CN101255273A - Method for preparing luminescent rear earth-polyethylene glycol polymer composites - Google Patents
Method for preparing luminescent rear earth-polyethylene glycol polymer composites Download PDFInfo
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Abstract
The invention belongs to luminescent polymers technical field, especially a preparation method of luminescent rare earth-polyethylene glycol polymers. The preparation method comprises: grafting the aromatic organic micromolecule in an inorganic silicon framework to obtain organic bridge molecule by organic synthesis; decorating functional group in polyethylene glycol (PEG400) to obtain polymer bridge molecule by the same decorating method; assembling the organic bridge molecule, polymer bridge molecule and rare earth ion together by coordinate link to obtain rare earth complexes; the rare earth complexes being subjected to hydrolytic polycondensation reaction between the two bridge molecules by collosol-gel method to finally produce xerogel, so that the organic polymers with long carbon chain are set in silica network matrix by coordination bond and covalent bond, and finally the finished product can be obtained after drying and ageing process. The experiment condition is mild and can be realized at room temperature, the operability and the reproductivity is good. The products have stable quality and good appearance and the grain size is controlled at range of micron and nanometre.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of preparation method of luminescent rear earth-polyethylene glycol polymer composites.
Background technology
The making rapid progress of current society progress makes already that the function of excavating out multiple material is compound, performance complement and optimization, prepare excellent performance hybrid material extremely urgent.Therefore the organic and inorganic system causes the very big concern of scientists immediately once appearance.A large amount of manpowers have all been dropped in countries in the world, and material resources and financial resources have been carried out intensive research to this material.Usually in fact, polymer composite has following characteristics: inorganics and polymkeric substance can realize that molecular level or nano-scale are compound, optical property is transparent, can be expected to prepare the matrix material that contains multiple function ingredients in same residuite, can become the back bone network of multiple photoreactive species; Has certain mechanical stability, snappiness, thermostability and light stability; Be processed into shape such as film, block and the fiber etc. of various different dimensions easily.Because this novel hybrid inorganic-organic materials is with the advantage of dual material, therefore this ergasia is at solid-state dye laser, flat pannel display, information transmission, high-tech areas such as optoelectronic switch, all having shown wide application prospect, is the uncharted field of international material science and information science research.
Rare earth element is described as the treasure-house of novel material because of the singularity of its electronic structure has characteristics such as light, electricity, magnetic.Rare earth ion, particularly Eu
3+And Tb
3+, based on the transition between the 4f electronic level, have the good characteristics of luminescence, so people have carried out a large amount of research to rare earth organic complex, synthesized the rare earth organic complex of parts such as rare earth and beta-diketon class, aromatic carboxylic acid class and heterocyclic.By the strong absorption of organic ligand and effectively energy transfer, it is luminous to make that rare earth compounding shows intensive, and luminous monochromaticity is better.But the disadvantage of pure rare earth organic coordination compound is that its light stability and thermostability are bad, has therefore limited their use.In order to have widened the range of application of luminescent rare earth complexes, rare earth compounding is incorporated in the matrix forms polymer composite 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.Relevant recently research concentrates on rare earth compounding substantially and is doped to inorganic or organically-modified matrix and original position synthesizing rare-earth twinkler etc.But therefore the hybrid material of method for preparing exists the rare earth compounding skewness and reunites easily owing to connect with weak interaction force between rare earth compounding and the inorganic matrix, and doping content is restricted, two alternate existence problem such as be separated.So, seek rare earth compounding is connected on the matrix scaffold by covalent linkage and can remedy above deficiency.Studies show that organic ligand is carried out passing through the cohydrolysis polycondensation behind the silylation modification, obtain the hybrid material that inorganic component and organic constituent are connected with the Si-C key with inorganic silicon oxygen network, further it is embedded in again and has in the high molecular weight polymers material, obtain rare earth luminous RE polymer composite, result of study subsequently shows, its feature emission has had tangible enhancing, and thermostability is greatly improved, and microscopic appearance has also had very big improvement.In addition, organic polymer simple in structure has become the focus of current research, mainly is because of himself the high ductility and the transparency, and in industrial important application.Especially polyoxyethylene glycol (PEG400) has good high-temperature stability, and is water-soluble, low volatility, water-absorbent and hypotoxicity.It has following several effect aspect industrial application: the polyoxyethylene glycol (PEG) that mixes in the resin can improve resin property greatly; Replace glycerine can improve the toughness of resin with polyoxyethylene glycol (PEG); In urethane resin, add polyoxyethylene glycol (PEG) and can improve its intensity and elasticity, make resin surface bright gloss be arranged in cold coating simultaneously; Polyoxyethylene glycol (PEG) is easy to dissolving resin, therefore can improve the resin film forming properties to a great extent; Polyoxyethylene glycol (PEG) also can be used as good auxiliary addition agent in plastics industry, as good static inhibitor in the PVC belt; Polyoxyethylene glycol (PEG) has been obtained widely in metal processing and has been used, and its good water-solubility has using value very much in slush casting, be good lubricant; And its low volatility makes it can be as solubility promoter, solder flux and wedding agent of solder and rubber and polyurethane product remover, loosening agent; In cork and sponge, because the low volatility and the water-absorbent of polyoxyethylene glycol (PEG), it can be used as good solubilizing agent, simultaneously, can also keep moisture.All polyoxyethylene glycol (PEG) all are the production of important chemical material intermediate, particularly polyoxyethylene glycol (PEG) multipolymer and polyoxyethylene glycol (PEG) ester.Therefore consider from above a plurality of angles, in the luminescence rare earth hybrid material, embed polyoxyethylene glycol (PEG) synthesising macromolecule copolymer matrix material to being to theoretical investigation or actual industrial application all has important effect by coordinate bond and covalent linkage.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of luminescent rear earth-polyethylene glycol polymer composites.
The preparation method of a kind of luminescent rear earth-polyethylene glycol polymer composites provided by the invention, concrete steps are as follows:
(1) preparation of organic bridge molecule:
The aromatic series organic molecule is dissolved in the organic solvent, place flask, be heated to 60-85 ℃, and reflux under this temperature, the organic solvent that will be dissolved with organo-silicon coupling agent in the reflux course splashes in the flask, whole solution continued under nitrogen atmosphere back flow reaction 12-17 hour, cooling, evaporate to dryness organic solvent, washing, purifying, obtaining grafting has the organic bridge molecule of organo-functional group, and aromatic series organic molecule and organo-silicon coupling agent mol ratio are 1: 1;
(2) preparation of high molecular polymer bridging molecule:
Polyoxyethylene glycol is dissolved in the organic solvent, place flask, be heated to 55-80 ℃, and under this temperature, reflux, the organic solvent that will be dissolved with organo-silicon coupling agent in the reflux course splashes in the flask, whole solution continued under nitrogen atmosphere back flow reaction 14-19 hour, cooling, evaporate to dryness organic solvent, washing, purifying, obtaining grafting has the polyoxyethylene glycol bridging molecule of coordination and hydrolysis functional group, and the mol ratio of polyoxyethylene glycol and organo-silicon coupling agent is 1: 2, and the molecular weight of polyoxyethylene glycol is PEG400;
(3) preparation of rare earth compounding:
The organic bridge molecule and step (2) the gained polyoxyethylene glycol bridging molecule drips of solution of step (1) gained are added in the ethanolic soln that is dissolved in rare earth nitrate, stir, coordination reaction under 20-30 ℃ of temperature, reaction times is 2-7 hour, obtain rare earth compounding, organic bridge molecule, the mol ratio of polyoxyethylene glycol bridging molecule and rare earth ion are 3: 1: 1;
(4) sol-gel process:
In the rare earth compounding of step (3) gained, add tetraethoxy and deionized water, the pH value of regulator solution, under 20-40 ℃ of temperature hydrolysis condensation reaction 5-10 hour, up to the generation solid gel; Wherein: the mol ratio of rare earth compounding, tetraethoxy and deionized water is 1: 6: 12-1: 8: 16;
(5) aging and drying treatment:
The gel of step (4) gained is aging, use absolute ethanol washing then, drying promptly gets desired product.
Among the present invention, the aromatic series organic molecule described in the step (1) be in 3-hydroxy niacin, salicylic acid, 2-hydroxy-3-methyl phenylformic acid or the 2-methyl m-phthalic acid etc. any.
Among the present invention, described in the step (1) described in organo-silicon coupling agent be the silica-based propyl isocyanate of triethoxy.
Among the present invention, organic solvent is anhydrous propanone, anhydrous diethyl ether, anhydrous pyridine, tetrahydrofuran (THF), nitrogen described in step (1) and the step (2), in nitrogen-dimethyl formamide or the chloroform etc. any.
Among the present invention, the rare earth nitrate described in the step (3) is europium nitrate or Terbium trinitrate.
Among the present invention, the pH value of solution is 6-7 in the step (4).
Among the present invention, aging temperature is 55-80 ℃ described in the step (5), and digestion time is 15-20 days.
Among the present invention, the described drying temperature of step (5) is 60-85 ℃, and be 3-8 days time of drying.
Luminescent rear earth-polyethylene glycol (PEG400) polymer composite that utilizes the inventive method to prepare, its pattern is regular, arrange evenly, rare earth ion feature emissive porwer is big, and there is not the organic and inorganic generation that is separated, have good thermostability and ductility, size of particles is at 800nm-1 μ m.
Among the present invention, sol gel reaction described in the step (3) is carried out under 20-40 ℃ of temperature, reaction can be divided into two stages: organic bridge molecule at first, hydrolysis reaction takes place respectively in the siloxane groups of polyoxyethylene glycol bridging molecule and tetraethoxy, then, by the organic bridge molecule, the Si-OH group that polyoxyethylene glycol bridging molecule and teos hydrolysis produce begins 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 to the gained gel in (5), and the aged process helps making the second alcohol and water that generates in the hydrolytie polycondensation process, and the solvent that adds in the reaction fully volatilizees.
Among the present invention, adopt the dehydrated alcohol repetitive scrubbing in the step (5).The purpose of washing is in order to remove disacidify and other impurity.Washing is carried out drying later, removes wherein moisture and ethanol thus, obtains having of one's own luminescent rear earth-polyethylene glycol (PEG400) polymer composite of microparticle system.
Its preparation method of a kind of luminescent rear earth-polyethylene glycol (PEG400) polymer composite that the present invention proposes, with organic molecule, the method that polyoxyethylene glycol grafts with covalency by the hydrolytie polycondensation process is received in the Si-O inorganic network, further inorganic network is embedded in the organic high molecular polymer with the form of chemical bond by coordination reaction, thereby realizing organic and inorganic grafting between mutually on the level of molecule.Organic molecule is as main energy absorption and donor, have high-quantum efficiency, high brightness and purity of color and reach color expressive force preferably, organic polymer has ductility and the transparency and the good thermostability of self, 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, and has reduced production cost, and can regulate and control to realize to be with regulation and control by molecular designing, obtains panchromatic luminescent device.In addition, the frivolous and snappiness of the quality of material is easier to make large-sized display panel.
A kind of luminescent rear earth-polyethylene glycol (PEG400) polymer composite of being produced by the inventive method and preparation method thereof photon absorbing intensity 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 cross-sectional scans electron microscope picture of the embodiment of the invention 3 gained luminescent rear earth-polyethylene glycol (PEG400) polymer composites.
Fig. 2 is the exciting light spectrogram of the embodiment of the invention 3 gained luminescent rear earth-polyethylene glycol (PEG400) polymer composites.
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
2.79g 3-hydroxy niacin is dissolved in the 20ml anhydrous propanone, joins in the three-necked flask and be heated to backflow.The 20ml anhydrous propanone solution that will be dissolved with the silica-based propyl isocyanate of 4.95g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 60 ℃, the 12h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times, and the oily organic bridge molecular system of gained is dissolved in the dehydrated alcohol, and are standby.
2.80g polyoxyethylene glycol (PEG400) is dissolved in the 20ml anhydrous propanone; join in the three-necked flask and be heated to backflow; the 30ml anhydrous propanone solution that will be dissolved with the silica-based propyl isocyanate of 9.90g triethoxy then dropwise adds; drip the whole solution temperature in back and be controlled in 55 ℃; 14h refluxes under nitrogen protection; cooling afterwards, decompression steams solvent.The transparent oily liquid that obtains is dissolved in the dehydrated alcohol, standby.
The ethanolic soln that adds europium nitrate in the ethanolic soln that is dissolved with organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule is to stir 2 hours under 20 ℃ the situation in temperature, obtains rare earth compounding.
Drip tetraethoxy and deionized water in the gained rare earth compounding, the pH value of regulator solution is 6.Wherein: the mol ratio of organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule, europium nitrate, tetraethoxy and deionized water is 3: 1: 1: 6: 12.Whole solution is 25 ℃ in temperature and stirred 5 hours down, obtains solid gel.
The solid gel of gained is transferred to burin-in process in the baking oven, and temperature is controlled at 55 ℃, and digestion time is 15 days.At last, with resulting hybrid material repeatedly, under 60 ℃ temperature dry 3 days then, obtain luminescent rear earth-polyethylene glycol (PEG400) polymer composite with the dehydrated alcohol repetitive scrubbing.
Embodiment 2
The 2.76g salicylic acid is dissolved in the 20ml anhydrous diethyl ether, joins in the three-necked flask and be heated to backflow.The 20ml anhydrous ether solution that will be dissolved with the silica-based propyl isocyanate of 4.95g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 65 ℃, the 13h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organic bridge molecular system of gained is dissolved in the dehydrated alcohol, standby.
(PEG400) is dissolved in the 20ml anhydrous diethyl ether with the 2.80g polyoxyethylene glycol, joins in the three-necked flask and is heated to backflow.The 30ml anhydrous ether solution that will be dissolved with the silica-based propyl isocyanate of 9.90g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 60 ℃, the 15h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.The transparent oily liquid that obtains is dissolved in the dehydrated alcohol, standby.
The ethanolic soln that adds europium nitrate in the ethanolic soln that is dissolved with organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule is to stir 3 hours under 22 ℃ the situation in temperature, obtains rare earth compounding.
Drip tetraethoxy and deionized water in the gained rare earth compounding, regulating pH value is 6.Wherein: the mol ratio of organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule, europium nitrate, tetraethoxy and deionized water is 3: 1: 1: 6: 13.Whole solution is 20 ℃ in temperature and stirred 6 hours down, obtains 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 16 days.At last, with resulting hybrid material repeatedly, under 65 ℃ temperature dry 4 days then, obtain luminescent rear earth-polyethylene glycol (PEG400) polymer composite with the dehydrated alcohol repetitive scrubbing.
3.04g 2-hydroxy-3-methyl phenylformic acid is dissolved in the 20ml anhydrous pyridine, joins in the three-necked flask and be heated to backflow.The 20ml anhydrous pyridine solution that will be dissolved with the silica-based propyl isocyanate of 4.95g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 70 ℃, the 14h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organic bridge molecular system of gained is dissolved in the dehydrated alcohol, standby.
(PEG400) is dissolved in the 20ml anhydrous pyridine with the 2.80g polyoxyethylene glycol, joins in the three-necked flask and is heated to backflow.The 30ml anhydrous pyridine solution that will be dissolved with the silica-based propyl isocyanate of 9.90g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 65 ℃, the 16h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.The transparent oily liquid that obtains is dissolved in the dehydrated alcohol, standby.
To being dissolved with the organic bridge molecule, add the ethanolic soln of europium nitrate in the ethanolic soln of polyoxyethylene glycol (PEG400) bridging molecule, be to stir 4 hours under 24 ℃ the situation in temperature, obtain rare earth compounding.
Drip tetraethoxy and deionized water in the gained rare earth compounding, regulating pH value is 6.The mol ratio of organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule, europium nitrate, tetraethoxy and deionized water is 3: 1: 1: 6: 14.Whole solution is 25 ℃ in temperature and stirred 7 hours down, obtains solid gel.
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 17 days.At last, with resulting hybrid material repeatedly, under 70 ℃ temperature dry 5 days then, obtain luminescent rear earth-polyethylene glycol (PEG400) polymer composite with the dehydrated alcohol repetitive scrubbing.
The scanning electron microscope diagram emmission spectrum of this hybrid inorganic-organic materials respectively as depicted in figs. 1 and 2.As can be seen from Figure 1, this hybrid material presents more regular orderly planar circular configuration, and its diameter is 800nm-1 μ m, and generation is not separated between organic phase and the inorganic phase.From Fig. 2 emmission spectrum as can be seen, this material has very strong emission near green Region 543nm, is a kind of material more efficiently.
Embodiment 4
3.04g 2-hydroxy-3-methyl phenylformic acid is dissolved in the 20ml tetrahydrofuran (THF), joins in the three-necked flask and be heated to backflow.The 20ml tetrahydrofuran solution that will be dissolved with the silica-based propyl isocyanate of 4.95g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 75 ℃, the 15h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organic bridge molecular system of gained is dissolved in the dehydrated alcohol, standby.
(PEG400) is dissolved in the 20ml tetrahydrofuran (THF) with the 2.80g polyoxyethylene glycol, joins in the three-necked flask and is heated to backflow.The 30ml tetrahydrofuran solution that will be dissolved with the silica-based propyl isocyanate of 9.90g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 70 ℃, the 17h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.The transparent oily liquid that obtains is dissolved in the dehydrated alcohol, standby.
To having dissolved the organic bridge molecule, add the ethanolic soln of Terbium trinitrate in the ethanolic soln of polyoxyethylene glycol (PEG400) bridging molecule, be to stir 5 hours under 26 ℃ the situation in temperature, obtain rare earth compounding.
Drip tetraethoxy and deionized water in the gained rare earth compounding, regulating pH value is 7.Wherein: the mol ratio of organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule, Terbium trinitrate, tetraethoxy and deionized water is 3: 1: 1: 7: 14.Whole solution is 30 ℃ in temperature and stirred 8 hours down, obtains 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 18 days.At last, with resulting hybrid material repeatedly, under 75 ℃ temperature dry 6 days then, obtain luminescent rear earth-polyethylene glycol (PEG400) polymer composite with the dehydrated alcohol repetitive scrubbing.
Embodiment 5
3.60g 2-methyl m-phthalic acid is dissolved in 20ml nitrogen, in nitrogen-dimethyl formamide, joins in the three-necked flask and be heated to backflow.To be dissolved with the 20ml nitrogen of the silica-based propyl isocyanate of 4.95g triethoxy then, nitrogen-dimethyl formamide solution dropwise adds.Drip the whole solution temperature in back and be controlled in 80 ℃, the 16h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organic bridge molecular system of gained is dissolved in the dehydrated alcohol, standby.
(PEG400) is dissolved in 20ml nitrogen with the 2.80g polyoxyethylene glycol, in nitrogen-dimethyl formamide, joins in the three-necked flask and is heated to backflow.To be dissolved with the 30ml nitrogen of the silica-based propyl isocyanate of 9.90g triethoxy then, nitrogen-dimethyl formamide solution dropwise adds.Drip the whole solution temperature in back and be controlled in 75 ℃, the 18h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.The transparent oily liquid that obtains is dissolved in the dehydrated alcohol, standby.
The ethanolic soln that adds Terbium trinitrate in the ethanolic soln that has dissolved organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule is to stir 6 hours under 28 ℃ the situation in temperature, obtains rare earth compounding.
Drip tetraethoxy and deionized water in the gained rare earth compounding, regulating pH value is 7.The mol ratio of organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule, Terbium trinitrate, tetraethoxy and deionized water is 3: 1: 1: 8: 15.Whole solution is 35 ℃ in temperature and stirred 9 hours down, obtains solid gel.
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 19 days.At last, with resulting hybrid material repeatedly, under 80 ℃ temperature dry 7 days then, obtain luminescent rear earth-polyethylene glycol (PEG400) polymer composite with the dehydrated alcohol repetitive scrubbing.
Embodiment 6
3.60g 2-methyl m-phthalic acid is dissolved in the 20ml chloroform, joins in the three-necked flask and be heated to backflow.The 20ml chloroformic solution that will be dissolved with the silica-based propyl isocyanate of 4.95g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 85 ℃, the 15h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.Gains obtain light yellow oily liquid with 20ml hexanaphthene washing three times.The oily organic bridge molecular system of gained is dissolved in the dehydrated alcohol, standby.
(PEG400) is dissolved in the 20ml chloroform with the 2.80g polyoxyethylene glycol, joins in the three-necked flask and is heated to backflow.The 30ml chloroformic solution that will be dissolved with the silica-based propyl isocyanate of 9.90g triethoxy then dropwise adds.Drip the whole solution temperature in back and be controlled in 80 ℃, the 19h that under nitrogen protection, refluxes, cooling afterwards, decompression steams solvent.The transparent oily liquid that obtains is dissolved in the dehydrated alcohol, standby.
The ethanolic soln that adds Terbium trinitrate in the ethanolic soln that has dissolved organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule is to stir 7 hours under 30 ℃ the situation in temperature, obtains rare earth compounding.
Drip tetraethoxy and deionized water in the gained rare earth compounding, regulating pH value is 7.Wherein: the mol ratio of organic bridge molecule, polyoxyethylene glycol (PEG400) bridging molecule, Terbium trinitrate, tetraethoxy and deionized water is 3: 1: 1: 8: 16.Whole solution is 40 ℃ in temperature and stirred 10 hours down, obtains 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 20 days.At last, with resulting hybrid material repeatedly, under 85 ℃ temperature dry 8 days then, obtain luminescent rear earth-polyethylene glycol (PEG400) polymer composite 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 (8)
1, a kind of preparation method of luminescent rear earth-polyethylene glycol polymer composites is characterized in that concrete steps are as follows:
(1) preparation of organic bridge molecule:
The aromatic series organic molecule is dissolved in the organic solvent, place flask, be heated to 60-85 ℃, and reflux under this temperature, the organic solvent that will be dissolved with organo-silicon coupling agent in the reflux course splashes in the flask, whole solution continued under nitrogen atmosphere back flow reaction 12-17 hour, cooling, evaporate to dryness organic solvent, washing, purifying, obtaining grafting has the organic bridge molecule of organo-functional group, and aromatic series organic molecule and organo-silicon coupling agent mol ratio are 1: 1;
(2) preparation of high molecular polymer bridging molecule:
Polyoxyethylene glycol is dissolved in the organic solvent, place flask, be heated to 55-80 ℃, and under this temperature, reflux, the organic solvent that will be dissolved with organo-silicon coupling agent in the reflux course splashes in the flask, whole solution continued under nitrogen atmosphere back flow reaction 14-19 hour, cooling, evaporate to dryness organic solvent, washing, purifying, obtaining grafting has the polyoxyethylene glycol bridging molecule of coordination and hydrolysis functional group, and the mol ratio of polyoxyethylene glycol and organo-silicon coupling agent is 1: 2, and the molecular weight of polyoxyethylene glycol is PEG400;
(3) preparation of rare earth compounding:
The organic bridge molecule and step (2) the gained polyoxyethylene glycol bridging molecule drips of solution of step (1) gained are added in the ethanolic soln that is dissolved in rare earth nitrate, stir, coordination reaction under 20-30 ℃ of temperature, reaction times is 2-7 hour, obtain rare earth compounding, organic bridge molecule, the mol ratio of polyoxyethylene glycol bridging molecule and rare earth ion are 3: 1: 1;
(4) sol-gel process:
In the rare earth compounding of step (3) gained, add tetraethoxy and deionized water, the pH value of regulator solution, under 20-40 ℃ of temperature hydrolysis condensation reaction 5-10 hour, up to the generation solid gel; Wherein: the mol ratio of rare earth compounding, tetraethoxy and deionized water is 1: 6: 12-1: 8: 16;
(5) aging and drying treatment:
The gel of step (4) gained is aging, use absolute ethanol washing then, drying promptly gets desired product.
2, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1, it is characterized in that aromatic series organic molecule described in the step (1) be in 3-hydroxy niacin, salicylic acid, 2-hydroxy-3-methyl phenylformic acid or the 2-methyl m-phthalic acid any.
3, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1 is characterized in that organo-silicon coupling agent is the silica-based propyl isocyanate of triethoxy described in step (1) and the step (2).
4, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1, it is characterized in that organic solvent is anhydrous propanone, anhydrous diethyl ether, anhydrous pyridine, tetrahydrofuran (THF), nitrogen described in step (1) and the step (2), in nitrogen-dimethyl formamide or the chloroform any.
5, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1 is characterized in that rare earth nitrate is europium nitrate or Terbium trinitrate described in the step (3).
6, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1 is characterized in that the pH value of solution in the step (4) is 6-7.
7, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1 is characterized in that aging temperature is 55-80 ℃ described in the step (5), and digestion time is 15-20 days.
8, the preparation method of luminescent rear earth-polyethylene glycol polymer composites according to claim 1 is characterized in that drying temperature is 60-85 ℃ described in the step (5), and be 3-8 days time of drying.
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| CN101735799A (en) * | 2009-12-04 | 2010-06-16 | 同济大学 | Preparation method of organic/inorganic/polymeric composite luminescent material of sulfoxide functionalization rare earth |
| CN102618275A (en) * | 2012-03-14 | 2012-08-01 | 同济大学 | Method for preparing rare-earth organic and inorganic zinc oxide semiconductor nanopore composite luminescent material based on hydroxyl functionalization |
| CN102618260A (en) * | 2012-03-14 | 2012-08-01 | 同济大学 | Method for preparing carbon nano tube/silica network/ligand/rare-earth organic and inorganic composite luminescent material |
| CN102617762A (en) * | 2012-03-14 | 2012-08-01 | 同济大学 | Method for preparing rare-earth macromolecular composite luminescent material based on imidazole molecular bridge connection |
| CN102775982A (en) * | 2012-08-16 | 2012-11-14 | 上海理工大学 | Preparation method of high molecule functionalized rare earth/mesoporous fluorescent nano-material |
| CN102942921A (en) * | 2012-11-30 | 2013-02-27 | 上海理工大学 | Preparation method of polymer functional rare-earth/organic/inorganic mesoporous fluorescent material |
| CN108705632A (en) * | 2018-06-08 | 2018-10-26 | 阜南县宏达工艺品厂 | A method of promoting wicker products weatherability |
| CN111234253A (en) * | 2020-02-27 | 2020-06-05 | 吉林师范大学 | Preparation method of nano metal organic framework material |
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2008
- 2008-04-17 CN CN2008100361659A patent/CN101255273B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735799A (en) * | 2009-12-04 | 2010-06-16 | 同济大学 | Preparation method of organic/inorganic/polymeric composite luminescent material of sulfoxide functionalization rare earth |
| CN101735799B (en) * | 2009-12-04 | 2013-06-26 | 同济大学 | Preparation method of organic/inorganic/polymeric composite luminescent material of sulfoxide functionalization rare earth |
| CN102618275A (en) * | 2012-03-14 | 2012-08-01 | 同济大学 | Method for preparing rare-earth organic and inorganic zinc oxide semiconductor nanopore composite luminescent material based on hydroxyl functionalization |
| CN102618260A (en) * | 2012-03-14 | 2012-08-01 | 同济大学 | Method for preparing carbon nano tube/silica network/ligand/rare-earth organic and inorganic composite luminescent material |
| CN102617762A (en) * | 2012-03-14 | 2012-08-01 | 同济大学 | Method for preparing rare-earth macromolecular composite luminescent material based on imidazole molecular bridge connection |
| CN102618275B (en) * | 2012-03-14 | 2013-08-14 | 同济大学 | Method for preparing rare-earth organic and inorganic zinc oxide semiconductor nanopore composite luminescent material based on hydroxyl functionalization |
| CN102775982A (en) * | 2012-08-16 | 2012-11-14 | 上海理工大学 | Preparation method of high molecule functionalized rare earth/mesoporous fluorescent nano-material |
| CN102942921A (en) * | 2012-11-30 | 2013-02-27 | 上海理工大学 | Preparation method of polymer functional rare-earth/organic/inorganic mesoporous fluorescent material |
| CN108705632A (en) * | 2018-06-08 | 2018-10-26 | 阜南县宏达工艺品厂 | A method of promoting wicker products weatherability |
| CN111234253A (en) * | 2020-02-27 | 2020-06-05 | 吉林师范大学 | Preparation method of nano metal organic framework material |
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