CN101058620A - Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method - Google Patents
Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method Download PDFInfo
- Publication number
- CN101058620A CN101058620A CN 200710027892 CN200710027892A CN101058620A CN 101058620 A CN101058620 A CN 101058620A CN 200710027892 CN200710027892 CN 200710027892 CN 200710027892 A CN200710027892 A CN 200710027892A CN 101058620 A CN101058620 A CN 101058620A
- Authority
- CN
- China
- Prior art keywords
- oxine
- formula
- hole transport
- unitary
- salt
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a making method of bipolar compound with 8-hydroxy quinoline metal complex, which possesses general formula (1) or (2), wherein R is alkylene or aryl radical containing from 0 carbon atom to 10 carbon atoms; A is the cavity transfer unit; M1 is trivalent metal element in the formula (1); M2 of the formula is divalent metal element). The invention has a good stability, a good dissolving, a good film-forming property, and a good light efficiency, which reduces the consumption of the natural resources, provides the important meanings for the next superior flat surface display.
Description
Technical field
The present invention relates to luminescent material, be specifically related to a kind of linear polymer that contains the unitary oxine metal complexes of hole transport and preparation method thereof.
Background technology
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 becomes a research focus both domestic and external in recent years.This big area is shown have the organic electroluminescence device of distinguishing features such as active illuminating, light, thin, good contrast, non-angular dependency, energy consumption are low, simultaneously its used luminescent material is had higher requirement.
Several conceptual phases such as polymkeric substance that luminescent material has experienced inorganic electroluminescent powder, liquid crystal polymer, organic molecule (comprising metal complexes and organic compound) electroluminescent material, conjugated polymers, mixed up a metal-organic complex.Yet there is crystalline polamer in the electroluminous organic small molecular material in device preparation and work, and the life-span of electroluminescent device is reduced, and the mode of the fabricate devices of organic molecule EL material is mainly leaned on vacuum evaporation simultaneously, complicated process of preparation, and production cost is big; The complicated process of preparation of conjugated polymers, solubility property is poor, processing difficulties; The polymkeric substance that mixes up a metal-organic complex is separated easily, disperses inhomogeneously, and material property descends, and fluorescence intensity reduces, and fluorescence lifetime descends; Shortcomings such as that high molecular metal complex luminescent material, present synthetic method mainly exist is crosslinked, poorly soluble, film-forming properties difference can not satisfy the good electroluminescent device of processability.At present solvability and film-forming properties are bad owing to there is crosslinking structure for the oxine metal complexes of synthetic high molecular, and 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 purpose of this invention is to provide a kind of linear polymer that contains the unitary oxine metal complexes of hole transport and preparation method thereof.The linear polymer that contains the unitary oxine metal complexes of hole transport provided by the present invention, its structure have the general formula of following formula (1) or formula (2):
Formula (1) formula (2)
Wherein R represents to contain the alkylene base or the aryl of 0 to 10 carbon atom, and A represents the hole transport unit, the M of formula (1)
1The expression trivalent metallic element, the M of formula (2)
2The expression divalent metal element.
The preferred thiodiphenylamine in described hole transport unit, carbazole or triphenylamine.
Described M
1Be preferably Al, described M
2Be preferably Zn.
Wavy line is partly represented polymer segment in the structural formula.
