CN104892939A - Preparation method for phenyl silicon resin - Google Patents
Preparation method for phenyl silicon resin Download PDFInfo
- Publication number
- CN104892939A CN104892939A CN201410087951.7A CN201410087951A CN104892939A CN 104892939 A CN104892939 A CN 104892939A CN 201410087951 A CN201410087951 A CN 201410087951A CN 104892939 A CN104892939 A CN 104892939A
- Authority
- CN
- China
- Prior art keywords
- consumption
- organic solvent
- phenyl
- hydroxy group
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention discloses a preparation method for phenyl silicon resin, in particular to a preparation method for vinyl phenyl silicone resin which is high in refraction index and light transmittance and is applied to LED encapsulation and reinforcement. Hydrolysis reaction is first conducted on a mixed solution formed by phenyl tri-alkoxysilane, an organic solvent and water; an acid catalyst is added in hydrolysis product then to conduct polycondensation reaction; the prepared product is conducted by water washing neutralization; distillation is conducted to remove a majority of organic solvent; vacuum drying is conducted to remove residual low-boiling-point substances; hydroxyl phenyl silicone resin is prepared and obtained; the prepared hydroxyl phenyl silicone resin is taken as a raw material to be dissolved in the organic solvent; vinyl silane is added in the phenyl silicone resin organic solution end capped by hydroxyl, and is stirred uniformly; the acid catalyst is added in the mixed solution, and is stirred uniformly; the temperature is raised, and reaction is conducted; the obtained product, after neutralization and drying treatment, is conducted by suction filtration, distillation and vacuum drying to prepare the target product.
Description
Technical field
The present invention designs a kind of preparation method of phenyl polysiloxane, refers in particular to the preparation method of a kind of LED high refractive index, high transmission rate supporting material Vinylphenyl silicon resin.
Technical background
The mankind enter 21st century, and energy problem becomes increasingly conspicuous, save energy with tap a new source of energy of equal importance.Current, the energy that illumination consumes accounts for about 20% of world's total energy consumption.If can, life-span length, safety low by energy consumption, environmental protection new light sources replace conventional light source that is inefficient, high energy consumption, will a large amount of energy be saved.
Power light-emitting diode (Light Emitting Diode, LED) electric energy consumed is only 1/10 of conventional light source, and the mercury of inapplicable serious environment pollution, volume is little, life-span is long, low-heat, shockproof, waterproof, miniature, high brightness, easy light modulation, the advantages such as light beam is concentrated, be widely used in the backlight of liquid crystal display, traffic signal display light source, big area picture and text showing full-color screen, sign, Signal aspects, the panel board of automotive interior, acoustics indication lamp, the backlight of switch, reading light and outside brake lamp, taillight, the aspect such as side lamp and head lamp.LED is expected to the forth generation light source become after incandescent light, luminescent lamp, high-intensity gas discharge lamp.
The packaged material mainly bisphenol A-type transparent epoxy resin of current common LED, but along with the development of power-type LED, epoxy resin cannot meet power type LED encapsulation material to high refractive index, high transmission rate, the requirement that heat-resisting, ultraviolet resistance, low water absorption and coefficient of linear expansion are little.Easily there is xanthochromia in epoxy resin under UV-light long-term irradiation, the thermal conductivity of epoxy resin is 0.2W/ (mK) left and right in addition, it is the poor conductor of heat, high thermal resistance can cause heat radiation bad, junction temperature of chip raises rapidly, accelerate device light decay, the stress that even can produce because expanding causes open circuit.
Organosilicon has high refractive index, high pass light rate as packaged material, Heat stability is good, and the advantage such as the little and water absorbability of stress is low, its performance is better than epoxy resin far away.Many large-scale organosilicon manufacturing enterprises have in succession dropped into a large amount of manpower and materials and have developed polytype organosilicon encapsulating material in the world, as JCR6175,0E6450, EG6301 etc. of DOW CORNING exploitation, LPS5547, X-35-305 etc. of SHIN-ETSU HANTOTAI's exploitation, and domestic research and development at power type LED encapsulation material and produce relatively backwardness, domestic market is to the demand major part dependence on import of power type LED encapsulation material.Power type LED encapsulation material, except requiring to have except high refractive index, transmittance and UV radiation, also requires that material must possess certain basic mechanical performance.The vulcanized mechanical of non-reinforcement is very poor, cannot meet the demands, so reinforcing filler must be added carry out reinforcement to packaged material, but be easy to the adding of filler produce negative impact to the refractive index of packaged material and transmittance, this just has higher requirement to the selection of reinforced filling.
Summary of the invention
The present invention is directed to deficiency of the prior art, the invention discloses a kind of cheaper starting materials, method simple to operate: by phenyl trialkoxysilane, first the mixing solutions of the composition of organic solvent and water is hydrolyzed and reacts, then under acid catalyst katalysis, carry out polycondensation, by the products therefrom of preparation washing neutralization, distillation, vacuum-drying, prepare terminal hydroxy group phenyl polysiloxane, with the terminal hydroxy group end-blocking phenyl polysiloxane prepared for raw material, be dissolved in organic solvent, vinyl silanes is added in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking, react under acid catalyst effect, products therefrom is neutralized, dry, suction filtration, distillation, vacuum-drying, target product can be obtained.The characteristics such as phenyl vinyl polysiloxane prepared by the method has high refractive index, high transmittance, resistant of high or low temperature is good, good weatherability, radiation hardness are good, be particularly suitable for the reinforcement of LED encapsulation material, the aspect such as peeling force conditioning agent and other additive of surface treatment agent, releasing agent, defoamer, release agent, brightening agent, add-on type release agent can also be applied to.
The present invention is achieved by following technical proposals:
A preparation method for the Vinylphenyl silicon resin of reinforcement LED encapsulation material, is characterized in that carrying out in the steps below:
(1) phenyl trialkoxysilane, organic solvent and water are mixed, stir under nitrogen atmosphere, be hydrolyzed reaction;
(2), after reaction terminates, heat up, add acid catalyst, carry out polycondensation;
(3), after reaction terminates, standing, layering, gets upper oil phase, with 25 DEG C ~ 75 DEG C deionized waters, oil phase is washed to neutrality, obtains the organic solution of terminal hydroxy group phenyl polysiloxane;
(4) organic solution of gained terminal hydroxy group phenyl polysiloxane is distilled, removing majority of organic solvent, then at-0.1MPa ~ 0.085MPa, at 80 DEG C ~ 120 DEG C, dry 6h ~ 12h.Terminal hydroxy group phenyl polysiloxane can be obtained;
(5) obtained terminal hydroxy group phenyl polysiloxane is dissolved in organic solvent, under nitrogen atmosphere, in the organic solution of terminal hydroxy group phenyl polysiloxane, add vinyl silanes, stir, in mixing solutions, add acid catalyst under stirring, promote reaction further;
(6) reaction terminates rear cooling, under stirring, add strong base-weak acid salt to neutralize, stir 0.5h ~ 4h, then add siccative and dewater, stir 0.5h ~ 2h, by neutralization, dry complete mixing solutions suction filtration, distillation, removing majority of organic solvent, vacuum-drying removing low-boiling-point substance, can prepare final product.
As preferably, the phenyl trialkoxysilane as polymer monomer described in above-mentioned preparation method is phenyltrimethoxysila,e (PhSi (OMe)
3), phenyl triethoxysilane (PhSi (OEt)
3) in one or more, wherein: Ph is phenyl, Me is methyl, and Et is ethyl;
Described mixes phenyl trialkoxysilane, organic solvent and water, and organic solvent is one or more in ether, ethanol, Virahol, propyl carbinol, tetrahydrofuran (THF), benzene,toluene,xylene;
Described mixes phenyl trialkoxysilane, organic solvent and water, and be hydrolyzed under stirring reaction, and the temperature of hydrolysis reaction is 20 DEG C ~ 80 DEG C, and the time of hydrolysis reaction is 0.5h ~ 5h;
Add acid catalyst described in step (2), the acid catalyst added is one or more in tosic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Zeo-karb;
The acid catalyst that adds described in step (2) carries out polycondensation, and the temperature of condensation reaction is 30 DEG C ~ 100 DEG C, and the time of condensation reaction is 3h ~ 12h;
Distillation removing majority of organic solvent described in step (4), distillation temperature is 20 DEG C ~ 100 DEG C, and distillation time is 1h ~ 12h;
Described is dissolved in organic solvent by terminal hydroxy group phenyl polysiloxane, and organic solvent is one or more in ether, ethanol, Virahol, propyl carbinol, tetrahydrofuran (THF), benzene,toluene,xylene;
Described adds in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking by vinyl silanes, vinyl silanes is one or more of divinyl tetramethyl disiloxane ((ViMe2Si) 20) or Vinyldimethylethoxysilane (ViSiMe2 (OEt)), wherein: Vi is vinyl; Described being added by vinyl silanes in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking stirs, and the time of stirring is 0.5h ~ 4h, and the temperature of stirring is 20 DEG C ~ 80 DEG C;
Described to add vinyl silanes terminal hydroxy group end-blocking phenyl polysiloxane organic solution in add acid catalyst, the kind of acid catalyst is one or more in tosic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Zeo-karb;
Described to add vinyl silanes terminal hydroxy group phenyl polysiloxane organic solution in add acid catalyst, stir, churning time is 0.5h ~ 4h, and whipping temp is 20 DEG C ~ 80 DEG C;
Further promotion reaction described in step (5), the temperature of reaction is 40 DEG C ~ i00 DEG C, and the time of reaction is 2h ~ 15h;
Under described stirring, add strong base-weak acid salt and neutralize, the strong base-weak acid salt added is one or more in sodium carbonate, sodium acetate, sodium phosphate, sodium bicarbonate;
Described adds siccative removing residual moisture, and siccative used is one or more in Calcium Chloride Powder Anhydrous, anhydrous magnesium sulfate, anhydrous cupric sulfate, molecular sieve;
Described distillation removing majority of organic solvent, distillation temperature is 20 DEG C ~ 100 DEG C, and distillation time is 1h ~ 12h;
As preferably, phenyl trialkoxysilane, organic solvent and water being mixed described in above-mentioned preparation method, the consumption of organic solvent is 1 ~ 8 times of monomer consumption (quality), and the consumption of water is monomer consumption (quality) 1 ~ 12 times;
As better selection, the consumption of the organic solvent described in above-mentioned preparation method is 2 ~ 6 times of monomer consumption (quality), and the consumption of water is monomer consumption (quality) 2 ~ 8 times;
As preferably, acid catalyst described in above-mentioned preparation method's step (2) is one or more in tosic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Zeo-karb, and the consumption of acid catalyst is 5% ~ 30% of monomer consumption (quality);
As preferably, the consumption of the organic solvent described in above-mentioned preparation method is 4 ~ 20 times of the terminal hydroxy group phenyl polysiloxane consumption (quality) added.
As preferably, the consumption adding vinyl silanes described in above-mentioned preparation method is 5% ~ 50% of the terminal hydroxy group phenyl polysiloxane consumption (quality) added;
As preferably, acid catalyst described in above-mentioned preparation method's step (5) is one or more in tosic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Zeo-karb, add the consumption of acid catalyst for adding terminal hydroxy group phenyl polysiloxane consumption (quality) 1% ~ 30%, as more preferably selecting, the consumption of acid catalyst is for adding terminal hydroxy group phenyl polysiloxane consumption (quality) 2% ~ 20%.
This patent adopts phenyl trialkoxysilane to be raw material, its hydrolysis reaction comparatively chlorosilane monomer such as phenyl-trichloro-silicane is slow, is easy to control its structure and molecular weight, product is formed comparatively even, gel-free produces, and effectively raises transmittance and the productive rate of product; Adopt acids as catalyzer in addition, be conducive to preparing degree of branching high, the reinforcing filler that Spatial Dimension is large.
Beneficial effect: the Vinylphenyl silicon resin prepared by method of the present invention, has uniform space structure, can provide three-dimensional crosslinked network, significantly improve the mechanical property of packaged material for the packaged material after reinforcement.The refractive index of obtained Vinylphenyl silicon resin is more than 1.55, transmittance >95%, Spatial Dimension is large, and thermal stability is excellent, be particularly suitable for the reinforcement of LED encapsulation material, also may be used for other seal gums, joint sealant and sizing agent.
Embodiment
The present invention can be further illustrated by following embodiment, but embodiment is not limiting the scope of the invention.
Embodiment 1
Phenyltrimethoxysila,e 20 parts is added in the four-hole boiling flask of 250ml drying, dimethylbenzene 50 parts, deionized water 70 parts, under nitrogen atmosphere, at 20 DEG C, rapid stirring, hydrolysis reaction 5h, be warmed up to 75 DEG C, add 3.6 parts of concentrated hydrochloric acids (37wt%), polycondensation 10h, stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 65 DEG C, distillation 2h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 100 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250ml drying, add toluene 100 parts again, Vinyldimethylethoxysilane 4 parts, 1h is stirred at 30 DEG C, add 3 parts of concentrated hydrochloric acids (37wt%), 1h is stirred at 30 DEG C, be warming up to 60 DEG C of reaction 7h, then stopped reaction, cooling, add in 3 parts of sodium carbonate powder under stirring and 0.5h, add 5 parts of molecular sieves again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the solution of water white transparency Vinylphenyl silicon resin, gained solution is distilled 2h at 70 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5565, records vinyl mass percentage 3.2% through chemical titration.
Embodiment 2
Phenyl triethoxysilane 20 parts is added in the four-hole bottle of 250ml drying, toluene 50 parts, deionized water 160 parts, under nitrogen atmosphere, rapid stirring at 80 DEG C, hydrolysis reaction 0.5h, be warmed up to 75 DEG C, add 6 vitriol oils (96wt%), polycondensation 8h, then stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 20 DEG C, distillation 12h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 100 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250ml drying, add dimethylbenzene 80 parts again, Vinyldimethylethoxysilane 3 parts, 1h is stirred at 50 DEG C, add 1 part of concentrated nitric acid (69wt%), 1h is stirred at 50 DEG C, be warming up to 60 DEG C of reaction 8h, then stopped reaction, cooling, 2 parts of sodium bicarbonates are added under stirring, in 2 parts of sodium hydrogen carbonate powders and 0.5h, add 5 parts of Calcium Chloride Powder Anhydrouss again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the solution of water white transparency Vinylphenyl silicon resin, gained solution is distilled 4h at 60 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5575, records vinyl mass percentage 2.2% through chemical titration.
Embodiment 3
Phenyltrimethoxysila,e 20 parts is added in the four-hole bottle of 250ml drying, dimethylbenzene 50 parts, Virahol 50 parts, deionized water 60 parts, under nitrogen atmosphere, rapid stirring at 35 DEG C, hydrolysis reaction 2h, be warmed up to 80 DEG C, add 3 parts of Zeo-karbs, polycondensation 12h, then stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 45 DEG C, distillation 8h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 100 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250ml drying, add propyl carbinol 80 parts again, divinyl tetramethyl disiloxane 4 parts, 1h is stirred at 30 DEG C, add 0.5g concentrated hydrochloric acid (37wt%), 1h is stirred at 30 DEG C, be warming up to 800 DEG C of reaction 6h, then stopped reaction, cooling, add in 6 parts of sodium hydrogen carbonate powders under stirring and 0.5h, add 4 parts of anhydrous cupric sulfates again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the solution of water white transparency Vinylphenyl silicon resin, 1h is distilled by gained solution 100 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5560, records vinyl mass percentage 3.0% through chemical titration.
Embodiment 4
Phenyltrimethoxysila,e 20 parts is added in the four-hole bottle of 250ml drying, Virahol 100 parts, deionized water 20 parts, under nitrogen atmosphere, rapid stirring at 60 DEG C, hydrolysis reaction 2h, be warmed up to 75 DEG C, add 4 parts of acetic acid (99.5wt%), polycondensation 5h, then stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 65 DEG C, distillation 2h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under i00 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250ml drying, add 20 parts, Siping City's furans again, Vinyldimethylethoxysilane 4 parts, 1h is stirred at 50 DEG C, add 2 parts of concentrated hydrochloric acids (37wt%), 1h is stirred at 50 DEG C, be warming up to 60 DEG C of reaction 10h, then stopped reaction, cooling, add in 5 parts of sodium phosphate powder under stirring and 0.5h, add 5 parts of molecular sieves again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the toluene solution of water white transparency Vinylphenyl silicon resin, gained solution is distilled 2h at 70 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5545, records vinyl mass percentage 3.21% through chemical titration.
Embodiment 5
Phenyltrimethoxysila,e 10 parts is added in the four-hole bottle of 250ml drying, phenyl triethoxysilane 10 parts, benzene 50 parts, deionized water 30 parts, under nitrogen atmosphere, rapid stirring at 60 DEG C, hydrolysis reaction 2h, be warmed up to 65 DEG C, add 3.6 parts of tosic acid, polycondensation 10h, then stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 65 DEG C, distillation 2h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 100 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250ml drying, add ethanol 200 parts again, Vinyldimethylethoxysilane part, 1h is stirred at 30 DEG C, add tosic acid 2 parts, 1h is stirred at 30 DEG C, be warming up to 60 DEG C of reaction 7h, then stopped reaction, cooling, add in 6 parts of sodium hydrogen carbonate powders under stirring and 0.5h, add 5 parts of molecular sieves again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the solution of water white transparency Vinylphenyl silicon resin, gained solution is distilled 2h at 70 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5578, records vinyl mass percentage 3.65% through chemical titration.
Embodiment 6
Phenyltrimethoxysila,e 20 parts is added in the four-hole bottle of 250ml drying, ethanol 50 parts, Virahol 50 parts of deionizations, 70 parts, water, under nitrogen atmosphere, rapid stirring at 25 DEG C, hydrolysis reaction 2h, be warmed up to 90 DEG C, add 3 parts of Zeo-karbs, polycondensation 10h, then stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 65 DEG C, distillation 2h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 100 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250mi drying, add toluene 80 parts again, Vinyldimethylethoxysilane 5 parts, 1h is stirred at 30 DEG C, add 1 part of concentrated hydrochloric acid (37wt%), 1h is stirred at 30 DEG C, be warming up to 70 DEG C of reaction 6h, then stopped reaction, cooling, add in 6 parts of sodium hydrogen carbonate powders under stirring and 0.5h, add 5 parts of molecular sieves again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the solution of water white transparency Vinylphenyl silicon resin, gained solution is distilled 2h at 70 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5559, records vinyl mass percentage 2.85% through chemical titration.
Embodiment 7
Phenyltrimethoxysila,e 20 parts is added in the four-hole bottle of 250ml drying, dimethylbenzene 30 parts, toluene 30 parts, Virahol 15 parts, deionized water 70 parts, under nitrogen atmosphere, rapid stirring at 55 DEG C, hydrolysis reaction 2h, be warmed up to 75 DEG C, add 2.5 parts of concentrated hydrochloric acids (37wt%), polycondensation 12h, then stopped reaction, stratification, get upper oil phase, neutrality is washed to deionized water, to the neutral solution being dissolved with resin product be washed under nitrogen atmosphere, at 75 DEG C, distillation 2h, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 100 DEG C/-0.1MPa, both water white transparency product end hydroxy phenyl silicone resin was obtained, under nitrogen atmosphere, the terminal hydroxy group phenyl polysiloxane 10 parts preparing gained is added in the four-hole boiling flask of 250ml drying, add toluene 50 parts again, Vinyldimethylethoxysilane 0.5 part, 1h is stirred at 45 DEG C, add 2 parts of concentrated hydrochloric acids (37wt%), 1h is stirred at 45 DEG C, be warming up to 70 DEG C of reaction 8h, then stopped reaction, cooling, add in 6 parts of sodium hydrogen carbonate powders under stirring and 0.5h, add 5 parts of molecular sieves again and stir lower dry 1h, by gained mixing solutions suction filtration, obtain the solution of water white transparency Vinylphenyl silicon resin, gained solution is distilled 2h at 70 DEG C, distillation products therefrom is poured in culture dish, low-boiling-point substance is removed under 80 DEG C/-0.1MPa, final product Vinylphenyl silicon resin can be obtained.Products therefrom nD25=1.5576, records vinyl mass percentage 2.19% through chemical titration.
Claims (9)
1. a preparation method for phenyl polysiloxane, is characterized in that:
(1) phenyl trialkoxysilane, organic solvent and water are mixed, stir under nitrogen atmosphere, be hydrolyzed reaction;
(2), after reaction terminates, add acid catalyst, carry out polycondensation;
(3), after reaction terminates, standing, layering, gets upper oil phase, with 25 DEG C ~ 75 DEG C deionized waters, oil phase is washed to neutrality, obtains the organic solution of terminal hydroxy group phenyl polysiloxane;
(4) organic solution of gained terminal hydroxy group phenyl polysiloxane is distilled, removing organic solvent, then at-0.1MPa ~ 0.085MPa, at 80 DEG C ~ 120 DEG C, dry 6h ~ 12h.Terminal hydroxy group phenyl polysiloxane can be obtained;
(5) obtained terminal hydroxy group phenyl polysiloxane is dissolved in organic solvent, under nitrogen atmosphere, in the organic solution of terminal hydroxy group phenyl polysiloxane, add vinyl silanes, stir, in mixing solutions, add acid catalyst under stirring, promote reaction further;
(6) reaction terminates rear cooling, under stirring, add strong base-weak acid salt to neutralize, stir 0.5h ~ 4h, then add siccative and dewater, stir 0.5h ~ 2h, by neutralization, dry complete mixing solutions suction filtration, distillation, removing majority of organic solvent, vacuum-drying removing low-boiling-point substance, can prepare final product.
2. preparation method according to claim 1, is characterized in that:
The described phenyl trialkoxysilane as polymer monomer is phenyltrimethoxysila,e (PhSi (OMe)
3), phenyl triethoxysilane (PhSi (OEt)
3) in one or more, Ph is phenyl, and Me is methyl, and Et is ethyl;
Described mixes phenyl trialkoxysilane, organic solvent and water, and organic solvent is one or more in ether, ethanol, Virahol, propyl carbinol, tetrahydrofuran (THF), benzene,toluene,xylene;
Described mixes phenyl trialkoxysilane, organic solvent and water, and be hydrolyzed under stirring reaction, and the temperature of hydrolysis reaction is 20 DEG C ~ 80 DEG C,
The time of hydrolysis reaction is 0.5h ~ 5h;
Add acid catalyst described in step (2), the acid catalyst added is one or more in tosic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Zeo-karb;
The acid catalyst that adds described in step (2) carries out condensation reaction, and the temperature of condensation reaction is 30 DEG C ~ 100 DEG C, and the time of condensation reaction is 3h ~ 12h;
Distillation removing majority of organic solvent described in step (4), distillation temperature is 20 DEG C ~ 100 DEG C, and distillation time is 1h ~ 12h;
Described is dissolved in organic solvent by terminal hydroxy group phenyl polysiloxane, and organic solvent is one or more in ether, ethanol, Virahol, propyl carbinol, tetrahydrofuran (THF), benzene,toluene,xylene;
Described adds in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking by vinyl silanes, vinyl silanes is divinyl tetramethyl disiloxane ((ViMe
2si)
2or Vinyldimethylethoxysilane (ViSiMe O)
2(OEt)) one or more, wherein, Vi is vinyl;
Described being added by vinyl silanes in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking stirs, and the time of stirring is 0.5h ~ 4h, and the temperature of stirring is 20 DEG C ~ 80 DEG C;
Described to add vinyl silanes terminal hydroxy group end-blocking phenyl polysiloxane organic solution in add acid catalyst, the kind of acid catalyst is one or more in tosic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Zeo-karb;
Described to add vinyl silanes terminal hydroxy group phenyl polysiloxane organic solution in add acid catalyst, stir, churning time is 0.5h ~ 4h, and whipping temp is 20 DEG C ~ 80 DEG C;
Further promotion reaction described in step (5), the temperature of reaction is 40 DEG C ~ 100 DEG C, and the time of reaction is 2h ~ 15h;
Under described stirring, add strong base-weak acid salt and neutralize, the strong base-weak acid salt added is one or more in sodium carbonate, sodium acetate, sodium phosphate, sodium bicarbonate;
Described adds siccative removing residual moisture, and siccative used is one or more in Calcium Chloride Powder Anhydrous, anhydrous magnesium sulfate, anhydrous cupric sulfate, molecular sieve;
Described distillation removing majority of organic solvent, distillation temperature is 20 DEG C ~ 100 DEG C, and distillation time is 1h ~ 12h.
3. each method of system according to claim 1, it is characterized in that: described mixes phenyl trialkoxysilane, organic solvent and water, the consumption of organic solvent is 1 ~ 8 times of phenyl trialkoxysilane consumption (quality), and the consumption of water is phenyl trialkoxysilane consumption (quality) 1 ~ 12 times.
4. preparation method according to claim 3, it is characterized in that: the consumption of described organic solvent is 2 ~ 6 times of phenyl trialkoxysilane consumption (quality), the consumption of water is phenyl trialkoxysilane consumption (quality) 2 ~ 8 times.
5. preparation method according to claim 1, is characterized in that: the consumption of the acid catalyst described in step (2) is 5% ~ 30% of phenyl trialkoxysilane consumption (quality).
6. preparation method according to claim 1, is characterized in that: the consumption of the organic solvent described in step (5) is 4 ~ 20 times of the terminal hydroxy group phenyl polysiloxane consumption (quality) added.
7. preparation method according to claim 1, is characterized in that: the described consumption adding vinyl silanes is 5% ~ 50% of the terminal hydroxy group phenyl polysiloxane consumption (quality) added.
8. each method of system according to claim 2, is characterized in that: the consumption of the acid catalyst described in step (5) is for adding terminal hydroxy group phenyl polysiloxane consumption (quality) 1% ~ 30%.
9. preparation method according to claim 1, is characterized in that the consumption of described acid catalyst is for adding terminal hydroxy group phenyl polysiloxane consumption (quality) 2% ~ 20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410087951.7A CN104892939B (en) | 2014-03-05 | 2014-03-05 | A kind of preparation method of phenyl polysiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410087951.7A CN104892939B (en) | 2014-03-05 | 2014-03-05 | A kind of preparation method of phenyl polysiloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104892939A true CN104892939A (en) | 2015-09-09 |
| CN104892939B CN104892939B (en) | 2017-11-28 |
Family
ID=54025936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410087951.7A Expired - Fee Related CN104892939B (en) | 2014-03-05 | 2014-03-05 | A kind of preparation method of phenyl polysiloxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104892939B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175728A (en) * | 2015-10-27 | 2015-12-23 | 江苏麒祥高新材料有限公司 | Preparation method of phenyl silicone resin packaging material used for electronic components |
| CN106065073A (en) * | 2016-05-31 | 2016-11-02 | 上海回天新材料有限公司 | Vinyl polysiloxane, and its production and use |
| CN106750312A (en) * | 2017-03-27 | 2017-05-31 | 成都硅宝科技股份有限公司 | Phenyl DT silicones and preparation method thereof |
| CN108893091A (en) * | 2018-05-18 | 2018-11-27 | 江苏中南建设装饰有限公司 | A kind of curtain wall fluorescence sealant and preparation method thereof |
| CN110387043A (en) * | 2019-07-12 | 2019-10-29 | 湖北大学 | Dendroid organo-silicon compound and preparation method thereof with multiterminal functional group |
| CN110483783A (en) * | 2019-08-16 | 2019-11-22 | 湖北兴瑞硅材料有限公司 | A kind of phenyl vinyl polysiloxane preparation method |
| CN110591098A (en) * | 2019-10-09 | 2019-12-20 | 浙江新安化工集团股份有限公司 | Methyl phenyl vinyl silicone oil and preparation method and application thereof |
| CN111234229A (en) * | 2020-02-26 | 2020-06-05 | 华南理工大学 | Vinyl phenyl silicone resin for LED packaging adhesive and preparation method and application thereof |
| WO2021042262A1 (en) * | 2019-09-03 | 2021-03-11 | Dow Silicones Corporation | Method for producing organopolysiloxane |
| CN112646186A (en) * | 2020-12-16 | 2021-04-13 | 上海大学 | Method for preparing organic silicon resin coating by utilizing hydrolytic polymerization of organic silane |
| CN113398991A (en) * | 2021-05-26 | 2021-09-17 | 华东理工大学 | Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56151731A (en) * | 1980-04-25 | 1981-11-24 | Japan Synthetic Rubber Co Ltd | Preparation of silicone resin |
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
| CN102690416A (en) * | 2012-06-13 | 2012-09-26 | 江苏宏达新材料股份有限公司 | High-refractive index silicon resin and preparation method thereof |
| KR20130011932A (en) * | 2011-07-22 | 2013-01-30 | 나가세케무텍쿠스가부시키가이샤 | Resin composition for forming optical component |
| CN102952271A (en) * | 2012-06-07 | 2013-03-06 | 安徽众星新材料有限公司 | High-refraction-index silicon resin as well as preparation method and application thereof |
-
2014
- 2014-03-05 CN CN201410087951.7A patent/CN104892939B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56151731A (en) * | 1980-04-25 | 1981-11-24 | Japan Synthetic Rubber Co Ltd | Preparation of silicone resin |
| KR20130011932A (en) * | 2011-07-22 | 2013-01-30 | 나가세케무텍쿠스가부시키가이샤 | Resin composition for forming optical component |
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
| CN102952271A (en) * | 2012-06-07 | 2013-03-06 | 安徽众星新材料有限公司 | High-refraction-index silicon resin as well as preparation method and application thereof |
| CN102690416A (en) * | 2012-06-13 | 2012-09-26 | 江苏宏达新材料股份有限公司 | High-refractive index silicon resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 姜亚，等: ""苯基三甲氧基硅烷水解动力学研究"", 《有机硅材料》 * |
| 汪晓璐，等: ""高折射率苯基乙烯基透明硅树脂的制备与固化性能"", 《化工新型材料》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175728A (en) * | 2015-10-27 | 2015-12-23 | 江苏麒祥高新材料有限公司 | Preparation method of phenyl silicone resin packaging material used for electronic components |
| CN106065073A (en) * | 2016-05-31 | 2016-11-02 | 上海回天新材料有限公司 | Vinyl polysiloxane, and its production and use |
| CN106065073B (en) * | 2016-05-31 | 2019-04-19 | 上海回天新材料有限公司 | Vinyl polysiloxane, and its preparation method and application |
| CN106750312A (en) * | 2017-03-27 | 2017-05-31 | 成都硅宝科技股份有限公司 | Phenyl DT silicones and preparation method thereof |
| CN106750312B (en) * | 2017-03-27 | 2020-07-17 | 成都硅宝科技股份有限公司 | Phenyl DT (bismuth telluride) silicone resin and preparation method thereof |
| CN108893091A (en) * | 2018-05-18 | 2018-11-27 | 江苏中南建设装饰有限公司 | A kind of curtain wall fluorescence sealant and preparation method thereof |
| CN108893091B (en) * | 2018-05-18 | 2020-12-25 | 江苏中南建设装饰有限公司 | Fluorescent sealant for curtain wall and preparation method thereof |
| CN110387043A (en) * | 2019-07-12 | 2019-10-29 | 湖北大学 | Dendroid organo-silicon compound and preparation method thereof with multiterminal functional group |
| CN110483783B (en) * | 2019-08-16 | 2021-08-31 | 湖北兴瑞硅材料有限公司 | Preparation method of phenyl vinyl silicone resin |
| CN110483783A (en) * | 2019-08-16 | 2019-11-22 | 湖北兴瑞硅材料有限公司 | A kind of phenyl vinyl polysiloxane preparation method |
| WO2021042262A1 (en) * | 2019-09-03 | 2021-03-11 | Dow Silicones Corporation | Method for producing organopolysiloxane |
| CN110591098A (en) * | 2019-10-09 | 2019-12-20 | 浙江新安化工集团股份有限公司 | Methyl phenyl vinyl silicone oil and preparation method and application thereof |
| CN111234229A (en) * | 2020-02-26 | 2020-06-05 | 华南理工大学 | Vinyl phenyl silicone resin for LED packaging adhesive and preparation method and application thereof |
| CN111234229B (en) * | 2020-02-26 | 2021-12-21 | 华南理工大学 | Vinyl phenyl silicone resin for LED packaging adhesive and preparation method and application thereof |
| CN112646186A (en) * | 2020-12-16 | 2021-04-13 | 上海大学 | Method for preparing organic silicon resin coating by utilizing hydrolytic polymerization of organic silane |
| CN112646186B (en) * | 2020-12-16 | 2021-10-12 | 上海大学 | Method for preparing organic silicon resin coating by utilizing hydrolytic polymerization of organic silane |
| CN113398991A (en) * | 2021-05-26 | 2021-09-17 | 华东理工大学 | Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892939B (en) | 2017-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892939A (en) | Preparation method for phenyl silicon resin | |
| CN104974349B (en) | A kind of preparation method of silicones | |
| CN101475689B (en) | Preparation of methyl phenyl vinyl silicon resin | |
| CN102898651B (en) | Preparation method of vinylphenyl silicon resin for LED (light-emitting diode) packaging | |
| CN102898650B (en) | MTQ silicon resin with T-chain unit containing phenyl and preparation method thereof | |
| CN101343365A (en) | Preparation method for methyl phenyl vinyl polysiloxane for packaging LED | |
| CN101880396B (en) | Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation | |
| CN101215381B (en) | Method for preparing methylphenyl hydrogen-containing silicone oil | |
| CN104004491A (en) | LED ultraviolet curable organosilicon encapsulation adhesive and preparation method thereof | |
| CN102504270B (en) | High-performance organic silicon electronic pouring sealant and preparation method and application thereof | |
| CN101851333B (en) | Method for preparing methyl phenyl hydrogen-containing silicone oil by rare earth super acid catalysis | |
| CN101323667A (en) | Preparation of methyl vinyl MQ resin for LED encapsulated strengthening | |
| CN103360603B (en) | A kind of LED phenyl vinyl polysiloxane and preparation method thereof | |
| CN102888001B (en) | Vinylphenyl silicon resin | |
| CN103012798B (en) | Preparation method of methyl phenyl vinyl silicone resin | |
| CN104073215A (en) | Preparation method for nano silicon dioxide modified organic silicon sealant for packaging of light emitting diode (LED) | |
| CN105802532A (en) | Silicon boron tackifier, preparation method thereof and application thereof in double-component LED packaging gel | |
| CN102898648A (en) | Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof | |
| CN102516500A (en) | Organic silicon modified epoxy resin for packaging LED (Light Emitting Diode), and preparation method and application thereof | |
| CN104211965A (en) | Preparation method for net-like methyl phenyl vinyl polysiloxane for LED packaging | |
| CN104277222A (en) | Phenyl hydrogen-containing silicone resin for LED encapsulation and preparation method of phenyl hydrogen-containing silicone resin | |
| CN104892940B (en) | A kind of preparation method of siloxanes | |
| CN103834178A (en) | Organic silicon resin as well as preparation method and application thereof | |
| CN100556954C (en) | Light emitting diode encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing | |
| CN104212408B (en) | Filling glue of a kind of phenyl system high refractive index LED and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171128 Termination date: 20210305 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |