CN1295218C - Olefin monomers of multi-functional group 8-hydroxyquinoline metal complex and their preparation process and application - Google Patents
Olefin monomers of multi-functional group 8-hydroxyquinoline metal complex and their preparation process and application Download PDFInfo
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- CN1295218C CN1295218C CNB2004100277006A CN200410027700A CN1295218C CN 1295218 C CN1295218 C CN 1295218C CN B2004100277006 A CNB2004100277006 A CN B2004100277006A CN 200410027700 A CN200410027700 A CN 200410027700A CN 1295218 C CN1295218 C CN 1295218C
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Abstract
The present invention relates to an olefin monomer of an 8-hydroxyquinoline metal coordination compound with a polymerisable functional group and the following structure, and a preparation method and a purpose thereof. In the preparation method, olefin compounds comprising reaction functional groups react with modified 8-hydroxyquinoline for synthesizing 8-hydroxyquinoline ligand olefin monomers which are matched with metal ions and 8-hydroxyquinoline for generating olefin monomers comprising 8-hydroxyquinoline metal coordination compounds. The olefin monomer has the advantages of simple processing technology, few device investments, cost saving, good solubility, high stability and high luminous efficiency; both of the olefin monomer or macromolecule metal coordination compounds formed by the olefin monomer and other olefin monomers through radical copolymerization can be used for preparing luminescent materials and electron transport materials of organic/ macromolecule electroluminescent plane display devices with large area.
Description
Technical field
The present invention relates to vinyl monomer and method for making and purposes that a class contains the oxine metal complexes.Especially can form linear copolymer with other kind vinyl polymerizations, contain the vinyl monomer and its production and use of the oxine metal complexes of a polymerizable functional group.
Technical background
Along with the arrival of information age, novel, efficient, light-weight organic electroluminescent flat-panel screens (OLEDs) more and more gets more and more people's extensive concerning, and has become a domestic and international research focus in recent years.Along with the raising of the whole society to health, environmental protection, resource and energy utilization attention degree, people have proposed more and more higher requirement to luminescent material.The luminescent material that particularly has special processing characteristics and special light electrical property for making is especially to being used to make the requirement that luminescent material that big area shows has an organic electroluminescence device of distinguishing features such as active illuminating, light, thin, good contrast, non-angular dependency, energy consumption are low has proposed intimate harshness.
The luminescent material that the organic/polymer electroluminescent device is used requires not only that good stability, good film-forming property, the solvability of material is good, long service life, luminous intensity height, and wishes that good mechanical property, complete processing are simple, makes that device is convenient, production cost is low etc.Luminescent material has following a few class at present, have following some shortcomings respectively: 1 electroluminous organic small molecular material, in device preparation and work, there is crystalline polamer, the life-span of electroluminescent device is reduced, the mode of the fabricate devices of organic molecule EL material is mainly by vacuum evaporation simultaneously, complicated process of preparation, production cost is big; 2 conjugated polymerss, complicated process of preparation, solubility property is undesirable, processing difficulties; 3 mix up the polymkeric substance of a metal-organic complex, are separated easily, disperse inhomogeneously, and material property descends, and fluorescence intensity reduces, and fluorescence lifetime descends; 4 high molecular metal complex luminescent materials, present synthetic method is a lot, mainly has shortcomings such as crosslinked, poorly soluble, film-forming properties difference, can not satisfy the good electroluminescent device of processability.The research of the oxine metal complexes of synthetic high molecular is less at present, solvability and film-forming properties are bad owing to there is crosslinking structure mostly for the oxine metal complexes of the high molecular of bibliographical information, when the oxine metal complexes partly accounted for superpolymer weight and mostly is 20% left and right sides most, polymer just was difficult to be dissolved in usual vehicle.
Summary of the invention
The object of the invention is to provide the vinyl monomer of the oxine metal complexes that contains a polymerizable functional group that a kind of solubility property is good, luminous efficiency is high.This monomer not only itself can be luminous, and can be by to obtain structure height controlled with other kind alkene class copolymerizations, and solubility property is good, the high-molecular luminous material of good film-forming property.
