CN104961898B - A kind of preparation method of the hydrogeneous silicones of epoxide modified phenyl - Google Patents
A kind of preparation method of the hydrogeneous silicones of epoxide modified phenyl Download PDFInfo
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Abstract
A kind of preparation method of the hydrogeneous silicones of epoxide modified phenyl, comprises the following steps：（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, mixed material is obtained after stirring, and heating makes mixed material be warming up to 60-130 DEG C；Then in the case of stirring, the thermotonus of 60-130 DEG C of holding after the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals, completion of dropping is added dropwise into mixed material 4-12 hours；Stop heating after completion of the reaction and stir, and be cooled to 20-30 DEG C, obtain synthetic reaction product；（2）Purifying：Synthesis reaction product is purified, the hydrogeneous silicones of epoxide modified phenyl is obtained.Reaction condition of the present invention is gentle, preparation technology is simple, and the properties of product of preparation are excellent, it is adaptable to the polymer basis polymer of LED Packaging Industries, make encapsulating material that both there is superior light transmittance, heat endurance, weatherability, pliability, there is excellent mechanical performance, adhesive property again.
Description
Technical field
The present invention relates to organic high molecular compound, and in particular to a kind of preparation side of the epoxide modified hydrogeneous silicones of phenyl
Method.
Background technology
With the increasingly exhaustion of resource on the earth, energy-conservation has become a problem of social development must consider.And it is electric
Power consumption then accounts for the 13% of terminal energy sources consumption proportion, wherein the electric power consumed in illumination accounts for the 1/5 of wastage in bulk or weight electric power.Such as
Fruit replaces existing illuminator in illumination using more energy-efficient light fixture, by the effectively save energy because of illumination consumption
Source.Compared with traditional illuminator, LED（Light emitting diode）Because have more energy efficient, power-efficient it is higher, more protection regard
Power, service life are longer, colour rendering is good, environmentally friendly, recyclable, healthy without the significant advantage of ultraviolet, safety etc., what it developed
Prospect ten/good, and up to the present could not also find that LED light source can be replaced.In national LED illumination industrial policy
Under environment constantly improve, LED industry scale rapid development is all obtained in terms of backlight, display screen, traffic signal display light source
Arrive wider application, and come into high-power, high brightness Rapid development stage, this encapsulating material to LED
Higher requirement can be proposed.
Early stage LED encapsulation uses epoxy resin, mainly values its excellent caking property, corrosion resistance and electrical property
Can, but epoxy resin cured product has the shortcomings that matter is crisp, impact strength low and high temperature turns yellow, weatherability is poor, seriously limits
Application of the epoxy resin in LED field.
Organic siliconresin because with special O-Si-O bond structures, making it have superior light transmittance, it is heat endurance, weather-proof
The correlated performances such as property, pliability, instead of epoxy resin gradually.But simple organic siliconresin mechanical strength is slightly worse, does not also have
The standby adhesive property to base material, this causes organic siliconresin encapsulating material to be peeled off in the case of external force or cold and hot contraction with base material,
Can not effectively protection element, or even cause the direct failure of element open circuit.In order to improve the bond effect of organic siliconresin, at present
Mostly directly add epoxies coupling agent, tackifier etc. into organic siliconresin, but because epoxies coupling agent, tackifier etc. with
The poor compatibility of organic siliconresin, and with deliquescent characteristic, simple physical mixed easily makes whole system turn white, and occurs
Floccule, or even gel, so that the stability that encapsulating material is stored is influenceed, and it is saturating to cause the LED product after package curing to occur
Cross the low flaw of rate.
If the advantage of epoxy resin and organic siliconresin can be integrated, mutually make up, make encapsulating material that there is epoxy
The excellent mechanical performance of resin, adhesive property, have the superpower weatherability of organic siliconresin, resistance to yellowing, excellent thermal oxide again
Stability and electrical insulating property, it is just perfect.How to allow organic siliconresin and epoxy resin perfect adaptation, played in performance very well
Complementation, it has also become one of direction researched and developed now.So far, relevant report carrys out modified epoxy tree using organosilicon
Fat, but because of its main body or epoxy resin, its matter is crisp and the shortcomings of heat endurance is poor, weatherability is poor or obvious, and technique is multiple
Miscellaneous, applicability is poor.Epoxy resin modified organosilicon resin is used, based on organic siliconresin, current epoxy modified silicone
The method of resin is mostly condensation method, and adhesive property and compatibility improve, but condensed type reaction side reaction is more, closes
It is difficult to control into process, composite structure uniformity is poor, and complex process, it is difficult to is widely popularized and comes.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of the hydrogeneous silicones of epoxide modified phenyl, this
Plant preparation method and epoxy radicals accessed by Si―H addition reaction method in organic siliconresin, reaction condition is gentle, and preparation technology is simple,
Obtained properties of product are excellent.The technical scheme of use is as follows：
A kind of preparation method of the hydrogeneous silicones of epoxide modified phenyl, it is characterised in that comprise the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, after stirring
To mixed material, and heating makes mixed material be warming up to 60-130 DEG C；Then in the case of stirring（Mixed material is entered
Row stirring）, it is added dropwise after the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals, completion of dropping and keeps into mixed material
60-130 DEG C of thermotonus 4-12 hours；Stop heating after completion of the reaction and stir, and be cooled to 20-30 DEG C, closed
Into reaction product；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified, and obtains epoxide modified phenyl Silicon Containing Hydrogen tree
Fat.
Step（2）In, to step（1）Obtained synthetic reaction product is purified, and refers to remove in synthetic reaction product
Solvent, catalyst and unreacted monomer.
Preferred steps（1）In, the time for adding of the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is 0.5-
3 hours.
Step（1）In the hydrogeneous silicones of phenyl to be modified main body.Preferred steps（1）In, the phenyl Silicon Containing Hydrogen tree
The hydrogen content of fat is 0.05-0.5%（Weight）, during 25 DEG C of its viscosity@=500-25000mPa.s, its refractive index is more than 1.5.More
It is preferred that the hydrogen content of the hydrogeneous silicones of phenyl is 0.3%（Weight）, during 25 DEG C of its viscosity@=1000mPa.s.
Preferred steps（1）In, the catalyst is solid supported type platinum catalyst, and wherein loaded article is silica
（SiO2）, carbon（C）Or aluminum oxide（Al2O3）, the consumption of catalyst is the 6-60 ‰ of phenyl Silicon Containing Hydrogen weight resin.More preferably bear
Loading is silica（SiO2）.Using solid supported type platinum catalyst, while catalytic effect is ensured, after reaction terminates
It just can easily be removed with by simply filtering, make there is no residual catalyst in product, be effectively guaranteed the steady of product
It is qualitative.
Preferred steps（1）In, the solvent orange 2 A be dimethylbenzene, toluene, hexamethylene, acetone and carbon tetrachloride in one kind or
Many of combination.More preferably solvent orange 2 A is toluene and dimethylbenzene according to 3:The mixed liquor that 1 weight proportion is mixed to get.It is excellent
The consumption for selecting solvent orange 2 A is 0.5-3 times of phenyl Silicon Containing Hydrogen weight resin.
Preferred steps（1）In, the monomer containing vinyl and epoxy radicals is allyl glycidyl ether, methacrylic acid
Ethylene oxidic ester and one kind in 1,2- epoxy -5- hexenes or many of combination.It is more preferably described to contain vinyl and epoxy
The monomer of base is allyl glycidyl ether.
Preferred steps（1）In, vinyl contained by the monomer containing vinyl and epoxy radicals and the hydrogeneous silicones institute of phenyl
The mol ratio of hydrosilyl group-containing is 0.2-1.3：1.
Preferred steps（1）In, the polymerization inhibitor is hydroquinones（HQ）, 1,4-benzoquinone（PBQ）, methylnaphthohydroquinone（THQ）, to hydroxyl
Base methyl phenyl ethers anisole（HQMME）, 2- TBHQs（MTBHQ）And 2,5 di tert butyl hydroquinone（2,5-DTBHQ）In
A kind of or many of combination.More preferably described polymerization inhibitor is MEHQ, and its dissolubility in organic solvent is good,
Product colour is most shallow, and the transmitance of product is not influenceed.
Preferred steps（1）In, the consumption of the polymerization inhibitor is the 0.2-2.5 ‰ of phenyl Silicon Containing Hydrogen weight resin.
Preferred steps（2）In, it is to the method that synthesis reaction product is purified：Synthetic reaction product is dilute with solvent B
Release, be filtrated to get the first filtrate；Charcoal absorption is added into the first filtrate again to decolourize, and is then filtered to remove activated carbon, is obtained
Second filtrate（Second filtrate is usually colourless transparent liquid）；Then the second filtrate is added in rotary evaporator, in vacuum
It is spin concentration 1-4 hours under conditions of 40-70 DEG C for -0.075--0.096MPa, temperature, obtains initial concentration liquid；Again
In vacuum it is that -0.090--0.096MPa, temperature are further concentration 4- under conditions of 100-150 DEG C by initial concentration liquid
12 hours, obtain the hydrogeneous silicones of epoxide modified phenyl.
Step（2）In, filtering for the first time can remove the solid in synthetic reaction product（Such as solid impurity, solid supported
Type platinum catalyst etc.）, activated carbon can be removed for the second time by filtering, and spin concentration can remove most of low-boiling-point substance（Predominantly solvent,
That is solvent orange 2 A and solvent B）, further concentration（High temperature is vacuumized）Remnants low-boiling-point substance and unreacted monomer can be extracted.
More preferably step（2）In, the solvent B is one kind in dimethylbenzene, toluene, hexamethylene, acetone and carbon tetrachloride
Or many of combination.More preferably described solvent B is acetone.It is preferred that the consumption of the solvent B is the hydrogeneous silicones weight of phenyl
0.5-3 times of amount.
More preferably step（2）In, the activated carbon is nano active carbon, and the consumption of activated carbon is the hydrogeneous silicones weight of phenyl
The 5-10% of amount.
Above-mentioned steps（2）In, activated carbon can be filtered off using two-filtration devices, wherein：First heavy filtration device is available fixed
Measure filter paper（Its aperture is 1-3 microns, such as Advantec Japan No.5A quantitative filter papers）, can tentatively remove most activity
Charcoal；Second heavy filtration device can coordinate fritted glass filter with 0.25um filter membranes, to ensure the complete removal of nano active carbon.
Preferred steps（2）In, the rotary speed of rotary evaporator is 20-80 revs/min.More preferably step（2）In, rotation
The rotary speed for turning evaporator is 40 revs/min.
The space structure of epoxide modified phenyl Silicon Containing Hydrogen molecular resin made from the above method can be dumbbell shaped, T-shaped or sky
Between space network.
The present invention compared with prior art, with advantages below and beneficial effect：
（1）The present invention, which uses hydrosilation method, makes epoxy radicals be linked into the hydrogeneous resin of phenyl（Containing vinyl and ring
Vinyl in the monomer of epoxide is reacted with the silicon hydrogen-based in the hydrogeneous silicones of phenyl, and epoxy radicals is linked into the hydrogeneous resin of phenyl
In）, raw material is easy to get, and reaction condition is gentle, and side reaction is few, and preparation technology is simple, and building-up process is easily controlled, pollution-free, is easy to
Industrialization.
（2）The hydrogeneous silicones of epoxide modified phenyl prepared by the present invention, can accomplish the uniformity with organosilicon systems,
While providing caking property by epoxy radicals, efficiently solve and add epoxies coupling in the prior art to improve caking property
Miscibility caused by agent, tackifier is poor, the easy moisture absorption deliquescence the problems such as, therefore, the epoxide modified phenyl for preparing of the present invention
Silicon Containing Hydrogen resin property is excellent, both with superior light transmittance, heat endurance, weatherability, pliability, has excellent machinery again
Performance, adhesive property.
The polymer basis that the hydrogeneous silicones of epoxide modified phenyl prepared by the present invention is applied to LED Packaging Industries polymerize
Thing, on the premise of other performances are not reduced, greatly improves adhesion strength of the encapsulating material to base material, so as to ensure that LED members
Service life of the part under various mal-conditions.The hydrogeneous silicones of epoxide modified phenyl produced by the present invention can as tackifier or
Crosslinking agent.
Embodiment
Embodiment 1
In the present embodiment, the preparation method of the epoxide modified hydrogeneous silicones of phenyl comprises the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, after stirring
To mixed material, and heating makes mixed material be warming up to 70 DEG C；Then in the case of stirring（Mixed material is stirred
Mix）, the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is added dropwise into mixed material（Containing vinyl and epoxy radicals
The time for adding of the mixed liquor of monomer and polymerization inhibitor is 0.5 hour）, 70 DEG C of thermotonus is kept after completion of dropping 4 hours；Instead
Stop heating after should finishing and stir, and be cooled to 20 DEG C, obtain synthetic reaction product；
This step（1）In, the hydrogen content of the hydrogeneous silicones of phenyl is 0.3%（Weight）, during 25 DEG C of its viscosity@=
1000mPa.s, its refractive index is 1.52；The catalyst is solid supported type platinum catalyst, and wherein loaded article is titanium dioxide
Silicon（SiO2）, the consumption of catalyst is the 6 ‰ of phenyl Silicon Containing Hydrogen weight resin；The solvent orange 2 A is carbon tetrachloride, the use of solvent orange 2 A
Measure as 0.5 times of phenyl Silicon Containing Hydrogen weight resin；The monomer containing vinyl and epoxy radicals is allyl glycidyl ether, alkene
The mol ratio of vinyl contained by propyl glycidyl ether and silicon hydrogen-based contained by the hydrogeneous silicones of phenyl is 0.2：1；The polymerization inhibitor
For MEHQ（HQMME）, the consumption of polymerization inhibitor is the 0.5 ‰ of phenyl Silicon Containing Hydrogen weight resin；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified, and is specially：By synthetic reaction product with molten
Agent B dilutes, and is filtrated to get the first filtrate（It can be filtered with quantitative filter paper）；Again charcoal absorption is added into the first filtrate to take off
Color, is then filtered to remove activated carbon, obtains the second filtrate；Then by the second filtrate add rotary evaporator in, vacuum for-
0.085MPa, temperature are spin concentration 3 hours under conditions of 50 DEG C（The rotary speed of rotary evaporator is 40 revs/min）, obtain
To initial concentration liquid；It is again that -0.093MPa, temperature are further concentration 4 under conditions of 100 DEG C in vacuum by initial concentration liquid
Hour, obtain the hydrogeneous silicones of epoxide modified phenyl.
This step（2）In, the solvent B is acetone, and the consumption of the solvent B is the 0.8 of phenyl Silicon Containing Hydrogen weight resin
Times；The activated carbon is nano active carbon, and the consumption of activated carbon is the 5% of phenyl Silicon Containing Hydrogen weight resin.
Above-mentioned steps（2）In, filtering for the first time can remove the solid in synthetic reaction product（Such as solid impurity, solid
Load type platinum Au catalyst etc.）, activated carbon can be removed for the second time by filtering, and spin concentration can remove most of low-boiling-point substance（Predominantly
Solvent, i.e. solvent orange 2 A and solvent B）, further concentration（High temperature is vacuumized）Remnants low-boiling-point substance and unreacted monomer can be extracted.
Above-mentioned steps（2）In, activated carbon can be filtered off using two-filtration devices, wherein：First heavy filtration device is available fixed
Measure filter paper（Its aperture is 1-3 microns, such as Advantec Japan No.5A quantitative filter papers）；Second heavy filtration device can use 0.25um
Filter membrane coordinates fritted glass filter.
The hydrogeneous silicones of epoxide modified phenyl produced above tests associated products by FTIR, NMR, with silicon phenyl key
（SiPh）For constant basic key, SiH is calculated remaining（Molar percentage）≈ 80%, epoxy radicals storage rate >=90%；Surveyed by ICP
Try catalyst platinum constituent content≤5ppm.
Embodiment 2
In the present embodiment, the preparation method of the epoxide modified hydrogeneous silicones of phenyl comprises the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, after stirring
To mixed material, and heating makes mixed material be warming up to 80 DEG C；Then in the case of stirring（Mixed material is stirred
Mix）, the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is added dropwise into mixed material（Containing vinyl and epoxy radicals
The time for adding of the mixed liquor of monomer and polymerization inhibitor is 1 hour）, 80 DEG C of thermotonus is kept after completion of dropping 6 hours；Reaction
Stop heating after finishing and stir, and be cooled to 20 DEG C, obtain synthetic reaction product；
This step（1）In, the hydrogen content of the hydrogeneous silicones of phenyl is 0.3%（Weight）, during 25 DEG C of its viscosity@=
10000mPa.s, its refractive index is 1.53；The catalyst is solid supported type platinum catalyst, and wherein loaded article is titanium dioxide
Silicon（SiO2）, the consumption of catalyst is the 18 ‰ of phenyl Silicon Containing Hydrogen weight resin；The solvent orange 2 A is hexamethylene, the consumption of solvent orange 2 A
For 1 times of phenyl Silicon Containing Hydrogen weight resin；The monomer containing vinyl and epoxy radicals is allyl glycidyl ether, pi-allyl
The mol ratio of vinyl contained by glycidol ether and silicon hydrogen-based contained by the hydrogeneous silicones of phenyl is 0.5：1；The polymerization inhibitor for pair
Hydroxyanisol（HQMME）, the consumption of polymerization inhibitor is the 1 ‰ of phenyl Silicon Containing Hydrogen weight resin；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified, and is specially：By synthetic reaction product with molten
Agent B dilutes, and is filtrated to get the first filtrate（It can be filtered with quantitative filter paper）；Again charcoal absorption is added into the first filtrate to take off
Color, is then filtered to remove activated carbon, obtains the second filtrate；Then by the second filtrate add rotary evaporator in, vacuum for-
0.096MPa, temperature are spin concentration 2 hours under conditions of 60 DEG C（The rotary speed of rotary evaporator is 50 revs/min）, obtain
To initial concentration liquid；It is again that -0.096MPa, temperature are further concentration 6 under conditions of 110 DEG C in vacuum by initial concentration liquid
Hour, obtain the hydrogeneous silicones of epoxide modified phenyl.
This step（2）In, the solvent B is acetone, and solvent B consumption is 1 times of phenyl Silicon Containing Hydrogen weight resin；It is described
Activated carbon is nano active carbon, and the consumption of activated carbon is the 8% of phenyl Silicon Containing Hydrogen weight resin.
Above-mentioned steps（2）In, filtering for the first time can remove the solid in synthetic reaction product（Such as solid impurity, solid
Load type platinum Au catalyst etc.）, activated carbon can be removed for the second time by filtering, and spin concentration can remove most of low-boiling-point substance（Predominantly
Solvent, i.e. solvent orange 2 A and solvent B）, further concentration（High temperature is vacuumized）Remnants low-boiling-point substance and unreacted monomer can be extracted.
Above-mentioned steps（2）In, activated carbon can be filtered off using two-filtration devices, wherein：First heavy filtration device is available fixed
Measure filter paper（Its aperture is 1-3 microns, such as Advantec Japan No.5A quantitative filter papers）；Second heavy filtration device can use 0.25um
Filter membrane coordinates fritted glass filter.
The hydrogeneous silicones of epoxide modified phenyl produced above tests associated products by FTIR, NMR, with silicon phenyl key
（SiPh）For constant basic key, SiH is calculated remaining（Molar percentage）≈ 52%, epoxy radicals storage rate >=91.5%；Pass through ICP
Test catalyst platinum constituent content≤5ppm.
Embodiment 3
In the present embodiment, the preparation method of the epoxide modified hydrogeneous silicones of phenyl comprises the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, after stirring
To mixed material, and heating makes mixed material be warming up to 100 DEG C；Then in the case of stirring（Mixed material is stirred
Mix）, the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is added dropwise into mixed material（Containing vinyl and epoxy radicals
The time for adding of the mixed liquor of monomer and polymerization inhibitor is 1.8 hours）, 100 DEG C of thermotonus is kept after completion of dropping 6 hours；
Stop heating after completion of the reaction and stir, and be cooled to 25 DEG C, obtain synthetic reaction product；
This step（1）In, the hydrogen content of the hydrogeneous silicones of phenyl is 0.1%（Weight）, during 25 DEG C of its viscosity@=
5000mPa.s, its refractive index is 1.51；The catalyst is solid supported type platinum catalyst, and wherein loaded article is aluminum oxide
（Al2O3）, the consumption of catalyst is the 30 ‰ of phenyl Silicon Containing Hydrogen weight resin；The solvent orange 2 A is toluene and dimethylbenzene according to 3:1
The mixed liquor that is mixed to get of weight proportion, the consumption of solvent orange 2 A is 3 times of phenyl Silicon Containing Hydrogen weight resin；It is described to contain vinyl
And the monomer of epoxy radicals is GMA, vinyl contained by GMA and phenyl are hydrogeneous
The mol ratio of silicones institute hydrosilyl group-containing is 0.9：1；The polymerization inhibitor is hydroquinones（HQ）, the consumption of polymerization inhibitor contains for phenyl
The 1.5 ‰ of hydrogen silicones weight；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified, and is specially：By synthetic reaction product with molten
Agent B dilutes, and is filtrated to get the first filtrate（It can be filtered with quantitative filter paper）；Again charcoal absorption is added into the first filtrate to take off
Color, is then filtered to remove activated carbon, obtains the second filtrate；Then by the second filtrate add rotary evaporator in, vacuum for-
0.075MPa, temperature are spin concentration 1 hour under conditions of 70 DEG C（The rotary speed of rotary evaporator is 80 revs/min）, obtain
To initial concentration liquid；It is again that -0.090MPa, temperature are further to concentrate under conditions of 130 DEG C in vacuum by initial concentration liquid
12 hours, obtain the hydrogeneous silicones of epoxide modified phenyl.
This step（2）In, the solvent B is toluene, and the consumption of the solvent B is 2 times of phenyl Silicon Containing Hydrogen weight resin；
The activated carbon is nano active carbon, and the consumption of activated carbon is the 10% of phenyl Silicon Containing Hydrogen weight resin.
Above-mentioned steps（2）In, filtering for the first time can remove the solid in synthetic reaction product（Such as solid impurity, solid
Load type platinum Au catalyst etc.）, activated carbon can be removed for the second time by filtering, and spin concentration can remove most of low-boiling-point substance（Predominantly
Solvent, i.e. solvent orange 2 A and solvent B）, further concentration（High temperature is vacuumized）Remnants low-boiling-point substance and unreacted monomer can be extracted.
Above-mentioned steps（2）In, activated carbon can be filtered off using two-filtration devices, wherein：First heavy filtration device is available fixed
Measure filter paper（Its aperture is 1-3 microns, such as Advantec Japan No.5A quantitative filter papers）；Second heavy filtration device can use 0.25um
Filter membrane coordinates fritted glass filter.
The hydrogeneous silicones of epoxide modified phenyl produced above tests associated products by FTIR, NMR, with silicon phenyl key
（SiPh）For constant basic key, SiH is calculated remaining（Molar percentage）≈ 17.8%, epoxy radicals storage rate >=89.4%；Pass through
ICP test catalyst platinums constituent content≤5ppm.
Embodiment 4
In the present embodiment, the preparation method of the epoxide modified hydrogeneous silicones of phenyl comprises the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, after stirring
To mixed material, and heating makes mixed material be warming up to 130 DEG C；Then in the case of stirring（Mixed material is stirred
Mix）, the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is added dropwise into mixed material（Containing vinyl and epoxy radicals
The time for adding of the mixed liquor of monomer and polymerization inhibitor is 3 hours）, 130 DEG C of thermotonus is kept after completion of dropping 4 hours；Instead
Stop heating after should finishing and stir, and be cooled to 30 DEG C, obtain synthetic reaction product；
This step（1）In, the hydrogen content of the hydrogeneous silicones of phenyl is 0.5%（Weight）, during 25 DEG C of its viscosity@=
25000mPa.s, its refractive index is more than 1.54；The catalyst is solid supported type platinum catalyst, and wherein loaded article is carbon
（C）, the consumption of catalyst is the 45 ‰ of phenyl Silicon Containing Hydrogen weight resin；The solvent orange 2 A is dimethylbenzene, and the consumption of solvent orange 2 A is benzene
2 times of base Silicon Containing Hydrogen weight resin；The monomer containing vinyl and epoxy radicals is 1,2- epoxy -5- hexenes, 1,2- epoxy -5-
The mol ratio of vinyl contained by hexene and silicon hydrogen-based contained by the hydrogeneous silicones of phenyl is 1.15：1；The polymerization inhibitor is the 2- tert-butyl groups
Hydroquinones（MTBHQ）And 2,5 di tert butyl hydroquinone（2,5-DTBHQ）Combination, the consumption of polymerization inhibitor is hydrogeneous for phenyl
The 2 ‰ of silicones weight；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified, and is specially：By synthetic reaction product with molten
Agent B dilutes, and is filtrated to get the first filtrate（It can be filtered with quantitative filter paper）；Again charcoal absorption is added into the first filtrate to take off
Color, is then filtered to remove activated carbon, obtains the second filtrate；Then by the second filtrate add rotary evaporator in, vacuum for-
0.090MPa, temperature are spin concentration 4 hours under conditions of 60 DEG C（The rotary speed of rotary evaporator is 20 revs/min）, obtain
To initial concentration liquid；It is again that -0.095MPa, temperature are further concentration 4 under conditions of 150 DEG C in vacuum by initial concentration liquid
Hour, obtain the hydrogeneous silicones of epoxide modified phenyl.
This step（2）In, the solvent B is dimethylbenzene, and solvent B consumption is 3 times of phenyl Silicon Containing Hydrogen weight resin；Institute
Activated carbon is stated for nano active carbon, the consumption of activated carbon is the 5% of phenyl Silicon Containing Hydrogen weight resin.
Above-mentioned steps（2）In, filtering for the first time can remove the solid in synthetic reaction product（Such as solid impurity, solid
Load type platinum Au catalyst etc.）, activated carbon can be removed for the second time by filtering, and spin concentration can remove most of low-boiling-point substance（Predominantly
Solvent, i.e. solvent orange 2 A and solvent B）, further concentration（High temperature is vacuumized）Remnants low-boiling-point substance and unreacted monomer can be extracted.
Above-mentioned steps（2）In, activated carbon can be filtered off using two-filtration devices, wherein：First heavy filtration device is available fixed
Measure filter paper（Its aperture is 1-3 microns, such as Advantec Japan No.5A quantitative filter papers）；Second heavy filtration device can use 0.25um
Filter membrane coordinates fritted glass filter.
The hydrogeneous silicones of epoxide modified phenyl produced above tests associated products by FTIR, NMR, with silicon phenyl key
（SiPh）For constant basic key, SiH is calculated remaining（Molar percentage）≈ 7.6%, epoxy radicals storage rate >=85.3%；Pass through
ICP test catalyst platinums constituent content≤5ppm.
Embodiment 5
In the present embodiment, the preparation method of the epoxide modified hydrogeneous silicones of phenyl comprises the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, after stirring
To mixed material, and heating makes mixed material be warming up to 120 DEG C；Then in the case of stirring（Mixed material is stirred
Mix）, the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is added dropwise into mixed material（Containing vinyl and epoxy radicals
The time for adding of the mixed liquor of monomer and polymerization inhibitor is 2.5 hours）, 120 DEG C of thermotonus is kept after completion of dropping 5 hours；
Stop heating after completion of the reaction and stir, and be cooled to 28 DEG C, obtain synthetic reaction product；
This step（1）In, the hydrogen content of the hydrogeneous silicones of phenyl is 0.25%（Weight）, during 25 DEG C of its viscosity@=
20000mPa.s, its refractive index is 1.51；The catalyst is solid supported type platinum catalyst, and wherein loaded article is titanium dioxide
Silicon（SiO2）, the consumption of catalyst is the 60 ‰ of phenyl Silicon Containing Hydrogen weight resin；The solvent orange 2 A is dimethylbenzene, the consumption of solvent orange 2 A
For 0.8 times of phenyl Silicon Containing Hydrogen weight resin；The monomer containing vinyl and epoxy radicals is allyl glycidyl ether, allyl
The mol ratio of vinyl contained by base glycidol ether and silicon hydrogen-based contained by the hydrogeneous silicones of phenyl is 1.3：1；The polymerization inhibitor is
Methylnaphthohydroquinone（THQ）, the consumption of polymerization inhibitor is the 2.5 ‰ of phenyl Silicon Containing Hydrogen weight resin；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified, and is specially：By synthetic reaction product with molten
Agent B dilutes, and is filtrated to get the first filtrate（It can be filtered with quantitative filter paper）；Again charcoal absorption is added into the first filtrate to take off
Color, is then filtered to remove activated carbon, obtains the second filtrate；Then by the second filtrate add rotary evaporator in, vacuum for-
0.085MPa, temperature are spin concentration 4 hours under conditions of 50 DEG C（The rotary speed of rotary evaporator is 60 revs/min）, obtain
To initial concentration liquid；It is again that -0.090MPa, temperature are further concentration 8 under conditions of 140 DEG C in vacuum by initial concentration liquid
Hour, obtain the hydrogeneous silicones of epoxide modified phenyl.
This step（2）In, the solvent B is hexamethylene, and solvent B consumption is 2.5 times of phenyl Silicon Containing Hydrogen weight resin；
The activated carbon is nano active carbon, and the consumption of activated carbon is the 6% of phenyl Silicon Containing Hydrogen weight resin.
Above-mentioned steps（2）In, filtering for the first time can remove the solid in synthetic reaction product（Such as solid impurity, solid
Load type platinum Au catalyst etc.）, activated carbon can be removed for the second time by filtering, and spin concentration can remove most of low-boiling-point substance（Predominantly
Solvent, i.e. solvent orange 2 A and solvent B）, further concentration（High temperature is vacuumized）Remnants low-boiling-point substance and unreacted monomer can be extracted.
Above-mentioned steps（2）In, activated carbon can be filtered off using two-filtration devices, wherein：First heavy filtration device is available fixed
Measure filter paper（Its aperture is that aperture is 1-3 microns, such as Advantec Japan No.5A quantitative filter papers）；Second heavy filtration device can use
0.25um filter membranes coordinate fritted glass filter.
The hydrogeneous silicones of epoxide modified phenyl produced above tests associated products by FTIR, NMR, with silicon phenyl key
（SiPh）For constant basic key, SiH is calculated remaining（Molar percentage）≈ 0%, epoxy radicals storage rate >=86%；Surveyed by ICP
Try catalyst platinum constituent content≤5ppm.
Claims (9)
1. a kind of preparation method of the hydrogeneous silicones of epoxide modified phenyl, it is characterised in that comprise the following steps：
（1）Synthesis：The hydrogeneous silicones of phenyl, catalyst, solvent orange 2 A are sequentially added into reaction vessel, is mixed after stirring
Compound material, and heating makes mixed material be warming up to 60-130 DEG C；Then in the case of stirring, it is added dropwise and contains into mixed material
Keep 60-130 DEG C of thermotonus 4-12 small after the mixed liquor of the monomer and polymerization inhibitor of vinyl and epoxy radicals, completion of dropping
When；Stop heating after completion of the reaction and stir, and be cooled to 20-30 DEG C, obtain synthetic reaction product；
（2）Purifying：To step（1）Obtained synthetic reaction product is purified；
It is to the method that synthesis reaction product is purified：Synthetic reaction product is diluted with solvent B, the first filter is filtrated to get
Liquid；Charcoal absorption is added into the first filtrate again to decolourize, and is then filtered to remove activated carbon, is obtained the second filtrate；Then by
Two filtrates are added in rotary evaporator, be that -0.075--0.096MPa, temperature are to rotate under conditions of 40-70 DEG C in vacuum
Concentration 1-4 hours, obtains initial concentration liquid；It is again that -0.090--0.096MPa, temperature are in vacuum by initial concentration liquid
Further concentrated 4-12 hours under conditions of 100-150 DEG C, obtain the hydrogeneous silicones of epoxide modified phenyl.
2. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, the time for adding of the mixed liquor of monomer and polymerization inhibitor containing vinyl and epoxy radicals is 0.5-3 hours.
3. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, the hydrogen content of the hydrogeneous silicones of phenyl is 0.05-0.5%（Weight）, during 25 DEG C of its viscosity@=500-
25000mPa.s, its refractive index is more than 1.5.
4. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, the catalyst be solid supported type platinum catalyst, wherein loaded article be silica, carbon or aluminum oxide, catalyst
Consumption is the 6-60 ‰ of phenyl Silicon Containing Hydrogen weight resin.
5. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, the solvent orange 2 A is one kind in dimethylbenzene, toluene, hexamethylene, acetone and carbon tetrachloride or many of combination；Solvent orange 2 A
Consumption be 0.5-3 times of phenyl Silicon Containing Hydrogen weight resin.
6. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, the monomer containing vinyl and epoxy radicals is allyl glycidyl ether, GMA and 1,2- ring
One kind or many of combination in oxygen -5- hexenes.
7. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, vinyl contained by the monomer containing vinyl and epoxy radicals and the mol ratio of silicon hydrogen-based contained by the hydrogeneous silicones of phenyl are
0.2-1.3：1.
8. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（1）
In, the polymerization inhibitor is hydroquinones, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- TBHQs and 2,5- bis-
One kind or many of combination in TBHQ；The consumption of the polymerization inhibitor is phenyl Silicon Containing Hydrogen weight resin
0.2-2.5 ‰.
9. the preparation method of the hydrogeneous silicones of epoxide modified phenyl according to claim 1, it is characterised in that：Step（2）
In, the solvent B be dimethylbenzene, toluene, hexamethylene, acetone and carbon tetrachloride in one kind or many of combination, it is described
Solvent B consumption is 0.5-3 times of phenyl Silicon Containing Hydrogen weight resin.
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| CN101215381A (en) * | 2008-01-14 | 2008-07-09 | 杭州师范大学 | Method for preparing methylphenyl hydrogen-containing silicone oil |
| CN103588974A (en) * | 2013-11-11 | 2014-02-19 | 齐齐哈尔大学 | Synthesis method of epoxy group modified polyorganosiloxane flax soft finishing agent |
| CN104017218A (en) * | 2014-05-22 | 2014-09-03 | 浙江工业大学 | Method for synthesizing epoxy modified organosiloxane |
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| CN101215381A (en) * | 2008-01-14 | 2008-07-09 | 杭州师范大学 | Method for preparing methylphenyl hydrogen-containing silicone oil |
| CN103588974A (en) * | 2013-11-11 | 2014-02-19 | 齐齐哈尔大学 | Synthesis method of epoxy group modified polyorganosiloxane flax soft finishing agent |
| CN104017218A (en) * | 2014-05-22 | 2014-09-03 | 浙江工业大学 | Method for synthesizing epoxy modified organosiloxane |
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