The preparation method who contains the linear polymer of the unitary oxine metal complexes of hole transport of the present invention may further comprise the steps:
(1) in molar part, get modification 0.1～10 part of 10～100 parts of 1 part of oxine, polar organic solvents, catalyzer, contain 1～2 part of the unitary compound of hole transport and be blended in and carry out N-alkylated reaction or Ullmann reaction under the room temperature to 150 ℃, reacted 0.5 hour to two days, and promptly obtained containing the unitary oxine small molecules of hole transport part;
(2) get the compound of 0.1～10 part of metal ion, 0.1～20 parts contain the unitary oxine small molecules of hole transport part and are dissolved in 5～500 parts of polar organic solvents, stir under the room temperature, logical nitrogen, anhydrous condition reacted 1～10 day down, add 0.1～10 part of vinyl monomer that contains the oxine part, stir under the room temperature, continue reaction 1～30 day, filtration obtains filtrate, steaming desolventizes or adds precipitation solvent, and recrystallization, drying obtain containing the polarization compound vinyl monomer of the oxine metal complexes of a polymerizable functional group;
(3) get 1 part above-mentionedly contain the vinyl monomer of the oxine metal complexes of a polymerizable functional group, 0.1～100 part of copolymerization vinyl monomer is dissolved in 5～500 parts of polar organic solvents, add 0.01～0.5 part of radical initiator, 40～200 ℃ of following stirring reactions 1 hour to 3 days, through methanol extraction, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
The oxine of the described modification of described step (1) is to have-R
4The X group or-derivative of the oxine of Y; R wherein
4Expression alkyl, alkylsulfonyl or carbonyl; X represent hydrogen atom, halogen atom, hydroxyl, alkoxyl group, sulfydryl or-NHR
5, wherein-NHR
5In R
5Expression hydrogen atom, alkyl or halogen atom; Y represents halogen atom;
The described unitary compound of hole transport that contains is phenothiazines and derivative, carbazole and derivative thereof, triphen amine and derivative thereof;
Described polar organic solvent is ethanol, tetrahydrofuran (THF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), N, the mixture of one or more in the adjacent acyl triamine of dinethylformamide or hexamethyl etc.;
Described catalyzer is mineral alkali, organic bases, salt or metal species, described mineral alkali comprises salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate, described organic bases comprises triethylamine or pyridine, described salt comprises Cu (I) salt or Cu (II) salt, described mineral alkali is salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate, described organic bases is triethylamine or pyridine, and described metal species can be a copper.
The compound of the described metal ion of described step (2) is salt, alkali or the organo-metallic that contains main group metal ion, rare earth ion or transition metal ion.Described main group metal ion is Al preferably
3+, or Zn
2+, described rare earth ion is Eu preferably
3+Or Sm
3+, described transition metal ion is Ru preferably
3+Described metallic salt can be AlCl
3, Zn (CH
3COO)
2, Eu (NO
3)
2Deng, described bases can be LiOH etc., described organo-metallic is triethyl aluminum, zinc ethyl etc.
Radical initiator described in the described step (3) is azo-initiator or peroxide initiator.The preferred Diisopropyl azodicarboxylate of described azo-initiator, the preferred oxidation benzoyl of described peroxide initiator.
Wherein said umber all is meant molar part except that specifying.
The polarization compound vinyl monomer synthetic optimum condition that contains the oxine metal complexes of a polymerizable functional group is: the reactant consumption of step (2) is, by the mole umber, contain the unitary oxine small molecules of hole transport ligand 1～2 parts, 10～100 parts of polar organic solvents, 1 part of the compound of metal ion, stir under the room temperature, logical nitrogen, anhydrous condition reacted 2 days down, added 1 part of vinyl monomer that contains the oxine part.The described vinyl monomer that contains the oxine part can " contain the vinyl monomer of oxine metal complexes and the purposes of method for making thereof " with reference to Chinese patent, and (application number 200410027056.2) is synthetic.The linear polymer synthetic optimum condition that contains the unitary oxine metal complexes of hole transport is: the reactant consumption of step (3) is, by the mole umber, 1～2 part of the vinyl monomer that contains the oxine metal complexes of a polymerizable functional group, 1～50 part of copolymerization vinyl monomer, 10～100 parts of polar organic solvents, 0.05～0.2 part of radical initiator, 60～120 ℃ are stirred logical nitrogen, anhydrous condition reaction 6～48 hours down.Described preparation method is free-radical polymerized method, described polar organic solvent is ethanol, tetrahydrofuran (THF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, chloroform, benzene, N, the mixture of one or more in the N dimethyl formamide etc.; Azo-initiator and the peroxide initiator of described radical initiator for using always, as benzoyl peroxide (BPO), Diisopropyl azodicarboxylate (AIBN).