Another object of the present invention provides the preparation method of this vinyl monomer, is a kind of reaction conditions gentleness, and step is simple, the preparation method that productive rate is high.
A further object of the present invention provides the purposes of this vinyl monomer.
The vinyl monomer that contains the oxine metal complexes of a polymerizable functional group provided by the invention is to cooperate generation by containing the oxine vinyl monomer with metal ion, oxine, and structure is as follows:
Wherein: M is selected from trivalent metallic element,
M is selected from divalent metal element,
X is selected from the monovalence metallic element,
R
1Be selected from C
2-C
18Hydrocarbon (containing aromatic hydrocarbons) base, ester group, ether, amido etc.The preferred C of carbon chain lengths wherein
2-C
8
R
2, R
3, R
4Be selected from hydrogen and C
1-C
18Hydrocarbon (containing aromatic hydrocarbons) base.Wherein preferred hydrogen and C
1-C
8Hydrocarbon (containing aromatic hydrocarbons) base.
Wherein trivalent metal, divalent metal element and monovalence metallic element can comprise main group metal element (as Al, Mg, Li etc.), thulium (as Eu, Sm etc.), transition metal (as Zn, Ru etc.), difference preferred Al, Zn, Li.
But this preparation method who contains the oxine metal complexes vinyl monomer of a polymerizable functional group is by the synthetic oxine part vinyl monomer that contains of the oxine reaction of vinyl compound that contains reactive functionality and modification, cooperate with metal ion, oxine again generate contain oxine metal complexes vinyl monomer, its step comprises:
(a) but, get 100 parts of vinyl compounds that contain reactive functionality, the oxine that adds 0.1-100 part (preferred 0.5-50 part) modification, 0.01-20 part (preferred 0.01-2 part) catalyzer, 0.01-50 part (preferred 0.01-5 part) stopper, temperature are controlled at 40-150 ℃ and stir down, react 0.5 hour to two days, add 100-1000 part water then, the weak ammonia that drips weight concentration and be 1-10% obtains white precipitate, and the sherwood oil recrystallization obtains containing the vinyl monomer of oxine part;
(b), get the compound of 1 part of metal ion, 0-100 part (preferred 1-6 part) oxine is dissolved in 5-500 part (preferred 5-200 part) organic solvent, stir under the room temperature, logical nitrogen, anhydrous condition reacted 1-30 days down, add the vinyl monomer that contains the oxine part that 1-100 part (preferred 10-50 part) obtains through (a) step, stir under the room temperature, continue reaction 1-30 days, filtration obtains filtrate, steaming desolventizes or adds precipitation solvent, and recrystallization, drying obtain containing the vinyl monomer of the oxine metal complexes of a polymerizable functional group;
Wherein umber is all by the mole umber.
Wherein in (b) step, when the compound of metal ion is the monovalent metallic ion compound, then do not carry out the reaction (being that the oxine consumption is 0) with oxine, directly with the vinyl monomer that contains the oxine part that obtains through (a) step react product.
Step (a) but but described in the reactive functionality of the vinyl compound that contains reactive functionality can be-CH
2OH ,-CH
2X (X is a halogen atom) ,-CH
2NH
3,-COOH ,-COCl ,-CONH
2,-COOOC-etc.Vinyl compound can be C
3-C
18The hydro carbons (containing aromatic hydrocarbons) that has ethylene linkage, ethers, ester compound.As vinylcarbinol, vinyl benzyl chloride, C
3-C
18Unsaturated acid, C
3-C
18Unsaturated hydroxy alkyl ester, acrylic acid hydroxy alkyl ethers etc.
The oxine of described modification is for having-CH
2X (X is a halogen atom) ,-CH
2OH ,-CH
2NH
2Oxine hydrochloride Deng functional group.
Described catalyzer is an alkaline matter, can be highly basic or strong base weak acid salt: NaOH, Na
2CO
3, NaHCO
3, KOH, K
2CO
3, KHCO
3, sodium-acetate, Potassium ethanoate etc.
Described stopper can be aromatic series phenols or aminated compounds, as Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, methylene blue, p methoxy phenol etc.
