CN1597669A - 8- hydroxy quinoline bryhtening blue light and preparation method - Google Patents
8- hydroxy quinoline bryhtening blue light and preparation method Download PDFInfo
- Publication number
- CN1597669A CN1597669A CN 200410012430 CN200410012430A CN1597669A CN 1597669 A CN1597669 A CN 1597669A CN 200410012430 CN200410012430 CN 200410012430 CN 200410012430 A CN200410012430 A CN 200410012430A CN 1597669 A CN1597669 A CN 1597669A
- Authority
- CN
- China
- Prior art keywords
- oxine
- aluminium
- blue light
- green
- emitting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
A 8-hydroxyquinolyl aluminium able to emit blue light is prepared from 8-hydroxyquinoline crystal, anhydrous aluminium acetate, absolute methanol, acetone, pyridine and NN-dimethylformamide through reaction, washing, filtering, baking, vacuum heating, constant temp, cooling, N2 protection recrystallizingand test analysing.
Description
Technical field
The present invention relates to a kind of oxine aluminium and preparation method of blue light-emitting, belong to the research of electroluminescent organic material and the technical field of preparation method.
Background technology
Electroluminescent organic material is a kind of advanced luminescent material in the electronic industry, be usually used in organic electroluminescence device, it has that preparation technology is simple, low in energy consumption, Show Color is abundant,, thin thickness little, low voltage direct drive from main light emission, flat pannel display, volume, solidify entirely, advantages such as the visual angle is wide, big area demonstration, and luminous efficiency height, good brightness, long service life.
Oxine aluminium is the material of a kind of green light the most commonly used in the organic electroluminescence device, it has good film-forming properties, adopt the vacuum thermal evaporation membrane process, can form even compact, the film of tens nanometer thickness of free of pinholes, and good stability, the luminous efficiency height, luminosity is big, second-order transition temperature is higher, produce easily, synthesis technique is simple, and cost is low, the productive rate height, color, purity is all good, it is a kind of research comparative maturity, can carry out the electroluminescent organic material that preparation of industrialization is produced, but it is only limited to green light, the present still scientific research blank of the oxine aluminium of blue light-emitting.
In the existing blue electroluminescent organic material that turns blue, mainly contain: organic metal chelate complex, rare earth compounding, triphen diamine derivative and polymkeric substance etc., for example: oxine lithium, N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl) 1,1 '-biphenyl 4,4 '-diamines (is called for short: TPD), N, N '-phenylbenzene-N, N '-two (1-naphthyl) 1,1 '-biphenyl 4,4 '-diamines (is called for short: NPB), the material of these blue light-emittings is synthetic all very difficult with extraction, and yield is very low, and highly purified extraction is more difficult, the cost height is difficult in industrial circle and popularizes use.
Summary of the invention
Goal of the invention
The objective of the invention is present situation and deficiency at background technology, adopt brand-new chemical synthesis process, preparation technologies such as rational chemical substance proportioning, employing combination reaction, washing, filtration, precipitation, vacuum filtration, recrystallization, heating under vacuum, oven dry, extract the oxine aluminium of high purity, high quality, blue light-emitting, so that extracting, the preparation of the oxine aluminium of blue light-emitting becomes possibility, so that widespread use in industry.
Technical scheme
The chemical substance that the present invention uses has: oxine crystal, Glacial acetic acid aluminium, anhydrous methanol, acetone, N, and N '-dimethyl formamide, pyridine, its combination matching is: with gram, milliliter is measure unit.
Oxine crystal: 1.16-120 gram
Glacial acetic acid aluminium: 0.98-1.02 gram
Anhydrous methanol: 145-155 milliliter
Acetone: 395-405 milliliter
N, N '-dimethyl formamide: 49-51 milliliter
Pyridine: 49-51 milliliter
The best of breed proportioning of described chemical substance is: with gram, milliliter is measure unit:
Oxine crystal: 1.18 grams
Glacial acetic acid aluminium: 1.00 grams
Anhydrous methanol: 100 milliliters
Acetone: 400 milliliters
N, N '-dimethyl formamide: 50 milliliters
Chemical synthesis and preparation method of the present invention is as follows:
1) chooses chemical substance, carry out purity and handle
Will carry out vacuum-sublimation to the required oxine crystal of combination matching handles, make it become the higher oxine of purity, required Glacial acetic acid aluminium, anhydrous methanol, acetone, N, N '-dimethyl formamide, pyridine will carry out selected and control of purity, guarantee that its purity is more than 99%.
2) preparation reaction soln
By the best of breed proportioning oxine crystal and anhydrous methanol are carried out mixed dissolution, make the oxine methanol solution, its concentration is the 0.04-0.05 grams per milliliter.
By the best of breed proportioning Glacial acetic acid aluminium and anhydrous methanol are carried out mixed dissolution, make the Burow Solution methanol solution, its concentration is 0.02 0.03 grams per milliliter.
