CN105399958A - Hybrid organic silicon resin with framework structure containing Zr or containing Zr and Ti simultaneously and preparation method of organic silicon resin - Google Patents
Hybrid organic silicon resin with framework structure containing Zr or containing Zr and Ti simultaneously and preparation method of organic silicon resin Download PDFInfo
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- CN105399958A CN105399958A CN201510827075.1A CN201510827075A CN105399958A CN 105399958 A CN105399958 A CN 105399958A CN 201510827075 A CN201510827075 A CN 201510827075A CN 105399958 A CN105399958 A CN 105399958A
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Abstract
The invention relates to hybrid organic silicon resin with a framework structure containing Zr or containing Zr and Ti simultaneously and a preparation method of the organic silicon resin. The structure of the resin contains Si-O-Si, Si-O-Zr and Zr-O-Zr structural units, or is likely to contain Si-O-Ti, Ti-O-Ti and Ti-O-Zr structural units simultaneously. According to the preparation method of the resin, the hydrolytic condensation process of organic Zr or combined hydrolytic condensation of organic Zr and titanate is realized in an organic silicon resin solution with the low molecular weight, and the resin is prepared. The synthetic method is simple and easy to implement, and industrial production is facilitated. Zr is introduced, or Ti links are introduced simultaneously, so that the refraction index and the high-temperature resistance of the hybrid resin can be significantly improved. The organic silicon resin with the low molecular weight in raw materials is converted, and olefinic bonds or -Si-H active groups are easily introduced into the hybrid resin structure, so that the hybrid organic silicon resin can have the addition curing reaction.
Description
Technical field
The present invention relates to a kind of skeleton structure and contain zirconium or the silicone resin simultaneously containing titanium hydridization and preparation method thereof, belong to organic---inorganic hybrid material technical field.The zirconium (with titanium) introduced in resin links, and can significantly improve the specific refractory power of resin, weathering resistance and high and low temperature resistance; Lower molecular weight silicone resin unit easily can introduce rare key or-Si-H active group as reaction raw materials in resin structure, make zirconium (with titanium) hybrid organic silicon resin carry out addition curing, can be used as LED organosilicon encapsulating material, high-temperaure coating etc.
Background technology
Based on the semiconductor lighting of LED technology, there is the features such as efficient, energy-saving and environmental protection, long lifetime, easy care, be described as the new light sources of 21 century.But, along with the development of high power LED device, new demand is proposed to the aspect such as specific refractory power, ageing resistance of packaged material.
At present, the LED organosilicon material specific refractory power of high refractive index can reach between 1.50 ~ 1.55, a certain distance is had with chip specific refractory power (2 ~ 4), refractive index difference crosses the generation that conference causes total reflection, light reflection is returned chip internal and cannot effectively derive, therefore be necessary the specific refractory power improving packaged material, the generation of total reflection can be reduced, thus optical efficiency is got in raising.
Improve refractive index polymer adoptable method more, normally introduce the atom of high molar refraction or group (such as sulphur atom, halogen, condensed cyclic structure etc.) in the polymer or in polymkeric substance, add the inorganic nano-particle (TiO of high refractive index
2, ZrO
2, ZnS etc.), but most methods be not suitable for packaged LED.Concrete manifestation is as follows: in the alkene class optical resin of (1) thioretinite, vinyl-type monomer activity is poor, and induction period in polymerization is longer; Episulfide compounds because of the tension force of ternary sulphur ring comparatively large, less stable, is difficult to store; (2) polyimide and undesirable containing the fluorene structured optical resin transparency, processing temperature is very high; (3) halogen-containing resin weathering resistance is poor, the impact of easy light, heat and variable color, and against the requirement of environmental protection; (4) inorganic nano-particle complex optics resin existence and stability and transparent problem, often make film coating and use, organizer phase material is more difficult.
This patent is with the method for hydrolytic condensation, prepare a kind of skeleton structure and contain zirconium or the silicone resin simultaneously containing titanium hydridization, containing Si-O-Si, Si-O-Zr and Zr-O-Zr structural unit in structure, or may simultaneously also containing Si-O-Ti, Ti-O-Ti and Ti-O-Zr structural unit.Introduce zirconium by the mode of chemical bonding in the polymer or introduce titanium link simultaneously, specific refractory power and the resistance to elevated temperatures of hybrid resin can be significantly improved, give the performances such as the high thermal resistance of its excellence, dielectricity and erosion resistance.Meanwhile, in resin structure, easily introducing rare key or-Si-H active group by changing lower molecular weight silicone resin, making hybrid organic silicon resin carry out addition curing.The skeleton structure of preparation contains zirconium or contains titanium hybrid organic silicon resin transparent simultaneously, viscosity and specific refractory power adjustable, there is superior weathering resistance and high and low temperature resistance, there is application prospect widely in LED organosilicon encapsulating material, high-temperaure coating etc.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of skeleton structure and contains zirconium or the silicone resin simultaneously containing titanium hydridization and preparation method thereof, can be used as LED organosilicon encapsulating material, high-temperaure coating etc., have that specific refractory power is high, the feature of good weatherability, high and low temperature resistance excellence, easily realized the regulation and control of the viscosity of titaniferous silicone resin, specific refractory power and addition curing response capacity by the kind and proportioning controlling raw material.
A kind of skeleton structure of the present invention contains zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that, prepared by the hydrolytic condensation process realizing organic zirconium in lower molecular weight silicone resin solution or the cohydrolysis condensation realizing organic zirconium and titanic acid ester, technique is simple, easy suitability for industrialized production, containing Si-O-Si, Si-O-Zr and Zr-O-Zr structural unit in resin structure, or may simultaneously also containing Si-O-Ti, Ti-O-Ti and Ti-O-Zr segment.
A kind of skeleton structure of the present invention contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that, comprises the steps:
(1) under an inert atmosphere, the mixture of lower molecular weight silicone resin, solvent, organic zirconium monomer or organic zirconium and titanate ester monomers is joined in reaction vessel, in whipping process, slowly drip catalyzer and water wherein; Or under an inert atmosphere, lower molecular weight silicone resin, solvent, catalyzer and water are joined in reaction vessel, after being fully uniformly mixed, slowly drip the mixture of organic zirconium monomer or organic zirconium and titanate ester monomers wherein; Organic zirconium monomer and titanate ester monomers are referred to as organo-metallic ester monomer, the mass ratio of organo-metallic ester monomer and lower molecular weight silicone resin is 0 ~ 15:1, and is not 0; Solvent and reaction raw materials total mass ratio are 0.2 ~ 5:1; The total mass ratio that catalyst levels accounts for reaction system is 0 ~ 5%, and does not comprise 0; The mol ratio of adding water and organo-metallic ester monomer is 0.5 ~ 5:1.
(2) after being added dropwise to complete, hydrolysis-condensation reaction 2 ~ 12 hours at 70 ~ 120 DEG C; After reaction terminates, the catalyzer in washing removal system; After being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, can obtain transparent skeleton structure and contain zirconium or the silicone resin simultaneously containing titanium hydridization.
Described lower molecular weight silicone resin is the water white silicone resin in visible region, and can be one or more in the type silicone resins such as MTQ, MT, MQ, MDT, MDQ, DT, DQ, DTQ, TQ, MDTQ, molecular weight can be 0 ~ 3000.
Described organic zirconium monomer can be one or more in zirconium-n-propylate, zirconium iso-propoxide, zirconium-n-butylate, zirconium tert-butoxide, isopropoxy zirconium iso-propoxide, methyl ethyl diketone zirconium, tetraethoxy zirconium, cyclopentadienyl tri-chlorination zirconium, two (n-butyl cyclopentadienyl) zirconium dichloride, two (ethyicydopentadi etanyf group) zirconium dichloride, two (pentamethylcyclopentadiene base) zirconium dichloride, two (isopropylcyclopentadienyl) zirconium dichloride, two (tetramethyl-ring pentadienyl) zirconium dichloride.
Described titanate ester monomers can be one or more in tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate, tetrabutyl titanate, tetrabutyl titanate, two (acetylacetone based) di-isopropyl titanic acid ester, isopropoxy three (dioctylphosphoric acid ester) titanic acid ester, the oily acyloxy titanic acid ester of sec.-propyl three, three Unimac 5680 isopropyl titanates.
Guaranteeing that under organic zirconium monomer existent condition, organic zirconium monomer can mix (can be free of and have titanate ester monomers) by arbitrary proportion with titanate ester monomers, is referred to as organo-metallic ester monomer by organic zirconium monomer and titanate ester monomers.
Described solvent comprises one or more in benzene,toluene,xylene, normal hexane, normal heptane, hexanaphthene, methyl alcohol, ethanol, Virahol, propyl carbinol, acetone, butanone, tetrahydrofuran (THF) etc., preferred toluene.
Described catalyzer can be an acidic catalyst or basic catalyst, comprise organic acid (such as acetic acid etc.), mineral acid (such as hydrochloric acid, sulfuric acid etc.), strong acidic ion resin, organic bases (such as pyridine, triethylamine etc.), mineral alkali (such as potassium hydroxide, sodium hydroxide, dried barium hydroxide etc.), preferred basic catalyst.
Described lower molecular weight silicone resin can have active reactive group or not have active reactive group.The described lower molecular weight silicone resin with active reactive group is the lower molecular weight silicone resin with addition reaction active group containing ethylene linkage or Si-H.
A kind of skeleton structure that preparation method of the present invention obtains contains zirconium or the silicone resin simultaneously containing titanium hydridization, its structural formula following (not exclusively summarize structural formula of the present invention, but technological method of the present invention can be described):
Structural formula Wave line represent in other repeated structural units be attached thereto any one, alkyl residual after non-complete hydrolysis, any one completely in the hydroxyl that remains of condensation.
The invention has the beneficial effects as follows: contain zirconium or the silicone resin simultaneously containing titanium hydridization by a kind of skeleton structure prepared by the present invention, containing Si-O-Si, Si-O-Zr and Zr-O-Zr structural unit in structure, or simultaneously also containing Si-O-Ti, Ti-O-Ti and Ti-O-Zr segment, and may can introduce the Si-H needed for can reacting for addition curing or rare bond structure.Its specific refractory power can be adjustable between 1.4 ~ 2.0, has high refractive index, transmittance, superior weathering resistance and high and low temperature resistance.Synthetic method is simple, is easy to suitability for industrialized production, has application prospect widely in LED organosilicon encapsulating material, high-temperaure coating etc.
Embodiment
Present invention is described for following illustrative example, and example, only for explaining the present invention, is not intended to limit application of the present invention.
Embodiment 1
25.2g vinyl MT silicone resin (number-average molecular weight is 830), 200g toluene, the 0.1g vitriol oil and 8.0g water are put into there-necked flask, slowly drip 84.11g zirconium-n-butylate, after being added dropwise to complete at 80 DEG C dehydration condensation 6 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin 45.8g, resin index is 1.67/25 DEG C.
Embodiment 2
50.0g is put into there-necked flask containing Si-H base MQ silicone resin (number-average molecular weight is 1308), 34.6g zirconium iso-propoxide and 120g toluene, slow dropping 0.2g potassium hydroxide and the mixture of 4.5g water, after being added dropwise to complete at 110 DEG C dehydration condensation 5 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .59.2g, resin index is 1.56/25 DEG C.
Embodiment 3
25.0g is put into there-necked flask containing ethenylphenyl MDT silicone resin (number-average molecular weight is 560), 112.74g zirconium tert-butoxide and 180g toluene, slow dropping 0.3g potassium hydroxide and the mixture of 10.6g water, after being added dropwise to complete at 110 DEG C dehydration condensation 8 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .56.6g, resin index is 1.72/25 DEG C.
Embodiment 4
10.0g is put into there-necked flask containing Si-H base MDQ silicone resin (number-average molecular weight is 1210), 145.0g zirconium iso-propoxide and 220g toluene, slow dropping 0.4g acetic acid and the mixture of 15.8g water, after being added dropwise to complete at 110 DEG C dehydration condensation 12 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .58.7g, resin index is 1.80/25 DEG C.
Embodiment 5
50.0g is put into there-necked flask containing phenyl DQ silicone resin (number-average molecular weight is 2230), 16.8g zirconium-n-butylate and 120g toluene, slowly drips the mixture of 0.2g acetic acid and 2.0g water, after being added dropwise to complete at 110 DEG C dehydration condensation 12 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .50.5g, resin index is 1.54/25 DEG C.
Embodiment 6
50.0g is put into there-necked flask containing ethenylphenyl DT silicone resin (number-average molecular weight is 528), 150g toluene, 0.6g triethylamine and 5.3g water, after being fully uniformly mixed, in system, slowly drip the mixture of 33.8g zirconium-n-butylate and 20.0g tetrabutyl titanate, after being added dropwise to complete at 110 DEG C dehydration condensation 4 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .58.6g, resin index is 1.60/25 DEG C.
Embodiment 7
18.0g is put into there-necked flask containing ethenylphenyl MDT silicone resin (number-average molecular weight is 650), 38.5g zirconium iso-propoxide, 68g tetrabutyl titanate and 200g toluene, slow dropping 0.5g triethylamine and the mixture of 11.5g water, after being added dropwise to complete at 100 DEG C dehydration condensation 6 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .42.6g, resin index is 1.74/25 DEG C.
Embodiment 8
28.0g is put into there-necked flask containing ethenylphenyl MT silicone resin (number-average molecular weight is 1750), 38.5g zirconium iso-propoxide, 16g tetrabutyl titanate and 100g toluene, slow dropping 0.3g triethylamine and the mixture of 13.2g water, after being added dropwise to complete at 100 DEG C dehydration condensation 4 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .42.6g, resin index is 1.64/25 DEG C.
Embodiment 9
28.0g is put into there-necked flask containing ethenylphenyl MT silicone resin (number-average molecular weight is 1750), 17.3g zirconium iso-propoxide, 2.8g tetrabutyl titanate and 100g toluene, slow dropping 0.3g triethylamine and the mixture of 2.4g water, after being added dropwise to complete at 100 DEG C dehydration condensation 4 hours.After reaction terminates, the catalyzer in washing removing system, after being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, and obtain transparent titaniferous silicone resin .29.9g, resin index is 1.53/25 DEG C.
Claims (8)
1. skeleton structure contains a preparation method for zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that, comprises the steps:
Under an inert atmosphere, the mixture of lower molecular weight silicone resin, solvent, organic zirconium monomer or organic zirconium and titanate ester monomers is joined in reaction vessel, in whipping process, slowly drip catalyzer and water wherein; Or under an inert atmosphere, lower molecular weight silicone resin, solvent, catalyzer and water are joined in reaction vessel, after being fully uniformly mixed, slowly drip the mixture of organic zirconium monomer or organic zirconium and titanate ester monomers wherein; Organic zirconium monomer and titanate ester monomers are referred to as organo-metallic ester monomer, the mass ratio of organo-metallic ester monomer and lower molecular weight silicone resin is 0 ~ 15:1, and is not 0; Solvent and reaction raw materials total mass ratio are 0.2 ~ 5:1; The total mass ratio that catalyst levels accounts for reaction system is 0 ~ 5%, and does not comprise 0; The mol ratio of adding water and organo-metallic ester monomer is 0.5 ~ 5:1;
After being added dropwise to complete, hydrolysis-condensation reaction 2 ~ 12 hours at 70 ~ 120 DEG C; After reaction terminates, the catalyzer in washing removal system; After being washed till neutral organic phase drying, filtering, vacuum is revolved to boil off and is desolventized and small-molecule substance, can obtain transparent skeleton structure and contain zirconium or the silicone resin simultaneously containing titanium hydridization.
2. a kind of skeleton structure according to claim 1 contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that: described lower molecular weight silicone resin is the water white silicone resin in visible region, can be one or more in MTQ, MT, MQ, MDT, MDQ, DT, DQ, DTQ, TQ, MDTQ type silicone resin, molecular weight be 0 ~ 3000.
3. a kind of skeleton structure according to claim 1 contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that: described organic zirconium monomer is zirconium-n-propylate, zirconium iso-propoxide, zirconium-n-butylate, zirconium tert-butoxide, isopropoxy zirconium iso-propoxide, methyl ethyl diketone zirconium, tetraethoxy zirconium, cyclopentadienyl tri-chlorination zirconium, two (n-butyl cyclopentadienyl) zirconium dichloride, two (ethyicydopentadi etanyf group) zirconium dichloride, two (pentamethylcyclopentadiene base) zirconium dichloride, two (isopropylcyclopentadienyl) zirconium dichloride, one or more in two (tetramethyl-ring pentadienyl) zirconium dichloride, described titanate ester monomers is one or more in tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate, tetrabutyl titanate, tetrabutyl titanate, two (acetylacetone based) di-isopropyl titanic acid ester, isopropoxy three (dioctylphosphoric acid ester) titanic acid ester, the oily acyloxy titanic acid ester of sec.-propyl three, three Unimac 5680 isopropyl titanates, guaranteeing that, under organic zirconium monomer existent condition, organic zirconium monomer can mix (can be free of and have titanate ester monomers) by arbitrary proportion with titanate ester monomers.
4. a kind of skeleton structure according to claim 1 contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that: described solvent comprises one or more in benzene,toluene,xylene, normal hexane, normal heptane, hexanaphthene, methyl alcohol, ethanol, Virahol, propyl carbinol, acetone, butanone, tetrahydrofuran (THF) etc.
5. a kind of skeleton structure according to claim 1 contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that: described catalyzer is an acidic catalyst or basic catalyst, comprise organic acid, mineral acid, strong acidic ion resin, organic bases, mineral alkali.
6. a kind of skeleton structure according to claim 2 contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that: described lower molecular weight silicone resin can have active reactive group or not have active reactive group.
7. a kind of skeleton structure according to claim 6 contains the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization, it is characterized in that: the described lower molecular weight silicone resin with active reactive group is the lower molecular weight silicone resin with addition reaction active group containing ethylene linkage or Si-H.
8. the preparation method of zirconium or the silicone resin simultaneously containing titanium hydridization is contained according to the arbitrary described a kind of skeleton structure of claim 1-7, it is characterized in that: containing Si-O-Si, Si-O-Zr or Zr-O-Zr structural unit in prepared hybrid organic silicon resin structure, or simultaneously also containing Si-O-Ti, Ti-O-Ti and Ti-O-Zr structural unit.
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| CN110732043A (en) * | 2019-09-03 | 2020-01-31 | 四川国纳科技有限公司 | Preparation method of enhanced lumbar lateral interbody fusion cage |
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| CN114230800A (en) * | 2021-12-30 | 2022-03-25 | 东北大学 | Zirconium modified silicon resin impregnating compound and preparation method and application thereof |
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| CN115536849A (en) * | 2022-10-12 | 2022-12-30 | 美信新材料股份有限公司 | Titanium hybrid MQ silicon resin, anti-sagging heat conduction gel, preparation method of anti-sagging heat conduction gel and electronic instrument |
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| CN106381051A (en) * | 2016-08-23 | 2017-02-08 | 杭州国为光伏技术有限公司 | Photovoltaic coated glass protective solution, preparation method and application thereof |
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| CN115536849A (en) * | 2022-10-12 | 2022-12-30 | 美信新材料股份有限公司 | Titanium hybrid MQ silicon resin, anti-sagging heat conduction gel, preparation method of anti-sagging heat conduction gel and electronic instrument |
| CN115536849B (en) * | 2022-10-12 | 2023-07-14 | 美信新材料股份有限公司 | Titanium hybridized MQ silicon resin, anti-vertical flow heat conduction gel, preparation method thereof and electronic instrument |
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Application publication date: 20160316 |