stir 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Comparative example 3
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 100 parts and the tetramethyl disiloxane of mass parts 3 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 90 DEG C, and to add mass parts be 0.06 part
super acids, stops heating and stirs the toluene solution obtaining middle silicone product, being cooled to room temperature after 2 hours, use deionization to wash 4 times to neutral, put into by Calcium Chloride Powder Anhydrous in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, removing low-boiling-point substance and toluene, obtain modified polyorganosiloxane.
The above-mentioned methyl vinyl silicon oil of thickening reinforcement modified polyorganosiloxane 25 mass parts of this comparative example being synthesized, 75 mass parts, the inhibitor of specified amount and catalyzer stir 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.Detect properties according to above-mentioned testing method, result is as shown in table 1.
Comparative example 4
Be that to add mass parts in the methylvinyl-polysiloxane of 100 parts be the toluene of 80 parts and the tetramethyl disiloxane of mass parts 4 parts to mass parts, after treating that methylvinyl-polysiloxane is dissolved, be warming up to 85 DEG C, and add the trifluoromethayl sulfonic acid that mass parts is 0.08 part, stop heating after 8 hours and stir the toluene solution obtaining middle silicone product, be cooled to room temperature, deionization is used to wash 4 times to neutral, Calcium Chloride Powder Anhydrous is put in the solution of middle silicone product, to remove the moisture in solution.After solution clarification, after filtering out Calcium Chloride Powder Anhydrous, removing low-boiling-point substance and toluene, obtain modified polyorganosiloxane.
The above-mentioned methyl vinyl silicon oil of modified polyorganosiloxane 25 mass parts of this comparative example being synthesized, 75 mass parts, the inhibitor of specified amount and catalyzer stir 5 minutes in planetary stirrer, then the amount of required containing hydrogen silicone oil during SiH/Vi=1.3 is added, stirring is continued 10 minutes in planetary stirrer, finally in vacuum defoamation machine, carry out deaeration, obtain LED composition.
The experimental result of table 1 embodiment and comparative example
As can be seen from the result of table 1, the bond strength of the composition of embodiment 1-4 is obviously better than comparative example 1-4, intensity improves more than 6 times, even reaches 10 times, illustrates that the LED composition that thickening reinforcement modified polyorganosiloxane of the present invention is re-dubbed has excellent bond properties.In addition, the property retention of cured article hardness, composition transmittance, cured article transmittance and tensile strength aspect is good, can meet or exceed the level of comparative example.
Above content is in conjunction with concrete embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made.
Claims (10)
1. a thickening reinforcement modified polyorganosiloxane, it is characterized in that, described modified polyorganosiloxane is through blocking agent the process middle silicone product obtained and the organic compound containing adhesion promoting groups and vinyl by methylvinyl-polysiloxane, under the effect of hydrosilylation catalyst, generated by addition reaction of silicon with hydrogen, wherein said adhesion promoting groups refers to the organic group strengthened with the cementability of substrate.
2. modified polyorganosiloxane according to claim 1, is characterized in that, described methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 0.8 ~ 1.2, and contents of ethylene is 3.5 ~ 5.5%;
Preferably, described methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 1.0, and contents of ethylene is 4.0%.
3. modified polyorganosiloxane according to claim 1, is characterized in that, the described organic compound containing adhesion promoting groups and vinyl exists one or two vinyl;
Preferably, the described organic compound containing adhesion promoting groups and vinyl is selected from the combination of a kind of in glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate or at least two kinds.
4. prepare a method for thickening reinforcement modified polyorganosiloxane, it is characterized in that, described method comprises: under catalyst action, uses end-capping reagent to carry out termination process to methylvinyl-polysiloxane and obtains middle silicone product; Then described middle silicone product is made to contact with the organic compound of vinyl with containing adhesion promoting groups, under the effect of hydrosilylation catalyst, generate described thickening reinforcement modified polyorganosiloxane by addition reaction of silicon with hydrogen, wherein said adhesion promoting groups refers to the organic group strengthened with the cementability of substrate.
5. method according to claim 4, is characterized in that, described methylvinyl-polysiloxane is the silicone resin of MQ type, and its R/Si value is 1.0, and contents of ethylene is 4%;
Preferably, described end-capping reagent is selected from the combination of a kind of in tetramethyl disiloxane of hexamethyldisiloxane, tetramethyl disiloxane, dimethyl methoxy silane and 1,3-two (3-glycidylpropyl)-1,1,3,3-or at least two kinds;
Preferably, the mass ratio of described methylvinyl-polysiloxane and described end-capping reagent is that every 100 mass parts methylvinyl-polysiloxane add 1-10 mass parts end-capping reagent, is more preferably every 100 mass parts methylvinyl-polysiloxane and adds 2-5 mass parts end-capping reagent;
Preferably, described termination process is carried out in organic solvent; More preferably, described organic solvent is the non-polar solvent of the combination being selected from a kind of in toluene, p-Xylol, m-xylene, hexamethyldisiloxane, normal hexane, hexanaphthene, sherwood oil, tetracol phenixin, Skellysolve A and iso-pentane or at least two kinds;
Preferably, described termination process is carried out at 80 DEG C-100 DEG C;
Preferably, the consumption of the catalyzer used in described termination process to add 0.01-0.5 mass parts of catalyst in 100 mass parts methylvinyl-polysiloxane, more preferably to add 0.05-0.1 mass parts of catalyst in 100 mass parts methylvinyl-polysiloxane;
Preferably, the catalyzer that described termination process uses is selected from
solid super-strong acid,
the combination of a kind of in super acids, acidic white earth, phosphonitrilic chloride, trifluoromethanesulfonic acid and p-methyl benzenesulfonic acid or at least two kinds.
6. method according to claim 4, is characterized in that, the described organic compound containing adhesion promoting groups and vinyl exists one or two vinyl;
Preferably, the described organic compound containing adhesion promoting groups and vinyl is selected from the combination of a kind of in glycidyl allyl ether, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and diallyl p phthalate or at least two kinds;
Preferably, the described add-on containing the organic compound of adhesion promoting groups and vinyl is the methylvinyl-polysiloxane initial relative to 100 mass parts, adds the organic compound that 5-25 mass parts contains adhesion promoting groups and vinyl;
Preferably, in described middle silicone product, Si-H molar weight and the described ratio containing the molar weight of the organic compound medium vinyl of adhesion promoting groups and vinyl are 0.1 ~ 1.0, are preferably 0.5;
Preferably, described hydrosilylation catalyst is selected from the combination of a kind of in platinum powder, platinum black, Platinic chloride, the aqueous isopropanol of Platinic chloride and the diolefine complex compound of Platinic chloride or at least two kinds;
Preferably, the add-on of described hydrosilylation catalyst is the methylvinyl-polysiloxane initial relative to 100 mass parts, add 0.01-0.5 mass parts hydrosilylation catalyst, be more preferably the methylvinyl-polysiloxane initial relative to 100 mass parts, add 0.02-0.1 mass parts hydrosilylation catalyst.
7. method according to claim 4, is characterized in that, described addition reaction of silicon with hydrogen carries out in organic solvent; More preferably, described organic solvent is the non-polar solvent of the combination being selected from a kind of in toluene, p-Xylol, m-xylene, hexamethyldisiloxane, normal hexane, hexanaphthene, sherwood oil, tetracol phenixin, Skellysolve A and iso-pentane or at least two kinds;
Preferably, described middle silicone product is made to carry out in the mode organic solution of described middle silicone product being added dropwise to the organic compound of described vinyl with contacting with the organic compound of vinyl containing adhesion promoting groups described in;
Preferably, the organic compound that the described organic solution by described middle silicone product is added dropwise to described vinyl carries out at 20-50 DEG C, and continues after completing described dropping to react 2-6h;
Preferably, after described continuation reaction 2-6h, temperature is increased to 90-110 DEG C, then continues reaction 2-5h, removing low-boiling-point substance and solvent, obtain modified polyorganosiloxane.
