CN104892939B - A kind of preparation method of phenyl polysiloxane - Google Patents
A kind of preparation method of phenyl polysiloxane Download PDFInfo
- Publication number
- CN104892939B CN104892939B CN201410087951.7A CN201410087951A CN104892939B CN 104892939 B CN104892939 B CN 104892939B CN 201410087951 A CN201410087951 A CN 201410087951A CN 104892939 B CN104892939 B CN 104892939B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- hydroxy group
- organic solvent
- acid
- 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.)
- Expired - Fee Related
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
It is especially a kind of for LED encapsulated strengthenings high refractive index, the preparation method of the Vinylphenyl silicon resin of high transmission rate the invention discloses a kind of preparation method of phenyl polysiloxane.The present invention is to use phenyl trialkoxysilane, reaction is hydrolyzed in the mixed solution of the composition of organic solvent and water first, then acid catalyst is added in hydrolysate again, carry out polycondensation reaction, the products therefrom of preparation is washed and neutralized, most of organic solvent is distilled off, vacuum drying removes residual low-boiling-point substance, terminal hydroxy group phenyl polysiloxane can be prepared, phenyl polysiloxane is blocked as raw material using the terminal hydroxy group being prepared, it is dissolved in organic solvent, vinyl silanes are added in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking, stir, acid catalyst is added in mixed solution, stir, temperature reaction, products therefrom is neutralized, filtered after drying process, distillation, then it is dried in vacuo, it can be prepared by target product.
Description
Technical field
The present invention designs a kind of preparation method of phenyl polysiloxane, refers in particular to a kind of LED encapsulation high refractive index, height
The preparation method of light transmittance supporting material Vinylphenyl silicon resin.
Technical background
The mankind enter 21st century, and energy problem becomes increasingly conspicuous, and it is of equal importance with tapping a new source of energy to save the energy.When
Before, the energy for illuminating consumption accounts for 20% or so of world's total energy consumption.If can use, energy consumption is low, long lifespan, safe and environment-friendly new
Light source replaces the inefficient, conventional light source of high energy consumption, will save the substantial amounts of energy.
The electric energy of power light-emitting diode (Light Emitting Diode, LED) consumption is only the 1/ of conventional light source
10, and the mercury of inapplicable serious pollution environment, small volume, long lifespan, low-heat, shockproof, waterproof, easily miniature, high brightness, tune
The advantages that light, light beam are concentrated, it is widely used in the backlight, traffic signal display light source, large area picture and text of LCDs
Show that full-color screen, sign, signal are shown, instrument board, acoustics indication lamp, the backlight of switch, the reading lamp of automotive interior
With brake lamp, taillight, side lamp and the head lamp etc. of outside.LED is expected to turn into after incandescent lamp, fluorescent lamp, high-intensity-gas
Forth generation light source after discharge lamp.
The encapsulating material of common LED is mainly bisphenol A-type transparent epoxy resin at present, but with the hair of power-type LED
Exhibition, epoxy resin can not meet power type LED encapsulation material to high refractive index, high transmission rate, heat-resisting, ultraviolet resistance, low suction
Water rate and the small requirement of linear expansion coefficient.Xanthochromia easily occurs for epoxy resin under ultraviolet light long-term irradiation, in addition asphalt mixtures modified by epoxy resin
The thermal conductivity of fat is 0.2W/ (mK) left and right, is the non-conductor of heat, and high thermal resistance can cause to radiate bad, and junction temperature of chip is fast
Speed rise, accelerates device light decay, or even can cause to open a way because of stress caused by expansion.
Organosilicon has high refractive index, high thang-kng rate as encapsulating material, and heat endurance is good, and stress is small and hygroscopicity is low
The advantages that, its performance is far better than epoxy resin.Many large-scale organosilicon manufacturing enterprises have put into substantial amounts of people in succession in the world
Power material resources develop JCR6175,0E6450, EG6301 of polytype organosilicon encapsulating material, such as DOW CORNING exploitation, letter
LPS5547, X-35-305 more developed etc., and the country relatively falls in the research and development and production of power type LED encapsulation material
Afterwards, domestic market largely relies on import to the demand of power type LED encapsulation material.Power type LED encapsulation material is except requiring
Beyond high refraction index, light transmittance and UV radiation, also require that material must possess certain basic mechanical
Performance.The vulcanized mechanical of non-reinforcement is very poor, can not meet to require, so must be added to reinforcing filler to encapsulation
Material carries out reinforcement, but the addition of filler is easy to produce negative impact to the index of refraction and light transmittance of encapsulating material, this
Just the selection to reinforced filling proposes higher requirement.