The compound of metal ion described in the step (b) is for containing the main group metal ion (as Al
3+, Mg
2+, Li
+Deng), rare earth ion is (as Eu
3+, Sm
3+Deng), transition metal ion is (as Ru
3+Deng) salt, bases, organo-metallic class etc., as AlCl
3, Mg (NO
3)
2, LiOH, zinc ethyl etc.The preferred Al of metal ion wherein
3+, Zn
2+
The preferred polar organic solvent of described organic solvent, as dehydrated alcohol, tetrahydrofuran (THF), toluene, dimethylbenzene, chloroform, benzene etc.
Described precipitation solvent can be selected from alkanes and water, as sherwood oil, and normal hexane, normal heptane, water etc.Preferred alkanes.
The vinyl monomer of the oxine metal complexes that contains a polymerizable functional group of the present invention itself or with other vinyl monomer by the high molecular metal complex that radical copolymerization forms, all can be used as preparation big area organic/polymer electroluminescent flat panel display device luminescent material and electron transport material.
The present invention is by synthesizing the vinyl monomer that contains the oxine part earlier, cooperate the vinyl monomer of the oxine metal complexes that contains a polymerizable functional group that generates again by a certain percentage with reaction sequence with metal ion, oxine, wherein have only to have alkene class functional group on the part.The solubility property of this material is good, and stability is high, luminous efficiency is high.If the vinyl monomer structural unit copolymerization that this material is good with solvability, the multipolymer transparency and deliquescent while can kept, by regulating the kind and the ratio of comonomer, obtain containing the unitary product of higher oxine metal complexes, improve luminous efficient, and realize height control, afterwards its luminescent properties of may command to copolymer structure.By infrared spectra,
1H-NMR, ultimate analysis proves the definite structure of the vinyl monomer of the oxine metal complexes that contains a polymerizable functional group; Fusing point＞120 ℃, heat decomposition temperature＞250 ℃, the photoelectric properties of this luminescent material are tested: ultra-violet absorption spectrum and photoluminescence spectra and corresponding oxine metal complexes small molecules meet.As: the vinyl monomer UV/vis λ that contains the oxine aluminium of a polymerizable functional group
Max=270nm, 389nm contains the vinyl monomer UV/vis λ of the oxine zinc of a polymerizable functional group
Max=404nm; The vinyl monomer PL λ that contains the oxine aluminium of a polymerizable functional group
Max=512nm; The vinyl monomer PL λ of oxine zinc
Max)=537nm.PL luminous efficiency 10%-60% proves described monomer and the identical glow peak of corresponding oxine metal complexes.
The vinyl monomer synthesis technique of the oxine metal complexes that contains a polymerizable functional group provided by the invention is simple, and the productive rate height can be used as electroluminescent material and electron transport material in the organic/polymer electroluminescent flat panel display device.
By the prepared luminescent material of synthetic method provided by the invention, compare with the oxine metal complexes luminescent material of additive method and feedstock production, complete processing is simple, and facility investment is few, save cost, the flat panel display device that develops superior performance of future generation is significant.
Embodiment
Following umber is all by the mole umber.
Embodiment 1
100 parts to vinyl benzyl chloride, adding-CH
25 parts of the substituent oxine hydrochlorides of OH, 0.05 under the catalysis of part sodium-acetate, 0.5 part benzoquinones is as stopper, temperature is controlled at 60 ℃ of stirrings, and 24h controls reaction, and reaction finishes to add 200 parts of water, drip an amount of weight concentration and be 3% weak ammonia to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=CH-Ar-CH
2OCH
2-oxine part vinyl monomer; Get 1 part of triethyl aluminum, 2.5 parts of oxines are dissolved in 60 parts of dehydrated alcohols, and stirring reaction is 3 days under the room temperature, leave standstill 1 day, add 6 parts and contain CH
2=CH-Ar-CH
2OCH
2-the vinyl monomer of oxine part, stirring reaction is 10 days under the room temperature, leaves standstill 1 day, filters and obtains filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=CH-Ar-CH
2OCH
2-the vinyl monomer of oxine aluminium.
Get this monomer of 5.0g, the 3.0g methacrylic ester is dissolved in 50ml toluene, adds 0.01g Diisopropyl azodicarboxylate (AIBN), and 80 ℃ of following stirring reactions 6 hours are poured the methyl alcohol reprecipitation into 3 times, obtain high-molecular luminous material.
