CN101250402A - Preparation of illuminant color adjustable tricolor organic-inorganic silicon-based hybrid material - Google Patents
Preparation of illuminant color adjustable tricolor organic-inorganic silicon-based hybrid material Download PDFInfo
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- CN101250402A CN101250402A CNA2008100352397A CN200810035239A CN101250402A CN 101250402 A CN101250402 A CN 101250402A CN A2008100352397 A CNA2008100352397 A CN A2008100352397A CN 200810035239 A CN200810035239 A CN 200810035239A CN 101250402 A CN101250402 A CN 101250402A
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Abstract
The invention belongs to the technical field for preparing rare earth luminescent material, which particularly relates to a process for preparing three primary colors inorganic-organic hybridized rare earth luminescent material whose illuminant colors can be adjusted. The process for preparation comprises the following specific steps: modifying the structure of aromatic derivation molecule with hydroxyl group, and leading in a specific coupling molecule, grafting inorganic molecule in Si-O organic network through a covalent bond and through further doing hydrolytic polycondensation with inorganic substrate, and finally getting inorganic-organic rare earth luminescent material. The process for preparation has mild preparation condition, which brings convenience for manufacturing and processing inorganic-organic hybridized material, lowers production cost, and can achieve energy band regulation through molecular design regulation. Different metal ions (europium ion, terbium ion and zinc ion) are respectively doped in the same silicon-based hybridized substrate, and three primary colors inorganic-organic hybridized rare earth luminescent materials which emit red color, green color and blue color are respectively prepared. Luminescent material which is finally got has the advantages of excellent thermal stability, high luminous efficiency and the like, therefore, the method has potential application value in the aspect of preparing illuminating material and ultra-thin plane display material.
Description
Technical field
The invention belongs to the rare earth luminescent material preparing technical field, be specifically related to the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of a kind of glow color.
Background technology
Rare earth compounding is incorporated in the matrix forms hybrid inorganic-organic materials and become the investigator and make great efforts the direction paid close attention in recent years, relevant bibliographical information has been arranged both at home and abroad, and partial results has realized commercial applications, at the life fluorescent probe, the plane liquid-crystal display, there is great potential using value in fields such as efficient laser.Nearest research concentrates on to be carried out passing through the cohydrolysis polycondensation behind the silylation modification to organic ligand, obtain the hybrid inorganic-organic materials that inorganic component and organic constituent are connected with the Si-C key, result of study subsequently shows, because the existence of organic constituent makes the material photo and thermal stability of final gained be greatly improved, and there is not phenomenon of phase separation to take place.Organic functions component wherein then effectively absorbs energy and passes to the rare earth ion at center, reaches the rare earth luminous effect of sensitization.
For the organic ligand that is silylated modification, in the prior art, mainly choose the aromatic derivant molecule that has carboxyl or amino with good photosensitization character.Again by with the precursor molecule of modified and inorganic matrix such as the further hydrolytie polycondensation of tetraethoxy, in conjunction with rare earth ion, obtain final hybrid inorganic-organic rare earth luminescent material by optical active group.But through years of researches, based on to having more thorough that preparation route that carboxyl or amino aromatic derivant molecule modify has been studied, if still wish to carry out on this basis darker wider research or the hybrid material difficulty of better character is all bigger.
Summary of the invention
The preparation method who the purpose of this invention is to provide the adjustable tricolor organic-inorganic silicon-based hybrid material of a kind of glow color.
