CN1594403A - Cross-linked high polymer containing 8-hydroxyquinoline metal complex and its preparation and use - Google Patents
Cross-linked high polymer containing 8-hydroxyquinoline metal complex and its preparation and use Download PDFInfo
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- CN1594403A CN1594403A CN 200410027705 CN200410027705A CN1594403A CN 1594403 A CN1594403 A CN 1594403A CN 200410027705 CN200410027705 CN 200410027705 CN 200410027705 A CN200410027705 A CN 200410027705A CN 1594403 A CN1594403 A CN 1594403A
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Abstract
The invention relates to a cross-linked high polymer containing 8-hydroxyquinoline metal complex with a molecular weight of 20000-100000, its preparing process consists of formulating solution from the monomer, coating onto the base, in inert gas atmosphere, solidifying under ultraviolet light or heating condition to form crosslinked macromolecule.
Description
Technical field
The present invention relates to a kind of cross-linked polymer luminescent material and method for making and purposes that contains the oxine metal complexes, especially high-molecular luminous material and method for making and the purposes that is cross-linked to form by the vinyl monomer of the oxine metal complexes that contains a plurality of polymerizable functional groups.
Technical background
The organic/polymer electroluminescent device is easy to realize large screen display because its driving voltage is low, the brightness height, and the visual angle is wide, and glow color is continuously adjustable etc., and advantage makes it become present information display technology field one big research focus.From the C.W.Tang of U.S. Kadak company in 1987 and co-worker thereof reported a kind of with oxine aluminium as luminescent layer, driving voltage is less than 10 volts, luminosity reaches 1000cd/m
2Since being the electroluminescent device of green light of 100h work-ing life, the researchist comes to realise wide application prospect and the value that oxine metal complexes (is representative with oxine aluminium and oxine zinc) is had in the organic electroluminescent field, thereby has dropped into a large amount of energy it is studied.Application to the oxine metal complexes is limited to dual mode usually in organic electroluminescence device at present: a kind of mode is the representative figure with Tang and Adachi, and it is directly used as the small molecules luminescent material; Another kind is that it is dispersed in certain polymeric matrix, formation mix up polymkeric substance as luminophore, mix up polymethylmethacrylate as oxine aluminium, polystyrene, PPV is in the materials such as PVK.Two kinds of methods all have obvious weak point in the practical application: it is to utilize the small molecules evaporation film-forming that common a kind of application mode in the past prepares electroluminescent device, because the high temperature during distillation easily makes small molecules produce oligopolymer or isomer, and device micromolecular crystallization of when work all can influence device lifetime greatly, and this mode be difficult for to realize the large-area device of preparation, with methods such as solution spin coating or spray printing relatively be a kind of expensive preparation technology; Though a kind of application mode in back solves these problems,, make material be separated within a short period of time and shortened the device working life because compatibility problem is difficult to solve between oxine metal complexes and polymeric matrix.The high molecular of oxine metal complexes is expected to address the above problem.At present the oxine metal complexes of synthetic high molecular research less, shortcoming such as there is preparation method's complexity mostly in the oxine metal complexes of the high molecular of bibliographical information, and productive rate is low, and the product solubility property is poor, and luminous efficiency is low.When the oxine metal complexes partly accounted for superpolymer weight and is generally 20% left and right sides, polymer just was difficult to be dissolved in usual vehicle.
It is fast that the UV curing method advantage is not only speed, easy to operate, and expense is low, pollutes and lack, and solidify by the spin coating soluble and monomeric again, solved the oxine metal and joined the relatively poor problem of the solubility property of thing family macromolecule in usual vehicle.Ultraviolet photocureable material is insoluble in usual vehicle because it forms crosslinking structure, can solve luminous high polymer multilayer device spin coating primer coating dissolved problem when preparing.The oxine metal is joined the thing weight content more than 50% in the cross-linked polymer of preparation.In addition because crosslinking structure Tg and heat decomposition temperature increase favourable raising device lifetime greatly than thermoplastic material.Also can realize device luminescent layer lithographic patterning simultaneously, be to realize organic/polymer indicating meter full color, one of method of high pixel.