The content of the invention
The present invention is directed to deficiency of the prior art, and the invention discloses a kind of cheap, the simple to operate method of raw material：Will
Reaction is hydrolyzed in the mixed solution of the composition of phenyl trialkoxysilane, organic solvent and water first, then in acid based catalyst
Under agent catalytic action, polycondensation reaction is carried out, the products therefrom washing of preparation is neutralized, distilled, vacuum drying, end hydroxyl is prepared
Base phenyl polysiloxane, phenyl polysiloxane is blocked as raw material using the terminal hydroxy group being prepared, is dissolved in organic solvent, by vinyl silicon
Alkane is added in the organic solution of the phenyl polysiloxane of terminal hydroxy group end-blocking, is reacted under acid catalyst effect, by products therefrom
With, dry, filter, distillation, vacuum drying, you can be made target product.Phenyl vinyl polysiloxane prepared by this method has
The characteristics such as high index of refraction, high light transmittance, resistant of high or low temperature are good, good weatherability, radiation hardness are good, are sealed particularly suitable for LED
The reinforcement of package material, surface conditioning agent, releasing agent, defoamer, antitack agent, brightener, add-on type antitack agent can also be applied to
Peeling force conditioning agent and other additives etc..
The present invention is achieved by following technical proposals：
A kind of preparation method of the Vinylphenyl silicon resin of reinforcement LED encapsulation material, it is characterized in that in the steps below
Carry out：
(1) phenyl trialkoxysilane, organic solvent and water are mixed, stirs under nitrogen atmosphere, reaction is hydrolyzed；
(2) after reaction terminates, heating, acid catalyst is added, carries out polycondensation reaction；
(3) after reaction terminates, stand, layering, upper oil phase is taken, during oil phase is washed to 25 DEG C~75 DEG C deionized waters
Property, obtain the organic solution of terminal hydroxy group phenyl polysiloxane；
(4) organic solution of gained terminal hydroxy group phenyl polysiloxane is distilled, removes most of organic solvent, then-
0.1MPa~0.085MPa, at 80 DEG C~120 DEG C, dry 6h~12h.It can obtain terminal hydroxy group phenyl polysiloxane；
(5) obtained terminal hydroxy group phenyl polysiloxane is dissolved in organic solvent, under nitrogen atmosphere, to terminal hydroxy group phenyl silicon
Vinyl silanes are added in the organic solution of resin, are stirred, add acid catalyst under stirring into mixed solution, enter one
Step promotes reaction；
(6) reaction cools down after terminating, and under stirring, adds strong base-weak acid salt and is neutralized, stir 0.5h~4h, then add
Drier is removed water, and stirs 0.5h~2h, and the mixed solution for neutralizing, having dried is filtered, distillation, removes most of organic solvent,
Vacuum drying removes low-boiling-point substance, you can final product is prepared.
Preferably, the phenyl trialkoxysilane as polymer monomer described in above-mentioned preparation method is phenyl three
Methoxy silane (PhSi (OMe)3), phenyl triethoxysilane (PhSi (OEt)3) in one or more, wherein：Ph is benzene
Base, Me are methyl, and Et is ethyl；
It is described to mix phenyl trialkoxysilane, organic solvent and water, organic solvent be ether, ethanol, isopropanol,
One or more in n-butanol, tetrahydrofuran, benzene,toluene,xylene；
Described mixes phenyl trialkoxysilane, organic solvent and water, and reaction, hydrolysis are hydrolyzed under stirring
Temperature be 20 DEG C~80 DEG C, the time of hydrolysis is 0.5h~5h；
Addition acid catalyst described in step (2), the acid catalyst of addition is p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid,
One or more in nitric acid, acetic acid, cationic ion-exchange resin；
Addition acid catalyst described in step (2) carries out polycondensation reaction, and the temperature of condensation reaction is 30 DEG C~100
DEG C, the time of condensation reaction is 3h~12h；
Most of organic solvent is distilled off described in step (4), vapo(u)rizing temperature is 20 DEG C~100 DEG C, distillation time
For 1h~12h；
Described is dissolved in terminal hydroxy group phenyl polysiloxane in organic solvent, and organic solvent is ether, ethanol, isopropanol, just
One or more in butanol, tetrahydrofuran, benzene,toluene,xylene；
In the organic solution of the described phenyl polysiloxane that vinyl silanes are added to terminal hydroxy group end-blocking, vinyl silanes are
Divinyl tetramethyl disiloxane ((ViMe2Si)2) or Vinyldimethylethoxysilane (ViSiMe O2(OEt))
One or more, wherein：Vi is vinyl；The described phenyl polysiloxane that vinyl silanes are added to terminal hydroxy group end-blocking it is organic
Stirred in solution, the time of stirring is 0.5h~4h, and the temperature of stirring is 20 DEG C~80 DEG C；
Acids is added in the organic solution of the described phenyl polysiloxane blocked to the terminal hydroxy group for adding vinyl silanes to urge
Agent, the species of acid catalyst is p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, one kind in cationic ion-exchange resin or
It is several；
Described adds acid catalyst into the organic solution for the terminal hydroxy group phenyl polysiloxane for adding vinyl silanes, stirs
Mix uniformly, mixing 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 neutralized, the strong base-weak acid salt of addition is sodium carbonate, sodium acetate,
One or more in sodium phosphate, sodium acid carbonate；
Described addition drier removes residual moisture, and drier used is anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous
One or more in copper sulphate, molecular sieve；
Described is distilled off most of organic solvent, and vapo(u)rizing temperature is 20 DEG C~100 DEG C, and distillation time is 1h~12h；
Preferably, mixing phenyl trialkoxysilane, organic solvent and water described in above-mentioned preparation method, organic
The dosage of solvent is 1~8 times of monomer dosage (quality), and the dosage of water is 1~12 times of monomer dosage (quality)；
As more preferably selecting, the dosage of the organic solvent described in above-mentioned preparation method is the 2~6 of monomer dosage (quality)
Times, the dosage of water is 2~8 times of monomer dosage (quality)；
Preferably, acid catalyst described in above-mentioned preparation method step (2) is p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid,
One or more in nitric acid, acetic acid, cationic ion-exchange resin, the dosage of acid catalyst are the 5% of monomer dosage (quality)
~30%；
Preferably, the dosage of the organic solvent described in above-mentioned preparation method is used for the terminal hydroxy group phenyl polysiloxane added
Measure 4~20 times of (quality).
Preferably, terminal hydroxy group phenyl silicon of the dosage of the addition vinyl silanes described in above-mentioned preparation method for addition
The 5%~50% of resin demand (quality)；
Preferably, acid catalyst described in above-mentioned preparation method step (5) is p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid,
One or more in nitric acid, acetic acid, cationic ion-exchange resin, the dosage for adding acid catalyst are addition terminal hydroxy group phenyl silicon
Resin demand (quality) 1%~30%, as more preferably selecting, the dosage of acid catalyst is used to add terminal hydroxy group phenyl polysiloxane
Measure (quality) 2%~20%.
This patent uses phenyl trialkoxysilane, and for raw material, its hydrolysis reaction is compared with chlorosilanes such as phenyl trichlorosilanes
Class monomer is slow, is easy to be controlled its structure and molecular weight so that product composition is more uniform, and no gel produces, effectively
The light transmittance and yield that improve product；As catalyst be advantageous to that degree of branching height, sky is prepared using acids in addition
Between the big reinforcing filler of dimension.
Beneficial effect：The Vinylphenyl silicon resin prepared with the method for the present invention, has uniform space structure, can be
Encapsulating material after reinforcement provides three-dimensional crosslinked network, significantly improves the mechanical property of encapsulating material.Obtained vinyl benzene
The refraction index of base silicones is more than 1.55, light transmittance>95%, Spatial Dimension is big, and thermal stability is excellent, particularly suitable for
The reinforcement of LED encapsulation material, it is also possible to for other fluid sealants, casting glue and adhesive.
Embodiment
The present invention can be further illustrated by examples below, but embodiment is not the limit to the scope of the present invention
System.
Embodiment 1
20 parts of phenyltrimethoxysila,e, 50 parts of dimethylbenzene, deionized water 70 are added in the four-hole boiling flask dried to 250ml
Part, under nitrogen atmosphere, at 20 DEG C, quick stirring, hydrolysis 5h, 75 DEG C are warming up to, add 3.6 parts of concentrated hydrochloric acids
(37wt%), polycondensation reaction 10h, stop reaction, stratification, take upper oil phase, neutrality is washed to deionized water, will wash
To the neutral solution dissolved with resin product under nitrogen atmosphere, at 65 DEG C, 2h is distilled, distillation products therefrom is poured into culture dish
In, low-boiling-point substance is removed under 100 DEG C/- 0.1MPa, both obtains water white transparency product end hydroxy phenyl silicones, under nitrogen atmosphere,
10 parts of the terminal hydroxy group phenyl polysiloxane that gained will be prepared is added in the four-hole boiling flask that 250ml are dried, and adds 100 parts of toluene, and two
4 parts of methyl ethylene Ethoxysilane, 1h is stirred at 30 DEG C, adds 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 stop reaction, cooling, stir it is lower add in 3 parts of carbonic acid sodium powders and 0.5h, add 5 parts points
The stirring of son sieve is lower to dry 1h, and gained mixed solution is filtered, obtains the solution of water white transparency Vinylphenyl silicon resin, by gained
Solution distills 2h at 70 DEG C, and distillation products therefrom is poured into culture dish, low-boiling-point substance is removed under 80 DEG C/- 0.1MPa, you can
Final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5565, vinyl quality hundred is measured through chemical titration
Divide content 3.2%.
Embodiment 2
20 parts of phenyl triethoxysilane of addition, 50 parts of toluene in the four-hole bottle dried to 250ml, 160 parts of deionized water,
Under nitrogen atmosphere, quickly stir at 80 DEG C, hydrolysis 0.5h, be warming up to 75 DEG C, add 6 concentrated sulfuric acids (96wt%), polycondensation
8h is reacted, then stops reaction, stratification, takes upper oil phase, neutrality is washed to deionized water, the molten of neutrality will be washed to
The solution for having resin product under nitrogen atmosphere, at 20 DEG C, distills 12h, distillation products therefrom is poured into culture dish, 100
DEG C/- 0.1MPa under remove low-boiling-point substance, both water white transparency product end hydroxy phenyl silicones, under nitrogen atmosphere, by preparing
10 parts of the terminal hydroxy group phenyl polysiloxane obtained is added in the four-hole boiling flask that 250ml are dried, and adds 80 parts of dimethylbenzene, dimethylvinylsiloxy
3 parts of base oxethyl silane, 1h is stirred at 50 DEG C, add 1 part of concentrated nitric acid (69wt%), stir 1h at 50 DEG C, be warming up to 60
DEG C reaction 8h, then stops reaction, cooling, stir it is lower add in 2 parts of sodium acid carbonates, 2 parts of sodium hydrogen carbonate powders and 0.5h, add
5 parts of anhydrous calcium chloride stirrings are lower to dry 1h, and gained mixed solution is filtered, obtains the molten of water white transparency Vinylphenyl silicon resin
Liquid, resulting solution is distilled into 4h at 60 DEG C, distillation products therefrom is poured into culture dish, removed under 80 DEG C/- 0.1MPa low
Boil thing, you can final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5575, second is measured through chemical titration
Alkenyl weight/mass percentage composition 2.2%.
Embodiment 3
20 parts of phenyltrimethoxysila,e of addition, 50 parts of dimethylbenzene in the four-hole bottle dried to 250ml, 50 parts of isopropanol,
60 parts of deionized water, under nitrogen atmosphere, quickly stirred at 35 DEG C, hydrolysis 2h, be warming up to 80 DEG C, add 3 parts of cations
Exchanger resin, polycondensation reaction 12h, then stop reaction, stratification, take upper oil phase, neutrality is washed to deionized water,
By the solution dissolved with resin product for being washed to neutrality under nitrogen atmosphere, at 45 DEG C, 8h is distilled, distillation products therefrom is poured into
In culture dish, low-boiling-point substance is removed under 100 DEG C/- 0.1MPa, water white transparency product end hydroxy phenyl silicones is both obtained, in nitrogen
Under atmosphere, 10 parts of terminal hydroxy group phenyl polysiloxane for preparing gained is added in the four-hole boiling flask that 250ml is dried, adds positive fourth
80 parts of alcohol, 4 parts of divinyl tetramethyl disiloxane, 1h is stirred at 30 DEG C, 0.5g concentrated hydrochloric acids (37wt%) are added, 30
1h is stirred at DEG C, is warming up to 800 DEG C of reaction 6h, then stops reacting, cooling, stirring is lower to add 6 parts of sodium hydrogen carbonate powders neutralizations
0.5h, the lower dry 1h of 4 parts of anhydrous cupric sulfate stirrings is added, gained mixed solution is filtered, obtains water white transparency vinyl benzene
The solution of base silicones, 1h will be distilled at 100 DEG C of resulting solution, distillation products therefrom poured into culture dish, 80 DEG C/-
Low-boiling-point substance is removed under 0.1MPa, you can final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5560, through changing
Learn titration and measure vinyl weight/mass percentage composition 3.0%.
Embodiment 4
20 parts of phenyltrimethoxysila,e, 100 parts of isopropanol, deionized water 20 are added in the four-hole bottle dried to 250ml
Part, under nitrogen atmosphere, quickly stirred at 60 DEG C, hydrolysis 2h, be warming up to 75 DEG C, add 4 parts of acetic acid (99.5wt%), contracting
Poly- reaction 5h, then stops reaction, stratification, takes upper oil phase, neutrality is washed to deionized water, will be washed to neutrality
Dissolved with resin product solution under nitrogen atmosphere, at 65 DEG C, distill 2h, will distillation products therefrom pour into culture dish, 1
Low-boiling-point substance is removed under 00 DEG C/- 0.1MPa, both obtains water white transparency product end hydroxy phenyl silicones, under nitrogen atmosphere, will
10 parts of terminal hydroxy group phenyl polysiloxane for preparing gained is added in the four-hole boiling flask that 250ml is dried, and adds 20 parts of tetrahydrofuran,
4 parts of Vinyldimethylethoxysilane, 1h is stirred at 50 DEG C, add 2 parts of concentrated hydrochloric acids (37wt%), stirred at 50 DEG C
1h, be warming up to 60 DEG C of reaction 10h, then stop reaction, cooling, stir it is lower add in 5 parts of phosphoric acid sodium powders and 0.5h, add 5
Part molecular sieve stirring is lower to dry 1h, gained mixed solution is filtered, the toluene for obtaining water white transparency Vinylphenyl silicon resin is molten
Liquid, resulting solution is distilled into 2h at 70 DEG C, distillation products therefrom is poured into culture dish, removed under 80 DEG C/- 0.1MPa low
Boil thing, you can final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5545, second is measured through chemical titration
Alkenyl weight/mass percentage composition 3.21%.
Embodiment 5
10 parts of phenyltrimethoxysila,e, 10 parts of phenyl triethoxysilane, benzene are added in the four-hole bottle dried to 250ml
50 parts, 30 parts of deionized water, under nitrogen atmosphere, quickly stirred at 60 DEG C, hydrolysis 2h, be warming up to 65 DEG C, add 3.6 parts
P-methyl benzenesulfonic acid, polycondensation reaction 10h, then stop reaction, stratification, take upper oil phase, neutrality is washed to deionized water,
By the solution dissolved with resin product for being washed to neutrality under nitrogen atmosphere, at 65 DEG C, 2h is distilled, distillation products therefrom is poured into
In culture dish, low-boiling-point substance is removed under 100 DEG C/- 0.1MPa, water white transparency product end hydroxy phenyl silicones is both obtained, in nitrogen
Under atmosphere, 10 parts of terminal hydroxy group phenyl polysiloxane for preparing gained is added in the four-hole boiling flask that 250ml is dried, adds ethanol
200 parts, Vinyldimethylethoxysilane part, 1h is stirred at 30 DEG C, add 2 parts of p-methyl benzenesulfonic acid, stirred at 30 DEG C
1h, be warming up to 60 DEG C of reaction 7h, then stop reaction, cooling, stir it is lower add in 6 parts of sodium hydrogen carbonate powders and 0.5h, add
5 parts of molecular sieve stirrings are lower to dry 1h, and gained mixed solution is filtered, obtains the solution of water white transparency Vinylphenyl silicon resin,
Resulting solution is distilled into 2h at 70 DEG C, distillation products therefrom is poured into culture dish, low boiling is removed under 80 DEG C/- 0.1MPa
Thing, you can final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5578, ethene is measured through chemical titration
Base weight/mass percentage composition 3.65%.
Embodiment 6
Add 20 parts of phenyltrimethoxysila,e in the four-hole bottle dried to 250ml, 50 parts of ethanol, 50 parts of isopropanol go from
Son, 70 parts of water, under nitrogen atmosphere, are quickly stirred, hydrolysis 2h at 25 DEG C, are warming up to 90 DEG C, add 3 parts of cation exchanges
Resin, polycondensation reaction 10h, then stop reaction, stratification, take upper oil phase, neutrality is washed to deionized water, will wash
To the neutral solution dissolved with resin product under nitrogen atmosphere, at 65 DEG C, 2h is distilled, distillation products therefrom is poured into culture dish
In, low-boiling-point substance is removed under 100 DEG C/- 0.1MPa, both obtains water white transparency product end hydroxy phenyl silicones, under nitrogen atmosphere,
10 parts of terminal hydroxy group phenyl polysiloxane for preparing gained is added in the four-hole boiling flask that 250mi is dried, adds 80 parts of toluene, diformazan
5 parts of base vinylethoxysilane, 1h is stirred at 30 DEG C, add 1 part of concentrated hydrochloric acid (37wt%), 1h is stirred at 30 DEG C, risen
Then temperature stops reaction to 70 DEG C of reaction 6h, cooling, stir it is lower add in 6 parts of sodium hydrogen carbonate powders and 0.5h, add 5 parts points
The stirring of son sieve is lower to dry 1h, and gained mixed solution is filtered, obtains the solution of water white transparency Vinylphenyl silicon resin, by gained
Solution distills 2h at 70 DEG C, and distillation products therefrom is poured into culture dish, low-boiling-point substance is removed under 80 DEG C/- 0.1MPa, you can
Final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5559, vinyl quality hundred is measured through chemical titration
Divide content 2.85%.
Embodiment 7
20 parts of phenyltrimethoxysila,e, 30 parts of dimethylbenzene, 30 parts of toluene, different is added in the four-hole bottle dried to 250ml
15 parts of propyl alcohol, 70 parts of deionized water, under nitrogen atmosphere, are quickly stirred, hydrolysis 2h at 55 DEG C, are warming up to 75 DEG C, are added
2.5 parts of concentrated hydrochloric acids (37wt%), polycondensation reaction 12h, then stop reaction, stratification, upper oil phase is taken, with deionized water water
Neutrality is washed till, at 75 DEG C, 2h is distilled, by distilling by the solution dissolved with resin product for being washed to neutrality under nitrogen atmosphere
Obtain product to pour into culture dish, low-boiling-point substance is removed under 100 DEG C/- 0.1MPa, both obtain water white transparency product end hydroxy phenyl silicon tree
Fat, under nitrogen atmosphere, 10 parts of terminal hydroxy group phenyl polysiloxane for preparing gained is added in the four-hole boiling flask that 250ml is dried, then
50 parts of toluene is added, 0.5 part of Vinyldimethylethoxysilane, 1h is stirred at 45 DEG C, adds 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 stop reaction, cooling, stirring is lower to add 6 parts of carbonic acid
In hydrogen sodium powder and 0.5h, add that 5 parts of molecular sieves stirrings are lower to dry 1h, gained mixed solution is filtered, obtains water white transparency second
The solution of alkenyl phenyl polysiloxane, resulting solution is distilled into 2h at 70 DEG C, distillation products therefrom is poured into culture dish, 80
DEG C/- 0.1MPa under remove low-boiling-point substance, you can final product Vinylphenyl silicon resin is made.Products therefrom nD25=1.5576,
Vinyl weight/mass percentage composition 2.19% is measured through chemical titration.
Claims (9)
- A kind of 1. preparation method of phenyl polysiloxane, it is characterised in that：(1) phenyl trialkoxysilane, organic solvent and water are mixed, stirs under nitrogen atmosphere, reaction is hydrolyzed；(2) after reaction terminates, acid catalyst is added, carries out polycondensation reaction；(3) after reaction terminates, stand, layering, take upper oil phase, oil phase is washed to neutrality with 25 DEG C~75 DEG C deionized waters, Obtain the organic solution of terminal hydroxy group phenyl polysiloxane；(4) organic solution of gained terminal hydroxy group phenyl polysiloxane is distilled, removes organic solvent, then -0.1MPa~ 0.085MPa, at 80 DEG C~120 DEG C, dry 6h~12h, you can obtain terminal hydroxy group phenyl polysiloxane；(5) obtained terminal hydroxy group phenyl polysiloxane is dissolved in organic solvent, under nitrogen atmosphere, to terminal hydroxy group phenyl polysiloxane Organic solution in add vinyl silanes, stir, add acid catalyst under stirring into mixed solution, further promote Enter reaction；(6) reaction cools down after terminating, and under stirring, adds strong base-weak acid salt and is neutralized, stir 0.5h~4h, then add drying Agent is removed water, and stirs 0.5h~2h, and the mixed solution for neutralizing, having dried is filtered, distillation, removes most of organic solvent, vacuum Dry and remove low-boiling-point substance, you can final product is prepared.
- 2. preparation method according to claim 1, it is characterised 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 ether, ethanol, isopropanol, positive fourth One or more in alcohol, tetrahydrofuran, benzene,toluene,xylene；Described mixes phenyl trialkoxysilane, organic solvent and water, and reaction, the temperature of hydrolysis are hydrolyzed under stirring Spend for 20 DEG C~80 DEG C, the time of hydrolysis is 0.5h~5h；Addition acid catalyst described in step (2), the acid catalyst of addition is p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid, nitre One or more in acid, acetic acid, cationic ion-exchange resin；Addition acid catalyst described in step (2) carries out condensation reaction, and the temperature of condensation reaction is 30 DEG C~100 DEG C, contracting The time for closing reaction is 3h~12h；Most of organic solvent is distilled off described in step (4), vapo(u)rizing temperature is 20 DEG C~100 DEG C, distillation time 1h ~12h；Described is dissolved in terminal hydroxy group phenyl polysiloxane in organic solvent, organic solvent be ether, ethanol, isopropanol, n-butanol, One or more in tetrahydrofuran, benzene,toluene,xylene；In the organic solution of the described phenyl polysiloxane that vinyl silanes are added to terminal hydroxy group end-blocking, vinyl silanes are diethyl Alkenyl tetramethyl disiloxane ((ViMe2Si)2) or Vinyldimethylethoxysilane (ViSiMe O2(OEt) one kind) or It is several, wherein, Vi is vinyl；Stirred in the organic solution of the described phenyl polysiloxane that vinyl silanes are added to terminal hydroxy group end-blocking, stirring when Between be 0.5h~4h, the temperature of stirring is 20 DEG C~80 DEG C；Acid catalyst is added in the organic solution of the described phenyl polysiloxane blocked to the terminal hydroxy group for adding vinyl silanes, The species of acid catalyst is the one or more in p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, cationic ion-exchange resin；Described adds acid catalyst into the organic solution for the terminal hydroxy group phenyl polysiloxane for adding vinyl silanes, and stirring is equal Even, mixing 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 are 40 DEG C~100 DEG C, time of reaction for 2h~ 15h；Under described stirring, add strong base-weak acid salt and neutralized, the strong base-weak acid salt of addition is sodium carbonate, sodium acetate, phosphoric acid One or more in sodium, sodium acid carbonate；Described addition drier removes residual moisture, and drier used is anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous slufuric acid One or more in copper, molecular sieve；Described is distilled off most of organic solvent, and vapo(u)rizing temperature is 20 DEG C~100 DEG C, and distillation time is 1h~12h.
- 3. preparation method according to claim 1, it is characterised in that：It is described by phenyl trialkoxysilane, You Jirong Agent and water mixing, the dosage of organic solvent are 1~8 times of phenyl trialkoxysilane quality, and the dosage of water is the alcoxyl of phenyl three 1~12 times of base silane quality.
- 4. preparation method according to claim 3, it is characterised in that：The dosage of described organic solvent is the alcoxyl of phenyl three 2~6 times of base silane quality, the dosage of water are 2~8 times of phenyl trialkoxysilane quality.
- 5. preparation method according to claim 1, it is characterised in that：The dosage of acid catalyst described in step (2) For the 5%~30% of phenyl trialkoxysilane quality.
- 6. preparation method according to claim 1, it is characterised in that：The dosage of organic solvent described in step (5) is 4~20 times of the terminal hydroxy group phenyl polysiloxane quality of addition.
- 7. preparation method according to claim 1, it is characterised in that：The dosage of described addition vinyl silanes is addition Terminal hydroxy group phenyl polysiloxane quality 5%~50%.
- 8. preparation method according to claim 2, it is characterised in that：The dosage of acid catalyst described in step (5) To add the 1%~30% of terminal hydroxy group phenyl polysiloxane quality.
- 9. preparation method according to claim 1, it is characterised in that the dosage of described acid catalyst is addition end hydroxyl The 2%~20% of base phenyl polysiloxane quality.
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 CN104892939A (en) | 2015-09-09 |
| CN104892939B true 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) |
Families Citing this family (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 |
| 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 |
| 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 |
| 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 |
| KR20220065782A (en) * | 2019-09-03 | 2022-05-20 | 다우 실리콘즈 코포레이션 | Method for preparing 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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Family Cites Families (2)
| 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 |
| JP2013023625A (en) * | 2011-07-22 | 2013-02-04 | Nagase Chemtex Corp | Resin composition for optical component molding |
-
2014
- 2014-03-05 CN CN201410087951.7A patent/CN104892939B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| "苯基三甲氧基硅烷水解动力学研究";姜亚，等;《有机硅材料》;20111231;第25卷(第4期);第225-228页 * |
| "高折射率苯基乙烯基透明硅树脂的制备与固化性能";汪晓璐，等;《化工新型材料》;20130430;第41卷(第4期);第65-68页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892939A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892939B (en) | A kind of preparation method of phenyl polysiloxane | |
| CN104974349B (en) | A kind of preparation method of silicones | |
| CN101475689B (en) | Preparation of methyl phenyl vinyl silicon resin | |
| CN105400446B (en) | A kind of high refractive index LED liquid casting glue tackifier and preparation method thereof | |
| CN102898650B (en) | MTQ silicon resin with T-chain unit containing phenyl and preparation method thereof | |
| CN104710621B (en) | Substrate bonding phenyl vinyl polysiloxane and its preparation method and application | |
| CN103342816B (en) | A kind of organic siliconresin and curable organopolysiloxane composition and application | |
| CN104892942B (en) | A kind of additional organosilicon rubber tackifier and preparation method | |
| CN104004491B (en) | A kind of LED ultraviolet curing organic silicon packaging plastic and preparation method thereof | |
| CN101891893B (en) | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED | |
| CN102898651B (en) | Preparation method of vinylphenyl silicon resin for LED (light-emitting diode) packaging | |
| CN103319692B (en) | A kind of high performance organo-silicon epoxy material and preparation method thereof and application | |
| CN103012798B (en) | Preparation method of methyl phenyl vinyl silicone resin | |
| CN102898648B (en) | Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof | |
| CN104073215A (en) | Preparation method for nano silicon dioxide modified organic silicon sealant for packaging of light emitting diode (LED) | |
| CN102888001B (en) | Vinylphenyl silicon resin | |
| CN104877138A (en) | Silicon resin with adhesive properties and preparation method of silicon resin | |
| CN101323667A (en) | Preparation of methyl vinyl MQ resin for LED encapsulated strengthening | |
| CN104955900B (en) | Solidification compound and its solidfied material comprising polysiloxanes | |
| CN106751893A (en) | A kind of refractive power LED encapsulation add-on type liquid silicon rubbers high and preparation method thereof | |
| CN106751346A (en) | The synthetic method of fluorochemical monomer modified organosilicon encapsulating material | |
| CN104892940B (en) | A kind of preparation method of siloxanes | |
| CN103834178B (en) | Organic silicon resin as well as preparation method and application thereof | |
| CN104292465A (en) | Epoxy-modified phenyl vinyl silicon resin and preparation method thereof | |
| CN104449551A (en) | LED packaging silica gel with high refractive index and yellowing resistance |
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 |