CN105218823B - The preparation method and application of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin - Google Patents
The preparation method and application of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and application of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, using vinylsiloxane, phenyl siloxane, alkylsiloxane hydrolytie polycondensation hour in acid condition, transparent vinyl polysiloxane is prepared；Then first titanate esters are hydrolyzed in acid condition, then adds zirconic acid ester monomer and carries out cohydrolysis, prepare the adjustable nano zircite cladding titanium oxide core/shell structure complex sol of refractive index；Vinyl polysiloxane is carried out hydridization with complex sol by a certain percentage again to react, a nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin is obtained after pumping solvent.Add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin prepared by the present invention has high refractive index, high transmittance, low water absorbable, anti-ultraviolet ageing performance, low internal stress and good heat resistance energy, preparation method cost of material of the present invention is low, simple for process, safety and environmental protection, is expected to be applied to LED encapsulation and optical material field.
Description
Technical field
The present invention relates to a kind of preparation method and applications of composite resin, more particularly to a kind of additional organosilicon
The preparation method and application of composite resin is applied to technical field of function materials.
Background technology
Light emitting diode (LED) is the another generation novel illumination light source after incandescent lamp and fluorescent lamp.And LED package materials
Material not only has the function of sealing and protecting chip, reduces junction temperature of chip and heat dissipation, while also having and avoiding LED by ring around
The influence of border humidity and temperature and reduction chip and air refraction are poor, to improve the function of effectively exporting of light.Cause
This, is for LED encapsulation material, good transmitance, high refractive index, heat-resisting, ultraviolet aging resistance and low stress and low water suction
Rate is that material institute is prerequisite.
LED encapsulating materials include epoxy resin, organosilicon, polymethyl methacrylate, makrolon, glass at present
Equal high transparency material.Wherein polymethyl methacrylate, makrolon and glass are used as outer layer lens material.And epoxy resin
It is mainly used as encapsulating material with organosilicon, it is also possible to make lens material, be that current LED encapsulates two big essential high molecular materials
Material.Epoxy resin generally all has many advantages, such as excellent cementability, leakproofness, electrical insulating property and corrosion resistance, but there is also
The shortcomings that can not be ignored：As refractive index it is relatively low, it is heated or absorb ultraviolet light after easily turn yellow, internal stress is big the problems such as.Therefore it grinds
Study carefully improves the performances such as its heat resistance, shrinkage, refractive index, hardness, but modified epoxy tree by being modified to epoxy resin
Still there are a certain distance with market demands in terms of heat-resisting and ultraviolet aging resistance for fat, therefore people begin look for substitute
The material of epoxy resin.Wherein organosilicon material has many advantages, such as high heat-resisting and ultraviolet aging resistance, high transparency and low stress,
Therefore gradually substituted epoxy resin is become to the mainstream of LED encapsulation material.But the refractive index ability 1.40 of traditional organosilicon material is left
The right side cannot meet requirement of the high-power LED encapsulation material to high refractive index.So there is researcher to begin through to organosilicon knot
High refractive index group is introduced in structure（Such as sulphur, benzene, phenol）, to improve the refractive index of organosilicon, realize that the refractive index of organosilicon exists
Change between 1.4~1.55.
Currently, the LED organosilicon material for packaging of patent literature mostly uses greatly containing the organic of unsaturated bond both at home and abroad
Silicon polymer is synthesized by hydrosilylation under the effect of the catalyst with the organosilicon polymer containing active hydrogen.It is this to add
At mode have many advantages, such as no coupling product, do not foam, shrinking percentage is small, reaction is easy to control, be widely used in organosilicon encapsulating material
Synthesis.For example, vinyl polysiloxane has been made using hydrolyzing chlorosilane condensation method in patent US 2005061437, then by it
Sulfidization molding is carried out under platinum catalyst effect with the containing hydrogen silicone oil containing phenyl, obtains LED encapsulating materials.Result of study table
Bright, the high refractive index of the encapsulating material is up to 1.51, and bending strength is 95~135MPa, and shore D hardness is 75~85, tensile strength
For 5.4MPa.The light transmittance that 500h is radiated by UV is down to 92% by 95%, and uv-resistance can be good.But prepare organosilicon using Hydrolyze method
There are hydrolysis rates to be difficult to control for resin, and remaining Cl-The deficiencies of influencing the performance of product.Patent US 7314770 passes through
Cationic open loop condensation method is by octamethylcy-clotetrasiloxane (D4) and tetramethyl divinyl disiloxane (MMVi) in H2SO4It urges
End-vinyl polysiloxanes is prepared under change, then it is mixed with a certain proportion of containing hydrogen silicone oil, catalyst and emulsion, using can
Light-exposed solidification or ultraviolet light solidification method have prepared the LED encapsulating materials of transmitance, hot property and good mechanical performance.But it utilizes
The synthesis technology that open loop condensation method prepares organic siliconresin is complicated, and solvent is the organic solvent being more toxic, and has one to environment
Fixed pollution.
In addition, due to being limited by group itself, high refractive index group is introduced in organosilicon come improve refractive index by
To certain limitation, so there is research to use high refractive index inorganic nano material (such as TiO2、ZrO2, ZnO, ZnS, PbS etc.) with have
Machine silicon materials compound modes synthesizes high refractive index encapsulating material.Patent US 20070221939 is related to a kind of nano combined
The preparation method of LED encapsulation material prepares nano-TiO using butyl titanate2Particle, and coated and be nucleated using magnesium compound/
Then shell structure uses organic monomer to carry out particle surface hydrophobically modified, finally by the processed core/shell structure of hydrophobicity
Type nano-particle is added in organic siliconresin, and the nano modified organosilicon encapsulating material of high refractive index about 1.70 is made.But its
Preparation process is complicated, is not suitable for large-scale production, and nano-particle is directly added into organic system, can cause to disperse uneven easy
There is a phenomenon where reuniting, to which light scattering occur, the transparency of material is reduced.
In conclusion there is also reactions to be difficult to control during at present prepared by LED encapsulation material, impurity remains, preparation process is multiple
The problems such as miscellaneous, Miscibility and environmental pollution.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The preparation method and application of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, using sol-gal process in environment friend
Core/shell structure zirconium oxide cladding titanium oxide modified vinyl silicones is prepared in good isopropanol medium.Pass through zirconium dioxide
The mode of cladding titanium dioxide reduces the photocatalytic activity of titanium dioxide, extends the service life of material.Pass through phenyl group
With the synergistic effect of zirconium, titanium elements, the refractive index of material is greatly improved.Since zirconium, titanium elements are connected in a manner of being chemically bonded
To using Si-O-Si as in the organic siliconresin of main chain, therefore in turn avoids inorganic nano-particle and be easy to reunite in organic media
The phenomenon that, addition curing is carried out finally by containing hydrogen silicone oil and transition-metal catalyst that the chain of silica containing phenyl is added, is had
There is the environmentally friendly add-on type nanometer zirconium titanium of high refraction, high light transmission, heat-resisting, ultraviolet aging resistance and low stress and agent of low hygroscopicity compound
Colloidal sol/organic-silicon hybridization resin.
Purpose is created to reach foregoing invention, using following technical proposals：
A kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, includes the following steps：
1. the preparation of vinyl polysiloxane：
A. according to the composition of raw materials for preparing vinyl organosilicon resin, raw material components and its weight percent are as follows：
Vinylsiloxane monomer 30~50%,
Phenyl siloxane monomer 20~40%,
Alkylsiloxane monomer 5~10%,
Solvent 20~30%,
Water 4~6%,
Acid regulator 0.5~2%；
Above-mentioned vinylsiloxane monomer preferably uses vinyltrimethoxysilane, vinyltriethoxysilane, first
Base vinyl dimethoxysilane, methyl vinyl diethoxysilane, dimethylvinylmethoxysiiane and dimethyl second
Any one monomer in alkenyl Ethoxysilane or arbitrary various of monomer mixture；Above-mentioned phenyl siloxane monomer preferably uses
Triphenylmethoxy siloxanes, triphen base oxethyl siloxanes, dimethoxydiphenylsilane, diphenyl diethoxy silane,
Any one monomer in aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane or the mixing of arbitrary various of monomer
Object；Abovementioned alkyl siloxanyl monomers preferably use trimethylmethoxysilane, trimethylethoxysilane, methyl trimethoxy oxygroup silicon
Any one list in oxygen alkane, methyltriethoxy silane oxygen alkane, triethyl group methoxy radical siloxane and ethyl triethoxy silicane oxygen alkane
Body or arbitrary various of monomer mixture；Above-mentioned acid regulator preferably use hydrochloric acid, glacial acetic acid, phosphoric acid, sulfuric acid, nitric acid, to toluene
Any one sour or arbitrary a variety of acid blend in sulfonic acid and citric acid；Above-mentioned solvent preferably uses methanol, ethyl alcohol, isopropanol
With in n-butanol any one organic solvent or arbitrary a variety of ORGANIC SOLVENT MIXTURESs；
B. by the composition of raw materials for preparing vinyl organosilicon resin used in the step a, raw material components is carried out and are claimed
The vinylsiloxane of corrresponding quality, phenyl siloxane, alkylsiloxane, are sequentially added in reaction vessel by amount,
Solvent, water and acid regulator are added, copolycondensation 2~12 hours is then carried out at 40~100 DEG C；It is mixed in raw material components
When, while water and the molar ratio of total alkoxy in all three monomers being made to control 1：0.5~1：Between 2 ratios；In addition same
When so that the molar ratio of total alkoxy and solvent in three kinds of monomers is controlled 1：0.75~1：Between 3 ratios, after completion of the reaction
Solid impurity in product is removed using filter method, obtains vinyl organosilicon resin, it is spare；
2. nano zircite coats the preparation of the core/shell structure complex sol of titanium oxide：
A. according to prepare nano zircite coat titanium oxide core/shell structure complex sol formula, raw material components and
Its weight percent is as follows：
Titanate ester monomers 20~40%,
Zirconic acid ester monomer 10~30%,
Solvent 20~50%,
Water 2~6%,
Acid regulator 4~6%；
Above-mentioned titanate ester monomers preferably use tetraisopropyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate, four positive fourth of metatitanic acid
Any one monomer in ester and triethanolamine titanate chelate or arbitrary various of monomer mixture；Above-mentioned zirconic acid ester monomer is preferred
Using in four n-propyl of zirconic acid, zirconium-n-butylate and triethanolamine chelate any one monomer or arbitrary various of monomer it is mixed
Close object；Above-mentioned acid regulator preferably uses appointing in hydrochloric acid, glacial acetic acid, phosphoric acid, sulfuric acid, nitric acid, p-methyl benzenesulfonic acid and citric acid
It anticipates a kind of sour or arbitrary a variety of acid blends；Above-mentioned solvent preferably uses any one in methanol, ethyl alcohol, isopropanol and n-butanol
Kind organic solvent or arbitrary a variety of ORGANIC SOLVENT MIXTURESs；
B. according to the core/shell structure complex sol for preparing nano zircite and coating titanium oxide used in the step a
Formula, first by titanate ester monomers be added reactor in, then with dropping funel be added dropwise solvent, water and acid regulator mixing
Object, time for adding are 0.5~1h, are then hydrolyzed no more than 3 hours, add zirconic acid ester monomer, then dripped with dropping funel
The mixture of solubilizer, water and acid regulator, time for adding are 0.5~1h, then the cohydrolysis 0.5~6 at 20~60 DEG C
Hour, the adjustable nanometer zirconium titanium complex sol of refractive index is prepared, it is spare；Nanometer zirconium titanium sol particle grain size is less than or equal to
20nm, form are amorphous；
3. the preparation of modified hybrid resin basis glue：
By the step 1. in prepare vinyl organosilicon resin and the step 2. in prepare nanometer zirconium titanium
Complex sol is 1 according to weight ratio：0.5~1：1.5 ratio is uniformly mixed at normal temperatures, when mixing using stirring 20~
30 hours, high speed dispersion 3~6 hours or 3~8 hours mixed methods of ultrasonic disperse, when vinyl organosilicon resin and nanometer
After zirconium titanium complex sol is sufficiently mixed, then with revolving instrument removed at 30~70 DEG C or with vacuum drying chamber at 80~100 DEG C
Transparent, refractive index and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon of viscosity is made in solvent, water and small-molecule substance
Hybrid resin, to obtain modified hybrid resin basis glue；
4. the preparation of add-on type hybrid resin：
A. according to the formula for preparing add-on type hybrid resin, raw material components and its weight percent are as follows：
Modified hybrid resin basis glue 49~69%,
Catalyst 0.1~1.0%,
Crosslinking agent 30~50%,
Levelling agent 0.5~1%,
Above-mentioned catalyst preferably uses arbitrary in platinum catalyst, Wilkinson rhodium catalysts and Kasrtdet catalyst
It is a kind of arbitrary a variety of；Above-mentioned crosslinking agent preferably uses methyl and phenyl hydrogen-containing silicon oil or the hydrogeneous resin of aminomethyl phenyl, when using methyl
When phenyl hydrogen-containing silicon oil is as crosslinking agent, methyl and phenyl hydrogen-containing silicon oil refers to keeping containing in liquid condition and strand at room temperature
The linear polysiloxane of multiple Si-H functional groups, the structural formula of methyl and phenyl hydrogen-containing silicon oil are as follows：
（1）
In above-mentioned chemical formula（1）In, R representatives-CH3 ,-Ph, et al；Or when using the hydrogeneous resin conduct of aminomethyl phenyl
When crosslinking agent, the hydrogeneous resin of aminomethyl phenyl refers to keeping containing multiple Si-H functional groups in liquid condition and strand at room temperature
The structural formula of thennoset polysiloxane with highly cross-linked structure, the hydrogeneous resin of aminomethyl phenyl is as follows：
（2）
In above-mentioned chemical formula（2）In, R representatives-CH3 ,-Ph, et al；Above-mentioned levelling agent preferably uses helping for Bi Ke chemistry
Agent BYK346, BYK-354, BYK-358 or BASF auxiliary agent EFKA-3580；
B. according to the formula for preparing add-on type hybrid resin used in the step a, by a certain amount of hybrid resin
10~20min is mixed with catalyst in basic glue, adds crosslinking agent after mixing, after continuing 30~60min of stirring,
It is placed in vacuum drying chamber, then the vacuum defoamation at 50~70 DEG C, is taken from vacuum drying chamber after 15~30min of deaeration
Go out, that is, transparent, refractive index and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity is made.
A kind of add-on type prepared by the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of the present invention
The application of hybrid resin, it is using injection molding method, the add-on type nanometer zirconium titanium prepared in above-mentioned steps step b 4. is compound
It in colloidal sol/organic-silicon hybridization resin injection mold or is coated on device surface, then by add-on type hybrid resin together with loading mould
Tool or device are cured together with being placed in air dry oven, and solidification temperature is 120-200 DEG C, hardening time 2-6h, system
Standby transparent solid shape exemplar or clear-coated film.The add-on type hybrid resin prepared using the present invention is preferred for LED encapsulation knots
Surface antireflective part, optical mirror slip transparent functional layer or the transparent optical device of structure, optical waveguide funtion part, solar cell
Preparation.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin prepared by the present invention has high refractive index, height thoroughly
Cross rate, low water absorbable, anti-ultraviolet ageing performance, low internal stress and good heat resistance energy；
2. preparation method raw material of the present invention is easy to get, cost of material is low, and reaction condition is mild, simple for process, safety and environmental protection, this
One technology is expected to be applied to LED encapsulation and optical material field, and the add-on type hybrid resin prepared using the present invention is used to prepare
Transparent solid shape exemplar or clear-coated film have high refractive index, high transmittance, low water absorbable and good heat resistance, especially
It is suitable for LED encapsulation, optical waveguide, the surface antireflective of solar cell, optical mirror slip and transparent optical devices, slim light
Application has more in terms of quantization concave lens and hyperopic lens, camera cell phone and digital camera eyeglass, light and handy projector optical camera lens
Advantage.
Description of the drawings
Fig. 1 is the preparation method stream of one add-on type nanometer zirconium titanium complex sol of the embodiment of the present invention/organic-silicon hybridization resin
Cheng Tu.
Fig. 2 is that add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin prepared by one method of the embodiment of the present invention applies
Layer transmittance curve figure.
Specific implementation mode
Details are as follows for the preferred embodiment of the present invention：
Embodiment one：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin
Preparation method includes the following steps：
1. the preparation of vinyl polysiloxane：35.0g vinyltrimethoxysilanes are added in three-necked flask, under stiring
60 DEG C are warming up to, 9.2g triethyl group methoxy silanes are slowly added to, continues to be warming up to 80 DEG C after stirring 15min, then slowly add
Enter 20.6g triphenylmethoxy siloxanes, add 27.8g n-butanols, 5.4g deionized waters and 2g dilute hydrochloric acid mixture, stir
It mixes 8 hours, is cooled to room temperature, the impurity in silicones is removed using filtering technique, uses filter method to remove after completion of the reaction
Solid impurity in product obtains the vinyl organosilicon resin of water white transparency, spare；
2. nano zircite coats the preparation of the core/shell structure complex sol of titanium oxide：25.5g butyl titanates are poured into
In boiling flask, be added 48.0g isopropanols, 4.05g deionized waters, 3g dust technologies mixture, hydrolyze 0.5h, be then added
The adjustable nanometer zirconium titanium complex sol of refractive index is prepared in 20.5g zirconium-n-butylates, cohydrolysis 1 hour at 40 DEG C, spare；
3. the preparation of modified hybrid resin basis glue：By the step 1. in prepare vinyl organosilicon resin and
The step 2. in prepare nanometer zirconium titanium complex sol according to weight proportion be 1.5:1 ratio carries out uniformly at normal temperatures
Mixing is stirred 4 hours when mixing using high speed dispersion, waits for that the reaction was complete, finally, is removed at 60 DEG C using Rotary Evaporators molten
Agent, water and small-molecule substance, are made transparent, refractive index and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon of viscosity is miscellaneous
Change resin, to obtain modified hybrid resin basis glue；
4. the preparation of add-on type hybrid resin：By the step 3. in prepare modification hybrid resin basis glue 63.0g
It is poured into boiling flask with 0.15gKasrtdet catalyst (Pt~2%), carries out mixing 15min, added again after mixing
Enter 36.0g methyl and phenyl hydrogen-containing silicon oils, the mass fraction containing active hydrogen of methyl and phenyl hydrogen-containing silicon oil is 0.5%, the refractive power at 25 DEG C
Rate is 1.52, continues after stirring 30min, is placed in vacuum drying chamber, at 50 DEG C, from vacuum after vacuum defoamation 30min
It is taken out in drying box, that is, transparent, refractive index and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization tree of viscosity is made
Fat.
The present embodiment is prepared for having high refractive index, high transmittance, low water absorbable, low internal stress and good heat resistance energy
Environmentally friendly add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, using vinylsiloxane, phenyl siloxane, alkyl silicon
Oxygen alkane in 40~100 DEG C of hydrolytie polycondensations 2~12 hours, prepares transparent vinyl polysiloxane in acid condition；Then first
Titanate esters are hydrolyzed in acid condition, zirconic acid ester monomer is then added and carries out cohydrolysis, prepare that refractive index is adjustable to be received
Rice zirconium oxide coats titanium oxide core/shell structure complex sol；Vinyl polysiloxane and complex sol are carried out by a certain percentage again
Hydridization is reacted, and a nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin is obtained after pumping solvent；Finally in hybrid resin
Methyl and phenyl hydrogen-containing silicon oil and transition-metal catalyst is added, stirs evenly and is coated on base material, by addition manufactured in the present embodiment
Type nanometer zirconium titanium complex sol/organic-silicon hybridization resin prepares film in base material, and cures 2h at 180 DEG C, obtains transmitance
The film for being 1.62 for 99%, refractive index, referring to Fig. 2.The present embodiment preparation method cost of material is low, simple for process, safety collar
It protects, is expected to be applied to LED encapsulation and optical material field.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, including
Following steps：
1. the preparation of vinyl polysiloxane：This step is identical as one step of embodiment；
2. nano zircite coats the preparation of the core/shell structure complex sol of titanium oxide：This step and one step of embodiment
It is identical；
3. the preparation of modified hybrid resin basis glue：This step is identical as one step of embodiment；
4. the preparation of add-on type hybrid resin：By the step 3. in prepare modification hybrid resin basis glue 63.0g
It is added in boiling flask with 0.15gKasrtdet catalyst (% of Pt~2), carries out mixing 15min, added again after mixing
Enter the hydrogeneous resin of 42.0g aminomethyl phenyls, the mass fraction containing active hydrogen of the hydrogeneous resin of aminomethyl phenyl is 0.5%, the refractive power at 25 DEG C
Rate is 1.50, continues after stirring 30min, is placed in vacuum drying chamber, at 50 DEG C, from vacuum after vacuum defoamation 30min
It is taken out in drying box, that is, transparent, refractive index and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization tree of viscosity is made
Fat.
Add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin manufactured in the present embodiment is used into injection molding legal system
Standby film, and cure 32h at 150 DEG C, obtain the film that transmitance is 98%, refractive index is 1.59.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, including
Following steps：
1. the preparation of vinyl polysiloxane：Be added in three-necked flask 32.0g methylvinyldimethoxysilanes,
24.4g diphenyl dimethoxies siloxanes and 7.2g methyl trimethoxy oxygroup siloxanes, are warming up to 70 DEG C, add under stiring
The mixture of 30.0g isopropanols, 5.4g deionized waters and 1.0 acetic acid, continues mechanical agitation 10 hours, is cooled to room temperature, and uses
Filtering technique removes the impurity in silicones, uses filter method to remove the solid impurity in product after completion of the reaction, obtains nothing
The transparent vinyl organosilicon resin of color, it is spare；
2. nano zircite coats the preparation of the core/shell structure complex sol of titanium oxide：26.8g tetraisopropyl titanates are fallen
Enter in boiling flask, be added 44.7g ethyl alcohol, 5.4g deionized waters and 1.5g dilute hydrochloric acid mixture, hydrolyze 0.5h, add
The adjustable nanometer zirconium titanium complex sol of refractive index is prepared in 21.6g zirconium-n-butylates, cohydrolysis 0.5 hour at 60 DEG C, spare；
3. the preparation of modified hybrid resin basis glue：This step is identical as one step of embodiment；
4. the preparation of add-on type hybrid resin：By the step 3. in prepare modification hybrid resin basis glue 60.5g
It is added in boiling flask with 0.5gKasrtdet catalyst (% of Pt~2), carries out mixing 15min, added again after mixing
Enter 39.0g methyl and phenyl hydrogen-containing silicon oils, the mass fraction containing active hydrogen of methyl and phenyl hydrogen-containing silicon oil is 0.5%, the refractive power at 25 DEG C
Rate is 1.52, continues after stirring 30min, is placed in vacuum drying chamber, at 50 DEG C, from vacuum after vacuum defoamation 30min
It is taken out in drying box, that is, transparent, refractive index and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization tree of viscosity is made
Fat.
Add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin manufactured in the present embodiment is used into injection molding legal system
Standby film, and cure 5h at 120 DEG C, obtain the film that transmitance is 98%, refractive index is 1.60.
Example IV：
The present embodiment and embodiment three are essentially identical, are particular in that：
In the present embodiment, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, including
Following steps：
1. the preparation of vinyl polysiloxane：This step is identical as one step of embodiment；
2. nano zircite coats the preparation of the core/shell structure complex sol of titanium oxide：This step and one step of embodiment
It is identical；
3. the preparation of modified hybrid resin basis glue：By the step 1. in prepare vinyl organosilicon resin and
The step 2. in prepare nanometer zirconium titanium complex sol according to weight proportion be 1:1.2 ratio carries out uniformly at normal temperatures
Mixing is stirred 6 hours when mixing using high speed dispersion, waits for that the reaction was complete, finally, is removed at 60 DEG C using Rotary Evaporators molten
Agent, water and small-molecule substance, are made transparent, refractive index and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon of viscosity is miscellaneous
Change resin, to obtain modified hybrid resin basis glue；
4. the preparation of add-on type hybrid resin：
By the step 3. in prepare modification hybrid resin basis glue 68.5g and 0.45gKasrtdet catalyst (Pt
~2 %) it is added in boiling flask, mixing 15min is carried out, adds 31.0g methyl and phenyl hydrogen-containing silicon oils after mixing,
The mass fraction containing active hydrogen of methyl and phenyl hydrogen-containing silicon oil is 0.5%, and the index of refraction at 25 DEG C is 1.52, continues to stir 30min
Afterwards, be placed in vacuum drying chamber, at 50 DEG C, taken out from vacuum drying chamber after vacuum defoamation 30min, that is, be made it is transparent,
Refractive index and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
Add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin manufactured in the present embodiment is used into injection molding legal system
Standby film, and cure 5h at 120 DEG C, obtain the film that transmitance is 97%, refractive index is 1.64.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
It is former without departing from the technology of the preparation method and application of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of the present invention
Reason and inventive concept, belong to protection scope of the present invention.
Claims (12)
1. a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, which is characterized in that including as follows
Step：
1. the preparation of vinyl polysiloxane：
A. according to the composition of raw materials for preparing vinyl organosilicon resin, raw material components and its weight percent are as follows：
B. by the composition of raw materials for preparing vinyl organosilicon resin used in the step a, raw material components weighing is carried out, is pressed
The vinylsiloxane, phenyl siloxane, alkylsiloxane of corrresponding quality are added in reaction vessel by sequencing, are added
Then solvent, water and acid regulator carry out copolycondensation 2~12 hours at 40~100 DEG C；When raw material components are mixed, together
When so that the molar ratio of total alkoxy in water and all three monomers is controlled 1：0.5~1：Between 2 ratios；In addition while also making
The molar ratio of total alkoxy and solvent in three kinds of monomers is controlled 1：0.75~1：Between 3 ratios, used after completion of the reaction
Filtering method removes the solid impurity in product, obtains vinyl organosilicon resin, spare；
2. nano zircite coats the preparation of the core/shell structure complex sol of titanium oxide：
A. the formula for coating the core/shell structure complex sol of titanium oxide according to nano zircite is prepared, raw material components and its again
It is as follows to measure percentage：
B. matching according to the core/shell structure complex sol for preparing nano zircite cladding titanium oxide used in the step a
Titanate ester monomers are added in reactor first for side, then the mixture of solvent, water and acid regulator is added dropwise with dropping funel, drop
It is 0.5~1h between added-time, is then hydrolyzed no more than 3 hours, adds zirconic acid ester monomer, then molten with dropping funel dropwise addition
Agent, water and acid regulator mixture, time for adding is 0.5~1h, then cohydrolysis 0.5~6 hour at 20~60 DEG C,
The adjustable nanometer zirconium titanium complex sol of refractive index is prepared, it is spare；Nanometer zirconium titanium sol particle grain size is less than or equal to 20nm,
Form is amorphous；
3. the preparation of modified hybrid resin basis glue：
By the step 1. in prepare vinyl organosilicon resin and the step 2. in prepare nanometer zirconium titanium it is compound
Colloidal sol is 1 according to weight ratio：0.5~1：1.5 ratio is uniformly mixed at normal temperatures, small using stirring 20~30 when mixing
When, high speed dispersion 3~6 hours or 3~8 hours mixed methods of ultrasonic disperse, when vinyl organosilicon resin and nanometer zirconium titanium
After complex sol is sufficiently mixed, then with revolving instrument removed at 80~100 DEG C at 30~70 DEG C or with vacuum drying chamber solvent,
Transparent, refractive index and the adjustable nanometer zirconium titanium complex sol of viscosity/vinyl organosilicon hydridization tree is made in water and small-molecule substance
Fat, to obtain modified hybrid resin basis glue；
4. the preparation of add-on type hybrid resin：
A. according to the formula for preparing add-on type hybrid resin, raw material components and its weight percent are as follows：
B. according to the formula for preparing add-on type hybrid resin used in the step a, by a certain amount of hybrid resin basis
10~20min is mixed with catalyst in glue, adds crosslinking agent after mixing, after continuing 30~60min of stirring, is placed in true
In empty drying box, the then vacuum defoamation at 50~70 DEG C is taken out after 15~30min of deaeration from vacuum drying chamber, that is, is made
Transparent, refractive index and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
2. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 1., the vinylsiloxane monomer is vinyltrimethoxysilane, vinyl three
Ethoxysilane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, dimethylvinylsiloxy ylmethoxy silicon
Any one monomer in alkane and Vinyldimethylethoxysilane or arbitrary various of monomer mixture.
3. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 1., the phenyl siloxane monomer is triphenylmethoxy siloxanes, triphenyl ethoxy
Radical siloxane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane and aminomethyl phenyl
Any one monomer in diethoxy silane or arbitrary various of monomer mixture.
4. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 1., the alkylsiloxane monomer is trimethylmethoxysilane, front three base oxethyl
Silane, methyl trimethoxy oxygroup siloxanes, methyltriethoxy silane oxygen alkane, triethyl group methoxy radical siloxane and ethyl triethoxy silicane
Any one monomer in oxygen alkane or arbitrary various of monomer mixture.
5. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 2., the titanate ester monomers are metatitanic acid orthocarbonate, tetrabutyl titanate, four positive fourth of metatitanic acid
Any one monomer in ester and triethanolamine titanate chelate or arbitrary various of monomer mixture；The zirconic acid ester monomer is zirconium
Sour four n-propyls, zirconium-n-butylate and any one monomer in triethanolamine chelate or arbitrary various of monomer mixture.
6. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 1. and in the step a of the step 2., the acid regulator be hydrochloric acid, glacial acetic acid,
Any one sour or arbitrary a variety of acid blend in phosphoric acid, sulfuric acid, nitric acid, p-methyl benzenesulfonic acid and citric acid.
7. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 1. and in the step a of the step 2., the solvent is methanol, ethyl alcohol, isopropanol
With in n-butanol any one organic solvent or arbitrary a variety of ORGANIC SOLVENT MIXTURESs.
8. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 4., the catalyst is that platinum catalyst, Wilkinson rhodium catalysts and Kasrtdet are urged
Any one in agent is arbitrary a variety of.
9. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, feature
It is：In the step a of the step 4., the crosslinking agent be methyl and phenyl hydrogen-containing silicon oil or the hydrogeneous resin of aminomethyl phenyl, when
When using methyl and phenyl hydrogen-containing silicon oil as crosslinking agent, methyl and phenyl hydrogen-containing silicon oil refers to keeping liquid condition and molecule at room temperature
Contain the linear polysiloxane of multiple Si-H functional groups in chain, the structural formula of methyl and phenyl hydrogen-containing silicon oil is as follows：
In above-mentioned chemical formula (1), R representatives-CH3Or-Ph；Or when using the hydrogeneous resin of aminomethyl phenyl as crosslinking agent, first
The hydrogeneous resin of base phenyl refers to keeping containing multiple Si-H functional groups there is height to hand in liquid condition and strand at room temperature
It is coupled the thennoset polysiloxane of structure, the structural formula of the hydrogeneous resin of aminomethyl phenyl is as follows：
In above-mentioned chemical formula (2), R representatives-CH3 ,-Ph.
10. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, special
Sign is：In the step a of the step 4., the levelling agent is auxiliary agent B YK346, BYK-354, BYK-358 of Bi Ke chemistry
Or BASF auxiliary agent EFKA-3580.
11. prepared by a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin described in claim 1
The application of add-on type hybrid resin, it is characterised in that：Using injection molding method, by what is prepared in step step b 4.
In add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin injection mold or coated on device surface, then by add-on type
Hybrid resin is cured, solidification temperature 120-200 together with mold or device is loaded together with being placed in air dry oven
DEG C, hardening time 2-6h prepares transparent solid shape exemplar or clear-coated film.
12. according to the application of add-on type hybrid resin described in claim 11, it is characterised in that：It is used using add-on type hybrid resin
In LED encapsulation structure, optical waveguide funtion part, the surface antireflective part of solar cell, optical mirror slip transparent functional layer or
The preparation of transparent optical device.
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| CN103289098A (en) * | 2013-05-24 | 2013-09-11 | 东莞上海大学纳米技术研究院 | Organic silicon nano composite material and preparation method thereof |
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| CN103289098A (en) * | 2013-05-24 | 2013-09-11 | 东莞上海大学纳米技术研究院 | Organic silicon nano composite material and preparation method thereof |
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