3) chemical reaction of the α type oxine aluminium of green light
1. the oxine methanol solution is poured in the flask with four necks,round bottom, stirred with electric mixer, heat with electric mantle, Heating temperature is 60 °-70 ℃.
2. the Burow Solution methanol solution is splashed in the four-hole boiling flask slowly by dropping funnel, the speed of splashing into is that 2-3 drips/second, stirs while splashing into, and makes its uniform mixing, finishes until splashing into.
3. after the Burow Solution methanol solution drips off, take off dropping funnel, on same a bite of four-hole boiling flask, change reflux condensing tube, carry out reflow treatment, feed mobile recirculated water in prolong, the methanol gas that evaporates from four-hole boiling flask enters return line, and the methanol gas in the return line is under the cooling effect of prolong, form liquid, flow backwards again by return line and get back in the four-hole boiling flask.
4. in the process of hybrid reaction, continuously import nitrogen in four-hole boiling flask, carry out nitrogen protection by test tube, stop airborne oxygen to enter, with the gas velocity of gas meter control nitrogen, gas velocity is the 20-40 ml/min.
5. the time of oxine methanol solution and Burow Solution methanol solution combination reaction is 2-3 hour, and temperature of reaction is 60 °-70 ℃.
6. the combination reaction equation is as follows:
In the formula: OH---hydroxyl
N---nitrogen
O---oxygen
Al (CH
3OO)
3---Burow Solution
CH
3COOH---acetic acid
α---green glow type
4) purification of the α type oxine aluminium of green light
1. filter, precipitate: with combination reaction solution, in conical hopper, filter, precipitate, obtain yellowish green precipitated product with qualitative filter paper.
2. with anhydrous methanol washing, filtration, precipitation: yellowish green product is placed washing container, wash, in conical hopper, filter, precipitate then, repeat 4 times, obtain the higher yellow-green precipitate product of purity with qualitative filter paper with anhydrous methanol.
3. recrystallization is handled: after washing, filtration, precipitation are finished, the yellow-green precipitate product is carried out 4 recrystallizations handle, add 100 milliliters in acetone, 400 milliliters in shared acetone at every turn; Easily be dissolved in acetone according to oxine, oxine aluminium is insoluble to the characteristic of acetone, oxine aluminium and acetone that purity is higher are poured in the there-necked flask, heated and stirred then, Heating temperature is to 65 ℃ of the boiling points of acetone, constant temperature, boiling 5-6 minute, pour into while hot then and give in the good B of heat, be provided with three layers of qualitative filter paper in the B, rapidly with vacuum pump suction filtration acetone boiling solution, the oxine that is dissolved in acetone is taken away with suction filtration liquid, and the oxine aluminium that is insoluble to acetone is stayed on the filter paper, promptly obtains highly purified oxine aluminium.
4. oven dry: the product after recrystallization is handled places drying baker to carry out drying treatment, and bake out temperature is 70 °-80 ℃, and drying time is 2 hours, promptly obtains the yellow-green colour oxine aluminium powder form of highly purified green light after the oven dry.
5) the β type oxine aluminium of blue light-emitting is synthetic
The highly purified oxine aluminium powder form of green light is placed round bottom single port flask, the single port flask places electrically heated to put, carry out heating under vacuum then, vacuum tightness≤0.1 MPa in the single port flask, when temperature is heated to 370 °-390 ℃, constant temperature 0.5 hour, stop heating then, make it slow naturally cooling, during to 20 ℃ ± 3 ℃ of normal temperature, close vacuum pump, the oxine powder in the single port flask is greyish-green, and the greyish-green powder is the β type oxine aluminium of the lower blue light-emitting of purity.
The chemical equation of building-up reactions is as follows:
In the formula: Al---aluminium
O---oxygen
N---nitrogen
α---green glow type
β---blu-ray type
6) purification of the β type oxine aluminium of blue light-emitting
1. N, N '-dimethyl formamide washing: the oxine aluminium powder form of greyish-green is placed washing container, add N then, 25 milliliters of N '-dimethyl formamide wash, and use magnetic stirrer, and the wash agitation time is 2-3 hour.
2. filter, precipitate: with product powder and N, N '-dimethyl formamide is mixed into washing soln, places the conical hopper that is provided with qualitative filter paper, filters, precipitates, and obtains the oxine aluminium of the higher blue light-emitting of purity.
3. N, N '-dimethyl formamide washing, filter, precipitation will repeat 2 times.
4. pyridine washing: the product that 3. step obtains is put to the molten device of washing, placed in the stink cupboard, add 25 milliliters of pyridines, wash, use magnetic stirrer, washing, churning time are 2-3 hour.
5. filtration, heavy: the solution after the pyridine washing places the conical hopper that is provided with qualitative filter paper, filters, precipitates, and obtains the oxine aluminium of highly purified blue light-emitting.
6. pyridine washing, filtration, precipitation will repeat 2 times.