Embodiment 2
100 parts of hydroxyethyl methylacrylates add and contain-CH
25 parts of the substituent oxine hydrochlorides of Cl, 0.1 under the catalysis of part sodium-acetate, 1 part of para hydroxybenzene phenol is as stopper, temperature is controlled at 80 ℃ of stirrings, and 10h controls reaction, and reaction finishes to add 1000 parts of water, drip an amount of weight concentration and be 5% weak ammonia to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the vinyl monomer of oxine part; Get 1 part of aluminum chloride and be dissolved in 45 parts of chloroforms, 2.1 parts of oxines, stirring reaction is 6 days under the room temperature, leaves standstill 1 day, adds 4 parts and contains CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the vinyl monomer of oxine part, stirring reaction is 8 days under the room temperature, leaves standstill 1 day, filters and obtains filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the vinyl monomer of oxine aluminium.
Get this monomer of 10.0g, the 60g hydroxyethyl methylacrylate is dissolved in 100ml toluene, adds 0.02g benzoyl peroxide (BPO), 60 ℃ of following stirring reactions 24 hours are poured the methyl alcohol reprecipitation into 3 times, obtain high-molecular luminous material.
Embodiment 3
100 parts to vinyl chloride, adding-CH
210 parts of the substituent oxine hydrochlorides of OH, 0.5 under the catalysis of part sodium-acetate, 2 parts of benzoquinones are as stopper, temperature is controlled at 100 ℃ of stirrings, and 18h controls reaction, and reaction finishes to add 200 parts of water, drip an amount of weight concentration and be 3% weak ammonia to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=CHOCH
2-the vinyl monomer of oxine part; Get 1 part of aluminum isopropylate and be dissolved in 10 parts of toluene, add 2.5 parts of oxines, stirring reaction is 1 day under the room temperature, adds 1.2 parts and contains CH
2=CHOCH
2-the vinyl monomer of oxine part, stirring reaction is 3 days under the room temperature, leaves standstill 1 day, filters and obtains filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=CHOCH
2-the vinyl monomer of oxine aluminium
Get this class monomer of 7.5g, 4.5g vinylbenzene is dissolved in 75ml toluene, adds 0.015gAIBN, 80 ℃ of following stirring reactions 6 hours are poured the methyl alcohol reprecipitation into 3 times, obtain high-molecular luminous material.
Embodiment 4
100 parts of 6-hexenoic acids add and contain-CH
2NH
22 parts of substituent oxine hydrochlorides, 0.5 under the catalysis of part sodium-acetate, 2 parts of benzoquinones are as stopper, temperature is controlled at 100 ℃ of stirrings, and 8h controls reaction, and reaction finishes to add 500 parts of water, drip an amount of weight concentration and be 8% weak ammonia to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=CH-(CH
2)
3-CONHCH
2-the vinyl monomer of oxine part; Get 1 part of zinc acetate and be dissolved in 15 parts of tetrahydrofuran (THF)s, add 1.5 parts of oxines, stirring reaction is 10 days under the room temperature, leaves standstill 1 day, adds 3 parts and contains CH
2=CH-(CH
2)
3-CONHCH
2-the vinyl monomer of oxine part, stirring reaction is 3 days under the room temperature, leaves standstill 1 day, filters and obtains filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=CH-(CH
3)
3-CONHCH
2-the vinyl monomer of oxine zinc.
Get this class monomer of 2.5g, 100g vinylformic acid is dissolved in 25ml toluene, adds 0.005gBPO, 60 ℃ of following stirring reactions 24 hours are poured the methyl alcohol reprecipitation into 3 times, obtain high-molecular luminous material.
Embodiment 5
100 parts of methacrylic chlorides add and contain-CH
210 parts of the substituent oxine hydrochlorides of OH, 2.5 under the catalysis of part sodium-acetate, 3 parts of para hydroxybenzene phenol are as stopper, temperature is controlled at 100 ℃ of stirrings, and 8h controls reaction, and reaction finishes to add 500 parts of water, dripping an amount of weight concentration is that 5% weak ammonia is to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=C (CH
3)-COO-CH
2-the vinyl monomer of oxine part.Get 1 part of zinc chloride and be dissolved in 45 parts of chloroforms, add 1 part of oxine, stirring reaction is 15 days under the room temperature, leaves standstill 1 day, adds 4 parts and contains CH
2=C (CH
3)-COO-CH
2-the vinyl monomer of oxine part, stirring reaction is 1 day under the room temperature, leaves standstill 1 day, filters and obtains filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing CH
2=C (CH
3)-COO-CH
2-the vinyl monomer of oxine zinc.
Get this monomer of 9.5g, 8.5g vinylbenzene is dissolved in 75ml toluene, adds 0.015gAIBN, 80 ℃ of following stirring reactions 6 hours are poured the methyl alcohol reprecipitation into 3 times, obtain high-molecular luminous material.
Embodiment 6
100 parts of amino hexenes of 6-add and contain-CH
22 parts of the substituent oxine hydrochlorides of Cl, under the catalysis of 2 parts of sodium-acetates, 5 parts of benzoquinones are as stopper, temperature is controlled at 150 ℃ of stirrings, and 1h controls reaction, and reaction finishes to add 800 parts of water, drip an amount of weight concentration and be 6% weak ammonia to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=CH-(CH
2)
3-CH
2NHCH
2-the vinyl monomer of oxine part; Get 1 part of lithium hydroxide, add 3 parts and contain CH
2=CH-(CH
2)
3-CH
2NHCH
2-the vinyl monomer of oxine part be dissolved in 15 parts of tetrahydrofuran (THF)s, stirring reaction is 3 days under the room temperature, leaves standstill 1 day, filters and obtains filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing CH
2=CH-(CH
2)
3-CH
2NHCH
2-the vinyl monomer of oxine lithium.
Get this monomer of 2.5g, 100g vinylformic acid is dissolved in 25ml toluene, adds 0.005gBPO, 60 ℃ of following stirring reactions 24 hours are poured the methyl alcohol reprecipitation into 3 times, obtain high-molecular luminous material.
Claims (10)
- The vinyl monomer of the oxine metal complexes that contains a polymerizable functional group that 1, structure is following:Wherein: M is selected from trivalent metallic element,M is selected from divalent metal element,X is selected from the monovalence metallic element,R 1Be selected from C 2-C 18Ester group, ether, amido,R 2, R 3, R 4Be selected from hydrogen and C 1-C 18Alkyl.
- 2, the vinyl monomer of claim 1, wherein trivalent metal, divalent metal element and monovalence metallic element are selected from main group metal element, thulium or transition metal respectively.
- 3, claim 1 or 2 vinyl monomer, wherein M is Al, and m is Zn, and x is Li.
- 4, claim 1 or 2 vinyl monomer, R wherein 1Carbon chain lengths be C 2-C 8R 2, R 3, R 4Be selected from hydrogen and C 1-C 8Alkyl.
- 5, the preparation method of the arbitrary vinyl monomer of claim 1～4, but be the vinyl compound by containing reactive functionality and the synthetic oxine part vinyl monomer that contains of oxine reaction of modification, cooperate with metal ion, oxine again generate contain oxine metal complexes vinyl monomer, its step comprises:(a) but, get 100 parts of vinyl compounds that contain reactive functionality, the oxine that adds the modification of 0.1-100 part, 0.01-20 part highly basic or strong base weak acid salt catalyzer, 0.01-50 part aromatic series phenols or aminated compounds stopper, temperature are controlled at 40-150 ℃ and stir down, react 0.5 hour to two days, add 100-1000 part water then, the weak ammonia that drips weight concentration and be 1-10% obtains white precipitate, and the sherwood oil recrystallization obtains containing the vinyl monomer of oxine part;(b), get the compound of 1 part of metal ion, 0-100 part oxine is dissolved in 5-500 part organic solvent, stir under the room temperature, logical nitrogen, anhydrous condition reacted 1-30 days down, added 1-100 part through the vinyl monomer that contains the oxine part that (a) step obtains, and stirred under the room temperature, continue reaction 1-30 days, filtration obtains filtrate, steams to desolventize or add precipitation solvent, and recrystallization, drying obtain containing the vinyl monomer of the oxine metal complexes of a polymerizable functional group;Wherein umber is all by the mole umber.
- 6, the method for claim 5, wherein in (b) step, when the compound of metal ion is the monovalent metallic ion compound, then the oxine consumption is 0, do not carry out the reaction with oxine, directly with the vinyl monomer that contains the oxine part that obtains through (a) step react product.
- 7, claim 5 or 6 method, wherein step (a) but but described in the reactive functionality of the vinyl compound that contains reactive functionality be-CH 2OH ,-CH 2X ,-CH 2NH 3,-COOH ,-COCl ,-CONH 2Or-COOOC-, vinyl compound is C 3-C 18The hydro carbons, ethers or the ester compound that have ethylene linkage; The oxine of described modification is for having-CH 2X ,-CH 2OH or-CH 2NH 2The oxine hydrochloride of functional group; Wherein X is a halogen atom.
- 8, claim 5 or 6 method, wherein the compound of metal ion described in the step (b) is selected from salt, bases or the organo-metallic class that contains main group metal ion, rare earth ion, transition metal ion; Described organic solvent is selected from polar organic solvent; Described precipitation solvent is selected from alkanes and water.
- 9, the method for claim 8, wherein metal ion is selected from Al 3+Or Zn 2+Precipitation solvent is selected from alkanes.
- 10, arbitrary vinyl monomer of claim 1～4 itself or the high molecular metal complex that forms by radical copolymerization with other vinyl monomer are as preparation organic/polymer electroluminescent flat panel display device luminescent material and electron transport material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100277006A CN1295218C (en) | 2004-06-18 | 2004-06-18 | Olefin monomers of multi-functional group 8-hydroxyquinoline metal complex and their preparation process and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100277006A CN1295218C (en) | 2004-06-18 | 2004-06-18 | Olefin monomers of multi-functional group 8-hydroxyquinoline metal complex and their preparation process and application |
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| CN1295218C true CN1295218C (en) | 2007-01-17 |
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| CN1314671C (en) * | 2004-04-30 | 2007-05-09 | 中国科学院广州化学研究所 | Olefin monomer containing 8-hydroxyquinoline metal complex and its production method and use |
| FR2913976B1 (en) * | 2007-03-23 | 2013-04-26 | Biopharmed | DERIVATIVES OF THE AMINE HYDROXYQUINOLINE CLASSES FOR THE TREATMENT OF CANCERS. |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000252072A (en) * | 1999-03-03 | 2000-09-14 | Honda Motor Co Ltd | Organic electroluminescent element and manufacture thereof |
| CN1282735A (en) * | 2000-08-26 | 2001-02-07 | 暨南大学 | Amphiphili 8-hydroxyquinoline complex, its preparing process and its application in electroluminescence |
| JP2002352959A (en) * | 2001-05-28 | 2002-12-06 | Canon Inc | Organic light-emitting element and manufacturing method therefor, display using the element, photosensitizer exposure equipment using the element, and illumination equipment using the element |
| CN1569837A (en) * | 2004-04-30 | 2005-01-26 | 中国科学院广州化学研究所 | Olefin monomer containing 8-hydroxyquinoline metal complex and its production method and use |
-
2004
- 2004-06-18 CN CNB2004100277006A patent/CN1295218C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000252072A (en) * | 1999-03-03 | 2000-09-14 | Honda Motor Co Ltd | Organic electroluminescent element and manufacture thereof |
| CN1282735A (en) * | 2000-08-26 | 2001-02-07 | 暨南大学 | Amphiphili 8-hydroxyquinoline complex, its preparing process and its application in electroluminescence |
| JP2002352959A (en) * | 2001-05-28 | 2002-12-06 | Canon Inc | Organic light-emitting element and manufacturing method therefor, display using the element, photosensitizer exposure equipment using the element, and illumination equipment using the element |
| CN1569837A (en) * | 2004-04-30 | 2005-01-26 | 中国科学院广州化学研究所 | Olefin monomer containing 8-hydroxyquinoline metal complex and its production method and use |
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