The preparation method of the tricolor organic-inorganic silicon-based hybrid material that the glow color that the present invention proposes is adjustable, the aromatic derivant molecule that will have hydroxyl carries out structural modification and introduces specific coupling molecule, by organic molecule being passed through the covalent linkage grafting in the Si-O inorganic network, finally obtain the hybrid inorganic-organic rare earth luminescent material again with the further hydrolytie polycondensation of inorganic matrix.Concrete steps are as follows:
(1) preparation of presoma:
The aromatic derivant that will contain hydroxyl is dissolved in the organic solvent, to wherein adding organo-silicon coupling agent, under nitrogen protection reflux 6-10 hour, the control reflux temperature is 80 ℃-100 ℃, the evaporate to dryness organic solvent, products therefrom washs, purifying, obtains the organosilicon presoma of grafting 1 organic functions group; Wherein: containing the aromatic derivant of hydroxyl and the mol ratio of organo-silicon coupling agent is 0.8: 1-1.2: 1;
(2) sol-gel process:
In the organosilicon presoma of step (1) gained, add tetraethoxy, rare earth nitrate or zinc acetate respectively, the Ph value of regulator solution, under 20-40 ℃ of temperature hydrolysis condensation reaction 5-10 hour, up to the generation of solid gel; Wherein: the mol ratio of organosilicon presoma, tetraethoxy, rare earth nitrate is 3: 6: 1; The mol ratio of organosilicon presoma, tetraethoxy, zinc acetate is 2: 4: 1.
(3) aging and drying treatment:
With the gel burin-in process of step (2) gained, promptly obtain the hybrid inorganic-organic luminescent material of covalent linkage keyed jointing.
Among the present invention, the aromatic derivant that contains hydroxyl described in the step (1) is Alpha-hydroxy pyridine or tiron, and organo-silicon coupling agent is the silica-based propyl isocyanate of triethoxy.
Among the present invention, the organic solvent described in the step (1) is DMF (nitrogen dimethylformamide) or pyridine.
Among the present invention, rare earth nitrate is europium nitrate, Terbium trinitrate and zinc acetate described in the step (2).
Among the present invention, the scope of Ph value is between acid 1-3 in the step (2).
Among the present invention, hydrolysis temperature is 20-40 ℃ described in the step (2).
Among the present invention, aging temperature is 60-80 ℃ in the step (3), and digestion time is 10-30 days.
Hybrid inorganic-organic luminescent material prepared according to the methods of the invention is characterized in that having good optics, and pattern is regular, arrange evenly, and the generation that is separated of no organic and inorganic, particle size is at 100-500nm.
Big and transformation efficiency is high by the hybrid inorganic-organic luminescent material photon absorbing intensity of the inventive method preparation, microscopic appearance is regular, not having between organic phase and the inorganic phase is separated produce and size distribution even, favorable dispersity.In addition, the required mild condition of the inventive method, workable, favorable reproducibility, and products obtained therefrom steady quality.
Description of drawings
Fig. 1 is the embodiment of the invention 1 gained doping Eu
3+The fluorogram of hybrid luminescent materials.
Fig. 2 is the embodiment of the invention 2 gained doping Tb
3+The fluorogram of hybrid luminescent materials.
Fig. 3 is the embodiment of the invention 3 gained doping of Zn
2+The fluorogram of hybrid luminescent materials.
Embodiment
The present invention below will be described in more detail by reference example, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
1mmol Alpha-hydroxy pyridine is dissolved in 10mlDMF, adds in the three-necked bottle and be heated to backflow.The 10mlDMF solution that will be dissolved with the silica-based propyl isocyanate of 0.8mmol triethoxy then dropwise adds.At 80 ℃ of backflow 6h, reduce pressure and steam solvent, obtains light yellow oily liquid by cooling under nitrogen protection for whole solution after dripping.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy and europium nitrate then.The amount of substance ratio of organosilicon presoma, tetraethoxy and europium nitrate is 3: 6: 1.The Ph value of regulator solution is 1, and hydrolysis condensation reaction 5h under 20 ℃ of temperature is up to the generation of solid gel.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 60 ℃, and digestion time is 10 days, finally obtains being doped with the organic-inorganic silicon-based hybrid material of europium ion.
Embodiment 2
1mmol Alpha-hydroxy pyridine is dissolved in 10mlDMF, adds in the three-necked bottle and be heated to backflow.The 10mlDMF solution that will be dissolved with the silica-based propyl isocyanate of 1mmol triethoxy then dropwise adds.Drip the whole solution in back 90 ℃ of backflow 8h under nitrogen protection, cooling, decompression steams solvent, obtains light yellow oily liquid.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy and Terbium trinitrate then.The amount of substance ratio of organosilicon presoma, tetraethoxy and Terbium trinitrate is 3: 6: 1.The Ph value of regulator solution is 2, and hydrolysis condensation reaction 8h under 30 ℃ of temperature is up to the generation of solid gel.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 70 ℃, and digestion time is 20 days, finally obtains being doped with the organic-inorganic silicon-based hybrid material of terbium ion.
1mmol Alpha-hydroxy pyridine is dissolved in 10mlDMF, adds in the three-necked bottle and be heated to backflow.The 10mlDMF solution that will be dissolved with the silica-based propyl isocyanate of 1.2mmol triethoxy then dropwise adds.Drip the whole solution in back 100 ℃ of backflow 10h under nitrogen protection, cooling, decompression steams solvent, obtains light yellow oily liquid.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy and zinc acetate then.The amount of substance ratio of organosilicon presoma, tetraethoxy and zinc acetate is 2: 4: 1.The Ph value of regulator solution is 3, and hydrolysis condensation reaction 10h under 40 ℃ of temperature is up to the generation of solid gel.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 80 ℃, and digestion time is 30 days, finally obtains being doped with the organic-inorganic silicon-based hybrid material of zine ion.
The 1mmol tiron is dissolved in the 10ml pyridine, adds in the three-necked bottle and be heated to backflow.The 10ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 0.8mmol triethoxy then dropwise adds.Drip the whole solution in back 80 ℃ of backflow 6h under nitrogen protection, cooling, decompression steams solvent, obtains light yellow oily liquid.The oily organosilicon presoma of gained is dissolved in the pyridine, adds tetraethoxy and europium nitrate then.The amount of substance ratio of organosilicon presoma, tetraethoxy and europium nitrate is 3: 6: 1.The Ph value of regulator solution is 1, and hydrolysis condensation reaction 5h under 20 ℃ of temperature is up to the generation of solid gel.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 60 ℃, and digestion time is 10 days, finally obtains being doped with the organic-inorganic silicon-based hybrid material of europium ion.
The 1mmol tiron is dissolved in the 10ml pyridine, adds in the three-necked bottle and be heated to backflow.The 10ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 1mmol triethoxy then dropwise adds.Drip the whole solution in back 90 ℃ of backflow 8h under nitrogen protection, cooling, decompression steams solvent, obtains light yellow oily liquid.The oily organosilicon presoma of gained is dissolved in the pyridine, adds tetraethoxy and Terbium trinitrate then.The amount of substance ratio of organosilicon presoma, tetraethoxy and Terbium trinitrate is 3: 6: 1.The Ph value of regulator solution is 2, and hydrolysis condensation reaction 8h under 30 ℃ of temperature is up to the generation of solid gel.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 70 ℃, and digestion time is 20 days, finally obtains being doped with the organic-inorganic silicon-based hybrid material of terbium ion.
Embodiment 6
The 1mmol tiron is dissolved in the 10ml pyridine, adds in the three-necked bottle and be heated to backflow.The 10ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 1.2mmol triethoxy then dropwise adds.Drip the whole solution in back 100 ℃ of backflow 10h under nitrogen protection, cooling, decompression steams solvent, obtains light yellow oily liquid.The oily organosilicon presoma of gained is dissolved in the pyridine, adds tetraethoxy and zinc acetate then.The amount of substance ratio of organosilicon presoma, tetraethoxy and zinc acetate is 2: 4: 1.The Ph value of regulator solution is 3, and hydrolysis condensation reaction 10h under 40 ℃ of temperature is up to the generation of solid gel.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 80 ℃, and digestion time is 30 days, finally obtains being doped with the organic-inorganic silicon-based hybrid material of zine ion.
Claims (6)
1, the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of a kind of glow color is characterized in that concrete steps are as follows:
(1) preparation of presoma:
The aromatic derivant that will contain hydroxyl is dissolved in the organic solvent, to wherein adding organo-silicon coupling agent, under nitrogen protection reflux 6-10 hour, the control reflux temperature is 80 ℃-100 ℃, the evaporate to dryness organic solvent, products therefrom washs, purifying, obtains the organosilicon presoma of grafting organic functions group; Wherein: containing the aromatic derivant of hydroxyl and the mol ratio of organo-silicon coupling agent is 1: 0.8-1: 1.2;
(2) sol-gel process:
In the organosilicon presoma of step (1) gained, add tetraethoxy, rare earth nitrate or zinc acetate respectively, the Ph value of regulator solution, under 20-40 ℃ of temperature hydrolysis condensation reaction 5-10 hour, up to the generation of solid gel; Wherein: the mol ratio of organosilicon presoma, tetraethoxy, rare earth nitrate is 3: 6: 1; The mol ratio of organosilicon presoma, tetraethoxy, zinc acetate is 2: 4: 1;
(3) aging and drying treatment:
With the gel burin-in process of step (2) gained, promptly obtain the hybrid inorganic-organic luminescent material of covalent linkage keyed jointing.
2, the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of glow color according to claim 1, the aromatic derivant that it is characterized in that containing described in the step (1) hydroxyl is Alpha-hydroxy pyridine or tiron, and organo-silicon coupling agent is the silica-based propyl isocyanate of triethoxy.
3, the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of glow color according to claim 1 is characterized in that the organic solvent described in the step (1) is nitrogen dimethylformamide or pyridine.
4, the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of glow color according to claim 1, it is characterized in that rare earth nitrate described in the step (2) be in europium nitrate, Terbium trinitrate or the Dysprosium trinitrate any.
5, the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of glow color according to claim 1 is characterized in that the scope of Ph value in the step (2) is acid 1-3.
6, the preparation method of the adjustable tricolor organic-inorganic silicon-based hybrid material of glow color according to claim 1 is characterized in that aging temperature is 60-80 ℃ in the step (3), and digestion time is 10-30 days.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194776A (en) * | 2014-09-09 | 2014-12-10 | 吉林大学 | Functionalized rare-earth complex organic/inorganic hybrid luminescent material and preparation method thereof |
| CN108713078A (en) * | 2015-12-10 | 2018-10-26 | 阿克蒂赛尔有限责任公司 | The processing of textile material |
| 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 |
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| US6861091B2 (en) * | 2000-12-27 | 2005-03-01 | Canon Kabushiki Kaisha | Self-assembly of organic-inorganic nanocomposite thin films for use in hybrid organic light emitting devices (HLED) |
| CN1257948C (en) * | 2004-10-18 | 2006-05-31 | 暨南大学 | Organic-inorganic hybrid paint and its preparing method |
| CN1803971A (en) * | 2005-12-30 | 2006-07-19 | 中国科学院上海硅酸盐研究所 | Method for preparing 8-hydroxyquinoline aluminium/silicone oxide composite luminescent material |
| CN101112995A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for preparing organic-inorganic hybrid integral material |
| CN100556543C (en) * | 2007-02-15 | 2009-11-04 | 湖南中烟工业有限责任公司 | A kind of orderly organic-inorganic hybrid mesoporous silica and loaded with nano gold copper-base alloy and their preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194776A (en) * | 2014-09-09 | 2014-12-10 | 吉林大学 | Functionalized rare-earth complex organic/inorganic hybrid luminescent material and preparation method thereof |
| CN108713078A (en) * | 2015-12-10 | 2018-10-26 | 阿克蒂赛尔有限责任公司 | The processing of textile material |
| CN108713078B (en) * | 2015-12-10 | 2020-11-17 | 阿克蒂赛尔有限责任公司 | Treatment of textile materials |
| 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 |
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