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):
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 dinethylformamide 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.