7. oven dry: with the product of pyridine washing, filtration, post precipitation, place drying baker to carry out drying treatment, bake out temperature is 100 °-120 ℃, and drying time is 2 hours, obtain the product powder of celandine green after the oven dry, i.e. the β type oxine aluminium of highly purified blue light-emitting.
7) Performance Detection contrast
The β type oxine aluminium powder form of the blue light-emitting of the celandine green that combination reaction is obtained, carry out purity, form, color and luster, structure, Performance Detection, and compare with the α type oxine aluminium powder form of yellowish green green light, carry out the crystalline structure comparative analysis with the X-ray diffraction analysis instrument, carry out the granule-morphology comparative analysis with scanning electron microscope, carry out the luminescent properties comparative analysis with fluorescence spectrum Emanations Analysis instrument.
8) packing and storing
The β type oxine aluminium powder form of blue light-emitting packed into, and airtight lucifuge stores in the brown transparent ground glass vessel, places drying, shady and cool environment, and envrionment temperature is 20 ℃ ± 3 ℃, strict waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode.
It is to carry out in the heating under vacuum container of vacuum tightness≤0.1 MPa that the oxine calorize of described blue light-emitting is closed reaction, the heating under vacuum temperature is minimum to be 〉=370 ℃, be up to≤390 ℃, constant temperature, soaking time is minimum is 〉=25 minutes, is up to≤35 minutes.
Described oxine calorize is closed the nitrogen protection of reaction; be continuously by pneumatic tube input nitrogen in combination reaction container four-hole boiling flask; stop airborne oxygen to enter, the gas velocity of nitrogen is the 20-40 ml/min, with the control of gas velocity controller.
The employed chemical substance of combination reaction of the α type oxine aluminium of described green light, the β type oxine aluminium of blue light-emitting is anhydrous type, in combination reaction, must not there be water substance to infiltrate, in the whole process that preparation is extracted, all under anhydrous state, carries out and finish.
Beneficial effect
The present invention compares with background technology, make the oxine aluminium of synthetic blue light-emitting become possibility, filled up the blank of organic electro luminous material 8-hydroxy quinoline aluminium blue light-emitting, produced a kind of electroluminescent organic material of novel blue light-emitting, the oxine aluminum is abundant, and the source is sufficient, and it is simple to extract synthetic method, as long as control heating under vacuum temperature and constant temperature time well, can obtain the product powder of blue light-emitting, use equipment is few, and synthetic cost is low, being easy to carry out industrialization produces, the product purity height can reach more than 96%, and it is big to substitute synthetic difficulty, productive rate is few, purity is low, the oxine lithium of expensive blue light-emitting, N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (being called for short TPD), N, N '-phenylbenzene-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (being called for short NPB), can be widely used in electronic industry and luminous field, be the electroluminescent organic material of very good blue light-emitting.
Description of drawings
Fig. 1 is the oxine aluminum Preparation Method schema of blue light-emitting
Fig. 2 is the oxine aluminium X-ray diffractogram of green light
Fig. 3 is the oxine aluminium X-ray diffractogram of blue light-emitting
Fig. 4 is the oxine aluminium of green light and the oxine aluminium photoluminescence spectrum data contrast table of blue light-emitting
Embodiment
The present invention will be further described below in conjunction with accompanying drawing.
Shown in Figure 1, the oxine aluminium of preparation blue light-emitting will carry out in strict accordance with preparation method and technical process, and each technology numerical value is wanted strict control, operation according to the order of sequence.
To preparing required chemical substance material: oxine crystal, Glacial acetic acid aluminium, anhydrous methanol, acetone, N, it is strict selected and carry out control of purity that N '-dimethyl formamide, pyridine want, purity is 99%, definitely can not there be water substance to sneak into, prevent to generate by product, thereby influence the luminescent properties of product, will carry out vacuum-sublimation to main chemical material oxine and handle, higher to guarantee its crystal purity.
During preparation chemical reaction solution, must strict control by best proportioning, to the oxine methanol solution of preparation, its concentration is the 0.04-0.05 grams per milliliter, and its concentration of Glacial acetic acid aluminium methanol solution is the 0.02-0.03 grams per milliliter.
The extraction of the oxine aluminium of green light is to prepare for the extraction preparation of the oxine aluminium of blue light-emitting, the product that directly influences blue light-emitting is produced quality, employed equipment: flask with four necks,round bottom, flask with three necks,round bottom, round bottom single port flask, conical hopper, B, washing container, setting filter paper, test tube, return line, flask, magnetic stirring apparatus, electric mixer, heating jacket, vacuum pump, stink cupboard, drying baker, thermometer, gas meter etc. will keep clean, must not pollute.
The qualitative filter paper that filtering-depositing uses must good, even, the zero defect of compactness, to guarantee filter quality.
The oxine aluminium product that filtering-depositing obtains is mud shape or bulk, and the product that obtains after the oven dry is Powdered.
