CN102243411A - Method for preparing rare-earth beta diketone-base functionalized non-linear optical composite material - Google Patents
Method for preparing rare-earth beta diketone-base functionalized non-linear optical composite material Download PDFInfo
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Abstract
The invention belongs to the technical field of non-linear hybridized optical materials, in particular relates to a method for preparing a rare-earth beta diketone-base functionalized non-linear optical composite material. The method comprises the following steps of: modifying beta diketone organic molecules respectively by an organic synthesis method to obtain a functionalized molecule bridge and synthesize para-styryl pyridine of organic small molecules; further assembling beta-diketone organic bridge molecules, the organic small molecules and rare-earth ions into a rare-earth coordination complex by coordination bonds; and adding tetraethoxysilane to make the rare-earth coordination complex subjected to co-hydrolytic poly-condensation, and obtaining xerogel by a sol gel method. By the method, the organic molecules having an electronic conjugated system and an electronic transfer structure and the rare-earth ions are connected by coordination reaction, and the rare-earth ions are connected with the organic bridge molecules at the same time, so organic matters, inorganic matters and rare earth are bonded by high covalent bonds and coordination bonds on molecular level, and an optical composite material which is stable in chemical and thermo-mechanic property, regular in surface appearance and non-linear is obtained. The method for preparing the rare-earth beta diketone-base functionalized non-linear optical composite material has the advantages that: experimental conditions are mild; the optical composite material can be directly obtained at room temperature; operability is high; repeatability is good; the quality of the obtained optical composite material is stable; and the appearance is regular.
Description
Technical field
The invention belongs to nonlinear optics hybrid material preparing technical field, be specifically related to a kind of preparation method of rare earth β diketone base functionalization nonlinear optics compound substance.
Background technology
Material is as the material base of human society life, and Development of Materials promotes human material progress and social progress.Along with the fast development of modern science and technology, adapt to the continuing to bring out of various new materials of hi-tech, human demand to the advanced function material has greatly promoted the research and development of various advanced materials.The high speed development of current infotech, the transmission of bulk information, storage, exchange and processing have promoted the development of novel information storage material.Utilize photoelectron or full photon information and image to be handled as carrier, and, various nonlinear optical materials are become the research focus of vast researcher along with the develop rapidly in practical fields such as optical communication, photoelectron and optical information processing.Nonlinear optical material has widespread use at aspects such as laser freuqency doubling, electrooptical modulation, optical storage, light amplitude limit and photoswitches, is to realize with the photoelectron technology being the material base of the modern information technologies of core.The hybrid inorganic-organic nonlinear material since its to have the superior photism pliability of the good thermal stability of inorganic material and mechanical property and organic material concurrently non-linear and have a higher non-linearity coefficient, make it as the novel nonlinear optical material of a class, become the focus that people explore new nonlinear optical material.
Organic-inorganic nonlinear optics compound substance has following characteristics: can realize the mode of organic non-linear molecule with chemical bonding is combined with each other.The transparency, rigidity and the resistance to elevated temperatures of inorganic material can be combined with non-linear optical property, the elasticity of organic material by MOLECULE DESIGN, have advantage organic, inorganic material concurrently.
Rare earth element is described as the treasure-house of new material because of the singularity of its electronic structure has characteristics such as light, electricity, magnetic.People have carried out many about the optical property of rare earth ion and the research of magnetic performance material, it is all to have obtained development at full speed in fundamental research or in practical application, and it is good non-linear that it is had.Therefore, people have carried out a large amount of research to the rare earth organic complex nonlinear optical material, have synthesized the rare earth organic complex of parts such as two two ketones of rare earth and β, aromatic carboxylic acid class and heterocyclic.But the light stability of the difference of pure rare earth organic coordination compound and thermal stability can not be used it widely in social life.The development of hybrid material and good performance thereof make to prepare the focus that organic-inorganic hybrid material becomes Recent study in the inorganic matrix by rare earth compounding is incorporated into.Relevant bibliographical information has been arranged both at home and abroad, and partial results realized commercial the application, at the life fluorescence probe, light shutter device, there is greatly potential using value in fields such as efficient laser.By non-linear active organic functional molecular being introduced the material of the simple physical doping preparation of silane precursor, having skewness easily reunites, exist to be separated and shortcoming such as relaxation phenomena, rare earth compounding is connected on the inorganic matrix by covalent bond then can overcomes above shortcoming.Organic ligand is modified, then by the cohydrolysis polycondensation reaction, obtain having the hybrid material of inorganic network, be incorporated in the hybrid material by coordination at the rare earth ion that will have specific function, the organic-inorganic nonlinear optics compound substance of system not only possesses good thermal stability but also has the higher non-linearity coefficient.
This scheme relates to numerous ambits in theory as inorganic chemistry, organic chemistry, high polymer chemistry, colloid and surface chemistry etc., resultant rare-earth hybridized Nonlinear Composite has many potential using values, be expected to promote the development of numerous areas such as phototube switch, optical information processing, optical storage, optical-fibre communications, underwater communication, laser countermeasure (s) and nuclear fusion, liquid crystal, information storage medium, microelectronic component, all have profound significance for basic and applied research.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of rare earth β diketone base functionalization nonlinear optics compound substance.It is with in the two effect grafting inorganic matrixes of diketone rare earth compounding by covalent bond and coordination bond of organic β, thereby in the grafting that has realized on the level of molecule between organic and the inorganic matrix, prepared rare earth nonlinear optical material with premium properties, and to the secondary polarizability of molecule, symmetrical structure is studied, and analyzes its influence to nonlinear factor.
The preparation method of a kind of novel rare-earth β diketone base functionalization nonlinear optics compound substance that the present invention proposes, concrete steps are as follows:
(1) preparation of organic bridge molecule:
The adding of β diketone base is filled in the round-bottomed flask of organic solvent, under stirring condition, the organic solvent solution that adds sodium hydride, under 70-80 ℃ of condition, reflux 1.8-2.2h under the protection of nitrogen atmosphere, then organo silane coupling agent is dropwise splashed in the flask of stirring, continuing under 60-80 ℃ solution reaction temperature and protection of nitrogen gas refluxes stirred 12-18 hour, cooling gained solution, with Rotary Evaporators evaporate to dryness organic solvent, cleaning product, purifying obtains target product: β diketone base, the mol ratio of sodium hydride and organo-silicon coupling agent is 1:1:1;
(2) preparation of organic molecule:
Paranitrobenzaldehyde is dissolved in the organic solvent, place flask, add the 4-picoline, be heated to 70-80 ℃, and under this temperature, reflux, under nitrogen atmosphere back flow reaction 12-16 hour, put into ice cube, the NaOH neutralization with 50% obtains solid, get faint yellow solid with ethyl alcohol recrystallization, the mol ratio of paranitrobenzaldehyde and 4-picoline is 1:1;
(3) organic bridge molecule, high molecular polymer and rare-earth ion coordination reaction:
Under the condition of room temperature, with the organic bridge molecular melting of step (1) gained to organic solvent N, in the N dimethyl formamide, under stirring condition, the ethanolic solution of the organic molecule of step (2) gained and the ethanolic solution of rare earth nitrades are slowly dropwise splashed into respectively in the solution of step (1), coordination reaction takes place, the reaction time is 4-6 hour, obtain rare earth compounding, wherein: the mol ratio of organic bridge molecule, organic molecule and rare earth nitrades is 3:2:1;
(4) sol-gel process:
Under stirring condition, in the rare earth compounding of step (3) gained, splash into and add ethyl orthosilicate and deionized water, it is acid that the pH value of regulator solution is, accelerate its hydrolytie polycondensation, under the condition of room temperature hydrolysis condensation reaction 10-12 hour then, in the reaction: the mol ratio of rare earth compounding, ethyl orthosilicate and deionized water was 1:3:12;
(5) aging and dried:
The gel of step (4) gained was worn out 10-15 days under 60-90 ℃ temperature, the gained colloid substance is ground obtain pressed powder, with absolute ethyl alcohol and deionized water products obtained therefrom is washed then, drying promptly gets the final goal product.
Among the present invention, β diketone base described in the step (1) be in hexafluoroacetylacetone, thenoyltrifluoroacetone, trifluoroacetylacetone (TFA) or the β-naphthoyltrifluoroacetone any.
Among the present invention, the organo-silicon coupling agent described in the step (1) is the silica-based propyl isocyanate of triethoxy.
Among the present invention, organic solvent is absolute ethyl alcohol, tetrahydrofuran, acetic anhydride nitrogen described in step (1) and the step (2), in nitrogen-dimethyl formamide or the chloroform any.
Among the present invention, rare earth nitrades is an erbium nitrate described in the step (3).
Among the present invention, the pH value of control solution is 6-7 in the step (4).
Among the present invention, baking temperature is 60-70 ℃ described in the step (5), and be 4-8 days drying time.
The β diketone base functionalization nonlinear optics compound substance that utilizes the inventive method to prepare, its pattern is regular, arranges evenly, and inorganic organic phase mixes, and has good thermal stability and ductility and higher non-linearity coefficient.The structure of products therefrom, pattern, thermal stability, non-linear, composition can adopt X-ray powder diffraction (SAXRD), scanning electron microscope (SEM), differential thermal analysis (DTA) (TGA) respectively, the Nd-YAG laser instrument, and fourier transform infrared spectroscopy (FTIR) and fluorescence spectrum etc. characterize.
The preparation method of a kind of novel rare-earth β diketone base functionalization nonlinear optics compound substance that the present invention proposes, in the course of reaction of hydrolytie polycondensation, the beta diketone organism is received in the Si-O inorganic network with the method for covalency grafting, obtain the inorganic phase on molecular level and the grafting of organic phase, effectively avoided the generation of the phenomenon of phase separation of inorganic organic phase.In prepared system, beta diketone molecule as main energy absorption and donor, not only have high-quantum efficiency, high brightness and excitation and reach color expressive force preferably, and big conjugated system arranged, be both organic molecule, have the push-and-pull electron system, the electron transfer structure as second part, therefore after organic molecule being introduced, can be so that the gained compound substance can have higher second order polarization coefficient.Meanwhile, thermally-stabilised and the mechanicalness that inorganics is good, make our prepared composite non-linear optical material have the good non-linear of inorganic good stable and organic conjugate system concurrently, make prepared material can be widely used in the various aspects of life, we adopt, and the method with collosol and gel prepares inorganic organic non-linear compound substance under the condition of room temperature, not only production cost is low, and can obtain, compares the non-linear material preferably with vast purposes with organic non-linear optical properties with traditional inorganic nonlinear material.In addition, we can on molecular level, carry out structure flexible design, cut out, obtain best optical nonlinearity response and other specific optical property.
By a kind of novel rare-earth β diketone base functionalization nonlinear optics compound substance polarizability height that the inventive method is produced, the characteristics of the regular grade of microscopic appearance.At last, the inventive method workable, favorable reproducibility, economical and effective meets the Principles of Economy of Green Chemistry, products obtained therefrom steady quality.
Description of drawings
Fig. 1 is the two diketo functionalization nonlinear optics composite cross-sections scanning electron microscope diagrams of a kind of novel rare-earth β of the embodiment of the invention 1 gained.
Embodiment
Further specify the present invention below by embodiment, but protection scope of the present invention is not limited to these embodiment.Raw material in the embodiment of the invention is available from Shanghai traditional Chinese medicines group, and it is pure to be analysis.
Embodiment 1
Taking by weighing the adding of 0.104g hexafluoroacetylacetone is equipped with in the three-neck flask of 20ml tetrahydrofuran solution; stirring makes its dissolving; dropwise add the 6ml anhydrous tetrahydrofuran solution that is dissolved with the 0.012g sodium hydride then; under 70 ℃ condition; nitrogen protection reflux 2h dropwise adds the 6ml tetrahydrofuran solution that is dissolved with the silica-based propyl isocyanate of 0.123g triethoxy under condition of stirring.Keep whole solution temperature at 65 ℃ then, backflow 12h is cooled to room temperature under the nitrogen protection, and decompression steams organic solvent.Wash products therefrom three times with the 8ml cyclohexane, obtain light yellow oily liquid.N with 16ml, the hexafluoroacetylacetone bridging molecule of N solvent dimethylformamide dissolving gained, the erbium nitrate of getting organic molecule p-nitrophenyl vinylpyridine 0.226g and 0.231g then is dissolved in ethanolic solution and the erbium nitrate ethanolic solution that obtains the p-nitrophenyl vinylpyridine in the absolute ethyl alcohol respectively, under stirring condition, the N that the ethanolic solution of the ethanolic solution of prepared p-nitrophenyl vinylpyridine and erbium nitrate is successively dropwise added dissolved oil organic bridge molecular system, in the N dimethyl formamide solution, the control temperature of reaction is at 35 ℃, carry out coordination, dropwise drip ethanolic solution and the deionized water that is dissolved with the 0.104g ethyl orthosilicate behind the 2h, with the salt acid for adjusting pH value is 6, hydrolysis condensation reaction 12h.The mol ratio of hexafluoroacetylacetone, p-nitrophenyl vinylpyridine, rare earth nitrades, ethyl orthosilicate and deionized water is 3:2:1:3:12.Solid gel with gained is transferred to burin-in process in the baking oven then, and temperature is controlled at 65 ℃, and digestion time is 15 days.At last, resulting hybrid material ground with mortar obtain powdery solid, carry out repeated multiple times washing with absolute ethyl alcohol and deionized water, put into 60 ℃ dry 3 days of baking oven, obtain rare earth-hexafluoroacetylacetone-p-nitrophenyl vinylpyridine nonlinear optics compound substance.
After testing: the powder frequency-doubled effect of Er system is 1.3 times of KDP, does not have to absorb in 0.6-2 mm.
Embodiment 2
The 0.111g thenoyltrifluoroacetone is joined in the three-neck flask of the tetrahydrofuran that fills 20ml; stirring makes its dissolving; the tetrahydrofuran solution that dropwise adds the 6ml that is dissolved with the 0.012g sodium hydride then; under 70 ℃ condition; nitrogen protection reflux 2h, the 6ml tetrahydrofuran solution that will be dissolved with the silica-based propyl isocyanate of 0.123g triethoxy then dropwise adds.Make it then under the condition of 65 ℃ of nitrogen protections, stirring reaction 12h, cooling, decompression steams solvent.Wash products obtained therefrom three times with the 12ml cyclohexane, obtain light yellow oily liquid.N with 16ml, the thenoyltrifluoroacetone bridging molecule of N solvent dimethylformamide dissolving gained, organic molecule p-nitrophenyl vinylpyridine 0.226g that gets then and the erbium nitrate of 0.231g are dissolved in ethanolic solution and the erbium nitrate ethanolic solution that obtains the p-nitrophenyl vinylpyridine in the absolute ethyl alcohol respectively, under stirring condition, the N that the ethanolic solution of the ethanolic solution of prepared p-nitrophenyl vinylpyridine and erbium nitrate is successively dropwise added dissolved oil organic bridge molecular system, in the N dimethyl formamide solution, the control temperature of reaction is at 35 ℃, carry out coordination, dropwise drip ethanolic solution and the deionized water that is dissolved with the 0.104g ethyl orthosilicate behind the 2h, with the salt acid for adjusting pH value is 6, hydrolysis condensation reaction 12h.The mol ratio of thenoyltrifluoroacetone, p-nitrophenyl vinylpyridine, rare earth nitrades, ethyl orthosilicate and deionized water is 3:2:1:3:12.Solid gel with gained is transferred to burin-in process in the baking oven then, and temperature is controlled at 65 ℃, and digestion time is 15 days.At last, resulting hybrid material ground with mortar obtain powdery solid, carry out repeated multiple times washing with absolute ethyl alcohol and deionized water, put into 60 ℃ dry 3 days of baking oven, obtain rare earth-thenoyltrifluoroacetone-p-nitrophenyl vinylpyridine nonlinear optics compound substance.
Embodiment 3
0.077 trifluoroacetylacetone (TFA) is joined in the three-neck flask of the tetrahydrofuran that fills 20ml; stirring makes its dissolving; the tetrahydrofuran solution that dropwise adds the 6ml that is dissolved with the 0.012g sodium hydride then; under 70 ℃ condition; nitrogen protection reflux 2h, the 6ml tetrahydrofuran solution that will be dissolved with the silica-based propyl isocyanate of 0.123g triethoxy then dropwise adds.Make it then under the condition of 65 ℃ of nitrogen protections, stirring reaction 12h, cooling, decompression steams solvent.Wash products obtained therefrom three times with the 12ml cyclohexane, obtain light yellow oily liquid.N with 16ml, the trifluoroacetylacetone (TFA) bridging molecule of N solvent dimethylformamide dissolving gained, get the organic molecule 0.226g of step (2) gained and the erbium nitrate of 0.231g then and be dissolved in ethanolic solution and the erbium nitrate ethanolic solution that obtains the p-nitrophenyl vinylpyridine in the absolute ethyl alcohol respectively, under stirring condition, the N that the ethanolic solution of the ethanolic solution of prepared p-nitrophenyl vinylpyridine and erbium nitrate is successively dropwise added dissolved oil organic bridge molecular system, in the N dimethyl formamide solution, the control temperature of reaction is at 35 ℃, carry out coordination, dropwise drip ethanolic solution and the deionized water that is dissolved with the 0.104g ethyl orthosilicate behind the 2h, with the salt acid for adjusting pH value is 6, hydrolysis condensation reaction 12h.The mol ratio of trifluoroacetylacetone (TFA), p-nitrophenyl vinylpyridine, rare earth nitrades, ethyl orthosilicate and deionized water is 3:2:1:3:12.Solid gel with gained is transferred to burin-in process in the baking oven then, and temperature is controlled at 65 ℃, and digestion time is 15 days.At last, resulting hybrid material ground with mortar obtain powdery solid, carry out repeated multiple times washing with absolute ethyl alcohol and deionized water, put into 60 ℃ dry 3 days of baking oven, obtain rare earth-trifluoroacetylacetone (TFA)-p-nitrophenyl vinylpyridine nonlinear optics compound substance.
Embodiment 4
0.133g β-naphthoyltrifluoroacetone is joined in the three-neck flask of the tetrahydrofuran that fills 20ml; stirring makes its dissolving; the tetrahydrofuran solution that dropwise adds the 6ml that is dissolved with the 0.012g sodium hydride then; under 70 ℃ condition; nitrogen protection reflux 2h, the 6ml tetrahydrofuran solution that will be dissolved with the silica-based propyl isocyanate of 0.123g triethoxy then dropwise adds.Make it then under the condition of 65 ℃ of nitrogen protections, stirring reaction 12h, cooling, decompression steams solvent.Wash products obtained therefrom three times with the 12ml cyclohexane, obtain light yellow oily liquid.N with 16ml, β-naphthoyltrifluoroacetone the bridging molecule of N solvent dimethylformamide dissolving gained, get the organic molecule 0.226g of step (2) gained and the erbium nitrate of 0.231g then and be dissolved in ethanolic solution and the erbium nitrate ethanolic solution that obtains the p-nitrophenyl vinylpyridine in the absolute ethyl alcohol respectively, under stirring condition, the N that the ethanolic solution of the ethanolic solution of prepared p-nitrophenyl vinylpyridine and erbium nitrate is successively dropwise added dissolved oil organic bridge molecular system, in the N dimethyl formamide solution, the control temperature of reaction is at 35 ℃, carry out coordination, dropwise drip ethanolic solution and the deionized water that is dissolved with the 0.104g ethyl orthosilicate behind the 2h, with the salt acid for adjusting pH value is 6, hydrolysis condensation reaction 12h.The mol ratio of β-naphthoyltrifluoroacetone, p-nitrophenyl vinylpyridine, rare earth nitrades, ethyl orthosilicate and deionized water is 3:2:1:3:12.Solid gel with gained is transferred to burin-in process in the baking oven then, and temperature is controlled at 65 ℃, and digestion time is 15 days.At last, resulting hybrid material ground with mortar obtain powdery solid, carry out repeated multiple times washing with absolute ethyl alcohol and deionized water, put into 60 ℃ dry 3 days of baking oven, obtain rare earth-β-naphthoyltrifluoroacetone-p-nitrophenyl vinylpyridine nonlinear optics compound substance.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (7)
1. the preparation method of a rare earth β diketone base functionalization nonlinear optics compound substance is characterized in that concrete steps are as follows:
(1) preparation of organic bridge molecule:
The adding of β diketone base is filled in the round-bottomed flask of organic solvent, under stirring condition, the organic solvent solution that adds sodium hydride, under 70-80 ℃ of condition, reflux 1.8-2.2h under the protection of nitrogen atmosphere, then organo silane coupling agent is dropwise splashed in the flask of stirring, continuing under 60-80 ℃ solution reaction temperature and protection of nitrogen gas refluxes stirred 12-18 hour, cooling gained solution, with Rotary Evaporators evaporate to dryness organic solvent, cleaning product, purifying obtains target product: β diketone base, the mol ratio of sodium hydride and organo-silicon coupling agent is 1:1:1;
(2) preparation of organic molecule:
Paranitrobenzaldehyde is dissolved in the organic solvent, place flask, add the 4-picoline, be heated to 70-80 ℃, and under this temperature, reflux, under nitrogen atmosphere back flow reaction 12-16 hour, put into ice cube, the NaOH neutralization with 50% obtains solid, get faint yellow solid with ethyl alcohol recrystallization, the mol ratio of paranitrobenzaldehyde and 4-picoline is 1:1;
(3) organic bridge molecule, high molecular polymer and rare-earth ion coordination reaction:
Under the condition of room temperature, with the organic bridge molecular melting of step (1) gained to organic solvent N, in the N dimethyl formamide, under stirring condition, the ethanolic solution of the organic molecule of step (2) gained and the ethanolic solution of rare earth nitrades are slowly dropwise splashed into respectively in the solution of step (1), coordination reaction takes place, the reaction time is 4-6 hour, obtain rare earth compounding, wherein: the mol ratio of organic bridge molecule, organic molecule and rare earth nitrades is 3:2:1;
(4) sol-gel process:
Under stirring condition, in the rare earth compounding of step (3) gained, splash into and add ethyl orthosilicate and deionized water, it is acid that the pH value of regulator solution is, accelerate its hydrolytie polycondensation, under the condition of room temperature hydrolysis condensation reaction 10-12 hour then, in the reaction: the mol ratio of rare earth compounding, ethyl orthosilicate and deionized water was 1:3:12;
(5) aging and dried:
The gel of step (4) gained was worn out 10-15 days under 60-90 ℃ temperature, the gained colloid substance is ground obtain pressed powder, with absolute ethyl alcohol and deionized water products obtained therefrom is washed then, drying promptly gets the final goal product.
2. the preparation method of β diketone base functionalization nonlinear optics compound substance according to claim 1, it is characterized in that β diketone base described in the step (1) be in hexafluoroacetylacetone, thenoyltrifluoroacetone, trifluoroacetylacetone (TFA) or the β-naphthoyltrifluoroacetone any.
3. the preparation method of rare earth β diketone base functionalization nonlinear optics compound substance according to claim 1 is characterized in that the organo-silicon coupling agent described in the step (1) is the silica-based propyl isocyanate of triethoxy.
4. the preparation method of rare earth β diketone base functionalization nonlinear optics compound substance according to claim 1, it is characterized in that organic solvent is absolute ethyl alcohol, tetrahydrofuran, acetic anhydride nitrogen described in step (1) and the step (2), in nitrogen-dimethyl formamide or the chloroform any.
5. the preparation method of rare earth β diketone base functionalization nonlinear optics compound substance according to claim 1 is characterized in that rare earth nitrades is an erbium nitrate described in the step (3).
6. the preparation method of rare earth β diketone base functionalization nonlinear optics compound substance according to claim 1 is characterized in that the pH value of control solution in the step (4) is 6-7.
7. the preparation method of rare earth β diketone base functionalization nonlinear optics compound substance according to claim 1 is characterized in that baking temperature is 60-70 ℃ described in the step (5), and be 4-8 days drying time.
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| CN110330660A (en) * | 2019-06-11 | 2019-10-15 | 河北科技大学 | A kind of preparation method and applications of the rare-earth europium hybrid luminescent materials with aluminium ion sensing capabilities |
| CN114195833A (en) * | 2021-12-27 | 2022-03-18 | 郑州轻工业大学 | Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007091483A1 (en) * | 2006-02-09 | 2007-08-16 | Nagaoka University Of Technology | Optical component and method for manufacturing the same |
| CN101220266A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing beta-diketone functionalization rare earth mesoporous hybridisation luminescent material |
| CN101368097A (en) * | 2008-10-09 | 2009-02-18 | 同济大学 | Process for producing luminous rare earth-beta-diketone-polyvinyl pyridine macromolecule composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007091483A1 (en) * | 2006-02-09 | 2007-08-16 | Nagaoka University Of Technology | Optical component and method for manufacturing the same |
| CN101220266A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing beta-diketone functionalization rare earth mesoporous hybridisation luminescent material |
| CN101368097A (en) * | 2008-10-09 | 2009-02-18 | 同济大学 | Process for producing luminous rare earth-beta-diketone-polyvinyl pyridine macromolecule composite material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110330660A (en) * | 2019-06-11 | 2019-10-15 | 河北科技大学 | A kind of preparation method and applications of the rare-earth europium hybrid luminescent materials with aluminium ion sensing capabilities |
| CN110330660B (en) * | 2019-06-11 | 2021-07-20 | 河北科技大学 | Preparation method and application of rare earth europium hybrid luminescent material with aluminum ion sensing performance |
| CN114195833A (en) * | 2021-12-27 | 2022-03-18 | 郑州轻工业大学 | Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and preparation method thereof |
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