The method that is heating and curing is not only easy to operate, and expense is low, pollutes and lacks, and solidify by the spin coating soluble and monomeric again, has solved the oxine metal and has joined the relatively poor problem of the solubility property of thing family macromolecule in usual vehicle.Thermosetting material is insoluble in usual vehicle because it forms crosslinking structure, can solve luminous high polymer multilayer device spin coating primer coating dissolved problem when preparing.This method is more convenient than the presoma two-step approach and the opposite polarity solvent method of present general preparation multilayer device, and does not influence the small molecule by-product generation of device lifetime.The oxine metal is joined the thing weight content more than 50% in the cross-linked polymer of preparation.In addition because crosslinking structure Tg and heat decomposition temperature increase favourable raising device lifetime greatly than corresponding thermoplastic material.
Summary of the invention
The object of the invention is to provide a kind of is convenient to process, the high molecular oxine metal complexes that contains the oxine metal complexes transparent, that luminous efficiency is high.This stability of material height, be convenient to prepare big area, multilayer, display device that cost is low.
Another object of the present invention provides the preparation method of this superpolymer.
A further object of the present invention provides the purposes of this superpolymer.
The invention provides high molecular oxine metal complexes luminescent material is the oxine metal ion match vinyl monomer that contains a plurality of polymerizable functional groups by a kind of, and direct polymerization forms under the UV-irradiation or under the heating condition.Wherein the weight content of oxine metal complexes is the 1-80% of superpolymer weight.
The cross-linked high polymer that contains the oxine metal complexes provided by the invention is the structural unit that is expressed from the next, and the molecular weight that is cross-linked to form is 20000～100000 superpolymer.
Wherein: M represents trivalent metallic element, preferred Al,
M represents divalent metal element, preferred Zn,
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.
The preparation method who contains the cross-linked high polymer of oxine metal complexes provided by the invention is, the monomer wiring solution-forming, is spun on the matrix, solidify to form cross-linked polymer under UV-light or under the heating condition, and its step comprises:
In the vinyl monomer of 1 part of oxine metal complexes that contains a plurality of polymerizable functional groups, add 0.01-10 part (preferred 0.01-0.1 part) initiator, 5-500 part (preferred 10-100 part) organic solvent, on the spin coating matrix, under inert gas conditions, UV-irradiation 1-10000s (preferred 10-200s) or 20-200 ℃ of (preferred 80-160 ℃) heating 0.5-100h obtain product.
Wherein said polyreaction is light-initiated radical polymerization of UV-light or thermal initiation radical polymerization.
Described initiator comprises light trigger or thermal initiator, and ultraviolet light polymerization adopts light trigger, and light trigger is selected from light triggers such as bitter almond oil camphor, benzil ketals derivatives class, acetophenone derivs class, benzophenone initiator.Thermal initiator is then adopted in thermofixation, and thermal initiator is selected from thermal initiators such as azo-initiator and peroxide initiator.
The preferred polar organic solvent of described organic solvent is as dehydrated alcohol, tetrahydrofuran (THF), toluene, dimethylbenzene, chloroform, benzene.
The cross-linked high polymer that contains the oxine metal complexes provided by the invention can be used as electroluminescent material and the electron transport material in the organic electroluminescent flat panel display device.
The oxine metal ion match vinyl monomer that contains a plurality of polymerizable functional groups that adopts among the present invention, structure is as follows:
Wherein: M is selected from trivalent metallic element,
M is selected from divalent metal 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.), respectively preferred Al, Zn.
The oxine metal complexes vinyl monomer preparation method who contains a plurality of polymerizable functional groups is by the synthetic oxine vinyl monomer that contains, cooperate the vinyl monomer of the oxine metal complexes that contains a plurality of polymerizable functional groups that generates again with metal ion, 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 dropping weight concentration is that the weak ammonia of 1-10% obtains white precipitate, and the sherwood oil recrystallization obtains containing oxine part vinyl monomer.
(b), get the compound of 1 part of metal ion, the vinyl monomer that contains the oxine part that adding 0.5-50 part (preferred 1-10 part) makes through (a) step is dissolved in 5-100 part organic solvent, 20-150 ℃ is stirred down, fed nitrogen, anhydrous condition reaction down in 1-10 days, steam solvent or add precipitation agent, recrystallization, drying obtain containing the vinyl monomer of the oxine metal complexes of a plurality of polymerizable functional groups;
Wherein umber is all by the mole umber.
Step (a) but but described in the vinyl compound that contains reactive functionality in reactive functionality can be-CH
2OH ,-CH
2X (X is a halogen atom) ,-CH
2NH
3,-COOH ,-COCl ,-CONH
2,-COOOC-.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 that the main group metal ion is (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 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.
Described precipitation solvent can be selected from alkanes and water, as sherwood oil, and normal hexane, normal heptane, water etc.Preferred alkanes.
The present invention is by the vinyl monomer of the good oxine metal complexes that contains a plurality of polymerizable functional groups of solvability, after the spin-coating film, radical polymerization has formed good film-forming property under UV-light or heating condition again, stability is high, oxine metal complexes content height, the luminescent material that luminous efficiency is high.This material has the good transparency.
Synthetic of the present invention contains the cross-linked polymer of oxine metal complexes by infrared spectra, solvent washing test, and the photoetching test forms crosslinking structure really; Characterize by the thermomechanical property of differential thermal analysis, prove that this material has excellent thermomechanical property (do not have Tg to show within 300 ℃, heat decomposition temperature＞350 ℃) material; Photoelectric properties to this luminescent material are tested: ultra-violet absorption spectrum (the cross-linked polymer UV/vis λ of oxine aluminium
Max)=270nm, 389nm; The cross-linked polymer UV/vis λ of oxine zinc
Max)=380nm), fluorescence spectrum (the cross-linked polymer fluores λ of oxine aluminium
Max=538nm; The cross-linked polymer fluores λ of oxine zinc
Max)=558nm), prove described polymkeric substance and the identical glow peak of corresponding oxine metal complexes, PL luminous efficiency 30%-60%, (ITO/PEDT/ contains the cross-linked polymer of oxine aluminium or zinc/LiF/Al), electroluminescent peak (the cross-linked polymer fluores λ of oxine aluminium to electroluminescent device
Max=580nm; The cross-linked polymer fluores λ of oxine zinc
Max)=590nm), internal quantum efficiency illustrates that greater than 0.1% this is the luminescent material that a class can be used to prepare electroluminescent device.
By the prepared luminescent material of polymerization process provided by the invention, compare with the luminescent material of additive method and feedstock production that technology is simple, facility investment is few, with low cost, have good processing characteristics and photoelectric properties concurrently, can be used as electroluminescent material and electron transport material in the organic/polymer electroluminescent flat panel display device, significant for the flat panel display device of development superior performance of future generation.
Embodiment
Following umber is all by the mole umber.
Embodiment 1
100 parts of hydroxyethyl methylacrylates add and contain-CH
220 parts of the substituent oxine hydrochlorides of Cl, 1.5 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 3 CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the vinyl monomer of oxine part; Get 1 part of Tai-Ace S 150 and be dissolved in 50 parts of chloroforms, add 8 parts and contain 3 CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the vinyl monomer of oxine part, 120 ℃ of following stirring reactions 3 days left standstill 1 day, filtered to get filtrate, aqueous precipitation filters and obtains solid, sherwood oil recrystallization 3 times obtains containing 3 CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-oxine aluminum complex vinyl monomer.
Get this monomer of 2.0g and be dissolved in the 20ml toluene, add the 0.02g bitter almond oil camphor, be spun on conductive glass (ito glass) sheet (1000nm), in nitrogen under the room temperature at ultraviolet lamp (300nm, 100mWcm
-2) descend 100s to obtain the cross-linked polymer luminescent material.
Embodiment 2
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 triethyl aluminum and be dissolved in 10 parts of toluene, add 10 parts and contain CH
2=CHOCH
2-the vinyl monomer of oxine part, 100 ℃ of following stirring reactions 3 days left standstill 1 day, filtered to get filtrate, and added methanol extraction, filtered and obtained solid, sherwood oil recrystallization 3 times obtains containing 3 CH
2=CHOCH
2-the monomer of oxine aluminum complex.
Get this monomer monomer of 1.0g and be dissolved in the 30ml tetrahydrofuran (THF), add 0.01g benzoyl peroxide (BPO), be spun on (2000nm) on the conductive glass sheet, 120 ℃ of 6h of heating in nitrogen, 120 ℃ of 6h of after fixing obtain the cross-linked polymer luminescent material.
Embodiment 3
100 parts to vinyl benzyl 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=CH-Ar-CH
2OCH
2-the vinyl monomer of oxine part; Get 1 part of triethyl aluminum and be dissolved in 10 parts of toluene, add 10 parts and contain CH
2=CH-Ar-CH
2OCH
2-the vinyl monomer of oxine part, 100 ℃ of following stirring reactions 3 days left standstill 1 day, filtered to get filtrate, and added methanol extraction, filtered and obtained solid, sherwood oil recrystallization 3 times obtains containing 3 CH
2=CH-Ar-CH
2OCH
2-the monomer of oxine aluminum complex.
Get this monomer of 0.5g and be dissolved in the 20ml chloroform, add the 0.1g benzil ketals, be spun on (1000nm) on the conductive glass sheet, room temperature is at ultraviolet lamp (300nm, 100mWcm in nitrogen
-2) descend 30s to obtain the cross-linked polymer luminescent material.
Embodiment 4
100 parts of amino hexenes of 6-add and contain-CH
250 parts of the substituent oxine hydrochlorides of Cl, under the catalysis of 1 part of sodium-acetate, 2.5 part benzoquinones is as stopper, temperature is controlled at 40 ℃ of stirrings, and 30h controls reaction, and reaction finishes to add 800 parts of water, dripping an amount of weight concentration is that 8% weak ammonia is to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=CH-(CH
2)
3-CH
2NHOCH
2-the vinyl monomer of oxine part; Get 1 part of zinc chloride and be dissolved in 50 parts of chloroforms, add 3 parts and contain CH
2=CH-(CH
2)
5-CH
2NHOCH
2-the vinyl monomer of oxine part, stirring reaction is 8 days under the room temperature, leaves standstill 1 day, filters to get filtrate, aqueous precipitation filters and obtains solid, sherwood oil recrystallization 3 times obtains containing 2 CH
2=CH-(CH
2)
3-CH
2NHCH
2-the monomer of oxine Zn complex.
Get this monomer of 2.0g and be dissolved in the 20ml toluene, add 0.02g Diisopropyl azodicarboxylate (AIBN), be spun on that (2000nm) heats 100 ℃ of 10h on the conductive glass sheet in nitrogen, 150 ℃ of 0.5h of after fixing obtain the cross-linked polymer luminescent 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 acetate and be dissolved in 50 parts of chloroforms, add 8 parts and contain CH
2=C (CH
3)-COO-CH
2-the vinyl monomer of oxine part, 120 ℃ of following stirring reactions 3 days left standstill 1 day, filtered to get filtrate, aqueous precipitation filters and obtains solid, sherwood oil recrystallization 3 times obtains containing 2 CH
2=C (CH
3)-COO-CH
2-the monomer of oxine Zn complex.
Get this monomer of 0.5g and be dissolved in the 20ml chloroform, add the 0.1g benzil ketals, be spun on (1000nm) on the conductive glass sheet, room temperature is at ultraviolet lamp (300nm, 100mWcm in nitrogen
-2) descend 90s to obtain the cross-linked polymer luminescent material.
Embodiment 6
100 parts of chlorallylenes add and contain-CH
230 parts of the substituent oxine hydrochlorides of OH, 0.2 under the catalysis of part sodium-acetate, 4 parts of benzoquinones are as stopper, temperature is controlled at 120 ℃ of stirrings, and 8h controls reaction, and reaction finishes to add 500 parts of water, dripping an amount of weight concentration is that 8% weak ammonia is to neutral, obtain white precipitate, sherwood oil recrystallization 3 times obtains containing CH
2=CH-CH
2-O-CH
2-the vinyl monomer of oxine part; Get 1 part of zinc ethyl and be dissolved in 30 parts of dehydrated alcohols, add 10 parts and contain CH
2=CH-CH
2-O-CH
2-the vinyl monomer of oxine part, 150 ℃ of following stirring reactions 1 day left standstill 1 day, filtered to get filtrate, aqueous precipitation filters and obtains solid, sherwood oil recrystallization 3 times obtains containing 2 CH
2=CH-CH
2-O-CH
2-the monomer of oxine Zn complex.
Get this monomer of 2.0g and be dissolved in the 20ml toluene, add 0.02g Diisopropyl azodicarboxylate (AIBN), be spun on that (2000nm) heats 120 ℃ of 1h on the conductive glass sheet in nitrogen, 120 ℃ of 0.5h of after fixing obtain the cross-linked polymer luminescent material.
Claims (10)
1, the structural unit that is expressed from the next, the molecular weight that is cross-linked to form are 20000～100000 the cross-linked high polymer that contains the oxine metal complexes:
Wherein: M is selected from trivalent metallic element,
M is selected from divalent metal element,
R
1Be selected from C
2-C
18Alkyl, ester group, ether, amido,
R
2, R
3, R
4Be selected from hydrogen and C
1-C
18Alkyl.
2, the superpolymer of claim 1, wherein M is Al, m is Zn.
3, claim 1 or 2 superpolymer, wherein R
1Carbon chain lengths is C
2-C
8, R
2, R
3, R
4Be selected from hydrogen and C
1-C
8Alkyl.
4, the preparation method of the arbitrary superpolymer of claim 1～3, be the monomer wiring solution-forming, be spun on the matrix, solidify to form cross-linked polymer under UV-light or under the heating condition, its step comprises: in the vinyl monomer of 1 part of oxine metal complexes that contains a plurality of polymerizable functional groups, add 0.01-10 part initiator, 5-500 part organic solvent is on the spin coating matrix, under inert gas conditions, UV-irradiation 1-10000s or 20-200 ℃ of heating 0.5-100h obtains product.
5, the method for claim 4 wherein adopts light trigger during ultraviolet light polymerization, and light trigger is selected from bitter almond oil camphor, benzil ketals derivatives class, acetophenone derivs class, benzophenone initiator.
6, the method for claim 5, wherein the ultraviolet light polymerization time is 10-200s.
7, the method for claim 4 wherein adopts thermal initiator during thermofixation, and thermal initiator is selected from azo-initiator and peroxide initiator.
8, the method for claim 7, wherein heat curing temperature is 80-160 ℃.
9, the arbitrary method of claim 4～8, wherein said organic solvent is selected from polar organic solvent dehydrated alcohol, tetrahydrofuran (THF), toluene, dimethylbenzene, chloroform, benzene.
10, the arbitrary superpolymer of claim 1～3 is as electroluminescent material and electron transport material in the organic electroluminescent flat panel display device.
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|---|---|---|---|
| CN 200410027705 CN1246368C (en) | 2004-06-18 | 2004-06-18 | Cross-linked high polymer containing 8-hydroxyquinoline metal complex and its preparation and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027705 CN1246368C (en) | 2004-06-18 | 2004-06-18 | Cross-linked high polymer containing 8-hydroxyquinoline metal complex and its preparation and use |
Publications (2)
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|---|---|
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| CN1246368C CN1246368C (en) | 2006-03-22 |
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ID=34663983
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056265A (en) * | 2005-08-25 | 2007-03-08 | Natl Starch & Chem Investment Holding Corp | Quinolinol and quinolinol derivative as adhesion promoter of die-attach adhesive |
| CN101058616B (en) * | 2007-04-30 | 2010-05-19 | 中国科学院广州化学研究所 | Crosslinking polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method |
| CN101962389A (en) * | 2010-09-13 | 2011-02-02 | 杭州师范大学 | Rare-earth compound olefin monomer and preparation method and application thereof |
| CN103000818A (en) * | 2012-12-11 | 2013-03-27 | 京东方科技集团股份有限公司 | Top-emitting organic light-emitting device (OLED) and preparation method and application thereof |
-
2004
- 2004-06-18 CN CN 200410027705 patent/CN1246368C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056265A (en) * | 2005-08-25 | 2007-03-08 | Natl Starch & Chem Investment Holding Corp | Quinolinol and quinolinol derivative as adhesion promoter of die-attach adhesive |
| CN101058616B (en) * | 2007-04-30 | 2010-05-19 | 中国科学院广州化学研究所 | Crosslinking polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method |
| CN101962389A (en) * | 2010-09-13 | 2011-02-02 | 杭州师范大学 | Rare-earth compound olefin monomer and preparation method and application thereof |
| CN101962389B (en) * | 2010-09-13 | 2012-12-19 | 杭州师范大学 | Rare-earth compound olefin monomer and preparation method and application thereof |
| CN103000818A (en) * | 2012-12-11 | 2013-03-27 | 京东方科技集团股份有限公司 | Top-emitting organic light-emitting device (OLED) and preparation method and application thereof |
| CN103000818B (en) * | 2012-12-11 | 2015-05-20 | 京东方科技集团股份有限公司 | Top-emitting organic light-emitting device (OLED) and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1246368C (en) | 2006-03-22 |
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