Embodiment 1:
Combination reaction, the extraction of the oxine aluminium of green light:
1. combination reaction: low-purity is extracted
Flask with four necks,round bottom is placed on the electric mantle, the oxine methanol solution is added in the four-hole boiling flask through liquid adding hole, then separating funnel is placed on the four-hole boiling flask, the Burow Solution methanol solution is slowly splashed into four-hole boiling flask by separating funnel, the speed of splashing into is that 2-3 drips/second, stir with electric mixer then, stir while splashing into; Another mouthful at four-hole boiling flask inserts pneumatic tube simultaneously, and input nitrogen carries out nitrogen protection, stops airborne oxygen to enter, and controls nitrogen flow with gas meter, and the oxide gas flow is the 20-40 ml/min; Another mouthful at four-hole boiling flask inserts the methanol gas return line, after electric mantle is opened, Heating temperature is 60 °-70 ℃, and methyl alcohol can become gas evaporation, discharges through return line, discharge in order to reduce methanol gas, prevent that the mixing solutions concentration in the four-hole boiling flask from raising,, be back in the four-hole boiling flask again after making the methanol gas condensation so methanol gas is carried out condensation with the mobile recirculated water of normal temperature, mixing solutions concentration in the bottle is remained unchanged substantially, keep weight and concentration balance.
Combination reaction is to finish under 60 °-70 ℃ heated condition, strict its temperature of control; Electric mixer is wanted uniform rotation, makes to stir; Nitrogen protection will from start to finish be carried out continuously, must not be interrupted, and refluxes and will carry out synchronously with methanol condensed; Condensed water temperature changes with seasonal variation, is advisable in indoor flow circuit can guarantee condensed water temperature, the methanol gas condensation is become reflux behind the liquid unimpeded.
After combination reaction is finished, can filter, precipitate with the conical hopper that is provided with qualitative filter paper, obtain the precipitated product of low-purity with reacted mixing solutions by pouring out in the four-hole boiling flask.
2. anhydrous methanol washing: higher degree extracts
Precipitated product is placed washing container, wash with anhydrous methanol, filter, precipitate with the conical hopper that is provided with qualitative filter paper then, repeat washing, filter, precipitate 4 times, the washing and filtering number of times is high more, product purity is good more, strict control loss, and post precipitation obtains the oxine aluminium product of the higher green light of purity.
3. the extraction of the oxine aluminium of highly purified green light: acetone recrystallization method purification processes
Flask with three necks,round bottom is placed electric mantle, a mouth by there-necked flask adds the higher oxine aluminium of purity, add acetone liquid then, become oxine aluminium acetone blend, inserting electric mixer in another mouthful stirs, begin heating, when Heating temperature rises to 65 ℃, oxine aluminium acetone blend boiling in the there-necked flask, after constant temperature 5-6 minute, under the blend boiling state, carry out vacuum filtration, vacuum filtration carries out in the barrel-shaped funnel of Bu Shi, be provided with three layers of qualitative filter paper in the B, and give heat, the ebullient blend is poured in the B by the mouth of there-necked flask, start vacuum pump simultaneously and carry out suction filtration rapidly, blend is by three layers of qualitative filter paper suction filtration, precipitation, oxine aluminium product has been stayed on the qualitative filter paper, the oxine acetone soln has entered container through vacuum filtration, thereby finished the recrystallization purification, because oxine aluminium is insoluble to acetone, and oxine is dissolved in acetone, and according to this characteristic, the oxine aluminium that is insoluble to acetone is stayed on the qualitative filter paper, the oxine that is dissolved in acetone is filtered to container with acetone liquid, the product of staying on the qualitative filter paper promptly is highly purified oxine aluminium, and recrystallization method is purified and will be repeated 4 times, and number of times is many more, purity is good more, note reducing loss.
Oxine aluminium after the recrystallization purification processes will carry out drying treatment in drying baker, bake out temperature is 70 °-80 ℃, drying time is 2 hours, promptly obtains the highly purified α type oxine aluminium yellow-green colour powder of green light after the oven dry, and its purity can reach 96%.
Embodiment 2:
1. the extraction of the low-purity oxine aluminium of blue light-emitting:
The extraction of the oxine aluminium of blue light-emitting is to carry out after the purification of the oxine aluminium of green light.
Vaccum heating method:
Round bottom single port flask is placed on the electric mantle, the oxine aluminium powder form of highly purified green light is placed the single port flask, on the single port flask, connect with vacuum pump by rubber hose with the Glass tubing that has sealing rubber plug, tighten sealing rubber plug then, open vacuum pump, make in the single port flask to be in vacuum state, vacuum tightness remains on≤0.1 MPa, begins heating simultaneously, make the temperature in the single port flask rise to 370 °-390 ℃, electric mantle is closed in constant temperature insulation 30 minutes then, stops heating, want strict control top temperature to exceed, in case burn, make single port flask and the interior slow naturally cooling of product powder thereof then, when temperature is reduced to 20 ℃ ± 3 ℃ normal temperature, close vacuum pump, open sealing rubber plug, take out the product powder, promptly obtain the oxine powder of greyish-green of the low-purity of blue light-emitting.
2. the extraction of the oxine aluminium of the higher degree of blue light-emitting:
N, N '-dimethyl formamide washing: greyish-green product powder is placed washing container, add N, 25 milliliters of N '-dimethyl formamide liquid, with magnetic stirrer 2-3 hour, then liquid is placed on the conical hopper that is provided with qualitative filter paper and filter, precipitate, use with quadrat method and carry out 2 times, promptly obtain the oxine aluminium of the greyish-green of the higher blue light-emitting of purity.
3. the extraction of the high purity oxine aluminium of blue light-emitting:
Pyridine washing: in stink cupboard, carry out
The oxine aluminium that purity is higher places washing container, adds 25 milliliters of pyridine liquid then, stirs with magnetic stirring apparatus, wash agitation 2-3 hour, in conical hopper, filter, precipitate with qualitative filter paper then, use with quadrat method and carry out 2 times, obtain product.
Drying treatment: with the product of pyridine washing, filtration, post precipitation, place drying baker to carry out drying treatment, bake out temperature is 100 °-120 ℃, drying time is 2 hours, take out then, promptly obtain the highly purified oxine powder of the celandine green of blue light-emitting, purity can reach 96%.
The chemosynthesis principle of the oxine aluminium of blue light-emitting is as follows: aforesaid chemical equation is:
From two formulas as can be seen: because the α type oxine aluminium powder form of green light has noncrystal characteristic, interior molecules is arranged quite disorderly, under vacuum heating conditions, when temperature rises to 370 °-390 ℃, molecule strenuous exercise also rearranges, form orderly molecular arrangement, slowly cooling, molecule will continue to keep ordered arrangement, show the crystalline characteristic,, caused being with of α type oxine aluminium to be widened because crystalline structure changes, therefore produce its luminescence phenomenon blue shift, also just caused the generation of the β type oxine aluminium of blue light-emitting.
The synthetic extraction of the oxine aluminum chemistry of green light is in proper order:
Oxine methanol solution+Burow Solution methanol solution---combination reaction------nitrogen protection---filtering-depositing---anhydrous methanol washing---acetone recrystallization is handled, vacuum filtration---dry 70 °-80 ℃, 2 hours---the generation α type oxine aluminium yellow-green colour powder that heats 60 °-70 ℃.
The oxine aluminium extraction of blue light-emitting is in proper order:
High-purity alpha type oxine aluminium---370 °-390 ℃ of heating under vacuum---constant temperature 30 minutes---naturally cool to normal temperature---generate greyish-green powder---N, N '-dimethyl formamide washing---filtering-depositing---pyridine washing---filter, precipitation---dry 100 °-120 ℃, 2 hours---generation β type oxine aluminium celandine green powder.
Conclusion: yellow-green colour oxine aluminium powder form green light.
Celandine green oxine aluminium powder form blue light-emitting.
Fig. 2 is the X-ray diffractogram of the α type oxine aluminium of green light, and X-coordinate is 2 times of diffraction angle, and ordinate zou is the strength values of diffraction peak.
Fig. 3 is the X-ray diffractogram of the β type oxine aluminium of blue light-emitting, and X-coordinate is 2 times of diffraction angle, and ordinate zou is the strength values of diffraction peak.
The diffractogram of Fig. 2, Fig. 3 is compared, the oxine aluminium diffraction peak intensity of β type blue light-emitting is greater than the oxine aluminium of α type green light, illustrate that the β type crystal structure is more complete, there is new crystalline structure to produce, and one 23.6 ° diffraction peak more than the oxine aluminium of the oxine aluminum ratio α type green light of β type blue light-emitting and one 25.4 ° diffraction peak.
Fig. 4 is the photoluminescence spectrum data contrast table of blue light β type and α green glow type oxine aluminium, be the luminescent properties of blue light β type and green glow α type is tested and to be compared with the fluorescent radiation spectrograph, at wavelength is under the exciting light of 365nm, record the photoluminescence spectrum data of two kinds of materials, find out that thus blue light β type maximum emission peak wavelength is 486.7nm, green glow α type maximum emission peak wavelength is 516.3nm, variation has also taken place in chromaticity coordinates, β type X value is 0.2189, the Y value is 0.3677, α type X value is 0.3159, and the Y value is 0.5479, and the halfwidth β type of emission peak is 92.8nm, the α type is 100.4nm, fluorescence emission spectrum is an a kind of significant data of weighing the photochromic purity of emission, and data are more little, and purity of color is good more.
The β type celandine green oxine aluminium powder form of blue light-emitting amplifies 1600 times of observations with scanning electron microscope, and product particles of powder pattern is an ice slush shape long strip shape.
The α type yellow-green colour oxine aluminium powder form of green light amplifies 1600 times of observations with scanning electron microscope, and product particles of powder pattern is circle grain of rice shape.
In extracting preparation process, because the influence of the plus-minus of the variation of Heating temperature, washing soln, filtration, precipitation, oven dry also can make the product particles of powder pattern of oxine aluminium that micro-variation takes place.
The proportioning of the β type oxine aluminum chemistry reactive material of synthetic blue light-emitting is to give in the quantitative range of determining earlier at one being provided with, and is the product unit of producing with the gram, when carrying out industrialization when synthetic, can be the product unit of producing by kilogram.
It is suitable that the β type oxine aluminium product of the blue light-emitting after synthetic places the brown glass vessel to save as, and is beneficial to the lucifuge protection.
Claims (4)
1, a kind of oxine aluminium and preparation method of blue light-emitting, it is characterized in that: the chemical substance that the present invention uses has oxine crystal, Glacial acetic acid aluminium, anhydrous methanol, acetone, N, N '-dimethyl formamide, pyridine, its combination matching is: with gram, milliliter is measure unit.
Oxine crystal: 1.16-120 gram
Glacial acetic acid aluminium: 0.98-1.02 gram
Anhydrous methanol: 145-155 milliliter
Acetone: 395-405 milliliter
N, N '-dimethyl formamide: 49-51 milliliter
Pyridine: 49-51 milliliter
The best of breed proportioning of described chemical substance is: with gram, milliliter is measure unit:
Oxine crystal: 1.18 grams
Glacial acetic acid aluminium: 1.00 grams
Anhydrous methanol: 100 milliliters
Acetone: 400 milliliters
N, N '-dimethyl formamide: 50 milliliters
Chemical synthesis and preparation method of the present invention is as follows:
1) chooses chemical substance, carry out purity and handle
Will carry out vacuum-sublimation to the required oxine crystal of combination matching handles, make it become the higher oxine of purity, required Glacial acetic acid aluminium, anhydrous methanol, acetone, N, N '-dimethyl formamide, pyridine will carry out selected and control of purity, guarantee that its purity is more than 99%.
2) preparation reaction soln
By the best of breed proportioning oxine crystal and anhydrous methanol are carried out mixed dissolution, make the oxine methanol solution, its concentration is the 0.04-0.05 grams per milliliter.
By the best of breed proportioning Glacial acetic acid aluminium and anhydrous methanol are carried out mixed dissolution, make the Burow Solution methanol solution, its concentration is the 0.02-0.03 grams per milliliter.
3) chemical reaction of the α type oxine aluminium of green light
1. the oxine methanol solution is poured in the flask with four necks,round bottom, stirred with electric mixer, heat with electric mantle, Heating temperature is 60 °-70 ℃.
2. the Burow Solution methanol solution is splashed in the four-hole boiling flask slowly by dropping funnel, the speed of splashing into is that 2-3 drips/second, stirs while splashing into, and makes its uniform mixing, finishes until splashing into.
3. after the Burow Solution methanol solution drips off, take off dropping funnel, on same a bite of four-hole boiling flask, change reflux condensing tube, carry out reflow treatment, feed mobile recirculated water in prolong, the methanol gas that evaporates from four-hole boiling flask enters return line, and the methanol gas in the return line is under the cooling effect of prolong, form liquid, flow backwards again by return line and get back in the four-hole boiling flask.
4. in the process of hybrid reaction, continuously import nitrogen in four-hole boiling flask, carry out nitrogen protection by test tube, stop airborne oxygen to enter, with the gas velocity of gas meter control nitrogen, gas velocity is the 20-40 ml/min.
5. the time of oxine methanol solution and Burow Solution methanol solution combination reaction is 2-3 hour, and temperature of reaction is 60 °-70 ℃.
6. the combination reaction equation is as follows:
In the formula: OH---hydroxyl
N---nitrogen
O---oxygen
Al (CH
3OO)
3---Burow Solution
CH
3COOH---acetic acid
α---green glow type
4) purification of the α type oxine aluminium of green light
1. filter, precipitate: with combination reaction solution, in conical hopper, filter, precipitate, obtain yellowish green precipitated product with qualitative filter paper.
2. with anhydrous methanol washing, filtration, precipitation: yellowish green product is placed washing container, wash, in conical hopper, filter, precipitate then, repeat 4 times, obtain the higher yellow-green precipitate product of purity with qualitative filter paper with anhydrous methanol.
3. recrystallization is handled: after washing, filtration, precipitation are finished, the yellow-green precipitate product is carried out 4 recrystallizations handle, add 100 milliliters in acetone, 400 milliliters in shared acetone at every turn; Easily be dissolved in acetone according to oxine, oxine aluminium is insoluble to the characteristic of acetone, oxine aluminium and acetone that purity is higher are poured in the there-necked flask, heated and stirred then, Heating temperature is to 65 ℃ of the boiling points of acetone, constant temperature, boiling 5-6 minute, pour into while hot then and give in the good B of heat, be provided with three layers of qualitative filter paper in the B, rapidly with vacuum pump suction filtration acetone boiling solution, the oxine that is dissolved in acetone is taken away with suction filtration liquid, and the oxine aluminium that is insoluble to acetone is stayed on the filter paper, promptly obtains highly purified oxine aluminium.
4. oven dry: the product after recrystallization is handled places drying baker to carry out drying treatment, and bake out temperature is 70 °-80 ℃, and drying time is 2 hours, promptly obtains the yellow-green colour oxine aluminium powder form of highly purified green light after the oven dry.
5) the β type oxine aluminium of blue light-emitting is synthetic
The highly purified oxine aluminium powder form of green light is placed round bottom single port flask, the single port flask places electrically heated to put, carry out heating under vacuum then, vacuum tightness≤0.1 MPa in the single port flask, when temperature is heated to 370 °-390 ℃, constant temperature 0.5 hour, stop heating then, make it slow naturally cooling, during to 20 ℃ ± 3 ℃ of normal temperature, close vacuum pump, the oxine powder in the single port flask is greyish-green, and the greyish-green powder is the β type oxine aluminium of the lower blue light-emitting of purity.
The chemical equation of building-up reactions is as follows:
In the formula: Al---aluminium
O---oxygen
N---nitrogen
α---green glow type
β---blu-ray type
6) purification of the β type oxine aluminium of blue light-emitting
1. N, N '-dimethyl formamide washing: the oxine aluminium powder form of greyish-green is placed washing container, add N then, 25 milliliters of N '-dimethyl formamide wash, and use magnetic stirrer, and the wash agitation time is 2-3 hour.
2. filter, precipitate: with product powder and N, N '-dimethyl formamide is mixed into washing soln, places the conical hopper that is provided with qualitative filter paper, filters, precipitates, and obtains the oxine aluminium of the higher blue light-emitting of purity.
3. N, N '-dimethyl formamide washing, filter, precipitation will repeat 2 times.
4. pyridine washing: the product that 3. step obtains is put to the molten device of washing, placed in the stink cupboard, add 25 milliliters of pyridines, wash, use magnetic stirrer, washing, churning time are 2-3 hour.
5. filtration, heavy: the solution after the pyridine washing places the conical hopper that is provided with qualitative filter paper, filters, precipitates, and obtains the oxine aluminium of highly purified blue light-emitting.
6. pyridine washing, filtration, precipitation will repeat 2 times.
7. oven dry: with the product of pyridine washing, filtration, post precipitation, place drying baker to carry out drying treatment, bake out temperature is 100 °-120 ℃, and drying time is 2 hours, obtain the product powder of celandine green after the oven dry, i.e. the β type oxine aluminium of highly purified blue light-emitting.
7) Performance Detection contrast
The β type oxine aluminium powder form of the blue light-emitting of the celandine green that combination reaction is obtained, carry out purity, form, color and luster, structure, Performance Detection, and compare with the α type oxine aluminium powder form of yellowish green green light, carry out the crystalline structure comparative analysis with the X-ray diffraction analysis instrument, carry out the granule-morphology comparative analysis with scanning electron microscope, carry out the luminescent properties comparative analysis with fluorescence spectrum Emanations Analysis instrument.
8) packing and storing
The β type oxine aluminium powder form of blue light-emitting packed into, and airtight lucifuge stores in the brown transparent ground glass vessel, places drying, shady and cool environment, and envrionment temperature is 20 ℃ ± 3 ℃, strict waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode.
2, the oxine aluminium and the preparation method of blue light-emitting according to claim 1, it is characterized in that: it is to carry out in the heating under vacuum container of vacuum tightness≤0.1 MPa that the oxine calorize of described blue light-emitting is closed reaction, the heating under vacuum temperature is minimum to be 〉=370 ℃, be up to≤390 ℃, constant temperature, soaking time is minimum is 〉=25 minutes, is up to≤35 minutes.
3, the oxine aluminium and the preparation method of blue light-emitting according to claim 1; it is characterized in that: described oxine calorize is closed the nitrogen protection of reaction; be continuously by pneumatic tube input nitrogen in combination reaction container four-hole trial jar; stop airborne oxygen to enter; the gas velocity of nitrogen is the 20-40 ml/min, controls with air flow meter.
4, the oxine aluminium and the preparation method of blue light-emitting according to claim 1, it is characterized in that: the employed chemical substance of combination reaction of the α type oxine aluminium of described green light, the oxine aluminium of blue light-emitting is anhydrous type, in combination reaction, must not there be water substance to infiltrate, in the whole process that preparation is extracted, all under anhydrous state, carries out and finish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100124301A CN1283628C (en) | 2004-07-19 | 2004-07-19 | 8- hydroxy quinoline bryhtening blue light and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100124301A CN1283628C (en) | 2004-07-19 | 2004-07-19 | 8- hydroxy quinoline bryhtening blue light and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597669A true CN1597669A (en) | 2005-03-23 |
| CN1283628C CN1283628C (en) | 2006-11-08 |
Family
ID=34662789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100124301A Expired - Fee Related CN1283628C (en) | 2004-07-19 | 2004-07-19 | 8- hydroxy quinoline bryhtening blue light and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1283628C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432054C (en) * | 2007-01-12 | 2008-11-12 | 太原理工大学 | Method for preparing hydroxylquinoline aluminium of blue green type mixing ligand |
| CN100436566C (en) * | 2006-07-27 | 2008-11-26 | 太原理工大学 | Process for preparing organic electroluminescence material bis (8-hydroxy quinoline lithium sodium) |
| CN101298497B (en) * | 2008-02-28 | 2011-08-31 | 中国科学院上海硅酸盐研究所 | Preparation of doping optical non-linear chromophore coordination high polymer |
| CN101270128B (en) * | 2007-03-23 | 2012-05-23 | 清华大学 | Method for preparing 8-hydroxyquinoline aluminum nanocrystalline |
| CN110922356A (en) * | 2019-12-03 | 2020-03-27 | 宁波南大光电材料有限公司 | Preparation method of electronic grade high-purity 8-hydroxyquinoline aluminum |
-
2004
- 2004-07-19 CN CNB2004100124301A patent/CN1283628C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436566C (en) * | 2006-07-27 | 2008-11-26 | 太原理工大学 | Process for preparing organic electroluminescence material bis (8-hydroxy quinoline lithium sodium) |
| CN100432054C (en) * | 2007-01-12 | 2008-11-12 | 太原理工大学 | Method for preparing hydroxylquinoline aluminium of blue green type mixing ligand |
| CN101270128B (en) * | 2007-03-23 | 2012-05-23 | 清华大学 | Method for preparing 8-hydroxyquinoline aluminum nanocrystalline |
| CN101298497B (en) * | 2008-02-28 | 2011-08-31 | 中国科学院上海硅酸盐研究所 | Preparation of doping optical non-linear chromophore coordination high polymer |
| CN110922356A (en) * | 2019-12-03 | 2020-03-27 | 宁波南大光电材料有限公司 | Preparation method of electronic grade high-purity 8-hydroxyquinoline aluminum |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1283628C (en) | 2006-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1718668A (en) | Preparation method of organic electro luminous material rare earth europium organic metal complex | |
| CN110846030B (en) | Single-component white-light carbon quantum dot, preparation method thereof and light-emitting device | |
| WO2021232578A1 (en) | Organic-inorganic hybrid perovskite capable of emitting room-temperature phosphorescence, preparation method therefor, and use thereof | |
| CN108690601A (en) | A kind of preparation method of hybrid inorganic-organic perovskite quantum dot and film | |
| CN113755166A (en) | Hydrophobic white light carbon dot and preparation method thereof | |
| CN110655655B (en) | Cyan fluorescent zinc-organic coordination polymer and preparation method and application thereof | |
| CN1283628C (en) | 8- hydroxy quinoline bryhtening blue light and preparation method | |
| JP2014077027A (en) | Method for producing fluorescent substance | |
| CN1179947C (en) | Preparation method of organic electro luminous material 8-hydroxy quinoline aluminium | |
| CN1202204C (en) | Organic electroluminescent light-emitting compound and module and device with it | |
| CN101060164A (en) | A blue and green light emitting LED and manufacture method | |
| CN108485658A (en) | The manufacturing method of fluorophor | |
| CN108456516A (en) | The manufacturing method of fluorophor | |
| CN1259317C (en) | Derivant of electrophosphorescence 1,8-naphthimide and luminous ligand thereof | |
| CN109943318B (en) | Modified YAG Ce fluorescent powder and preparation method thereof | |
| CN101044224A (en) | Precursor compound and crystallised compound of the alkaline-earth aluminate type, and methods of preparing and using the crystallised compound as phosphor | |
| CN1900213A (en) | Process for preparing organic electroluminescence material bis (8-hydroxy quinoline lithium sodium) | |
| CN1164712C (en) | Organic electroluminescence material and device | |
| CN108219161A (en) | Tb coordination polymer luminescent materials based on two kinds of rigid ligands and preparation method thereof | |
| CN1827607A (en) | Process for preparing blue light-emitting 2-(2-hydroxy phenyl) benzothiazole chelated beryllium | |
| CN111117605B (en) | Organic aluminum nanocrystalline and preparation method and application thereof | |
| CN1274783C (en) | Hexahydrogen bonded self-assembled supermolecular yellow-green luminescent material and its synthesizing method | |
| CN112961485B (en) | Polymer and cation co-enhanced CsPbBr3Synthetic method for luminescent property and stability of halogen perovskite | |
| CN107611239A (en) | A kind of coating processes of automobile lamp fluorescent material | |
| CN115197147B (en) | Perovskite single crystal material based on imidazole organic cations, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |