CN1718668A - Preparation method of organic electro luminous material rare earth europium organic metal complex - Google Patents
Preparation method of organic electro luminous material rare earth europium organic metal complex Download PDFInfo
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- CN1718668A CN1718668A CNA200510012659XA CN200510012659A CN1718668A CN 1718668 A CN1718668 A CN 1718668A CN A200510012659X A CNA200510012659X A CN A200510012659XA CN 200510012659 A CN200510012659 A CN 200510012659A CN 1718668 A CN1718668 A CN 1718668A
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Abstract
An Eu-organic metal match used as organic electroluminescent material is prepared through preparing europium chloride from europium oxide, respectively dissolving europium chloride, dibenzoyl methane and 1, 10-O-phenanthroline in alcohol, mixing at 70+/-5 deg.C, adding alkali twice for regulating pH value, reaction, washing three times, filtering, baking, recrystallizing three times and vacuum filter.
Description
Technical field:
The present invention relates to a kind of electroluminescent organic material, is the preparation method of the organometallic complex of central ion with the rare-earth europium ion, belongs to the research of electroluminescent organic material and device and the technical field of producing.
Background technology
Organic electroluminescence device has low voltage direct drive, high brightness, with great visual angle, easily realizes advantages such as colorize, dull and stereotyped big area demonstration, compare with inorganic electroluminescence device, easy, the good mechanical property of organic electroluminescence device processing, cost is low, compare with liquid crystal display device, the organic electroluminescence device response speed is fast, estimates in the near future, organic electroluminescence device will replace inorganic EL and liquid crystal display device, becomes following flat pannel display main body.
The research of organic electroluminescent starts from nineteen sixties, what used at that time is the organic materials crystal, need higher driving voltage, and luminosity and luminous efficiency are not high, fail to cause people's attention, the progress of two more than ten years is slow thereafter, has arrived twentieth century the 80s and 90s, oxine aluminium is as the appearance of the organic electroluminescence device of luminescent layer, but low voltage drive, just causes people's attention.
The luminescent material that is used for organic electroluminescence device mainly contains metal complexes, organic molecule dyestuff and organic polymer, the rare earth organometallic complex that belongs to the organometallic complex category, the peak width at half height degree of the big emission peak of matter is narrow in the emmission spectrum, 10 nanometers only, the purity of color height, this distinct advantages is that other luminescent materials are incomparable, and quantum yield almost can reach 100%, it is up-and-coming electroluminescent organic material, at present, required red of display device, green, the rare earth europium organic metal complex of blue two primary colours and the research of device thereof are in the starting stage, purification at rare earth europium organic metal complex, synthetic, detect aspects and also have a lot of deficiencies, be still waiting further experimental study, for example: the reparation technology flow process is unreasonable, the cost height, purity is low, of poor quality, extract yield is low, can not obtain highly purified rare earth europium organic metal complex in a large number.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly the deficiency at back of the body technology, adopt brand-new reparation technology flow and method, with reparation technologies such as rational chemical substance proportioning, dissolving, combination reaction, washing, filtration, heating, recrystallization, oven dry, to extract high purity, high yield, high-quality rare earth europium organic metal complex are so that in electronic industry and the widespread use of luminous field.
Technical scheme
The chemical substance that the present invention uses is: europium sesquioxide, 1, and 10-phenanthroline, diphenylpropane-1,3-dione(DPPO), triethylamine, dehydrated alcohol, concentrated hydrochloric acid, its combination matching is:
With gram, milliliter is measure unit:
Europium sesquioxide: 0.5 gram ± 0.05 gram
1,10-phenanthroline: 0.55 gram ± 0.05 gram
Diphenylpropane-1,3-dione(DPPO): 1.884 grams ± 0.05 gram
Dehydrated alcohol: 680 milliliters ± 1 milliliter
Triethylamine: 5 milliliters ± 0.1 milliliter
Concentrated hydrochloric acid: 15 milliliters ± 1 milliliter
Preparation method of the present invention is as follows:
1), selected chemical substance, carry out control of purity
The required chemical substance of combination matching is carried out selected, and carry out control of purity, its purity is:
Europium sesquioxide: 99.99%
1,10-phenanthroline: 98%
Diphenylpropane-1,3-dione(DPPO): 98%
Dehydrated alcohol: 99.9%
Triethylamine: 99.9%
Concentrated hydrochloric acid: concentration 36%
2), produce Europium trichloride
In the round bottom crucible, put into europium sesquioxide 0.5 gram ± 0.05 gram by proportioning, add 15 milliliters ± 1 milliliter of concentrated hydrochloric acid;
Place electrically heated to put heating in the round bottom crucible, Heating temperature is 80 ℃ ± 5 ℃, and be 120 minutes heat-up time;
Under heated condition, europium sesquioxide is dissolved in concentrated hydrochloric acid, and simultaneously, excessive concentrated hydrochloric acid slowly evaporates, and stays white powder, i.e. the Europium trichloride white powder.
3), dissolving Europium trichloride
The Europium trichloride white powder is placed beaker, add 20 milliliters of dehydrated alcohols, stir with the dry glass rod, place electrically heated to put heating in beaker then, Heating temperature is 50 ℃ ± 5 ℃, and be 10 minutes heat-up time, heats while stirring, clarifying Europium trichloride ethanolic soln is made in the Europium trichloride dissolving.
4), dissolving diphenylpropane-1,3-dione(DPPO)
Diphenylpropane-1,3-dione(DPPO) 1.884 grams ± 0.05 gram is placed the burning bosom, add 80 milliliters of dehydrated alcohols then, stir with the dry glass rod, place electrically heated to put heating in beaker then, Heating temperature is 50 ℃ ± 5 ℃, and be 10 minutes heat-up time, makes the diphenylpropane-1,3-dione(DPPO) ethanolic soln.
5), dissolve 1, the 10-phenanthroline
With 1,10-phenanthroline 0.55 gram ± 0.05 gram places beaker, adds 40 milliliters of dehydrated alcohols, stirs, and makes its dissolving, is 20 minutes between stirring, and carries out under 20 ℃ ± 3 ℃ of normal temperature, becomes 1,10-phenanthroline ethanolic soln.
6), rare-earth europium-diphenylpropane-1,3-dione(DPPO)-1, the producing of 10-phenanthroline ternary complex
The diphenylpropane-1,3-dione(DPPO) ethanolic soln is poured in the four-hole boiling flask, four mouths of four-hole boiling flask are being plugged in thermometer, dropping funnel, magnetic stirring apparatus, condensing reflux pipe respectively, four-hole boiling flask places electrically heated to put, the diphenylpropane-1,3-dione(DPPO) ethanolic soln to 70 in the electrically heated cover heating four-hole boiling flask ℃ ± 5 ℃;
The Europium trichloride ethanolic soln splashed in the four-hole boiling flask by dropping funnel mix, the time of splashing into is 30 minutes, stirs while splashing into, and becomes faint yellow after solution mixes;
Execute for the first time alkali, add 3 milliliters of triethylamines, regulating the acidity-basicity ph value is 6.5, at this moment the mixing solutions slant acidity;
With 1,10-phenanthroline ethanolic soln splashes into by dropping funnel in the four-hole boiling flask that fills mixing solutions, and the time of splashing into is 30 minutes, uses magnetic stirrer while splashing into, and constantly separates out yellow mercury oxide;
Execute for the second time alkali, add 2 milliliters of triethylamines, regulate acidity-basicity ph value to 7.2, this moment, the mixing solutions meta-alkalescence continued reaction 60 minutes, and the acidity-basicity ph value of reaction system no longer changes, and stops until reaction:
Leave standstill, filter, close electrically heated cover, magnetic stirring apparatus, condensing reflux pipe, reaction soln is poured in the beaker together with yellow mercury oxide, after leaving standstill 12 hours, reaction soln is placed long neck funnel, be filtered in the container with qualitative filter paper, on filter paper, obtain yellow mercury oxide, be i.e. the rare earth europium organic metal complex of low-purity;
In the producing of ternary complex, combination reaction will take place in mixing solutions, and the combination reaction formula is as follows:
In the formula:
EuCl
3: Europium trichloride
3HCl: concentrated hydrochloric acid
3H DB M: diphenylpropane-1,3-dione(DPPO)
Phen:1, the 10-phenanthroline
O: oxygen
OH: hydroxyl
N: nitrogen
Eu: europium
7), product washing, filter three times
The rare earth europium organic metal complex yellow mercury oxide of low-purity is placed beaker, add 80 milliliters of dehydrated alcohols, under 20 ℃ ± 3 ℃ states of normal temperature, with the magnetic stirrer washing, the time is 10 minutes;
Rare earth europium organic metal complex mixed solution with washing is filtered in long neck funnel in the product container with qualitative filter paper, and the throw out on the filter paper is the higher rare earth europium organic metal complex yellow powder of purity;
Washing, stirring, filtration repeat three times.
8), oven dry
The airtight vacuum drying oven that places of the container that fills product is dried, and bake out temperature is 80 ℃ ± 5 ℃, and drying time is 120 minutes.
9), product recrystallization purification processes is three times
The higher rare earth europium organic metal complex yellow powder of purity that washing, filtration, oven dry obtain is poured in the there-necked flask, add 100 milliliters of dehydrated alcohols, even with magnetic stirrer, become mixed solution, the water condensation return line is started working, and places electrically heated to put heating there-necked flask then, and Heating temperature is 75 ℃ ± 5 ℃, the mixed solution boiling, constant temperature 5 minutes;
Then, stop heating, have in the B of three layers of qualitative filter paper in while hot mixed solution being poured into, B is inserted on the vacuum filtration bottle, carry out suction filtration with vacuum pump, product is stayed on the qualitative filter paper, and ethanol waste liquid and by product are evacuated in the filter flask;
The recrystallization purification processes repeats three times, and the product on the qualitative filter paper is highly purified rare earth europium organic metal complex pale yellow powder.
10), secondary drying
Rare earth europium organic metal complex pale yellow powder through three recrystallization purification processes, place vacuum drying oven to carry out the oven dry second time, bake out temperature is 80 ℃ ± 5 ℃, and drying time is 120 minutes, promptly obtains highly purified rare earth europium organic metal complex pale yellow powder after the oven dry.
11), check and analysis contrast
To the rare earth europium organic metal complex pale yellow powder, carry out purity, form, pattern, color and luster, structure, Performance Detection analysis contrast, carry out structural analysis with infrared spectrometer, carry out the product ultimate analysis, carry out the luminescent properties analysis with spectrum Emanations Analysis instrument with elemental analyser.
12), packing and storing
The rare earth europium organic metal complex pale yellow powder of producing is placed brown transparent round mouth Glass Containers, airtight lucifuge stores, place the environment in drying, cool place, storing temp is 20 ℃ ± 3 ℃, waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode.
Described rare-earth europium-diphenylpropane-1,3-dione(DPPO)-1, the combination reaction temperature of 10-phenanthroline ternary complex are 70 ℃ ± 5 ℃, and secondary is executed alkali and added triethylamine, and the acidity-basicity ph value is constant by 6.5-7.2, and the reaction times is 120 minutes.
Described product recrystallization purification processes is carried out under mixed solution ebuillition of heated state, and Heating temperature is 75 ℃ ± 5 ℃, and be 5 minutes heat-up time, carries out vacuum filtration with three layers of qualitative filter paper, and recrystallization is handled and repeated three times.
Effect
The present invention compares with background technology has tangible advance, adopted brand-new reparation technology flow process, earlier the raw chemical material europium sesquioxide is made Europium trichloride, and then make the Europium trichloride ethanolic soln, the diphenylpropane-1,3-dione(DPPO) ethanolic soln, 1,10-phenanthroline ethanolic soln, under the heated condition of 70 ℃ ± 5 ℃ of solution, mix, execute alkali through secondary, adjust the acidity-basicity ph value, carry out combination reaction, generate the rare earth europium organic metal complex yellow powder of low-purity, through three washings, filter, oven dry, obtain the higher product powder of purity, through three recrystallization vacuum filtration purification processes, finally obtain highly purified rare earth europium organic metal complex pale yellow powder, its purity can reach 99%, this preparation method uses equipment few, technical process is simple, the productive rate height, purity is good, is the very good method of producing organic electro luminous material rare earth europium organic metal complex, and this material can be widely used in electronic industry and luminescence technology field.
Description of drawings
Fig. 1 is the reparation technology schema
Fig. 2 is Heating temperature, execute alkali time coordinate graph of a relation
Fig. 3 is the combination reaction state graph
Fig. 4 is recrystallization heating, mixing, whipped state figure
Fig. 5 is recrystallization vacuum filtration purification state graph
Fig. 6 is a rare earth europium organic metal complex photoluminescence collection of illustrative plates
Fig. 7 is a rare earth europium organic metal complex infrared absorption light collection of illustrative plates
Shown in the figure, each piece number inventory is as follows:
1, electrically heated cover, 2, four-hole boiling flask, 3, agitator, 4, dropping funnel, 5, condensing reflux pipe, 6, water-in, 7, water outlet, 8, gas port, 9, variable valve, 10, tapered plug, 11, tapered plug, 12, filter flask, 13, vacuum pump, 14, B, 15, tapered plug, 16, qualitative filter paper, 17, the liquid in-out mouth, 18, tapered plug, 19, thermometer, 20, there-necked flask.
Embodiment:
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be the process flow sheet of producing rare earth europium organic metal complex, carry out in strict accordance with technical process and technology numerical value, according to the order of sequence operation.
To preparing required chemical substance, it is selected to distinguish strictness, need carry out control of purity, avoids too much impurity to get involved, and prevents side reaction, in order to avoid influence the luminescent properties of product.
The chemical substance that combination reaction is used will be in strict accordance with proportioning with the accurate weighing of electronic scale, guarantees that combination reaction accurately carries out chemical combination according to mol ratio, optimizes reaction parameter, avoids waste.
When producing Europium trichloride, europium sesquioxide be mixed stirring, heating with excessive concentrated hydrochloric acid, strict control Heating temperature and time, under heated condition, excessive concentrated hydrochloric acid evaporation obtains the Europium trichloride white powder.
During dissolving Europium trichloride white powder, the dissolving back becomes clarifying Europium trichloride ethanolic soln.
Two stupid formyl methane dissolvings are to carry out under 50 ℃ ± 5 ℃ heated condition, add 80 milliliters of dehydrated alcohols according to proportioning, and stir, and heat can become the diphenylpropane-1,3-dione(DPPO) ethanolic soln in 10 minutes.
1, the adjacent phenanthroline dissolving of 10-is carried out under 20 ℃ ± 3 ℃ of normal temperature, adds 40 milliliters of dehydrated alcohols by proportioning, stirs 20 minutes, can become 1, the adjacent phenanthroline ethanolic soln of 10-.
It is to carry out under 70 ℃ ± 5 ℃ heated condition that three liquid mix, and needs secondary to execute alkali, adds triethylamine, to regulate the acidity-basicity ph value, makes it keep stable, and three liquid after mixing combination reaction will take place, and generate the rare earth europium organic metal complex product of low-purity.
The rare earth europium organic metal complex product will carry out three washings, filters, dry, and obtains the higher rare earth europium organic metal complex yellow powder of purity.
The rare earth europium organic metal complex yellow powder will carry out the recrystallization purification processes three times, promptly gets product to the end behind the secondary drying---highly purified rare earth europium organic metal complex pale yellow powder.
Conclusion: rare-earth europium-diphenylpropane-1,3-dione(DPPO)-1, generate the rare earth europium organic metal complex yellow mercury oxide of low-purity after the 10-phenanthroline ternary complex combination reaction, after three washings, filtration, obtain the higher rare earth europium organic metal complex yellow powder of purity, after three recrystallization purification processes, obtain highly purified rare earth europium organic metal complex pale yellow powder.
Shown in Figure 2, be Heating temperature, execute alkali time, constant temperature insulation coordinate graph of a relation, ordinate zou is a Heating temperature, X-coordinate is heat-up time, the A-B section is the constant temperature insulation period, and the D point adds the triethylamine time for executing for the first time alkali, and the E point adds the triethylamine time for executing for the second time alkali.
Shown in Figure 3, be the combination reaction state graph, top at electrically heated cover 1 is four-hole boiling flask 2, tapered plug 18 is equipped with on top at four-hole boiling flask 2 successively, thermometer 19, tapered plug 10, dropping funnel 4, variable valve 9, magnetic stirring apparatus 3, tapered plug 11, condensing reflux pipe 5, condensing reflux pipe 5 upper left quarters are water outlet 7, right lower quadrant is a water-in 6, top is gas port 8, four-hole boiling flask 2 inner bottom parts are the diphenylpropane-1,3-dione(DPPO) ethanolic soln, the Europium trichloride ethanolic soln, 1,10-phenanthroline ethanolic soln is splashed into respectively in the four-hole boiling flask 2 by dropping funnel 4, its rate of addition is regulated by variable valve 9, under electrically heated cover 1 heating alcohol mixed solution state, the limit dropping liquid, stir on the limit, the import and export 6 of condensing reflux pipe 5 simultaneously, 7 beginning water flowing circulating condensings, gas port 8 is given vent to anger, dropping liquid, after combination reaction is finished, close electrically heated cover 1 immediately.
Shown in Fig. 4,5, be recrystallization purification processes state, earlier the product alcohol mixeding liquid added in the there-necked flask 20 by liquid in-out mouth 17,1 heating of electrically heated cover, temperature is 75 ℃ ± 5 ℃, the mixed solution boiling, agitator 11 stirs, the 5 beginning condensations of condensing reflux pipe are given vent to anger; After mixing stirring, mixed solution in the there-necked flask 20 is poured in the B 14 on the filter flask 12 while hot by liquid in-out mouth 17, three layers of qualitative filter paper 16 are arranged in the B 14, vacuum pump 13 is opened, carry out vacuum filtration, the ethanol waste liquid enters in the filter flask 12, and the rare earth europium organic metal complex product is retained on the qualitative filter paper 16, recrystallization is handled and will be repeated three times, finally obtains highly purified rare earth europium organic metal complex pale yellow powder.
Shown in Figure 6, be rare earth europium organic metal complex photoluminescence collection of illustrative plates, ordinate zou is a relative intensity, X-coordinate is a nano wave length numerical value, is to obtain under the ultraviolet excitation of wavelength 365nm, can see the feature emission of europium, from energy level 5D
0-7F
0Transition be 580nm, from energy level 5D
0-7F
1Transition be 590nm, from energy level 5D
0-7F
2Transition be 620nm, from energy level 5D
0-7F
3Transition be 655nm, from energy level 5D
0-7F
4Transition be 695nm, 705nm.
Shown in Figure 7, for rare earth europium organic metal complex at 4400cm
-1To 400cm
-1Infrared absorption light collection of illustrative plates, ordinate zou are the transmitance percentage value, and X-coordinate is wave number numerical value cm
-1, 842.56cm
-1And 723.22cm
-1The place is 1, the carbon of 10-phenanthroline-hydrogen eigen vibration peak, 1549.91cm
-1And 1478.70cm
-1The place is 1, the two key eigen vibration peaks of the carbon-to-carbon double bond of 10-phenanthroline and carbon-nitrogen, 1518.78cm
-1The place is diphenylpropane-1,3-dione(DPPO) enol form eigen vibration peak, 609.39cm
-1The place is rare-earth europium title complex europium-nitrogen eigen vibration peak, 524.65cm
-1The place is rare-earth europium title complex europium-oxygen eigen vibration peak.
The proportioning of producing rare earth europium organic metal complex is what to determine in a quantitative range that sets in advance, is measure unit with gram, milliliter, when industrialization is produced, with kilogram, be upgraded to measure unit.
The ethanol waste liquid that produces in producing can recycle, with economical with materials.
Each preparation apparatus is in quasi-operating status;
Produce Europium trichloride: take by weighing europium sesquioxide 0.5 gram and place the round bottom crucible, add 15 milliliters of concentrated hydrochloric acids, place electrically heated to put heating in the round bottom crucible, 80 ℃ ± 5 ℃ of temperature, stir at 120 minutes time, the solution clarification, the concentrated hydrochloric acid evaporation obtains the Europium trichloride white powder;
The dissolving Europium trichloride:
The Europium trichloride white powder is placed beaker, add 20 milliliters of dehydrated alcohols, electrically heated cover heating ten minutes, 50 ℃ ± 5 ℃, stir, become the Europium trichloride ethanolic soln;
The dissolving hexichol adds acyl methane:
Take by weighing hexichol and add acyl methane 1.884 grams, place beaker, add 80 milliliters of dehydrated alcohols, place electrically heated to put heating in beaker, 50 ℃ ± 5 ℃ of temperature, stirred 10 minutes on limit heating, limit, to dissolving, close the electrically heated cover, make the diphenylpropane-1,3-dione(DPPO) ethanolic soln;
Dissolving 1, the 10-phenanthroline:
Take by weighing 1,10-phenanthroline 0.55 gram places beaker, adds 40 milliliters of dehydrated alcohols, stirs under 20 ℃ ± 3 ℃ of normal temperature, makes its dissolving, makes 1,10-phenanthroline ethanolic soln;
Rare-earth europium-diphenylpropane-1,3-dione(DPPO)-1,10-phenanthroline ternary complex combination reaction:
The diphenylpropane-1,3-dione(DPPO) ethanolic soln is placed four-hole boiling flask, four-hole boiling flask is placed on the electric mantle, open the electrically heated cover, temperature is 70 ℃ ± 5 ℃, heating diphenylpropane-1,3-dione(DPPO) ethanolic soln, the Europium trichloride ethanolic soln is splashed into four-hole boiling flask by dropping funnel, splash into 30 minutes time, agitator stirs, and the condensing reflux pipe is opened, solution mixes, and becomes faint yellow;
Execute for the first time alkali under heated condition, add 3 milliliters of triethylamines, the pH value is 6.5, slant acidity;
With 1,10-phenanthroline ethanolic soln is splashed in the four-hole boiling flask by dropping funnel, 30 minutes time, under heated condition, stir, and separate out yellow mercury oxide;
Execute for the second time alkali, add 2 milliliters of triethylamines, the pH value is 7.2, meta-alkalescence; Continue reaction 60 minutes, system pH is constant;
Combination reaction finishes, close electrically heated cover, magnetic stirring apparatus, condensing reflux pipe, obtain having the product solution of yellow mercury oxide, the product solution left standstill was filtered with qualitative filter paper after 12 hours, obtain yellow mercury oxide, i.e. the rare earth europium organic metal complex of low-purity;
Washing, filtration three times:
Yellow mercury oxide is placed beaker, add 80 milliliters of dehydrated alcohols, under 20 ℃ ± 3 ℃ of normal temperature, stirred 10 minutes, become mixed solution;
Have in mixed solution poured in the long neck funnel of qualitative filter paper and filter, on filter paper, obtain yellow mercury oxide;
Oven dry: yellow mercury oxide is collected in the product container, places vacuum drying oven, 80 ℃ ± 5 ℃ of temperature obtain the higher rare earth europium organic metal complex yellow powder of purity after the drying;
Recrystallization is purified three times
Yellow powder is poured in the there-necked flask, add 100 milliliters of dehydrated alcohols, become mixed solution, there-necked flask places electrically heated to put heating, 75 ℃ ± 5 ℃ of temperature, the mixed solution boiling, constant temperature 5 minutes is closed the electrically heated cover, has in while hot mixed solution being poured in the low B of three layers of qualitative filter, use the vacuum pump suction filtration, on filter paper, obtain pale yellow powder.
Secondary drying:
Pale yellow powder is collected in the container, places vacuum drying oven to dry, bake out temperature is 80 ℃ ± 5 ℃, and the time is 120 minutes, obtains highly purified rare earth europium organic metal complex pale yellow powder.
Claims (3)
1, a kind of preparation method of organic electro luminous material rare earth europium organic metal complex, it is characterized in that: the chemical substance that the present invention uses is: europium sesquioxide, 1,10-phenanthroline, diphenylpropane-1,3-dione(DPPO), triethylamine, dehydrated alcohol, concentrated hydrochloric acid, its combination matching is:
With gram, milliliter is measure unit:
Europium sesquioxide: 0.5 gram ± 0.05 gram
1,10-phenanthroline: 0.55 gram ± 0.05 gram
Diphenylpropane-1,3-dione(DPPO): 1.884 grams ± 0.05 gram
Dehydrated alcohol: 680 milliliters ± 1 milliliter
Triethylamine: 5 milliliters ± 0.1 milliliter
Concentrated hydrochloric acid: 15 milliliters ± 1 milliliter
Preparation method of the present invention is as follows:
1), selected chemical substance, carry out control of purity
The required chemical substance of combination matching is carried out selected, and carry out control of purity, its purity is:
Europium sesquioxide: 99.99%
1,10-phenanthroline: 98%
Diphenylpropane-1,3-dione(DPPO): 98%
Dehydrated alcohol: 99.9%
Triethylamine: 99.9%
Concentrated hydrochloric acid: concentration 36%
2), produce Europium trichloride
In the round bottom crucible, put into europium sesquioxide 0.5 gram ± 0.05 gram by proportioning, add 15 milliliters ± 1 milliliter of concentrated hydrochloric acid;
Place electrically heated to put heating in the round bottom crucible, Heating temperature is 80 ℃ ± 5 ℃, and be 120 minutes heat-up time;
Under heated condition, europium sesquioxide is dissolved in concentrated hydrochloric acid, and simultaneously, excessive concentrated hydrochloric acid slowly evaporates, and stays white powder, i.e. the Europium trichloride white powder.
3), dissolving Europium trichloride
The Europium trichloride white powder is placed beaker, add 20 milliliters of dehydrated alcohols, stir with the dry glass rod, place electrically heated to put heating in beaker then, Heating temperature is 50 ℃ ± 5 ℃, and be 10 minutes heat-up time, heats while stirring, clarifying Europium trichloride ethanolic soln is made in the Europium trichloride dissolving.
4), dissolving diphenylpropane-1,3-dione(DPPO)
Diphenylpropane-1,3-dione(DPPO) 1.884 grams ± 0.05 gram is placed the burning bosom, add 80 milliliters of dehydrated alcohols then, stir with the dry glass rod, place electrically heated to put heating in beaker then, Heating temperature is 50 ℃ ± 5 ℃, and be 10 minutes heat-up time, makes the diphenylpropane-1,3-dione(DPPO) ethanolic soln.
5), dissolve 1, the 10-phenanthroline
With 1,10-phenanthroline 0.55 gram ± 0.05 gram places beaker, adds 40 milliliters of dehydrated alcohols, stirs, and makes its dissolving, is 20 minutes between stirring, and carries out under 20 ℃ ± 3 ℃ of normal temperature, becomes 1,10-phenanthroline ethanolic soln.
6), rare-earth europium-diphenylpropane-1,3-dione(DPPO)-1, the producing of 10-phenanthroline ternary complex
The diphenylpropane-1,3-dione(DPPO) ethanolic soln is poured in the four-hole boiling flask, four mouths of four-hole boiling flask are being plugged in thermometer dropping funnel, magnetic stirring apparatus, condensing reflux pipe respectively, four-hole boiling flask places electrically heated to put, the diphenylpropane-1,3-dione(DPPO) ethanolic soln to 70 in the electrically heated cover heating four-hole boiling flask ℃ ± 5 ℃;
The Europium trichloride ethanolic soln splashed in the four-hole boiling flask by dropping funnel mix, the time of splashing into is 30 minutes, stirs while splashing into, and becomes faint yellow after solution mixes;
Execute for the first time alkali, add 3 milliliters of triethylamines, regulating the acidity-basicity ph value is 6.5, at this moment the mixing solutions slant acidity;
With 1,10-phenanthroline ethanolic soln splashes into by dropping funnel in the four-hole boiling flask that fills mixing solutions, and the time of splashing into is 30 minutes, uses magnetic stirrer while splashing into, and constantly separates out yellow mercury oxide;
Execute for the second time alkali, add 2 milliliters of triethylamines, regulate acidity-basicity ph value to 7.2, this moment, the mixing solutions meta-alkalescence continued reaction 60 minutes, and the acidity-basicity ph value of reaction system no longer changes, and stops until reaction;
Leave standstill, filter, close electrically heated cover, magnetic stirring apparatus, condensing reflux pipe, reaction soln is poured in the beaker together with yellow mercury oxide, after leaving standstill 12 hours, reaction soln is placed long neck funnel, be filtered in the container with qualitative filter paper, on filter paper, obtain yellow mercury oxide, be i.e. the rare earth europium organic metal complex of low-purity;
In the producing of ternary complex, combination reaction will take place in mixing solutions, and the combination reaction formula is as follows:
In the formula:
EuCl
3: Europium trichloride
3HCl: concentrated hydrochloric acid
3H DB M: diphenylpropane-1,3-dione(DPPO)
Phen:1, the 10-phenanthroline
O: oxygen
OH: hydroxyl
N: nitrogen
Eu: europium
7), product washing, filter three times
The rare earth europium organic metal complex yellow mercury oxide of low-purity is placed beaker, add 80 milliliters of dehydrated alcohols, under 20 ℃ ± 3 ℃ states of normal temperature, with the magnetic stirrer washing, the time is 10 minutes;
Rare earth europium organic metal complex mixed solution with washing is filtered in long neck funnel in the product container with qualitative filter paper, and the throw out on the filter paper is the higher rare earth europium organic metal complex yellow powder of purity;
Washing, stirring, filtration repeat three times.
8), oven dry
The airtight vacuum drying oven that places of the container that fills product is dried, and bake out temperature is 80 ℃ ± 5 ℃, and drying time is 120 minutes.
9), product recrystallization purification processes is three times
The higher rare earth europium organic metal complex yellow powder of purity that washing, filtration, oven dry obtain is poured in the there-necked flask, add 100 milliliters of dehydrated alcohols, even with magnetic stirrer, become mixed solution, the water condensation return line is started working, and places electrically heated to put heating there-necked flask then, and Heating temperature is 75 ℃ ± 5 ℃, the mixed solution boiling, constant temperature 5 minutes;
Then, stop heating, have in the B of three layers of qualitative filter paper in while hot mixed solution being poured into, B is inserted on the vacuum filtration bottle, carry out suction filtration with vacuum pump, product is stayed on the qualitative filter paper, and ethanol waste liquid and by product are evacuated in the filter flask;
The recrystallization purification processes repeats three times, and the product on the qualitative filter paper is highly purified rare earth europium organic metal complex pale yellow powder.
10), secondary drying
Rare earth europium organic metal complex pale yellow powder through three recrystallization purification processes, place vacuum drying oven to carry out the oven dry second time, bake out temperature is 80 ℃ ± 5 ℃, and drying time is 120 minutes, promptly obtains highly purified rare earth europium organic metal complex pale yellow powder after the oven dry.
11), check and analysis contrast
To the rare earth europium organic metal complex pale yellow powder, carry out purity, form, pattern, color and luster, structure, Performance Detection analysis contrast, carry out structural analysis with infrared spectrometer, carry out the product ultimate analysis, carry out the luminescent properties analysis with spectrum Emanations Analysis instrument with elemental analyser.
12), packing and storing
The rare earth europium organic metal complex pale yellow powder of producing is placed brown transparent round mouth Glass Containers, airtight lucifuge stores, place the environment in drying, cool place, storing temp is 20 ℃ ± 3 ℃, waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode.
2, the preparation method of organic electro luminous material rare earth europium organic metal complex according to claim 1, it is characterized in that: described rare-earth europium-diphenylpropane-1,3-dione(DPPO)-1, the combination reaction temperature of 10-phenanthroline ternary complex is 70 ℃ ± 5 ℃, secondary is executed alkali and is added triethylamine, the acidity-basicity ph value is constant by 6.5-7.2, and the reaction times is 120 minutes
3, the preparation method of organic electro luminous material rare earth europium organic metal complex according to claim 1, it is characterized in that: described product recrystallization purification processes is carried out under mixed solution ebuillition of heated state, Heating temperature is 75 ℃ ± 5 ℃, be 5 minutes heat-up time, carry out vacuum filtration with three layers of qualitative filter paper, recrystallization is handled and is repeated three times.
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