CN105218823A - The preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin and application - Google Patents
The preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin and application 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, adopt vinylsiloxane, phenyl siloxane, alkylsiloxane hydrolytie polycondensation hour in acid condition, prepare transparent vinyl polysiloxane; Then first titanic acid ester is hydrolyzed in acid condition, and then adds zirconate monomer and carry out cohydrolysis, prepare the adjustable nano zircite of specific refractory power coated titanium oxide core/shell structure complex sol; By a certain percentage vinyl polysiloxane and complex sol are carried out hydridization reaction again, after pumping solvent, obtain nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin.Add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin prepared by the present invention has high refractive index, high permeability, low water absorbable, anti-ultraviolet ageing performance, low internal stress and good heat resistance energy, preparation method's raw materials cost of the present invention is low, technique simple, safety and environmental protection, is expected to be applied to LED and optical material field.
Description
Technical field
The present invention relates to a kind of preparation method and application of composite resin, particularly relate to a kind of preparation method and application of additional organosilicon composite resin, be applied to technical field of function materials.
Background technology
Photodiode (LED) is the another generation novel illumination light source after incandescent light and luminescent lamp.And LED encapsulation material not only has sealing and protect IC, reduction junction temperature of chip and the effect of heat radiation; also have simultaneously and avoid LED be subject to the impact of ambient humidity and temperature and reduce chip and air refraction rate variance, thus improve the function of effective output of light.Therefore, for LED encapsulation material, good transmitance, high specific refractory power, heat-resisting, ultraviolet aging resistance and low-stress and low water absorption are that material institute is prerequisite.
Current LED packaged material comprises the high transparent materials such as epoxy resin, organosilicon, polymethylmethacrylate, polycarbonate, glass.Wherein polymethylmethacrylate, polycarbonate and glass are used as outer layer lens material.And epoxy resin and organosilicon are mainly used as packaged material, also can be used as lens material, is current LED two large essential high molecular materials.Epoxy resin generally all has the advantages such as excellent cementability, stopping property, electrical insulating property and erosion resistance, but also there is the shortcoming that can not be ignored: as lower in specific refractory power, be heated or absorb after ultraviolet problems such as easily turning yellow, internal stress is large.Therefore research is had to improve the performances such as its thermotolerance, shrinkability, specific refractory power, hardness by carrying out modification to epoxy resin, but still there is a certain distance with market demands in modified epoxy in heat-resisting and ultraviolet aging resistance, therefore people start to find can the material of displaced loop epoxy resins.Wherein organosilicon material has the advantages such as high heat-resisting and ultraviolet aging resistance, high transmission rate and low-stress, therefore progressively substituted epoxy resin is become the main flow of LED encapsulation material.But the specific refractory power of traditional organosilicon material ability about 1.40, can not meet the requirement of high-power LED encapsulation material to high refractive index.So have researchist to begin through introduce high refractive index group (as sulphur, benzene, phenol etc.) in organosilicon structures, improve organosilyl specific refractory power, realize organosilyl specific refractory power and change between 1.4 ~ 1.55.
At present, the organosilicon polymer of the most Bian of the LED organosilicon material of domestic and international patent literature containing unsaturated link(age) is synthesized by addition reaction of silicon with hydrogen under the effect of catalyzer with the organosilicon polymer containing reactive hydrogen.This addition mode has no coupling product, does not foam, the advantage such as shrinking percentage is little, easy control of reaction, is widely used in the synthesis of organosilicon encapsulating material.Such as, patent US2005061437 adopts hydrolyzing chlorosilane condensation method to obtain vinyl polysiloxane, then itself and the containing hydrogen silicone oil containing phenyl is carried out sulfidization molding under platinum catalyst effect, obtains LED packaged material.Result of study shows, the specific refractory power of this packaged material is up to 1.51, and flexural strength is 95 ~ 135MPa, shore D hardness is 75 ~ 85, and tensile strength is 5.4MPa.Transmittance through UV radiation 500h is down to 92% by 95%, and uv-resistance can be good.But utilizing hydrolysis method to prepare silicone resin, to there is hydrolysis rate wayward, and residual Cl
-the deficiencies such as the performance of product can be affected.Patent US7314770 passes through positively charged ion open loop condensation method by octamethylcyclotetrasiloxane (D
4) and tetramethyl divinyl disiloxane (MM
vi) at H
2sO
4prepare end-vinyl polysiloxane under catalysis, then it is mixed with a certain proportion of containing hydrogen silicone oil, catalyzer and sensitizer, adopt visible-light curing or ultraviolet light polymerization legal system for the LED encapsulation material of transmitance, thermal characteristics and good mechanical performance.But utilize open loop condensation method to prepare the synthesis technique complexity of silicone resin, and solvent is the organic solvent that toxicity is larger, has certain pollution to environment.
In addition, owing to being subject to the restriction of group itself, in organosilicon, introducing high refractive index group be subject to certain restrictions to improve specific refractory power, so there is research to adopt high refractive index inorganic nano material (as TiO
2, ZrO
2, ZnO, ZnS, PbS etc.) synthesize high refractive index packaged material with the mode of organosilicon material compound.Patent US20070221939 relates to a kind of preparation method of nano combined LED encapsulation material, namely adopts butyl (tetra) titanate to prepare nano-TiO
2particle, and adopt magnesium compound to be overmolding to core/shell structure, then adopt organic monomer to carry out hydrophobically modified to particle surface, finally the core/shell structure type nanoparticle of hydrophobicity process is joined in silicone resin, the nano modified organosilicon encapsulating material of obtained high refractive index about 1.70.But its complicated process of preparation, is not suitable for scale operation, and nanoparticle directly adds in organic system, can cause disperseing the uneven easy phenomenon occurring to reunite, thus scattering of light occurs, and reduces the transparency of material.
In sum, also there is the problems such as reaction is wayward, impurities left, complicated process of preparation, Miscibility and environmental pollution in current LED encapsulation material preparation.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of preparation method and application of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin are provided, adopt sol-gel method in eco-friendly isopropanol medium, prepared core/shell structure zirconium white coated titanium oxide modified vinyl silicone resin.Reduced the photocatalytic activity of titanium dioxide by the mode of zirconia-coated titanium dioxide, extend the work-ing life of material.By the synergy of phenyl group and zirconium, titanium elements, greatly improve the specific refractory power of material.Due to zirconium, titanium elements to be connected in the mode of chemical bonding with Si-O-Si be main chain silicone resin in, therefore turn avoid the phenomenon that inorganic nano-particle is easily reunited in organic medium, addition curing is carried out containing the containing hydrogen silicone oil of phenyl silica chain and transition-metal catalyst finally by adding, acquisition has high refraction, high printing opacity, the environmental protection add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of heat-resisting, ultraviolet aging resistance and low-stress and agent of low hygroscopicity.
Creating object for reaching foregoing invention, adopting following technical proposals:
A preparation method for add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, comprises the steps:
1. the preparation of vinyl polysiloxane:
A. according to the composition of raw materials preparing vinyl organosilicon resin, its feed composition and weight percent 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 adopts any one monomer in vinyltrimethoxy silane, vinyltriethoxysilane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, dimethylvinylmethoxysiiane and Vinyldimethylethoxysilane or any various of monomer mixture; Above-mentioned phenyl siloxane monomer preferably adopts any one monomer in triphenylmethoxy siloxanes, triphenyl oxyethyl group siloxanes, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane or any various of monomer mixture; Abovementioned alkyl siloxanyl monomers preferably adopts any one monomer in trimethylmethoxysilane, trimethylethoxysilane, methyl trimethoxy oxygen radical siloxane, methyltriethoxy silane oxygen alkane, triethyl methoxyl group siloxanes and ethyl triethoxy silicane oxygen alkane or any various of monomer mixture; Above-mentioned acid regulator preferably adopts any one acid or any multiple acid mixture in hydrochloric acid, Glacial acetic acid, phosphoric acid, sulfuric acid, nitric acid, tosic acid and citric acid; Above-mentioned solvent preferably adopts any one organic solvent in methyl alcohol, ethanol, Virahol and propyl carbinol or any multiple ORGANIC SOLVENT MIXTURES;
B. by the composition of raw materials preparing vinyl organosilicon resin adopted in described step a, carry out feed composition weighing, sequentially the vinylsiloxane of respective quality, phenyl siloxane, alkylsiloxane are joined in reaction vessel, add solvent, water and acid regulator again, then carry out copolycondensation 2 ~ 12 hours at 40 ~ 100 DEG C; When feed composition mixes, make the mol ratio of the total alkoxyl group in water and all three kinds of monomers control between 1:0.5 ~ 1:2 ratio simultaneously; Also make the mol ratio of the total alkoxyl group in three kinds of monomers and solvent control between 1:0.75 ~ 1:3 ratio in addition simultaneously, adopt the solid impurity in filter method removing product after completion of the reaction, obtain vinyl organosilicon resin, for subsequent use;
2. the preparation of the core/shell structure complex sol of the coated titanium oxide of nano zircite:
A. according to the formula of core/shell structure complex sol preparing the coated titanium oxide of nano zircite, its feed composition and weight percent as follows:
Titanate ester monomers 20 ~ 40%,
Zirconate monomer 10 ~ 30%,
Solvent 20 ~ 50%,
Water 2 ~ 6%,
Acid regulator 4 ~ 6%;
Above-mentioned titanate ester monomers preferably adopts any one monomer in titanium isopropylate, metatitanic acid orthocarbonate, tetrabutyl titanate, tetra-n-butyl titanate and triethanolamine titanate inner complex or any various of monomer mixture; Above-mentioned zirconate monomer preferably adopts any one monomer in zirconic acid four n-propyl, zirconium-n-butylate and triethanolamine inner complex or any various of monomer mixture; Above-mentioned acid regulator preferably adopts any one acid or any multiple acid mixture in hydrochloric acid, Glacial acetic acid, phosphoric acid, sulfuric acid, nitric acid, tosic acid and citric acid; Above-mentioned solvent preferably adopts any one organic solvent in methyl alcohol, ethanol, Virahol and propyl carbinol or any multiple ORGANIC SOLVENT MIXTURES;
B. according to the formula preparing the core/shell structure complex sol of the coated titanium oxide of nano zircite adopted in described step a, first titanate ester monomers is added in reactor, solvent is dripped again with dropping funnel, the mixture of water and acid regulator, time for adding is 0.5 ~ 1h, then be hydrolyzed and be no more than 3 hours, add zirconate monomer again, solvent is dripped again with dropping funnel, the mixture of water and acid regulator, time for adding is 0.5 ~ 1h, then cohydrolysis 0.5 ~ 6 hour at 20 ~ 60 DEG C, prepare the nanometer zirconium titanium complex sol that specific refractory power is adjustable, for subsequent use, nanometer zirconium titanium sol particle particle diameter is less than or equal to 20nm, and its form is amorphous,
3. the preparation of modification hybrid resin basis glue:
By described step 1. in preparation vinyl organosilicon resin and described step 2. in preparation nanometer zirconium titanium complex sol carry out Homogeneous phase mixing at normal temperatures according to the ratio that weight ratio is 1:0.5 ~ 1:1.5, stirring 20 ~ 30 hours are adopted during mixing, high speed dispersion 3 ~ 6 hours or the ultrasonic disperse blending means of 3 ~ 8 hours, after vinyl organosilicon resin and nanometer zirconium titanium complex sol fully mix, at 30 ~ 70 DEG C or with vacuum drying oven, at 80 ~ 100 DEG C, desolventizing is removed again with revolving steaming instrument, water and small-molecule substance, make transparent, specific refractory power and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin of viscosity, thus obtain modification hybrid resin basis glue,
4. the preparation of add-on type hybrid resin:
A. according to the formula preparing add-on type hybrid resin, its feed composition and weight percent as follows:
Modification hybrid resin basis glue 49 ~ 69%,
Catalyzer 0.1 ~ 1.0%,
Linking agent 30 ~ 50%,
Flow agent 0.5 ~ 1%,
Above-mentioned catalyzer preferably adopts any one in platinum catalyst, Wilkinson rhodium catalyst and Kasrtdet catalyzer multiple arbitrarily; Above-mentioned linking agent preferably adopts methyl and phenyl hydrogen-containing silicon oil or the hydrogeneous resin of aminomethyl phenyl, when adopting methyl and phenyl hydrogen-containing silicon oil as linking agent, methyl and phenyl hydrogen-containing silicon oil keeps liquid state under referring to room temperature and contains the linear polysiloxane of multiple Si-H functional group in molecular chain, and the structural formula of methyl and phenyl hydrogen-containing silicon oil is as follows:
（1）
In above-mentioned chemical formula (1), R representative-CH3 ,-Ph, etal; Or when adopting the hydrogeneous resin of aminomethyl phenyl as linking agent, liquid state is kept and containing the thennoset polysiloxane with highly cross-linked structure of multiple Si-H functional group in molecular chain, the structural formula of the hydrogeneous resin of aminomethyl phenyl is as follows under the hydrogeneous resin of aminomethyl phenyl refers to room temperature:
（2）
In above-mentioned chemical formula (2), R representative-CH3 ,-Ph, etal; Above-mentioned flow agent preferably adopts the auxiliary agent B YK346 of Bi Ke chemistry, BYK-354, BYK-358 or BASF auxiliary agent EFKA-3580;
B. according to the formula preparing add-on type hybrid resin adopted in described step a, a certain amount of hybrid resin basis glue and catalyst mix are stirred 10 ~ 20min, linking agent is added again after mixing, after continuing stirring 30 ~ 60min, be placed in vacuum drying oven, then vacuum defoamation at 50 ~ 70 DEG C, takes out after deaeration 15 ~ 30min from vacuum drying oven, namely makes transparent, specific refractory power and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
The application of add-on type hybrid resin prepared by a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of the present invention, adopt injection molding method, by in the add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin injection mould prepared in above-mentioned steps step b 4. or be coated on device surface, again add-on type hybrid resin is placed in air dry oven together in the lump together with loading mould or device, be cured, solidification value is 120-200 DEG C, set time is 2-6h, prepares transparent solid shape exemplar or clear-coated film.The add-on type hybrid resin prepared of the present invention is adopted to be preferred for the preparation of LED encapsulation structure, optical waveguides funtion part, the surperficial antireflective part of solar cell, optical mirror slip transparent functional layer or transparent optical device.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin that prepared by the present invention has high refractive index, high permeability, low water absorbable, anti-ultraviolet ageing performance, low internal stress and good heat resistance energy;
2. preparation method's raw material of the present invention is easy to get, raw materials cost is low, reaction conditions is gentle, technique is simple, safety and environmental protection, this technology is expected to be applied to LED and optical material field, add-on type hybrid resin prepared by employing the present invention is for the preparation of transparent solid shape exemplar or clear-coated film, there is high refractive index, high permeability, low water absorbable and good resistance toheat, be particularly useful for LED, optical waveguides, the surperficial antireflective of solar cell, optical mirror slip and transparent optical device, at slim lightweight concave lens and hyperopic lens, camera cell phone and digital camera eyeglass, the application of light and handy projector optical camera lens aspect has more advantage.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the embodiment of the present invention one add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin.
Fig. 2 is add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin coating transmittance curve figure prepared by the embodiment of the present invention one method.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment one:
In the present embodiment, see Fig. 1 and Fig. 2, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, comprises the steps:
1. the preparation of vinyl polysiloxane: add 35.0g vinyltrimethoxy silane in there-necked flask, under agitation be warming up to 60 DEG C, slowly add 9.2g triethyl methoxy silane, 80 DEG C are warming up to after continuing to stir 15min, then 20.6g triphenylmethoxy siloxanes is slowly added, add 27.8g propyl carbinol again, the mixture of 5.4g deionized water and 2g dilute hydrochloric acid, stir 8 hours, be cooled to room temperature, adopt the impurity in filtering technique removing silicone resin, adopt the solid impurity in filter method removing product after completion of the reaction, obtain water white vinyl organosilicon resin, for subsequent use,
2. the preparation of the core/shell structure complex sol of the coated titanium oxide of nano zircite: 25.5g tetrabutyl titanate is poured in Florence flask, add the mixture of 48.0g Virahol, 4.05g deionized water, 3g dust technology, hydrolysis 0.5h, then 20.5g zirconium-n-butylate is added, cohydrolysis 1 hour at 40 DEG C, prepare the nanometer zirconium titanium complex sol that specific refractory power is adjustable, for subsequent use;
3. modification hybrid resin basis glue preparation: by described step 1. in preparation vinyl organosilicon resin and described step 2. in preparation nanometer zirconium titanium complex sol carry out Homogeneous phase mixing at normal temperatures according to the ratio that weight proportion is 1.5:1, high speed dispersion is adopted to stir 4 hours during mixing, question response is complete, finally, use Rotary Evaporators at 60 DEG C except desolventizing, water and small-molecule substance, make transparent, specific refractory power and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin of viscosity, thus obtain modification hybrid resin basis glue;
4. the preparation of add-on type hybrid resin: by 3. the basic glue 63.0g of the middle modification hybrid resin prepared and 0.15gKasrtdet catalyzer (Pt ~ 2%) are poured in Florence flask in described step, carry out mix and blend 15min, 36.0g methyl and phenyl hydrogen-containing silicon oil is added again after mixing, methyl and phenyl hydrogen-containing silicon oil containing reactive hydrogen massfraction be 0.5%, refractive index at 25 DEG C is 1.52, after continuing to stir 30min, be placed in vacuum drying oven, at 50 DEG C, take out from vacuum drying oven after vacuum defoamation 30min, namely make transparent, specific refractory power and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
The present embodiment has prepared the environmental protection add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin with high refractive index, high permeability, low water absorbable, low internal stress and good heat resistance energy, adopt vinylsiloxane, phenyl siloxane, alkylsiloxane in acid condition in 40 ~ 100 DEG C of hydrolytie polycondensations 2 ~ 12 hours, prepare transparent vinyl polysiloxane; Then first titanic acid ester is hydrolyzed in acid condition, and then adds zirconate monomer and carry out cohydrolysis, prepare the adjustable nano zircite of specific refractory power coated titanium oxide core/shell structure complex sol; By a certain percentage vinyl polysiloxane and complex sol are carried out hydridization reaction again, after pumping solvent, obtain nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin; Finally in hybrid resin, add methyl and phenyl hydrogen-containing silicon oil and transition-metal catalyst, stir and coat base material, the add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin prepared by the present embodiment prepares film at base material, and 2h is solidified at 180 DEG C, obtain that transmitance is 99%, specific refractory power is the film of 1.62, see Fig. 2.The present embodiment preparation method raw materials cost is low, technique simple, safety and environmental protection, is expected to be applied to LED and optical material field.
embodiment two:
The present embodiment is substantially identical with embodiment one, and special feature is:
In the present embodiment, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, comprises the steps:
1. the preparation of vinyl polysiloxane: this step is identical with embodiment one step;
2. the preparation of the core/shell structure complex sol of the coated titanium oxide of nano zircite: this step is identical with embodiment one step;
3. the preparation of modification hybrid resin basis glue: this step is identical with embodiment one step;
4. the preparation of add-on type hybrid resin: by 3. the basic glue 63.0g of the middle modification hybrid resin prepared and 0.15gKasrtdet catalyzer (Pt ~ 2%) add in Florence flask in described step, carry out mix and blend 15min, the hydrogeneous resin of 42.0g aminomethyl phenyl is added again after mixing, the hydrogeneous resin of aminomethyl phenyl containing reactive hydrogen massfraction be 0.5%, refractive index at 25 DEG C is 1.50, after continuing to stir 30min, be placed in vacuum drying oven, at 50 DEG C, take out from vacuum drying oven after vacuum defoamation 30min, namely make transparent, specific refractory power and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
The add-on type nanometer zirconium titanium complex sol prepared by the present embodiment/organic-silicon hybridization resin adopts injection molding method to prepare film, and solidifies 32h at 150 DEG C, obtains that transmitance is 98%, specific refractory power is the film of 1.59.
embodiment three:
The present embodiment and previous embodiment are substantially identical, and special feature is:
In the present embodiment, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, comprises the steps:
1. the preparation of vinyl polysiloxane: add 32.0g methylvinyldimethoxysilane, 24.4g diphenyl dimethoxy siloxanes and 7.2g methyl trimethoxy oxygen radical siloxane in there-necked flask, under agitation be warming up to 70 DEG C, add the mixture of 30.0g Virahol, 5.4g deionized water and 1.0 acetic acid again, continue mechanical stirring 10 hours, be cooled to room temperature, adopt the impurity in filtering technique removing silicone resin, adopt the solid impurity in filter method removing product after completion of the reaction, obtain water white vinyl organosilicon resin, for subsequent use;
2. the preparation of the core/shell structure complex sol of the coated titanium oxide of nano zircite: 26.8g titanium isopropylate is poured in Florence flask, add the mixture of 44.7g ethanol, 5.4g deionized water and 1.5g dilute hydrochloric acid, hydrolysis 0.5h, add 21.6g zirconium-n-butylate again, cohydrolysis 0.5 hour at 60 DEG C, prepare the nanometer zirconium titanium complex sol that specific refractory power is adjustable, for subsequent use;
3. the preparation of modification hybrid resin basis glue: this step is identical with embodiment one step;
4. the preparation of add-on type hybrid resin: by 3. the basic glue 60.5g of the middle modification hybrid resin prepared and 0.5gKasrtdet catalyzer (Pt ~ 2%) add in Florence flask in described step, carry out mix and blend 15min, 39.0g methyl and phenyl hydrogen-containing silicon oil is added again after mixing, methyl and phenyl hydrogen-containing silicon oil containing reactive hydrogen massfraction be 0.5%, refractive index at 25 DEG C is 1.52, after continuing to stir 30min, be placed in vacuum drying oven, at 50 DEG C, take out from vacuum drying oven after vacuum defoamation 30min, namely make transparent, specific refractory power and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
The add-on type nanometer zirconium titanium complex sol prepared by the present embodiment/organic-silicon hybridization resin adopts injection molding method to prepare film, and solidifies 5h at 120 DEG C, obtains that transmitance is 98%, specific refractory power is the film of 1.60.
embodiment four:
The present embodiment is substantially identical with embodiment three, and special feature is:
In the present embodiment, a kind of preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, comprises the steps:
1. the preparation of vinyl polysiloxane: this step is identical with embodiment one step;
2. the preparation of the core/shell structure complex sol of the coated titanium oxide of nano zircite: this step is identical with embodiment one step;
3. modification hybrid resin basis glue preparation: by described step 1. in preparation vinyl organosilicon resin and described step 2. in preparation nanometer zirconium titanium complex sol carry out Homogeneous phase mixing at normal temperatures according to the ratio that weight proportion is 1:1.2, high speed dispersion is adopted to stir 6 hours during mixing, question response is complete, finally, use Rotary Evaporators at 60 DEG C except desolventizing, water and small-molecule substance, make transparent, specific refractory power and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin of viscosity, thus obtain modification hybrid resin basis glue;
4. the preparation of add-on type hybrid resin:
By in described step, 3. the basic glue 68.5g of the middle modification hybrid resin prepared and 0.45gKasrtdet catalyzer (Pt ~ 2%) add in Florence flask, carry out mix and blend 15min, 31.0g methyl and phenyl hydrogen-containing silicon oil is added again after mixing, methyl and phenyl hydrogen-containing silicon oil containing reactive hydrogen massfraction be 0.5%, refractive index at 25 DEG C is 1.52, after continuing to stir 30min, be placed in vacuum drying oven, at 50 DEG C, take out from vacuum drying oven after vacuum defoamation 30min, namely make transparent, specific refractory power and the adjustable add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin of viscosity.
The add-on type nanometer zirconium titanium complex sol prepared by the present embodiment/organic-silicon hybridization resin adopts injection molding method to prepare film, and solidifies 5h at 120 DEG C, obtains that transmitance is 97%, specific refractory power is the film of 1.64.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all spirit according to technical solution of the present invention and principle, substitute, combination or simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from the add-on type nanometer zirconium titanium complex sol/preparation method of organic-silicon hybridization resin of the present invention and the know-why of application and inventive concept, all protection scope of the present invention is belonged to.
Claims (12)
1. a preparation method for add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin, is characterized in that, comprise the steps:
1. the preparation of vinyl polysiloxane:
A. according to the composition of raw materials preparing vinyl organosilicon resin, its feed composition and weight percent 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%;
B. by the composition of raw materials preparing vinyl organosilicon resin adopted in described step a, carry out feed composition weighing, sequentially the vinylsiloxane of respective quality, phenyl siloxane, alkylsiloxane are joined in reaction vessel, add solvent, water and acid regulator again, then carry out copolycondensation 2 ~ 12 hours at 40 ~ 100 DEG C; When feed composition mixes, make the mol ratio of the total alkoxyl group in water and all three kinds of monomers control between 1:0.5 ~ 1:2 ratio simultaneously; Also make the mol ratio of the total alkoxyl group in three kinds of monomers and solvent control between 1:0.75 ~ 1:3 ratio in addition simultaneously, adopt the solid impurity in filter method removing product after completion of the reaction, obtain vinyl organosilicon resin, for subsequent use;
2. the preparation of the core/shell structure complex sol of the coated titanium oxide of nano zircite:
A. according to the formula of core/shell structure complex sol preparing the coated titanium oxide of nano zircite, its feed composition and weight percent as follows:
Titanate ester monomers 20 ~ 40%,
Zirconate monomer 10 ~ 30%,
Solvent 20 ~ 50%,
Water 2 ~ 6%,
Acid regulator 4 ~ 6%;
B. according to the formula preparing the core/shell structure complex sol of the coated titanium oxide of nano zircite adopted in described step a, first titanate ester monomers is added in reactor, solvent is dripped again with dropping funnel, the mixture of water and acid regulator, time for adding is 0.5 ~ 1h, then be hydrolyzed and be no more than 3 hours, add zirconate monomer again, solvent is dripped again with dropping funnel, the mixture of water and acid regulator, time for adding is 0.5 ~ 1h, then cohydrolysis 0.5 ~ 6 hour at 20 ~ 60 DEG C, prepare the nanometer zirconium titanium complex sol that specific refractory power is adjustable, for subsequent use, nanometer zirconium titanium sol particle particle diameter is less than or equal to 20nm, and its form is amorphous,
3. the preparation of modification hybrid resin basis glue:
By described step 1. in preparation vinyl organosilicon resin and described step 2. in preparation nanometer zirconium titanium complex sol carry out Homogeneous phase mixing at normal temperatures according to the ratio that weight ratio is 1:0.5 ~ 1:1.5, stirring 20 ~ 30 hours are adopted during mixing, high speed dispersion 3 ~ 6 hours or the ultrasonic disperse blending means of 3 ~ 8 hours, after vinyl organosilicon resin and nanometer zirconium titanium complex sol fully mix, at 30 ~ 70 DEG C or with vacuum drying oven, at 80 ~ 100 DEG C, desolventizing is removed again with revolving steaming instrument, water and small-molecule substance, make transparent, specific refractory power and the adjustable nanometer zirconium titanium complex sol/vinyl organosilicon hybrid resin of viscosity, thus obtain modification hybrid resin basis glue,
4. the preparation of add-on type hybrid resin:
A. according to the formula preparing add-on type hybrid resin, its feed composition and weight percent as follows:
Modification hybrid resin basis glue 49 ~ 69%,
Catalyzer 0.1 ~ 1.0%,
Linking agent 30 ~ 50%,
Flow agent 0.5 ~ 1%,
B. according to the formula preparing add-on type hybrid resin adopted in described step a, a certain amount of hybrid resin basis glue and catalyst mix are stirred 10 ~ 20min, linking agent is added again after mixing, after continuing stirring 30 ~ 60min, be placed in vacuum drying oven, then vacuum defoamation at 50 ~ 70 DEG C, takes out after deaeration 15 ~ 30min from vacuum drying oven, namely makes transparent, specific refractory power 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, it is characterized in that: in described step step a 1., described vinylsiloxane monomer is any one monomer in vinyltrimethoxy silane, vinyltriethoxysilane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, dimethylvinylmethoxysiiane and Vinyldimethylethoxysilane or various of monomer mixture arbitrarily.
3. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 1., described phenyl siloxane monomer is any one monomer in triphenylmethoxy siloxanes, triphenyl oxyethyl group siloxanes, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane or various of monomer mixture arbitrarily.
4. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 1., described alkylsiloxane monomer is any one monomer in trimethylmethoxysilane, trimethylethoxysilane, methyl trimethoxy oxygen radical siloxane, methyltriethoxy silane oxygen alkane, triethyl methoxyl group siloxanes and ethyl triethoxy silicane oxygen alkane or various of monomer mixture arbitrarily.
5. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 2., described titanate ester monomers is any one monomer in titanium isopropylate, metatitanic acid orthocarbonate, tetrabutyl titanate, tetra-n-butyl titanate and triethanolamine titanate inner complex or various of monomer mixture arbitrarily; Described zirconate monomer is any one monomer in zirconic acid four n-propyl, zirconium-n-butylate and triethanolamine inner complex or various of monomer mixture arbitrarily.
6. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 1. and in described step step a 2., described acid regulator is any one acid or any multiple acid mixture in hydrochloric acid, Glacial acetic acid, phosphoric acid, sulfuric acid, nitric acid, tosic 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, it is characterized in that: in described step step a 1. and in described step step a 2., described solvent is any one organic solvent in methyl alcohol, ethanol, Virahol and propyl carbinol or any multiple ORGANIC SOLVENT MIXTURES.
8. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 4., described catalyzer is that any one in platinum catalyst, Wilkinson rhodium catalyst and Kasrtdet catalyzer is multiple arbitrarily.
9. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 4., described linking agent is methyl and phenyl hydrogen-containing silicon oil or the hydrogeneous resin of aminomethyl phenyl, when adopting methyl and phenyl hydrogen-containing silicon oil as linking agent, methyl and phenyl hydrogen-containing silicon oil keeps liquid state under referring to room temperature and contains the linear polysiloxane of multiple Si-H functional group in molecular chain, and the structural formula of methyl and phenyl hydrogen-containing silicon oil is as follows:
（1）
In above-mentioned chemical formula (1), R representative-CH3 ,-Ph, etal; Or when adopting the hydrogeneous resin of aminomethyl phenyl as linking agent, liquid state is kept and containing the thennoset polysiloxane with highly cross-linked structure of multiple Si-H functional group in molecular chain, the structural formula of the hydrogeneous resin of aminomethyl phenyl is as follows under the hydrogeneous resin of aminomethyl phenyl refers to room temperature:
（2）
In above-mentioned chemical formula (2), R representative-CH3 ,-Ph, etal.
10. the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin according to claim 1, it is characterized in that: in described step step a 4., described flow agent is the auxiliary agent B YK346 of Bi Ke chemistry, BYK-354, BYK-358 or BASF auxiliary agent EFKA-3580.
The application of add-on type hybrid resin prepared by the preparation method of add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin described in 11. 1 kinds of claims 1, it is characterized in that: adopt injection molding method, by in the add-on type nanometer zirconium titanium complex sol/organic-silicon hybridization resin injection mould prepared in described step step b 4. or be coated on device surface, again add-on type hybrid resin is placed in air dry oven together in the lump together with loading mould or device, be cured, solidification value is 120-200 DEG C, set time is 2-6h, prepare transparent solid shape exemplar or clear-coated film.
12., according to the application of add-on type hybrid resin described in claim 11, is characterized in that: adopt add-on type hybrid resin to be used for the preparation of LED encapsulation structure, optical waveguides funtion part, the surperficial antireflective part of solar cell, optical mirror slip transparent functional layer or transparent optical device.
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| CN106633079A (en) * | 2016-12-31 | 2017-05-10 | 华南理工大学 | High refractive index silicon-zirconium hybrid resin and preparation method thereof |
| CN109476873A (en) * | 2016-07-18 | 2019-03-15 | Az电子材料（卢森堡）有限公司 | Preparation for LED encapsulation material |
| CN110387018A (en) * | 2019-07-19 | 2019-10-29 | 常州大学 | A kind of preparation method of sulfur-bearing polysiloxanes/polymethyl methacrylate light scattering composite material |
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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 |
| CN104725643A (en) * | 2014-12-26 | 2015-06-24 | 上海大学 | Preparation method and application of nano zirconium-titanium composite sol/organosilicon modified hybrid resin |
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| CN103131189A (en) * | 2013-01-05 | 2013-06-05 | 中科院广州化学有限公司 | Inorganic or organic hybridization nanocomposite for packaging light emitting diode (LED) and preparation method thereof |
| 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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| CN109476873A (en) * | 2016-07-18 | 2019-03-15 | Az电子材料（卢森堡）有限公司 | Preparation for LED encapsulation material |
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| CN106633079A (en) * | 2016-12-31 | 2017-05-10 | 华南理工大学 | High refractive index silicon-zirconium hybrid resin and preparation method thereof |
| CN106633079B (en) * | 2016-12-31 | 2019-05-14 | 华南理工大学 | A kind of high refractive index silicon zirconium hybrid resin and preparation method thereof |
| CN110387018A (en) * | 2019-07-19 | 2019-10-29 | 常州大学 | A kind of preparation method of sulfur-bearing polysiloxanes/polymethyl methacrylate light scattering composite material |
| CN110387018B (en) * | 2019-07-19 | 2021-12-21 | 常州大学 | Preparation method of sulfur-containing polysiloxane/polymethyl methacrylate light scattering composite material |
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