8. the method according to any one of claim 4-7, is characterized in that, described method comprises:
(1) be in the methylvinyl-polysiloxane of 100 parts, add the end-capping reagent that organic solvent that mass parts is 60-100 part and mass parts are 2-5 part to mass parts, after treating that described methylvinyl-polysiloxane is dissolved, be warming up to 80 DEG C-100 DEG C, and add the catalyzer that mass parts is 0.05-0.1 part, reacting after 1-8 hour stops heating and stirring to obtain the organic solvent solution of middle silicone product, be cooled to room temperature, use washed with de-ionized water 3-5 time to pH value close to neutrality, siccative is put in the solution of described middle silicone product, to remove the moisture in solution, preferably, described siccative is selected from the combination of a kind of in anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous and calcium oxide or at least two kinds, with
(2) after solution clarification, filter out described siccative, add 100-200 mass parts organic solvent, middle silicone product solution being added drop-wise at 20-50 DEG C 5-25 mass parts contains in the organic compound of adhesion promoting groups and vinyl and the mixing solutions of 0.02-0.1 mass parts hydrosilylation catalyst, after reaction 2-6h, temperature is increased to 90-110 DEG C, continues reaction 2-5h, reaction terminates rear removing low-boiling-point substance and solvent, obtains described modified polyorganosiloxane.
9. a LED composition, it is characterized in that, described composition comprises the obtained thickening reinforcement modified polyorganosiloxane of the thickening reinforcement modified polyorganosiloxane described in any one of claim 1-3 or the method described in any one of claim 4-8, and methyl vinyl silicon oil, inhibitor, solidifying agent and containing hydrogen silicone oil;
Preferably, the Average molecular formula of described methyl vinyl silicon oil is as follows:
ViMe
2siO (Me
2siO)
100siMeVi, wherein Me represents methyl, and Vi represents vinyl;
Preferably, described containing hydrogen silicone oil is tetramethyl-ring tetrasiloxane;
Preferably, described inhibitor is the combination of a kind of in ethynylcyclohexanol, 3-Phenyl-1-butyn-3-ol, 3-propyl group-ethyl acetylene-3-alcohol and 3-octyl group-ethyl acetylene-3-alcohol or at least two kinds, is more preferably ethynylcyclohexanol;
Preferably, described solidifying agent is the aqueous isopropanol of Platinic chloride, and more preferably, in the aqueous isopropanol of described Platinic chloride, the mass content of Pt is at 1000ppm-100000ppm, more preferably 10000ppm;
Preferably, in described composition, the content of each component is as follows, described thickening reinforcement modified polyorganosiloxane is 15-35 mass parts, described methyl vinyl silicon oil is 60-90 mass parts, described containing hydrogen silicone oil is amount required when SiH/Vi is 1.2 ~ 1.4 in described composition, described inhibitor is 0.01% ~ 0.5% of described composition total mass, and described solidifying agent is the 1-50ppm of described composition by the gauge of Pt;
Further preferably, in described composition, the content of each component is as follows, described thickening reinforcement modified polyorganosiloxane is 25 mass parts, described methyl vinyl silicon oil is 75 mass parts, described containing hydrogen silicone oil is amount required when SiH/Vi is 1.3 in described composition, described inhibitor is 0.05 of described composition total mass, and described solidifying agent is the 5ppm of described composition by the gauge of Pt.
10. the application of the thickening reinforcement modified polyorganosiloxane that the thickening reinforcement modified polyorganosiloxane as described in any one of claim 1-3 or the method as described in any one of claim 4-8 obtain in preparation LED composition.
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