CN102863623A - Process for preparing dendritic polymer modified high refractive index organic silicon resin - Google Patents
Process for preparing dendritic polymer modified high refractive index organic silicon resin Download PDFInfo
- Publication number
- CN102863623A CN102863623A CN2012103983068A CN201210398306A CN102863623A CN 102863623 A CN102863623 A CN 102863623A CN 2012103983068 A CN2012103983068 A CN 2012103983068A CN 201210398306 A CN201210398306 A CN 201210398306A CN 102863623 A CN102863623 A CN 102863623A
- Authority
- CN
- China
- Prior art keywords
- silicon
- branch
- polymer
- shape polymer
- ethylene base
- 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
Images
Abstract
The invention belongs to the technical field of organic silicon high polymer resin and discloses a dendritic polymer modified high refractive index organic silicon resin material which is used for packaging light emitting diodes and a preparation process of the material. The preparation process comprises the steps of conducting thermocuring on a dendritic polymer A and an organic silicon polymer B which contains silico ethenyl groups under the effect of a catalyst, or conducting thermocuring on a dendritic polymer A' and an organic silicon polymer B' which contains silicon-hydrogen groups under the effect of the catalyst, so that organic silicon resin is obtained, wherein the dendritic polymer A contains, by mole, 75-80% of silicon phenyl groups and 5-10% of silicon-hydrogen groups, and the dendritic polymer A' contains, by mole, 75-80% of silicon phenyl groups and 5-10% of silico ethenyl groups. The refractive index of the resin is higher than 1.58, and simultaneously, when the thickness is 1cm, the transmittance at a wavelength of 400nm exceeds 95%.
Description
Technical field
The invention belongs to organosilicon macromolecule resin technology field, particularly the organosilicon material of large-power light-emitting diodes (LED) encapsulation with high refractive index.
Background technology
Photodiode (Light Emitting Diode, be called for short LED) be that a class can directly be the luminous element of luminous energy with electric energy conversion, when namely applying forward current in the place of semi-conductor p-n junction, can send the light emitting semiconductor device of visible light, infrared light, UV-light.Because series of characteristics such as it has that operating voltage is low, current consumption is little, luminous efficiency is high, emission response time extremely short, photochromic pure, sound construction, shock resistance, vibration resistance, stable and reliable for performance, lightweight, volume is few and cost is low, thereby be widely used and the development of advancing by leaps and bounds is expected to become lighting source of new generation.Decades in the past, Resins, epoxy is because having good mechanical property, high transparent and the characteristics such as low-cost and be widely used as the LED packaged material.But under the current state of the art, great power LED can only be converted into luminous energy with the about power input of 5%-10%, and remaining is converted into heat energy.Too much heat can be to chip and packaged material injury on every side.Along with improving constantly and the development of white light LEDs of LED brightness and power, traditional transparent epoxy resin can not satisfy its encapsulation requirement at aspects such as the perviousness of short-wavelength light, light fastness aging, temperature tolerance, resistance to sudden heating.Therefore, in the encapsulation of great power LED, must seek other alternative package material.
Organosilyl main chain is that the Si-O-Si side group is methyl, whole molecular chain in the shape of a spiral, this special heterochain molecular structure is given its many excellent properties, as: Si-O bond distance and bond angle are all relatively large, and key is little to the steric hindrance that side group rotates, and segment is very submissive, thereby has preferably resistance to low temperature, the Si-O bond energy is relatively high simultaneously, makes it have preferably thermostability and weathering resistance, can (50-250 ℃) work in wide temperature range; Low surface energy (21-22mN/m) makes it have good hydrophobicity; Low surface tension and kindliness can increase the rate of permeation of polymeric system.These characteristics makes that the organosilicon transmittance is high, Heat stability is good, ultraviolet resistance is strong, internal stress is little, water absorbability is low, and performance obviously is better than Resins, epoxy, becomes the ideal chose of LED packaged material.Along with appearance and the development of high-light long-life white light LEDs and Lead-free Reflow Soldering technique, organosilicon LED packaged material receives domestic and international investigator's concern, becomes current LED packaged material new development trend and study hotspot.
Along with to how improving the further investigation of LED device luminous efficiency, to also having proposed Secretary as refractive index of the organosilicon material of packaged material etc.Because the chip specific refractory power is 2-4 approximately, such as GaN (n=2.5) far above Resins, epoxy or silicone resin packaged material specific refractory power (n=1.4-1.6), refractive index difference is excessive to cause total reflection to occur, light reflection is returned chip internal and can't effectively derive, the specific refractory power that therefore improves packaged material can reduce the generation of total reflection.For example, when the specific refractory power of packaged material was promoted to 1.7 from 1.5 the time, light had taken out improved efficiency nearly 30%; Therefore, refractive index difference reaches and is lifted out light transmittance efficiency between the specific refractory power reduction chip of lifting packaged material and packaged material, is present LED packaged material research and development main shaft.
Summary of the invention
In order to overcome existing silicone resin because can cause the deficiency of resin hardness increase when introducing the silicon phenyl, primary and foremost purpose of the present invention is to provide a kind of preparation method of branch-shape polymer modification high refractive index silicone resin.
The silicone resin that provides a kind of aforesaid method to prepare is provided.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of branch-shape polymer modification high refractive index silicone resin, comprise following operation steps: branch-shape polymer A and the organosilicon polymer B that contains silico ethylene base group are carried out thermofixation under catalyst action, or branch-shape polymer A ' and the organosilicon polymer B ' that contains silicon-hydrogen group carried out thermofixation under catalyst action, obtain silicone resin; Described branch-shape polymer A contains the silicon phenyl group of molar percentage 75～80% and the silicon-hydrogen group of molar percentage 5～10%; Described branch-shape polymer A ' contains 75～80% silicon phenyl groups of molar percentage and 5～10% silico ethylene base groups of molar percentage.
The consumption of described branch-shape polymer A and the organosilicon polymer B that contains silico ethylene base group is 1:2～2:1 with recently the calculating of amount of substance of silico ethylene base group that curing reaction occurs and silicon-hydrogen group, and described branch-shape polymer A ' and the consumption that contains the organosilicon polymer B ' of silicon-hydrogen group are the silico ethylene base group that reacts with the ratio of the amount of substance of silicon-hydrogen group is 1:2～2:1; The consumption of described catalyzer is branch-shape polymer A and the organosilicon polymer B gross weight that contains silico ethylene base group, or branch-shape polymer A ' and the 5～20ppm that contains the organosilicon polymer B ' gross weight of silicon-hydrogen group; The temperature of described thermofixation is 120～150 ℃, and be 2～4h set time; Described branch-shape polymer A is prepared by carrying out addition reaction of silicon with hydrogen by branch-shape polymer C and the triphenyl vinyl silanes that end contains silicon-hydrogen group, and the amount of substance of silico ethylene base group is 95～98% of silicon hydrogen group in the reaction raw materials.
The branch-shape polymer C that described end contains silicon-hydrogen group is prepared from accordance with the following methods:
(1) addition reaction: diphenyl silane, vinyl trichloro silane and chloroplatinic acid catalyst are mixed the rear 2～4h that react under 120～150 ℃ under protection of inert gas; Silicon hydrogen base in the described diphenyl silane and vinyl trichloro silane equimolar ratio; The consumption of described chloroplatinic acid catalyst is 5～50ppm of diphenyl silane and vinyl trichloro silane gross weight;
(2) reduction reaction: under protection of inert gas, add the diethyl ether solution with the lithium aluminum hydride of chlorine equimolar amount in the diethyl ether solution of step (1) products therefrom, and at 20～50 ℃ of lower stirring reaction 2～8h, after the reaction product is poured into water, use the separating funnel separatory, distillation, remove excessive moisture, vacuum is preserved, obtain 2 generation end contain the branch-shape polymer of silicon-hydrogen group;
(3) branch-shape polymer that step (2) gained 2 generation end is contained silicon-hydrogen group carries out the cyclical operation of step (1) and (2) again, obtains the branch-shape polymer C that a series of ends contain silicon-hydrogen group.
The described organosilicon polymer B that contains silico ethylene base group prepares in accordance with the following methods:
(1) hydrolytic condensation: the vinyl silanes of the chlorosilane of molar percentage 70～80% and molar percentage 10～20% poured in 0 ℃ the methyl alcohol of molar percentage 10～20%, mix the backward mixed solution of first alcohol and water that wherein drips extremely without till the γ-ray emission, dropwise the rear separating funnel separatory of using, the distillation desolventizing gets hydrolysis condensation product; The volume ratio of first alcohol and water is 1:1 in the mixed solution of described first alcohol and water;
(2) alkali condensation: add in the hydrolysis condensation product molar percentage 0.05～0.1% alkali, at 100～140 ℃ of lower reaction 8～12h; Products therefrom is extremely neutral with toluene dissolving and water repetitive scrubbing, and unreacted monomer and low-boiling-point substance are removed in underpressure distillation again, obtain containing the organosilicon polymer B of silico ethylene base group.
The described chlorosilane of step (1) is trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, diethyl dichlorosilane, ethyl trichlorosilane, tetrachloro silicane, diphenyl dichlorosilane, phenyl-trichloro-silicane or tri-phenyl chloride; Described vinyl silanes is methyl ethylene dichlorosilane, divinyl dichlorosilane, vinyl trichloro silane, trivinyl chlorosilane or dimethyl divinyl chlorosilane; The described alkali of step (2) is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood.
The branch-shape polymer C ' that described branch-shape polymer A ' contains silico ethylene base group by end carries out addition reaction of silicon with hydrogen with triphenyl hydrogen base silane and prepares, and the amount of substance of silicon hydrogen group is 95～98% of silico ethylene base group in the reaction raw materials.
The branch-shape polymer C ' that described end contains silico ethylene base group is prepared from accordance with the following methods:
(1) addition reaction: after dimethyl divinyl silane, trichlorosilane and chloroplatinic acid catalyst mixed under protection of inert gas at 120～150 ℃ of lower reaction 2～4h; Silico ethylene base and trichlorosilane equimolar ratio in the described dimethyl divinyl silane; The consumption of described chloroplatinic acid catalyst is 5～50ppm of dimethyl divinyl silane and trichlorosilane gross weight;
(2) reduction reaction: under protection of inert gas, in step (1) products therefrom, add tetrahydrofuran (THF), be cooled to 0～5 ℃, diethyl ether solution minute 8～10 addings in 3h with vinyl bromination magnesium, reaction mixture at room temperature continues to stir 24h, adds 0～5 ℃ of ammonium chloride solution and makes reaction terminating; Mixture is washed respectively 2～3 times with tetrahydrofuran (THF) and normal hexane successively, and separatory is got organic phase, and organic phase carried out filtering out insolubles again, and low-boiling-point substance is removed in distillation, obtain 2 generation end contain the branch-shape polymer of silico ethylene base group; Described vinyl bromination magnesium and step (1) products therefrom equimolar ratio;
(3) branch-shape polymer that step (2) gained 2 generation end is contained silico ethylene base group carries out the cyclical operation of step (1) and (2) again, obtains the branch-shape polymer C ' that a series of ends contain silico ethylene base group.
The described organosilicon polymer B ' that contains silicon-hydrogen group prepares in accordance with the following methods:
(1) hydrolytic condensation: the silicon hydride chlorid that contains of the chlorosilane of molar percentage 70～80% and molar percentage 10～20% is poured in 0 ℃ the methyl alcohol of molar percentage 10～20%, drip again the mixed solution of first alcohol and water after mixing, extremely without till the γ-ray emission, dropwise the rear separating funnel separatory of using, the distillation desolventizing gets hydrolysis condensation product; The volume ratio of first alcohol and water is 1:1 in the mixed solution of described first alcohol and water;
(2) sour condensation: the strong acid type macroporous ion exchange resin that adds molar percentage 1～2% in the hydrolysis condensation product is made catalyzer, at 70～120 ℃ of lower reaction 6～8h; Products therefrom is extremely neutral with toluene dissolving and water repetitive scrubbing, and unreacted monomer and low-boiling-point substance are removed in underpressure distillation again, obtain containing the organosilicon polymer B ' of silicon-hydrogen group.
The described chlorosilane of step (1) is trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, diethyl dichlorosilane, ethyl trichlorosilane, tetrachloro silicane, diphenyl dichlorosilane, phenyl-trichloro-silicane or tri-phenyl chloride; The described silicon hydride chlorid that contains is dichlorosilane, diphenyl chlorosilane, diphenyl dichlorosilane, a chlorosilane or trichlorosilane;
The silicone resin specific refractory power that aforesaid method prepares 〉=1.58; When described silicone resin material is 1cm at thickness of sample, at the transmitance of 400 nanometer wave strong points 〉=95%.
Principle of the present invention is: introduce the refractive index that the silicon phenyl can effectively improve silicone resin in structure, this also is the unique method that obtains at present the high index silicone resin simultaneously.Studies show that, specific refractory power is reached more than 1.55, phenyl content (phenyl and all substituent mol ratios) need to reach more than 55%.But, so high phenyl content meeting so that silicone resin become especially firmly and affect other mechanical properties.Branch-shape polymer has regular, exquisite perfect structure owing to this body structure is highly branched, and high algebraically is spherical in shape, and has nano-grade size.Therefore, branch-shape polymer can show good solubility, low viscosity.Also can show lower viscosity even the content of phenyl is very high, therefore, by introducing a large amount of phenyl in branch-shape polymer, and then this branch-shape polymer is incorporated in the silicone resin is the effective ways that obtain the high refractive index silicone resin.
The present invention compared with prior art has following advantage and beneficial effect: the present invention is simple to operate, pollutes little; Introduce a large amount of silicon phenyl, making the refractive index of resin become large, but can not cause the deficiencies such as resin hardness increase simultaneously, can satisfy well the requirement of the packaged material of great power LED.
Description of drawings
Fig. 1 is the structural representation of branch-shape polymer A.
Fig. 2 is the structural representation of branch-shape polymer A '.
Embodiment
Below in conjunction withspecific examples and drawings the present invention is described in further detail, but implementation method of the present invention is flexible, is not limited only to this routine described concrete operations mode.
Embodiment 1:
(1) branch-shape polymer A
1Synthetic
A, 75.2g diphenyl silane, 132.4g vinyl trichloro silane and 2mg Platinic chloride are stirred logical N in the 2L four-hole bottle
2Protection is cooled to room temperature after then placing 120 ℃ of oil cauldrons to stir 5h; In system, add ether, and constantly stir, make it abundant dissolving, continue logical N
2Protection makes temperature remain on 35 ℃, slowly drips the 106.4g lithium aluminum hydride with constant pressure funnel and form solution in ether; Drip off rear continuation reaction 5h; Reactant is poured into water removes unreacted reactant, separatory is got organic layer, and then underpressure distillation is removed moisture and namely obtained the dendrimer C that first-generation end is silicon-hydrogen group
1
B, above-mentioned gained first-generation end is the dendrimer C of silicon-hydrogen group
1In the 2L four-hole bottle, stir logical N with 458.4g triphenyl vinyl silanes and 4mg Platinic chloride
2Then protection places 120 ℃ of oil cauldrons to stir to be cooled to room temperature behind the 5h namely to obtain branch-shape polymer A
1
First-generation end is the dendrimer C of silicon-hydrogen group
1Carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:1.06 (4H), 1.50 (4H), 4.93 (6H), 7.37 (4H), 7.46 (4H), 7.55 (2H) .IR (KBr, cm
-1): 2925,2870,2580,1632,1589,1568,1485,1470,1428,1125, can determine that first-generation end is the dendrimer C of silicon-hydrogen group
1Structural formula as follows:
To branch-shape polymer A
1Carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:1.05 (12H), 1.50 (12H), 4.92 (2H), 7.37-7.60 (70H) .IR (KBr, cm
-1): 2924,2870,2578,1633,1590,1568,1480,1470,1428,1125, can determine branch-shape polymer A
1Structural formula as follows:
(2) polymer B is synthetic:
20g methyl ethylene dichlorosilane monomer, 100g diphenyl dichlorosilane and 20g divinyl dichlorosilane be dissolved in the 100g methyl alcohol form mixed solution, mixed solution joined (comprised 100g methyl alcohol and 400g water) in the methanol-water solution in the mixed solution of 2L there-necked flask and constantly stir, the maintenance temperature is room temperature; Dropwise rear separatory, get organic layer, then water is washed till neutrality with organic layer.Underpressure distillation except anhydrate, methyl alcohol and unreacted reactant, obtain prepolymer.Prepolymer is poured in the there-necked flask again, added 0.1gNaOH post-heating to 120 ℃ reaction 10h.Product is extremely neutral with toluene dissolving and water repetitive scrubbing.Unreacted monomer and low-boiling-point substance are removed in underpressure distillation, obtain polymer B.Polymer B is carried out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.19 (3H), 5.17 (3H), 5.3 (3H), 5.42 (3H), 7.37 (12H), 7.46 (12H), 7.55 (6H) .IR (KBr, cm
-1): 2962,2870,1590,1568,1480,1410,1260,1089, can determine that the structural formula of polymer B is as follows:
(3) with branch-shape polymer A
1With the polymer B component in molar ratio the 1:1 ratio mix (since the preparation A
1The time added Platinic chloride, therefore do not need to add again catalyzer), then row's bubble is injected in the mould of 10 * 50 * 50mm, then 70 ℃ of lower curing at 150 ℃ of insulation 2h, can obtain water white silica gel piece.The specific refractory power of test silicon film is that 1.580,400nm wavelength transmitance is 95%.Organic silica gel in silica obtained has structure as shown in Figure 1, and wherein middle solid head is comprised of following structural formula:
Wherein, n is natural number.
Embodiment 2:
(1) branch-shape polymer A
2Synthetic
Be the dendrimer C of silicon-hydrogen group with first-generation end
1Replace diphenyl silane, repeat embodiment 1 step a, obtain the dendrimer C that s-generation end is silicon-hydrogen group
2C
2React under the catalysis of Platinic chloride with the triphenyl vinyl silanes again and make branch-shape polymer A
2S-generation end is the dendrimer C of silicon-hydrogen group
2Carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:1.06 (4H), 1.50 (4H), 4.93 (6H), 7.37 (4H), 7.46 (4H), 7.55 (2H) .IR (KBr, cm
-1): 2925,2870,2580,1632,1589,1568,1485,1470,1428,1125, can determine that s-generation end is the dendrimer C of silicon-hydrogen group
2Structural formula as follows:
To branch-shape polymer A
2Carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:1.05 (12H), 1.50 (12H), 4.92 (2H), 7.37-7.60 (70H) .IR (KBr, cm
-1): 2924,2870,2578,1633,1590,1568,1480,1470,1428,1125, can determine branch-shape polymer A
2Structural formula as follows:
(2) polymer B is synthetic
Synthetic and the embodiment 1 of polymer B is just the same.
(3) with branch-shape polymer A
2With the B component in molar ratio the 1:1 ratio mix (since the preparation A
2The time added Platinic chloride, therefore do not need to add again catalyzer), then row's bubble is injected in the mould of 10 * 50 * 50mm, then 70 ℃ of lower curing at 150 ℃ of insulation 2h, can obtain water white silica gel piece.Test silicon film specific refractory power is that 1.582,400nm wavelength transmitance is 96%.Organic silica gel in silica obtained has structure as shown in Figure 1, and wherein middle solid head is comprised of following structural formula:
Wherein, n is natural number.
Embodiment 3:
(1) branch-shape polymer A
3Synthetic
Be the dendrimer C of silicon-hydrogen group with s-generation end
2Replace diphenyl silane, repeat embodiment 1 step a, obtain the dendrimer C that third generation end is silicon-hydrogen group
3C
3React under the catalysis of Platinic chloride with the triphenyl vinyl silanes again and make branch-shape polymer A
3Third generation end is the dendrimer C of silicon-hydrogen group
3Carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:1.06 (4H), 1.50 (4H), 4.93 (6H), 7.37 (4H), 7.46 (4H), 7.55 (2H) .IR (KBr, cm
-1): 2925,2870,2580,1632,1589,1568,1485,1470,1428,1125, can determine that third generation end is the dendrimer C of silicon-hydrogen group
3Structural formula as follows:
To branch-shape polymer A
3Carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:1.05 (12H), 1.50 (12H), 4.92 (2H), 7.37-7.60 (70H) .IR (KBr, cm
-1): 2924,2870,2578,1633,1590,1568,1480,1470,1428,1125, can determine branch-shape polymer A
3Structural formula as follows:
(2) polymer B is synthetic
Synthetic and the embodiment 1 of polymer B is just the same.
(3) with dendrimer A
3With the polymer B component in molar ratio 1:1 mix (since the preparation A
3The time added Platinic chloride, therefore do not need to add again catalyzer), then row's bubble is injected in the mould of 10 * 50 * 50mm, then 70 ℃ of lower curing at 150 ℃ of insulation 2h, can obtain water white.The specific refractory power of test silicon film is that 1.585,400nm wavelength transmitance is 96%.Organic silica gel in silica obtained has structure as shown in Figure 1, and wherein middle solid head is comprised of following structural formula:
Wherein, n is natural number.
Embodiment 4:
(1) branch-shape polymer A
1' synthetic
A, 46.4g dimethyl divinyl silane, 112g trichlorosilane and 2mg Platinic chloride are stirred logical N in the 2L four-hole bottle
2Protection is cooled to room temperature after then placing 120 ℃ of oil cauldrons to stir 5h; Add tetrahydrofuran (THF) in above-mentioned reaction product under protection of inert gas, be cooled to 0 ℃, with diethyl ether solution minute three addings in 3h of 314.4g vinyl bromination magnesium, reaction mixture at room temperature continues to stir 24h again.Add 0 ℃ of NH
4The Cl(saturated aqueous solution) makes reaction terminating.Water is used tetrahydrofuran (THF) and normal hexane washed twice successively, and organic phase carried out filtering out insolubles, and low-boiling-point substance is removed in distillation.Obtain end and contain silico ethylene base group (Si-CH
2=CH
2) branch-shape polymer C
1'.
B, C
1' mix and add the 4mg Platinic chloride with the 416g tri-phenyl-silane again and in the 2L four-hole bottle, stir, logical N
2Then protection places 120 ℃ of oil cauldrons to stir to be cooled to behind the 5h room temperature namely to obtain end and contains silicon phenyl group and silico ethylene base group (Si-CH
2=CH
2) branch-shape polymer A
1'.The dendrimer C that first-generation end is contained silico ethylene base group
1' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.21 (6H), 0.7 (8H), 1.29 (12H), 5.04 (12H), 5.70 (6H) .IR (KBr, cm
-1): 3020,2960,2925,2870,2850,16301470,1380, can determine that first-generation end is the dendrimer C of silicon-hydrogen group
1' structural formula as follows:
To branch-shape polymer A
1' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.21 (6H), 0.7 (16H), 1.29 (4H), 1.5 (8H), 5.04 (4H), 5.70 (2H), 7.37-7.55 (60H) .IR (KBr, cm
-1): 3020,2960,2925,2870,2850,1630,1590,1568,14801470,1380, can determine branch-shape polymer A
1' structural formula as follows:
(2) polymer B ' synthetic
Make temperature drop to 0 ℃ with ice bath 101g dichlorosilane, 222.5g diphenyl chlorosilane, 20g diphenyl dichlorosilane, the mixed solution of 10g one chlorosilane in 100g methyl alcohol, join again afterwards and (comprise 100g methyl alcohol and 400g water) in the methanol-water solution in the mixed solution of 2L there-necked flask and constantly stir.The acid that reaction produces absorbs with alkali, keeps dripping in the ice bath, dropwises rear continuation and stirs 2h, and separatory is got organic layer afterwards, and then water is washed till neutrality with organic layer.Underpressure distillation except anhydrate, methyl alcohol and unreacted reactant, obtain prepolymer.The prepolymer that obtains is poured in the there-necked flask again, to wherein adding 2g strong acid type macroporous ion exchange resin, at 90 ℃ of lower reaction 8h.Product is extremely neutral with toluene dissolving and water repetitive scrubbing.Unreacted monomer and low-boiling-point substance are removed in underpressure distillation, obtain polymer B '.To polymer B ' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:4.93 (26H), 7.37 (12H), 7.46 (12H), 7.55 (6H) .IR (KBr, cm
-1): 2962,2903,2165,1590,1568,1480,1411,1261,1089, can determine polymer B ' structural formula as follows:
(3) with branch-shape polymer A
1' and polymer B ' component in molar ratio 1:1 mixes (because preparation A
1' time added Platinic chloride, therefore do not need to add again catalyzer), then row's bubble is injected in the mould of 10 * 50 * 50mm, then 70 ℃ of lower curing at 150 ℃ of insulation 2h, can obtain water white silica gel piece.The specific refractory power of test silicon film is 1.581, is 95% in 400nm wavelength transmitance.Organic silica gel in silica obtained has structure as shown in Figure 2, and wherein middle solid head is comprised of following structural formula:
Wherein, n is natural number.
Embodiment 5:
(1) branch-shape polymer A
2' synthetic
Be silico ethylene base group (Si-CH with first-generation end
2=CH
2) dendrimer C
1' replace dimethyl divinyl silane, repeat embodiment 4 step a, obtain s-generation end and be silico ethylene base group (Si-CH
2=CH
2) dendrimer C
2'; C
2' react under the catalysis of Platinic chloride with tri-phenyl-silane again and make end and contain silicon phenyl group and silico ethylene base group (Si-CH
2=CH
2) branch-shape polymer A
2'.The dendrimer C that s-generation end is contained silico ethylene base group
2' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.21 (6H), 0.7 (8H), 1.29 (12H), 5.04 (12H), 5.70 (6H) .IR (KBr, cm
-1): 3020,2960,2925,2870,2850,16301470,1380, can determine that s-generation end is the dendrimer C of silicon-hydrogen group
2' structural formula as follows:
To branch-shape polymer A
2' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.21 (6H), 0.7 (16H), 1.29 (4H), 1.5 (8H), 5.04 (4H), 5.70 (2H), 7.37-7.55 (60H) .IR (KBr, cm
-1): 3020,2960,2925,2870,2850,1630,1590,1568,14801470,1380, can determine branch-shape polymer A
2' structural formula as follows:
(2) polymer B ' synthetic
Polymer B ' synthetic just the same with embodiment 4.
(3) with branch-shape polymer A
2' and polymer B ' in molar ratio 1:1 mixes (because preparation A
2' time added Platinic chloride, therefore do not need to add again catalyzer), then row's bubble is injected in the mould of 10 * 50 * 50mm, then 70 ℃ of lower curing at 150 ℃ of insulation 2h, can obtain water white silica gel piece.The specific refractory power of test silicon film is that 1.584,400nm wavelength transmitance is 95%.Organic silica gel in silica obtained has structure as shown in Figure 2, and wherein middle solid head is comprised of following structural formula:
Wherein, n is natural number.
Embodiment 6:
(1) branch-shape polymer A
3' synthetic
Be silico ethylene base group (Si-CH with s-generation end
2=CH
2) dendrimer C
2' replace dimethyl divinyl silane, repeat embodiment 4 step a, obtain third generation end and be silico ethylene base group (Si-CH
2=CH
2) dendrimer C
3' .C
3' react under the catalysis of Platinic chloride with tri-phenyl-silane again and make end and contain silicon phenyl group and silico ethylene base group (Si-CH
2=CH
2) branch-shape polymer A
3'.The dendrimer C that third generation end is contained silico ethylene base group
3' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.21 (6H), 0.7 (8H), 1.29 (12H), 5.04 (12H), 5.70 (6H) .IR (KBr, cm
-1): 3020,2960,2925,2870,2850,1,630 1470,1380, can determine that third generation end is the dendrimer C of silicon-hydrogen group
3' structural formula as follows:
To branch-shape polymer A
3' carry out phenetic analysis:
1H NMR (300MHz, CDCl
3) δ ppm:0.21 (6H), 0.7 (16H), 1.29 (4H), 1.5 (8H), 5.04 (4H), 5.70 (2H), 7.37-7.55 (60H) .IR (KBr, cm
-1): 3020,2960,2925,2870,2850,1630,1590,1568,14801470,1380, can determine branch-shape polymer A
3' structural formula as follows:
(2) polymer B ' synthetic
Polymer B ' synthetic just the same with embodiment 4.
(3) with A
3' and B ' component in molar ratio 1:1 mix (since the preparation A
3' time added Platinic chloride, therefore do not need to add again catalyzer), then row's bubble is injected in the mould of 10 * 50 * 50mm, then 70 ℃ of lower curing at 150 ℃ of insulation 2h, can obtain water white silica gel piece.Test silicon film specific refractory power is that 1.586,400nm wavelength transmitance is 96%.Organic silica gel in silica obtained has structure as shown in Figure 2, and wherein middle solid head is comprised of following structural formula:
Wherein, n is natural number.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a branch-shape polymer modification high refractive index silicone resin, it is characterized in that comprising following operation steps: branch-shape polymer A and the organosilicon polymer B that contains silico ethylene base group are carried out thermofixation under catalyst action, or branch-shape polymer A ' and the organosilicon polymer B ' that contains silicon-hydrogen group carried out thermofixation under catalyst action, obtain silicone resin; Described branch-shape polymer A contains the silicon phenyl group of molar percentage 75～80% and the silicon-hydrogen group of molar percentage 5～10%; Described branch-shape polymer A ' contains 75～80% silicon phenyl groups of molar percentage and 5～10% silico ethylene base groups of molar percentage.
2. preparation method according to claim 1, it is characterized in that: the consumption of described branch-shape polymer A and the organosilicon polymer B that contains silico ethylene base group is 1:2～2:1 with recently the calculating of amount of substance of silico ethylene base group that curing reaction occurs and silicon-hydrogen group, and described branch-shape polymer A ' and the consumption that contains the organosilicon polymer B ' of silicon-hydrogen group are the silico ethylene base group that reacts with the ratio of the amount of substance of silicon-hydrogen group is 1:2～2:1; The consumption of described catalyzer is branch-shape polymer A and the organosilicon polymer B gross weight that contains silico ethylene base group, or branch-shape polymer A ' and the 5～20ppm that contains the organosilicon polymer B ' gross weight of silicon-hydrogen group; The temperature of described thermofixation is 120～150 ℃, and be 2～4h set time; Described branch-shape polymer A is prepared by carrying out addition reaction of silicon with hydrogen by branch-shape polymer C and the triphenyl vinyl silanes that end contains silicon-hydrogen group, and the amount of substance of silico ethylene base group is 95～98% of silicon hydrogen group in the reaction raw materials.
3. preparation method according to claim 2, it is characterized in that: the branch-shape polymer C that described end contains silicon-hydrogen group is prepared from accordance with the following methods:
(1) addition reaction: diphenyl silane, vinyl trichloro silane and chloroplatinic acid catalyst are mixed the rear 2～4h that react under 120～150 ℃ under protection of inert gas; Silicon hydrogen base in the described diphenyl silane and vinyl trichloro silane equimolar ratio; The consumption of described chloroplatinic acid catalyst is 5～50ppm of diphenyl silane and vinyl trichloro silane gross weight;
(2) reduction reaction: under protection of inert gas, add the diethyl ether solution with the lithium aluminum hydride of chlorine equimolar amount in the diethyl ether solution of step (1) products therefrom, and at 20～50 ℃ of lower stirring reaction 2～8h, after the reaction product is poured into water, use the separating funnel separatory, distillation, remove excessive moisture, vacuum is preserved, obtain 2 generation end contain the branch-shape polymer of silicon-hydrogen group;
(3) branch-shape polymer that step (2) gained 2 generation end is contained silicon-hydrogen group carries out the cyclical operation of step (1) and (2) again, obtains the branch-shape polymer C that a series of ends contain silicon-hydrogen group.
4. preparation method according to claim 1, it is characterized in that: the described organosilicon polymer B that contains silico ethylene base group prepares in accordance with the following methods:
(1) hydrolytic condensation: the vinyl silanes of the chlorosilane of molar percentage 70～80% and molar percentage 10～20% poured in 0 ℃ the methyl alcohol of molar percentage 10～20%, mix the backward mixed solution of first alcohol and water that wherein drips extremely without till the γ-ray emission, dropwise the rear separating funnel separatory of using, the distillation desolventizing gets hydrolysis condensation product; The volume ratio of first alcohol and water is 1:1 in the mixed solution of described first alcohol and water;
(2) alkali condensation: add in the hydrolysis condensation product molar percentage 0.05～0.1% alkali, at 100～140 ℃ of lower reaction 8～12h; Products therefrom is extremely neutral with toluene dissolving and water repetitive scrubbing, and unreacted monomer and low-boiling-point substance are removed in underpressure distillation again, obtain containing the organosilicon polymer B of silico ethylene base group.
5. preparation method according to claim 4, it is characterized in that: the described chlorosilane of step (1) is trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, diethyl dichlorosilane, ethyl trichlorosilane, tetrachloro silicane, diphenyl dichlorosilane, phenyl-trichloro-silicane or tri-phenyl chloride; Described vinyl silanes is methyl ethylene dichlorosilane, divinyl dichlorosilane, vinyl trichloro silane, trivinyl chlorosilane or dimethyl divinyl chlorosilane; The described alkali of step (2) is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood.
6. preparation method according to claim 1, it is characterized in that: the branch-shape polymer C ' that described branch-shape polymer A ' contains silico ethylene base group by end carries out addition reaction of silicon with hydrogen with triphenyl hydrogen base silane and prepares, and the amount of substance of silicon hydrogen group is 95～98% of silico ethylene base group in the reaction raw materials.
7. preparation method according to claim 6, it is characterized in that: the branch-shape polymer C ' that described end contains silico ethylene base group is prepared from accordance with the following methods:
(1) addition reaction: after dimethyl divinyl silane, trichlorosilane and chloroplatinic acid catalyst mixed under protection of inert gas at 120～150 ℃ of lower reaction 2～4h; Silico ethylene base and trichlorosilane equimolar ratio in the described dimethyl divinyl silane; The consumption of described chloroplatinic acid catalyst is 5～50ppm of dimethyl divinyl silane and trichlorosilane gross weight;
(2) reduction reaction: under protection of inert gas, in step (1) products therefrom, add tetrahydrofuran (THF), be cooled to 0～5 ℃, diethyl ether solution minute 8～10 addings in 3h with vinyl bromination magnesium, reaction mixture at room temperature continues to stir 24h, adds 0～5 ℃ of ammonium chloride solution and makes reaction terminating; Mixture is washed respectively 2～3 times with tetrahydrofuran (THF) and normal hexane successively, and separatory is got organic phase, and organic phase carried out filtering out insolubles again, and low-boiling-point substance is removed in distillation, obtain 2 generation end contain the branch-shape polymer of silico ethylene base group; Described vinyl bromination magnesium and step (1) products therefrom equimolar ratio;
(3) branch-shape polymer that step (2) gained 2 generation end is contained silico ethylene base group carries out the cyclical operation of step (1) and (2) again, obtains the branch-shape polymer C ' that a series of ends contain silico ethylene base group.
8. preparation method according to claim 1, it is characterized in that: the described organosilicon polymer B ' that contains silicon-hydrogen group prepares in accordance with the following methods:
(1) hydrolytic condensation: the silicon hydride chlorid that contains of the chlorosilane of molar percentage 70～80% and molar percentage 10～20% is poured in 0 ℃ the methyl alcohol of molar percentage 10～20%, drip again the mixed solution of first alcohol and water after mixing, extremely without till the γ-ray emission, dropwise the rear separating funnel separatory of using, the distillation desolventizing gets hydrolysis condensation product; The volume ratio of first alcohol and water is 1:1 in the mixed solution of described first alcohol and water;
(2) sour condensation: the strong acid type macroporous ion exchange resin that adds molar percentage 1～2% in the hydrolysis condensation product is made catalyzer, at 70～120 ℃ of lower reaction 6～8h; Products therefrom is extremely neutral with toluene dissolving and water repetitive scrubbing, and unreacted monomer and low-boiling-point substance are removed in underpressure distillation again, obtain containing the organosilicon polymer B ' of silicon-hydrogen group.
9. preparation method according to claim 8, it is characterized in that: the described chlorosilane of step (1) is trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, diethyl dichlorosilane, ethyl trichlorosilane, tetrachloro silicane, diphenyl dichlorosilane, phenyl-trichloro-silicane or tri-phenyl chloride; The described silicon hydride chlorid that contains is dichlorosilane, diphenyl chlorosilane, diphenyl dichlorosilane, a chlorosilane or trichlorosilane.
10. the silicone resin for preparing of each described method is characterized in that: the specific refractory power of described silicone resin 〉=1.58 according to claim 1～9; When described silicone resin material is 1cm at thickness of sample, at the transmitance of 400 nanometer wave strong points 〉=95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210398306.8A CN102863623B (en) | 2012-10-18 | 2012-10-18 | Process for preparing dendritic polymer modified high refractive index organic silicon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210398306.8A CN102863623B (en) | 2012-10-18 | 2012-10-18 | Process for preparing dendritic polymer modified high refractive index organic silicon resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102863623A true CN102863623A (en) | 2013-01-09 |
| CN102863623B CN102863623B (en) | 2014-05-14 |
Family
ID=47442773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210398306.8A Active CN102863623B (en) | 2012-10-18 | 2012-10-18 | Process for preparing dendritic polymer modified high refractive index organic silicon resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102863623B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232601A (en) * | 2013-04-28 | 2013-08-07 | 成都硅宝科技股份有限公司 | Phenyl MDT silicon resin and preparation method thereof |
| CN109354676A (en) * | 2018-09-19 | 2019-02-19 | 常州钟恒新材料有限公司 | The preparation method of low surface tension PET copolyester material and the uncoated low surface tension PET film prepared using the material |
| CN112370577A (en) * | 2020-10-15 | 2021-02-19 | 浙江省肿瘤医院 | Portable fistula protection drainage mechanism |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101529277A (en) * | 2006-08-28 | 2009-09-09 | 道康宁公司 | Optical devices and silicone compositions and processes fabricating the optical devices |
-
2012
- 2012-10-18 CN CN201210398306.8A patent/CN102863623B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101529277A (en) * | 2006-08-28 | 2009-09-09 | 道康宁公司 | Optical devices and silicone compositions and processes fabricating the optical devices |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232601A (en) * | 2013-04-28 | 2013-08-07 | 成都硅宝科技股份有限公司 | Phenyl MDT silicon resin and preparation method thereof |
| CN109354676A (en) * | 2018-09-19 | 2019-02-19 | 常州钟恒新材料有限公司 | The preparation method of low surface tension PET copolyester material and the uncoated low surface tension PET film prepared using the material |
| CN109354676B (en) * | 2018-09-19 | 2020-11-06 | 常州钟恒新材料股份有限公司 | Preparation method of low-surface-tension PET copolyester material and non-coating low-surface-tension PET film prepared from material |
| CN112370577A (en) * | 2020-10-15 | 2021-02-19 | 浙江省肿瘤医院 | Portable fistula protection drainage mechanism |
| CN112370577B (en) * | 2020-10-15 | 2022-12-16 | 浙江省肿瘤医院 | Portable fistula protection drainage mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102863623B (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103122149B (en) | Optical package high refractive index High-transparency silicon rubber and its preparation method | |
| CN102516500B (en) | Organic silicon modified epoxy resin for packaging LED (Light Emitting Diode), and preparation method and application thereof | |
| CN101891893B (en) | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED | |
| CN104892939B (en) | A kind of preparation method of phenyl polysiloxane | |
| CN102807676B (en) | Phenyl modified epoxy organic silicon resin and preparation method thereof, organic silicon packaging adhesive and LED lamp | |
| CN103012798B (en) | Preparation method of methyl phenyl vinyl silicone resin | |
| CN103232601B (en) | Phenyl MDT silicon resin and preparation method thereof | |
| CN102181159A (en) | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof | |
| CN104974349B (en) | A kind of preparation method of silicones | |
| CN102391529A (en) | Preparation method of silicone resin type organic/inorganic hybrid material for packaging | |
| CN101343365A (en) | Preparation method for methyl phenyl vinyl polysiloxane for packaging LED | |
| CN104877138A (en) | Silicon resin with adhesive properties and preparation method of silicon resin | |
| CN102863623B (en) | Process for preparing dendritic polymer modified high refractive index organic silicon resin | |
| CN101619170A (en) | Preparation and application of silica gel for LED packaging | |
| CN103059306A (en) | High-refractive index transparent silicone resin and preparation method thereof | |
| CN101974228A (en) | Organic silica-gel material for encapsulating luminous element and preparation method thereof | |
| CN103848990A (en) | High-refractive index vinyl phenyl silicon resin for light-emitting diode (LED) package | |
| CN109880101A (en) | A kind of LED packaging plastic epoxidation modification phenyl polysiloxane and preparation method thereof | |
| CN103242531A (en) | Preparation method of phenyl hydrogen-containing MT silicone resin | |
| CN103130982A (en) | Composite method and solidifying method of fluorine-containing high temperature resisting organosilicon epoxy resin | |
| CN110229339B (en) | Phenyl vinyl siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof | |
| CN102433005A (en) | Liquid phenyl silica gel for LED and its preparation method | |
| CN108384010A (en) | A kind of LED packaging plastics epoxidation modification methyl phenyl silicone resin and preparation method thereof | |
| CN103834178B (en) | Organic silicon resin as well as preparation method and application thereof | |
| CN104031392A (en) | Addition-type silica gel, and preparation method and application 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |