CN101230266B - Method for preparing visible region blue-green conversion luminous inorganic-organic composite silicon based materials - Google Patents
Method for preparing visible region blue-green conversion luminous inorganic-organic composite silicon based materials Download PDFInfo
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- CN101230266B CN101230266B CN2008100340239A CN200810034023A CN101230266B CN 101230266 B CN101230266 B CN 101230266B CN 2008100340239 A CN2008100340239 A CN 2008100340239A CN 200810034023 A CN200810034023 A CN 200810034023A CN 101230266 B CN101230266 B CN 101230266B
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Abstract
The invention belongs to luminescent material technology field, in particular relates to a preparation method of visible light zone blue light green light conversion light-emitting organic-inorganic composite silicon-based material. Firstly, the invention grafts the organic molecule with Schiff base structure into inorganic silicon framework, and then uses the sol-gel method to obtain xerogel by conducting hydrolysis polycondensation reaction on the precursor of organosilicone; after further drying and aging, the hybrid material which has stable chemical and thermodynamic properties, has regular surface appearance, and uses blue-ray to excite green-ray emission, is produced. The method of the invention requires moderate experimental conditions, the composite silicon-based material of the invention can be produced in room temperature dispensing with high-temperature calcinations, the maneuverability is strong, and the reproducibility is well. The obtained product has stable quality andregular appearance.
Description
Technical field
The invention belongs to the luminescent material technical field, be specifically related to a kind of preparation method of visible region blue-green conversion luminous inorganic-organic composite silicon sill.
Background technology
In recent years, the function luminous organic material with distinct electrical minor structure and luminescent properties highlighted its critical role in Materials science day by day.Organic fluorescence materials all is widely used in fields such as industry, agricultural, medical science, national defence.Can be used as white dyes, fluorescence dye, high-visibility pigment, laser dyes, be used for fluorometric analysis, follow the tracks of detection, traffic sign, the scintillator of nuclear technique and the fluorescence optical collector in the solar energy converting technology etc.
The luminous organic material of research mainly concentrates on the luminous basis of rare earth organic complex at present.Can be divided into small molecules rare-earth complexes luminous material and rare earth high polymer complex luminescent material.The small molecules luminescent material takes place easily to reunite and produces concentration quenching, usually be to mix in the material of main part as guest materials, by energy shift excited produce luminous.This just caused its processibility, mechanicalness and stable aspect deficiency, simultaneously, cost of manufacture is higher relatively.Polymer device light weight is thin and have snappiness, is easier to make large-sized display panel, but its at aspects such as brightness, purity of color and color performances not as good as the small molecules luminescent material, fluorescence quantum efficiency is not high simultaneously.The photoabsorption of this type of embedded photoluminescent material is many at ultraviolet region, and can absorb enough abilities and carry out the research there be limited evidence currently of that useful energy transmits at visible region, simultaneously, owing to rare earth costs an arm and a leg, and complex manufacturing, be unfavorable for large-scale production.
External very extensive at present to the research of luminous organic material, luminescent properties from the aspects such as various performance parameters of synthetic method, material to material has carried out a large amount of research, some luminous organic material has been carried out mass production, the exploitation many places of domestic luminous organic material are in laboratory stage, and new kind is less, the scale operation report is also limited, and luminous organic material is as a kind of emerging functional materials, not only have important theory and be worth, and be a field that is full of wide development prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of visible region blue-green conversion luminous inorganic-organic composite silicon sill.
The preparation method of the visible region blue-green conversion luminous inorganic-organic composite silicon sill that the present invention proposes is that organic molecule is keyed in the Si-O inorganic network by covalent linkage, thereby is realizing organic and inorganic grafting between mutually on the level of molecule.Organic molecule has high-quantum efficiency, high brightness and purity of color and reaches color expressive force preferably as main energy absorption and donor.Simultaneously, because the introducing of inorganic network, good snappiness, mechanicalness and stability that it has high-molecular luminous material again and is had, on preparation technology, the experiment condition of sol-gel method gentleness is that the preparation and the processing of hybrid inorganic-organic materials is provided convenience, reduced production cost, and can regulate and control to realize to be with regulation and control, obtained panchromatic luminescent device by molecular designing.In addition, the frivolous and snappiness of the quality of material is easier to make large-sized display panel.
The purpose of this invention is to provide a kind of method of producing the hybrid inorganic-organic materials of covalent linkage keyed jointing, this material can carry out effective energy absorption in the visible blue district, and has very strong emissive power in green Region.This method by covalent linkage together with the grafting of organic and inorganic component, thereby overcome the weakness of material mechanical and less stable, and it is regular to obtain the surface, arranges orderly microtexture.
The preparation method of the visible region blue-green conversion luminous inorganic-organic composite silicon sill that the present invention proposes, concrete steps are as follows:
(1) preparation of presoma:
The double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the organic solvent, join in the flask, be heated to 50-60 ℃ of temperature, and under this temperature, reflux, drip the organic solvent that is dissolved with organo-silicon coupling agent in the reflux course, after being added dropwise to complete, whole solution continued under nitrogen atmosphere back flow reaction 8-10 hour, cooling, evaporate to dryness organic solvent, washing, purifying promptly obtain the silicon precursor that grafting has the organic functions group; The contract ratio of diamino thiocarbamide and the amount of substance of organo-silicon coupling agent of double salicylaldehyde is 1: 2-1: 2.4;
(2) sol-gel process:
Be to be dissolved in the anhydrous pyridine in the organosilicon presoma with step (1) gained, add deionized water, regulator solution pH value adds tetraethoxy, rare earth nitrate or Zinc diacetate dihydrate then, under the 20-40 ℃ of temperature hydrolysis condensation reaction 5-10 hour, up to the generation of solid gel; Wherein, the ratio of the amount of substance of organosilicon presoma and tetraethoxy is controlled at 1: 2-1: between 4, the ratio of the amount of substance of organosilicon presoma and rare earth nitrate or Zinc diacetate dihydrate is controlled at 3: 1-4: between 1, the ratio of the amount of substance of organosilicon presoma and deionized water is controlled at 1: 4-1: between 12.
(3) aging and drying treatment:
With the gel of step (2) gained under 60-80 ℃ of temperature aging 10-30 days, use dehydrated alcohol repetitive scrubbing (general 3-5 time) then, the solid ageing products after will washing at last under 60-70 ℃ temperature dry 3-6 days promptly gets desired product.
Among the present invention, organo-silicon coupling agent described in the step (1) is the silica-based propyl isocyanate of triethoxy.
Among the present invention, organic solvent is an anhydrous pyridine described in the step (1).
Among the present invention, the pH value has bigger influence to speed of response, and acidity or alkaline condition can promote hydrolysis condensation reaction.The scope of pH value described in the step (2) is between the acid 1-3 or between the alkaline 11-13, between the preferred 1-3.
Among the present invention, aging temperature is 60-80 ℃ described in the step (3), and digestion time is 10-30 days.
Among the present invention, drying temperature is 60-70 ℃ described in the step (3), and be 3-6 days time of drying.
The hybrid inorganic-organic materials that adopts the inventive method to prepare, it has effective energy absorption in the visible blue district, and has very strong emissive power in green Region.And pattern is regular, arranges evenly the generation that is separated of no organic and inorganic.
Among the present invention, sol gel reaction in the step (2) can be divided into two stages: at first hydrolysis reaction takes place respectively in the siloxane groups of organosilicon presoma and tetraethoxy, then, by between the organosilicon presoma or the Si-OH group that produces of organosilicon presoma and teos hydrolysis begin to take place the cohydrolysis polycondensation, thereby organic molecule is keyed in the silicon inorganic network by the Si-O-Si key.
Among the present invention, step is carried out burin-in process in (3), and the aged process helps making the second alcohol and water that generates in the hydrolytie polycondensation process, and the solvent DMF that adds in the reaction is fully volatilized.
Among the present invention, relate in the step (3) and use the dehydrated alcohol repetitive scrubbing.The purpose of washing is in order to remove disacidify and other impurity.Remove wherein moisture and ethanol thus, obtain having of one's own the hybrid inorganic-organic materials of microparticle system.
The optical conversion luminous hybrid inorganic-organic materials photon absorbing intensity of being produced by the inventive method of visible region is big and transformation efficiency is high, and microscopic appearance is regular, not having between organic phase and the inorganic phase is separated produce and size distribution even; In addition, its favorable dispersity.At last, the inventive method workable, favorable reproducibility, and products obtained therefrom steady quality.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the light conversion hybrid material of the embodiment of the invention 2 gained.Wherein, (a) magnification is 10000 times, and (b) magnification is 20000 times.
Fig. 2 is the light conversion hybrid material excitation spectrum of the embodiment of the invention 2 gained.
Fig. 3 is the light conversion hybrid material emmission spectrum of the embodiment of the invention 2 gained.
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.Raw material in the embodiment of the invention is analytical pure available from Shanghai traditional Chinese medicines group.
Embodiment 1
The 3.14g double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the 20ml anhydrous pyridine, joins in the three-necked flask and be heated to backflow.The 20ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 5.44g triethoxy then dropwise adds.Drip the back whole solution 8h that under nitrogen protection, refluxes, cooling, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organosilicon presoma of gained is dissolved among the DMF, adds deionized water then.The amount of substance ratio of organosilicon presoma and ionized water is 1: 4.Adding the salt acid for adjusting pH value then is 2, and whole solution is stirring reaction at room temperature, up to there being solid gel to generate.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 20 days.At last, with resulting hybrid material repeatedly, under 70 ℃ temperature dry 3 days then, obtain containing the contract hybrid material of diamino thiocarbamide organic molecule of double salicylaldehyde with the dehydrated alcohol repetitive scrubbing.
Embodiment 2
The 3.14g double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the 20ml anhydrous pyridine, joins in the three-necked flask and be heated to backflow.The 20ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 5.44g triethoxy then dropwise adds.Drip the back whole solution 9h that under nitrogen protection, refluxes, cooling, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy and deionized water then.The amount of substance ratio of organosilicon presoma, tetraethoxy and deionized water is 1: 4: 8, and adding the salt acid for adjusting pH value is 2, and whole solution is stirring reaction at room temperature, up to there being solid gel to generate.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 15 days.At last, with resulting hybrid material repeatedly, under 60 ℃ temperature dry 6 days then, obtain final hybrid material with the dehydrated alcohol repetitive scrubbing.
The scanning electron microscope diagram of this hybrid inorganic-organic materials, excitation spectrum and emmission spectrum are respectively as Fig. 1, Fig. 2 and shown in Figure 3.As can be seen from Figure 1, this hybrid material becomes evenly regular sheet structure, and its length is 5-10 μ m, and width is 0.5-1 μ m, and generation is not separated between organic phase and the inorganic phase.From the exciting of Fig. 2 and Fig. 3, emmission spectrum as can be seen, this hybrid material has very strong absorption at blue light region 443nm, and at 537nm very strong green emission is arranged.It is the more rare optical conversion luminous material of a kind of visible region blue green light.
Embodiment 3
The 3.14g double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the 20ml anhydrous pyridine, joins in the three-necked flask and be heated to backflow.The 20ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 5.44g triethoxy then dropwise adds.Drip the back whole solution 8h that under nitrogen protection, refluxes, cooling, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy, europium nitrate and deionized water then.The amount of substance ratio of organosilicon presoma, tetraethoxy, europium nitrate and deionized water is 3: 12: 1: 18.Whole solution is stirring reaction at room temperature, up to there being solid gel to generate.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.At last, with resulting hybrid material repeatedly, under 65 ℃ temperature dry 4 days then, obtain final hybrid material with the dehydrated alcohol repetitive scrubbing.
Embodiment 4
The 3.14g double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the 20ml anhydrous pyridine, joins in the three-necked flask and be heated to backflow.The 20ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 5.44g triethoxy then dropwise adds.Drip the back whole solution 8h that under nitrogen protection, refluxes, cooling, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy, Terbium trinitrate and deionized water then.The amount of substance ratio of organosilicon presoma, tetraethoxy, Terbium trinitrate and deionized water is 3: 12: 1: 24.Whole solution is stirring reaction at room temperature, up to there being solid gel to generate.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 75 ℃, and digestion time is 12 days.At last, with resulting hybrid material repeatedly, under 68 ℃ temperature dry 4 days then, obtain final hybrid material with the dehydrated alcohol repetitive scrubbing.
Embodiment 5
The 3.14g double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the 20ml anhydrous pyridine, joins in the three-necked flask and be heated to backflow.The 20ml pyridine solution that will be dissolved with the silica-based propyl isocyanate of 5.44g triethoxy then dropwise adds.Drip the back whole solution 8h that under nitrogen protection, refluxes, cooling, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organosilicon presoma of gained is dissolved among the DMF, adds tetraethoxy, Zinc diacetate dihydrate and deionized water then.The amount of substance ratio of organosilicon presoma, tetraethoxy, Zinc diacetate dihydrate and deionized water is 3: 12: 1: 30.Whole solution is stirring reaction at room temperature, up to there being solid gel to generate.The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 65 ℃, and digestion time is 28 days.At last, with resulting hybrid material repeatedly, under 62 ℃ temperature dry 5 days then, obtain final hybrid material with the dehydrated alcohol repetitive scrubbing.
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 (5)
1. the preparation method of a visible region blue-green conversion luminous inorganic-organic composite silicon sill is characterized in that concrete steps are as follows:
(1) preparation of presoma:
The double salicylaldehyde diamino thiocarbamide that contracts is dissolved in the organic solvent, join in the flask, be heated to 50-60 ℃ of temperature, and under this temperature, reflux, drip the organic solvent that is dissolved with organo-silicon coupling agent in the reflux course, after being added dropwise to complete, whole solution continued under nitrogen atmosphere back flow reaction 8-10 hour, cooling, evaporate to dryness organic solvent, washing, purifying promptly obtain the silicon precursor that grafting has the organic functions group; The contract ratio of diamino thiocarbamide and the amount of substance of organo-silicon coupling agent of double salicylaldehyde is 1: 2-1: 2.4;
(2) sol-gel process:
Be to be dissolved in the organic solvent in the organosilicon presoma with step (1) gained, add deionized water, regulator solution pH value adds tetraethoxy, rare earth nitrate or Zinc diacetate dihydrate then, under the 20-40 ℃ of temperature hydrolysis condensation reaction 5-10 hour, up to the generation of solid gel; Wherein, the organosilicon presoma is 1 with the ratio of the amount of substance of tetraethoxy: 2-1: 4, the organosilicon presoma is 3 with the ratio of the amount of substance of rare earth nitrate or Zinc diacetate dihydrate: 1-4: 1, and the organosilicon presoma is 1 with the ratio of the amount of substance of deionized water: 4-1: 12;
(3) aging and drying treatment:
The gel of step (2) gained is aging, use absolute ethanol washing then, drying promptly gets desired product;
Wherein: organo-silicon coupling agent described in the step (1) is the silica-based propyl isocyanate of triethoxy, and described organic solvent is an anhydrous pyridine.
2. the preparation method of visible region blue-green conversion luminous inorganic-organic composite silicon sill according to claim 1 is characterized in that pH value described in the step (2) is acid 1-3 or alkaline 11-13.
3. the preparation method of visible region blue-green conversion luminous inorganic-organic composite silicon sill according to claim 1 is characterized in that the pH value is 1-3.
4. the preparation method of visible region blue-green conversion luminous inorganic-organic composite silicon sill according to claim 1 is characterized in that aging temperature is 60-80 ℃ described in the step (3), and digestion time is 3-6 days.
5. the preparation method of visible region blue-green conversion luminous inorganic-organic composite silicon sill according to claim 1 is characterized in that drying temperature is 60-70 ℃ described in the step (3), and be 3-6 days time of drying.
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| CN1523076A (en) * | 2003-09-11 | 2004-08-25 | 复旦大学 | Magnetic fluorescent double functional microballoon with core-shell structure and preparation method thereof |
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| CN1523076A (en) * | 2003-09-11 | 2004-08-25 | 复旦大学 | Magnetic fluorescent double functional microballoon with core-shell structure and preparation method thereof |
Non-Patent Citations (6)
| Title |
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| Yan Bing et al..Sol2Gel Assembly and Luminescence of SiO2/ PEMA HybridMaterial Incorporated with Terbium Complex.JOURNAL OF RARE EARTHS20 5.2002,20(5),404-407. |
| Yan Bing et al..Sol2Gel Assembly and Luminescence of SiO2/ PEMA HybridMaterial Incorporated with Terbium Complex.JOURNAL OF RARE EARTHS20 5.2002,20(5),404-407. * |
| 周钰明等.PUT/SiO2复合材料的制备与表征.物理化学学报23 2.2007,23(2),223-227. |
| 周钰明等.PUT/SiO2复合材料的制备与表征.物理化学学报23 2.2007,23(2),223-227. * |
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| 潘晓霞等.二阶非线性光学活性聚酰亚胺有机-无机杂化材料的合成与表征.高等学校化学学报23 8.2002,23(8),1618-1621. * |
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