The wherein said copolymerization vinyl monomer of polarization compound vinyl monomer that contains the oxine metal complexes of a polymerizable functional group is the hydro carbons (comprising aromatic hydrocarbons) that has two keys, alcohols, carboxylic-acid or ester class etc., as vinyl carbinol, vinyl benzyl chloride, acrylate chloride class, vinylbenzene etc., C
3～C
18Unsaturated acids, C
3～C
18The unsaturated ester class comprises (methyl) esters of acrylic acid, (methyl) acrylic acid or the like, acrylic acid hydroxy alkyl ethers, acrylic acid hydroxy alkyl ester class etc.
The linear polymer that contains the unitary oxine metal complexes of hole transport of the present invention can be used as luminescent material and is used for the electroluminescent flat panel display device.
Because involved polarization compound is to adopt general N-alkylated reaction or Ullmann reaction among the present invention, the compound that will contain the oxine metal complexes, containing the unitary compound of hole transport joins in the reaction system, in the presence of catalyzer, reaction obtains the polarization compound linear polymer luminescent material that a class contains the unitary oxine metal complexes of hole transport.Such the two poles of the earth material is attached to electric transmission unit and the hole transport unit group by covalent linkage or link on the compound, the similar efficient of organic electroluminescence device that has obtained and made with the mixture of electron transport material and hole mobile material.By infrared spectra,
1H-NMR, ultimate analysis proves the existence that forms non-crosslinked structure and oxine metal complexes after the polymerization really; Molecular weight and molecular weight distribution (Mw=20000-100000) by GPC test multipolymer; Characterize by the thermomechanical property of differential thermal analysis, prove that this material has excellent thermomechanical property (Tg=120-140 ℃) material; Photoelectric properties to this luminescent material are tested: ultra-violet absorption spectrum (the polarization compound UV/vis λ of oxine aluminium
Max)=250nm, 399nm), fluorescence spectrum (the polarization compound fluores λ of oxine aluminium
Max=520nm), PL luminous efficiency 20%-50%, and studied the luminescent properties of this type of linear polymer luminescent material and introduced the influence of different hole transport unit to this luminescence center of oxine metal complexes.Material has good solvability, film-forming properties and stability, long service life, luminous efficiency height.
Luminescent material good stability of the present invention, solvability are good, good film-forming property, luminous efficiency height, synthesis technique are simple, with low cost, for the consumption that reduces natural resources, alleviate raw-material short situation, the flat panel display device that develops superior performance of future generation is significant.
Embodiment
By the following examples the present invention is further described, but the scope of the specific embodiment of the present invention is not limited thereto.
Embodiment 1:
Get the hydrochloride of 2.30g (0.01mol) 5-chloromethyl-oxine, 1.99g (0.01mol) thiodiphenylamine, 1.01g (0.01mol) triethylamine, 50mL (0.62mol) tetrahydrofuran (THF), join in the reactor together, 70 ℃ are stirred 5h down, filtration obtains saffron precipitation, and precipitation is dissolved in 20mL (0.26mol) N with tetrahydrofuran (THF) washing 3 times, in the dinethylformamide, with the neutralization of 1.01g (0.01mol) triethylamine, to filter, filtrate is poured in a large amount of sherwood oils, obtain ash gray precipitation, be and contain the oxine that thiodiphenylamine replaces.
Get the 0.01mol triethyl aluminum, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=CH-Ar-CH
2OCH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 5 times obtains containing a CH
2=CH-Ar-CH
2OCH
2-the polarization compound vinyl monomer of oxine aluminium.
Get this monomer of 0.001mol, 0.01mol vinylbenzene is dissolved in 20ml toluene, add 0.05g (0.0003mol) Diisopropyl azodicarboxylate (AIBN), 80 ℃ of following stirring reactions 6 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 2:
Get 2.71g (0.01mol) 5-iodo-oxine, 1.99g (0.01mol) thiodiphenylamine, 0.05g (0.0005mol) greening is cuprous, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide joins in the reactor together, and 120 ℃ are stirred 16h down, filter out post precipitation, the filtrate that obtains is poured in a large amount of sherwood oils, obtains ash gray precipitation, is to contain thiodiphenylamine conjugated oxine.
Get the 0.01mol triethyl aluminum, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the polarization compound vinyl monomer of oxine aluminium.
Get this monomer of 0.001mol, 0.1mol methacrylic ester is dissolved in 100mL (1.24mol), add 0.4g (0.0024mol) Diisopropyl azodicarboxylate (AIBN), 60 ℃ of following stirring reactions 48 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 3:
Get the hydrobromate of 3.19g (0.01mol) 5-brooethyl-oxine, 1.99g (0.01mol) thiodiphenylamine, 1.01g (0.01mol) triethylamine, 50mL (0.62mol) tetrahydrofuran (THF), join in the reactor together, 70 ℃ are stirred 5h down, filtration obtains saffron precipitation, and precipitation is dissolved in 20mL (0.26mol) N with tetrahydrofuran (THF) washing 5 times, in the dinethylformamide, with the neutralization of 1.01g (0.01mol) triethylamine, to filter, filtrate is poured in a large amount of sherwood oils, obtain ash gray precipitation, be and contain the oxine that thiodiphenylamine replaces.
Get 1.92g (0.01mol) zinc acetate, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=CH-(CH
2)
3-CONHCH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=CH-(CH
2)
3-CONHCH
2-the polarization compound vinyl monomer of oxine zinc.
Get this monomer of 0.001mol, 0.05mol vinylbenzene is dissolved in 50mL (0.62mol), add 0.2g (0.0012mol) Diisopropyl azodicarboxylate (AIBN), 70 ℃ of following stirring reactions 24 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 4:
Get 2.24g (0.01mol) 5-bromo-oxine, 1.69g (0.01mol) pentanoic, 0.07g (0.0005mol) cuprous bromide, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide joins in the reactor together, and 140 ℃ are stirred 16h down, cooling, filter out post precipitation, filtrate is poured in a large amount of sherwood oils, and the precipitated product that obtains is and contains the oxine that the class triphenylamine replaces.
Get 1.92g (0.01mol) zinc acetate, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that the class triphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=C (CH
3)-COO-CH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 4 times obtains containing a CH
2=C (CH
3)-COO-CH
2-the polarization compound vinyl monomer of oxine zinc.
Get this monomer of 0.001mol, 0.02mol hydroxyethyl methylacrylate is dissolved in 50mL (0.62mol), add 0.1g (0.0006mol) Diisopropyl azodicarboxylate (AIBN), 100 ℃ of following stirring reactions 8 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 5
Get 2.24g (0.01mol) 5-bromo-oxine, 1.69g (0.01mol) pentanoic, 0.07g (0.0005mol) cuprous bromide, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide joins in the reactor together, and 140 ℃ are stirred 16h down, cooling, filter out post precipitation, filtrate is poured in a large amount of sherwood oils, and the precipitated product that obtains is and contains the oxine that the class triphenylamine replaces.
Get 2.04 (0.01mol) aluminum isopropylate, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that the class triphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=C (CH
3)-COO-CH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 5 times obtains containing a CH
2=C (CH
3)-COO-CH
2-the polarization compound vinyl monomer of oxine aluminium.
Get this monomer of 0.001mol, 0.02mol Jia Jibingxisuanyizhi is dissolved in 50mL (0.62mol), add 0.1g (0.0006mol) Diisopropyl azodicarboxylate (AIBN), 120 ℃ of following stirring reactions 6 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 6:
Get 2.71g (0.01mol) 5-iodo-oxine, 1.99g (0.01mol) thiodiphenylamine, 0.05g (0.0005mol) greening is cuprous, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide joins in the reactor together, and 120 ℃ are stirred 16h down, filter out post precipitation, the filtrate that obtains is poured in a large amount of sherwood oils, obtains ash gray precipitation, is to contain thiodiphenylamine conjugated oxine.
Get the 0.01mol zinc ethyl, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the polarization compound vinyl monomer of oxine zinc.
Get this monomer of 0.001mol, 0.04mol methyl methacrylate is dissolved in 50mL (0.62mol), add 0.2g (0.0012mol) Diisopropyl azodicarboxylate (AIBN), 60 ℃ of following stirring reactions 36 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 7:
Get 2.71g (0.01mol) 5-iodo-oxine, 1.69g (0.01mol) pentanoic, 0.05g (0.0005mol) greening is cuprous, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide, join together in the reactor, 120 ℃ are stirred 16h down, filter out post precipitation, the filtrate that obtains is poured in a large amount of sherwood oils, and the precipitated product that obtains is and contains the oxine that the class triphenylamine replaces.
Get the 0.01mol zinc ethyl, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the polarization compound vinyl monomer of oxine zinc.
Get this monomer of 0.001mol, 0.04mol methyl methacrylate is dissolved in 50mL (0.62mol), add 0.2g (0.0012mol) Diisopropyl azodicarboxylate (AIBN), 60 ℃ of following stirring reactions 36 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 8:
Get 2.24g (0.01mol) 5-bromo-oxine, 1.69g (0.01mol) pentanoic, 0.05g (0.0005mol) greening is cuprous, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide, join together in the reactor, 120 ℃ are stirred 16h down, filter out post precipitation, the filtrate that obtains is poured in a large amount of sherwood oils, and the precipitated product that obtains is and contains the oxine that the class triphenylamine replaces.
Get 1.92g (0.01mol) zinc acetate, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=C (CH
3)-COO-CH
2CH
2-O-CH
2-the polarization compound vinyl monomer of oxine zinc.
Get this monomer of 0.001mol, 0.04mol methyl methacrylate is dissolved in 50mL (0.62mol), add 0.2g (0.0012mol) Diisopropyl azodicarboxylate (AIBN), 60 ℃ of following stirring reactions 36 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
Embodiment 9:
Get the hydrobromate of 3.19g (0.01mol) 5-brooethyl-oxine, 1.69g (0.01mol) pentanoic, 0.07g (0.0005mol) cuprous bromide, 1.75g (0.0125mol) salt of wormwood, 25mL (0.32mol) N, dinethylformamide joins in the reactor together, and 140 ℃ are stirred 16h down, cooling, filter out post precipitation, filtrate is poured in a large amount of sherwood oils, and the precipitated product that obtains is and contains the oxine that the class triphenylamine replaces.
Get 1.92g (0.01mol) zinc acetate, with the dissolving of 50mL (0.62mol) tetrahydrofuran (THF), slowly add 0.02mol and contain the oxine that thiodiphenylamine replaces, stirring reaction is 2 days under the room temperature, adds 0.01mol and contains CH
2=CH-(CH
2)
3-CONHCH
2-oxine part vinyl monomer, stirring reaction is 2 days under the room temperature, filters to obtain filtrate, steams solvent, sherwood oil recrystallization 3 times obtains containing a CH
2=CH-(CH
2)
3-CONHCH
2-the polarization compound vinyl monomer of oxine zinc.
Get this monomer of 0.001mol, 0.05mol vinylbenzene is dissolved in 50mL (0.62mol), adds 0.2g (0.0012mol) Diisopropyl azodicarboxylate (AIBN), 70 ℃ of following stirring reactions 24 hours, pour the methyl alcohol reprecipitation into 3 times, obtain containing the linear polymer of the unitary oxine zinc of hole transport.
Claims (9)
1, contain the linear polymer of the unitary oxine metal complexes of hole transport, it is characterized in that, structure has the general formula of following formula (1) or formula (2):
Formula (1) formula (2)
Wherein R represents to contain the alkylene base or the aryl of 0 to 10 carbon atom, and A represents the hole transport unit, the M of formula (1)
1The expression trivalent metallic element, the M of formula (2)
2The expression divalent metal element.
2, the compound of formula according to claim 1 (1) or formula (2) is characterized in that, described hole transport unit comprises thiodiphenylamine, carbazole or triphenylamine.
3, the compound of formula according to claim 1 (1) or formula (2) is characterized in that described M
1Be Al, described M
2Be Zn.
4, the described preparation method who contains the linear polymer of the unitary oxine metal complexes of hole transport of claim 1 is characterized in that, may further comprise the steps:
(1) in molar part, get modification 0.1～10 part of 10～100 parts of 1 part of oxine, polar organic solvents, catalyzer, contain 1～2 part of the unitary compound of hole transport and be blended in and carry out N-alkylated reaction or Ullmann reaction under the room temperature to 150 ℃, reacted 0.5 hour to two days, and promptly obtained containing the unitary oxine small molecules of hole transport part;
(2) get the compound of 0.1～10 part of metal ion, 0.1～20 parts contain the unitary oxine small molecules of hole transport part and are dissolved in 5～500 parts of polar organic solvents, stir under the room temperature, logical nitrogen, anhydrous condition reacted 1～10 day down, add 0.1～10 part of vinyl monomer that contains the oxine part, stir under the room temperature, continue reaction 1～30 day, filtration obtains filtrate, steaming desolventizes or adds precipitation solvent, and recrystallization, drying obtain containing the polarization compound vinyl monomer of the oxine metal complexes of a polymerizable functional group;
(3) get 1 part above-mentionedly contain the vinyl monomer of the oxine metal complexes of a polymerizable functional group, 0.1～100 part of copolymerization vinyl monomer is dissolved in 5～500 parts of polar organic solvents, add 0.01～0.5 part of radical initiator, 40～200 ℃ of following stirring reactions 1 hour to 3 days, through methanol extraction, obtain containing the linear polymer of the unitary oxine metal complexes of hole transport.
5, preparation method according to claim 4 is characterized in that, the oxine of the described modification of described step (1) is to have-R
4The X group or-derivative of the oxine of Y; R wherein
4Expression alkyl, alkylsulfonyl or carbonyl; X represent hydrogen atom, halogen atom, hydroxyl, alkoxyl group, sulfydryl or-NHR
5, wherein-NHR
5In R
5Expression hydrogen atom, alkyl or halogen atom; Y represents halogen atom;
The described unitary compound of hole transport that contains is phenothiazines and derivative, carbazole and derivative thereof, triphen amine and derivative thereof;
Described polar organic solvent is ethanol, tetrahydrofuran (THF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), N, the mixture of one or more in the adjacent acyl triamine of dinethylformamide or hexamethyl etc.;
Described catalyzer is mineral alkali, organic bases, salt or metal species, described mineral alkali comprises salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate, described organic bases comprises triethylamine or pyridine, described salt comprises Cu (I) salt or Cu (II) salt, described mineral alkali is salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate, described organic bases is triethylamine or pyridine, and described metal species can be a copper.
6, preparation method according to claim 4 is characterized in that, the compound of the described metal ion of described step (2) is salt, alkali or the organo-metallic that contains main group metal ion, rare earth ion or transition metal ion.
7, preparation method according to claim 6 is characterized in that, described main group metal ion is Al
3+, or Zn
2+, described rare earth ion is Eu
3+Or Sm
3+, described transition metal ion is Ru
3+Described salt can be AlCl
3, Zn (CH
3COO)
2Perhaps Eu (NO
3)
2, described bases can be LiOH, described organo-metallic can be triethyl aluminum or zinc ethyl.
8, preparation method according to claim 4 is characterized in that, the radical initiator described in the described step (3) is azo-initiator or peroxide initiator.
9, preparation method according to claim 8 is characterized in that, described azo-initiator is a Diisopropyl azodicarboxylate, and described peroxide initiator is the Oxybenzene formyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710027892A CN101058620B (en) | 2007-04-30 | 2007-04-30 | Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710027892A CN101058620B (en) | 2007-04-30 | 2007-04-30 | Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058620A true CN101058620A (en) | 2007-10-24 |
| CN101058620B CN101058620B (en) | 2010-05-19 |
Family
ID=38864936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710027892A Expired - Fee Related CN101058620B (en) | 2007-04-30 | 2007-04-30 | Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101058620B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191827A (en) * | 2018-02-09 | 2018-06-22 | 广东省石油与精细化工研究院 | A kind of quinoline triazole type rare earth compounding and its preparation method and application |
-
2007
- 2007-04-30 CN CN200710027892A patent/CN101058620B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191827A (en) * | 2018-02-09 | 2018-06-22 | 广东省石油与精细化工研究院 | A kind of quinoline triazole type rare earth compounding and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101058620B (en) | 2010-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108586318B (en) | Solution-processable thermally-activated delayed fluorescent material and preparation method thereof | |
| JP2007519800A (en) | Organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl unit and organic electroluminescent device produced using the same | |
| CN1680456A (en) | Electroactive polymer, device made therefrom and method | |
| CN1810817A (en) | Iridium complex of beta-diketone ligand and its electroluminescent device | |
| CN103436250A (en) | Rare earth polymer luminescent material with Tpy as neutral ligand, and preparation and application thereof | |
| CN101041667A (en) | Bipolar compound containing 8-hydroxyquinoline metal complex and preparation method thereof | |
| CN1786106A (en) | Acrylic ester and methyl acrylic ester kind side chain type luminous polymer and its synthesis | |
| CN116355130B (en) | Organic long afterglow polymer with blue light or full-color circular polarized luminescence and preparation method thereof | |
| CN110408007B (en) | Preparation method of POSS hybrid conjugated polymer | |
| CN111454435B (en) | Phenanthroimidazole unit-based electroluminescent polymer and preparation method and application thereof | |
| CN101058620B (en) | Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method | |
| CN107245037B (en) | Ladder-shaped macromolecule derivative and preparation method and application thereof | |
| CN1587342A (en) | Organic polymer material containing screw fluorene structure and its use | |
| CN101058616B (en) | Crosslinking polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method | |
| JP4295047B2 (en) | Luminescent organic polymer metal complex, luminescent organic polymer metal complex composition capable of wet film formation and method for producing the same | |
| CN1240733C (en) | Linear copolymer containing 8-hydroxyquinoline metal complex and its preparation and use | |
| CN1246368C (en) | Cross-linked high polymer containing 8-hydroxyquinoline metal complex and its preparation and use | |
| CN1295218C (en) | Olefin monomers of multi-functional group 8-hydroxyquinoline metal complex and their preparation process and application | |
| CN1314671C (en) | Olefin monomer containing 8-hydroxyquinoline metal complex and its production method and use | |
| CN101029134A (en) | Star-shaped polymer with ion iridium complex as core, its synthesis and use | |
| CN1600759A (en) | Luminescence oligomer in PPV category of containing biphenyl center | |
| CN1285628C (en) | Twist structured p-phenylene ethylene luminous polymer and use thereof | |
| CN1247636C (en) | Polymer with main chain possessing biphenyl flumaronitrile structural unit, its preparation method and uses | |
| CN114057922B (en) | Thermal activation delayed fluorescence polymer main body material with aggregation-induced fluorescence property | |
| JP2007063489A (en) | Material for producing organic el element, capable of performing wet type film formation, and organic el element |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: HAINAN ZHONGKEXIANG NEW MATERIAL TECHNOLOGY CO., L Free format text: FORMER OWNER: GUANGZHOU INST. OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20130528 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 510650 GUANGZHOU, GUANGDONG PROVINCE TO: 571152 HAIKOU, HAINAN PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130528 Address after: Office building 571152 Hainan city of Haikou province the national hi tech Development Zone Industrial Park Ridge room 98 Patentee after: Hainan Kexiang new Mstar Technology Ltd Address before: 510650 Tianhe District, Guangdong Province, willing to live in Guangzhou Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100519 Termination date: 20190430 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |