CN103709380B - Three fluorenamine polymer luminescent material and preparation method and application - Google Patents
Three fluorenamine polymer luminescent material and preparation method and application Download PDFInfo
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- CN103709380B CN103709380B CN201310659475.7A CN201310659475A CN103709380B CN 103709380 B CN103709380 B CN 103709380B CN 201310659475 A CN201310659475 A CN 201310659475A CN 103709380 B CN103709380 B CN 103709380B
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 boric acid ester Chemical class 0.000 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 238000005401 electroluminescence Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012300 argon atmosphere Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003808 methanol extraction Methods 0.000 claims description 10
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 6
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 3
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 claims 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 150000002220 fluorenes Chemical class 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000012648 alternating copolymerization Methods 0.000 abstract description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 40
- 238000005160 1H NMR spectroscopy Methods 0.000 description 28
- 239000007787 solid Substances 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 238000002189 fluorescence spectrum Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- RZOFQMLTEFDHQM-UHFFFAOYSA-N 2-nitro-9,9-dioctylfluorene Chemical compound [N+](=O)([O-])C1=CC=2C(C3=CC=CC=C3C=2C=C1)(CCCCCCCC)CCCCCCCC RZOFQMLTEFDHQM-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 2
- XFOHWECQTFIEIX-UHFFFAOYSA-N 2-nitrofluorene Chemical compound C1=CC=C2C3=CC=C([N+](=O)[O-])C=C3CC2=C1 XFOHWECQTFIEIX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)C1=CC=C2C3C=CC(N(C(CC45)=CC=C4c4ccc(C(C)C)cc4C5(*)I)c4ccc(C5=C(C6(*)*)C=C(*)CC5)c6c4)=CC3C(*)(*)C2C1 Chemical compound CC(C)C1=CC=C2C3C=CC(N(C(CC45)=CC=C4c4ccc(C(C)C)cc4C5(*)I)c4ccc(C5=C(C6(*)*)C=C(*)CC5)c6c4)=CC3C(*)(*)C2C1 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 125000003831 tetrazolyl group Chemical group 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LCKDOHRDONNZTG-UHFFFAOYSA-N 1,2-dibromo-9h-fluorene Chemical class C1=CC=C2CC3=C(Br)C(Br)=CC=C3C2=C1 LCKDOHRDONNZTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N C[n]1c(cccc2)c2c2c1cccc2 Chemical compound C[n]1c(cccc2)c2c2c1cccc2 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of three fluorenamine polymer luminescent material and preparation method and application, this material for skeleton, can regulate and control bipolarity and the glow color of luminescent material with three fluorenamines by changing the chemical structure containing three fluorenamine polymer luminescent material side chains; Chemical structure is as follows, and preparation method is using fluorenes as initial reaction raw materials, by a series of simple reaction, finally obtains subject polymer luminescent material with the Suzuki linked reaction of palladium chtalyst and two boric acid ester alternating copolymerizations of fluorenes.This materials synthesis is simple, purifies convenient; There is good solvability, film-forming properties and film morphology stability; There is high photoluminescence and electroluminescent efficiency.This materials application is in polymer electroluminescence LED lighting layer.
Description
The application is application number 201110028701.2, January 27 2011 applying date, the divisional application of title " three fluorenamine compounds, three fluorenamine polymer luminescent material and preparation method and application ".
Technical field
The present invention relates to a kind of luminescent conjugated polymers material, be specifically related to a kind of with three fluorenamines polymer luminescent material that is skeleton and preparation method thereof, and the application of this material in polymer LED.
Background technology
Since Burroughes and Friend reported first polymer LED (PLEDs), in recent two decades in the past, PLEDs causes the strong research and development interest of people in ultra-thin, the full-color and large-area flat-plate display of preparation, achieves huge progress simultaneously.The solution processable of PLEDs, makes people can carry out fabricate devices by low cost printing technology, such as spray ink Printing and silk screen printing, and compared to the small molecules Organic Light Emitting Diode of vacuum evaporation, it becomes original lower, commercially also more feasible.In order to realize flat pannel display based on PLEDs and solid state lighting, just need high performance red, green, blue luminescence polymer.Wherein blue light frequency-doubling both can as luminescent layer, also can as the material of main part of light-emitting guest, was obtained the light of long wavelength by the mode of energy trasfer or carrier capture.Most representative in existing polymkeric substance blue emitting material is polyfluorene, but because the rigid planar structure of fluorenes makes material easily form exciplex and longwave transmissions when luminescence, have a strong impact on the stability of the radiative saturated colour purity of device and glow color.Meanwhile, polyfluorene because lower minimumly occupy molecular orbital(MO) (HOMO) energy level, and causes higher hole to inject obstacle.
Summary of the invention
The object of the invention is to, for existing technical disadvantages, provide a kind of polymer luminescent material and preparation method thereof.It is high that this material has quantum yield, high color purity, the advantage that permanent stability are good, is applicable to high resolution total colouring and white-light illuminating.
Of the present invention also have an object to be the polymer electroluminescence material containing three fluorenamines to be applied to prepare polymer LED and illuminating device.
Object of the present invention is achieved through the following technical solutions:
A kind of three fluorenamine compounds, this compound has following chemical structure:
Wherein: R
1be alkyl or the alkoxyl group of lyotropy, carbonatoms is 1 ~ 20; X is the derivative of functional group, heterogeneous ring compound and carbazole.
The structure of described X is as follows:
h,
or-CN.
Described Ar has following structure:
or
The preparation method of above-mentioned three fluorenamine compounds, comprises the steps:
2-amido-9 is added in argon atmosphere downhill reaction bottle, 9-dioctyl fluorene inductor and be equivalent to 2-amido-9,5 times of 9-dioctyl fluorene inductor molar weight 2,7-bis-bromo-9,9-dioctyl fluorene, and with toluene dissolve, then add be equivalent to 2-amido-9,9-dioctyl fluorene inductor molar weight 1/40 Pd
2(dba)
3, 1/10 DPPF and 10 times
tbuONa, react 24 ~ 36 hours under reflux, reaction terminates rear naturally cooling, is extracted with ethyl acetate, and with saturated brine It, gained organic over anhydrous dried over mgso, suction filtration, the filtrate of gained, under reduced pressure except desolventizing, is separated by chromatographic column, steaming desolventizes and vacuum-drying, obtains three fluorenamine compounds.
Three fluorenamine polymer luminescent materials prepared by above-mentioned three fluorenamine compounds, have following chemical structure:
Or
Wherein: R
1be alkyl or the alkoxyl group of lyotropy, carbonatoms is 1 ~ 20; R
2various substituted radicals; X is the derivative of functional group, heterogeneous ring compound and carbazole; Y+z < 1, and 0 < y < 1,0≤z < 1, n=10 ~ 1000.
Preferably, as 0.01≤y < 0.5, z=0.1, R
2for H; As y=0.5, z=0, R
2for H.
The preparation method of above-mentioned luminescent material I, comprises the steps:
Suzuki linked reaction is adopted to prepare polymkeric substance, 9 are added in nitrogen or argon gas atmosphere downhill reaction bottle, 2 of 9-dialkyl fluorene, the two boric acid ester of 7-, be equivalent to three fluorenamine compound dissolutions of this pair of boric acid ester equimolar amount in the toluene of 30 ~ 150 times being equivalent to above-mentioned two kinds of reactant mole total amounts, add again and be equivalent to the above-mentioned tetraethyl ammonium hydroxide aqueous solution of two kinds of reactant mole total amounts 1 ~ 10 times and the catalyzer of 1% ~ 10%, stirring reaction 12 ~ 48 hours under reflux; After naturally cooling, then carry out end capping; Reaction terminates, and naturally cooling, goes out polymkeric substance with methanol extraction, and dried product uses methyl alcohol, acetone, tetrahydrofuran (THF) extracting 24 hours respectively, concentrated extract, and precipitate in methyl alcohol, final product is dry under vacuo, obtained luminescent material I.
The preparation method of above-mentioned luminescent material II and the difference of luminescent material I are:
Bromo-9, the 9-dioctyl fluorene reactants of 2,7-bis-are also added in Suzuki linked reaction system; When adding y part three fluorenamine compound, 0 < y≤0.5, then add 2,7-two boric acid esters and bromo-9, the 9-dioctyl fluorene of (0.5-y) part 2,7-bis-of 0.5 part of (molar fraction, lower same) 9,9-dialkyl fluorene, now z=0; Or
Dibromo dibenzothiophene-S is also added, S-dioxy and bromo-9, the 9-dioctyl fluorene of 2,7-bis-two kinds of reactants in Suzuki linked reaction system; When adding y part three fluorenamine compound, 0 < y < 0.5, z part dibromo dibenzothiophene-S, S-dioxy, 0 < z < 0.5, y+z≤0.5, then add 2,7-two boric acid ester and (0.5-y-z) parts 2 of 0.5 part of 9,9-dialkyl fluorene, bromo-9, the 9-dioctyl fluorene of 7-bis-.
Preferably, described catalyzer is the mixing of one or more that four (triphenyl phosphorus) close in palladium, palladium and thricyclohexyl phosphorus.
Described luminescent material is applied in polymer electroluminescence LED lighting layer as hole transport layer material.
The present invention is by introducing three fluorenamines at main polymer chain, at raising polymkeric substance HOMO energy level, while improving hole-injection characteristics, improve the solid space structure of polymkeric substance to avoid the formation of exciplex, thus the longwave transmissions that suppression causes thus, to improve the stability of radiative saturated colour purity and glow color.In addition, by introducing various group as on the fluorenes of polymer lateral chain, regulating and controlling the electron affinity of whole molecule, thus making prepared polymer luminescent material have certain bipolar performance.By the bipolarity of telomerized polymer, realize the balance that electric charge carrier in polymer light-emitting layer (electronics and hole) injects, transmits better, make the polymer electroluminescence diode prepared by the Solution processing techniques of rotary coating have good device performance.Meanwhile, by introducing different chromophoric groups in this position, can also realize the object of polymer luminescent material glow color.During preparation, using the fluorenes of cheapness as initial reaction raw materials, by a series of simple reaction, finally obtain subject polymer luminescent material with the Suzuki linked reaction of palladium chtalyst and two boric acid ester alternating copolymerizations of fluorenes; In addition, by introducing dibromo dibenzothiophene-S, S-dioxy, adopting the method for random copolymerization, obtaining the blue light material of Performance comparision excellence.This serial conjugated polymer luminescent material, as the emitting layer material making polymer electroluminescence diode, has boundless development and application prospect in the background light source, white-light illuminating light source etc. of large-area flat-plate full color display, liquid-crystal display.Therefore, compared to existing material and technology, tool of the present invention has the following advantages and beneficial effect:
(1) simple containing three fluorenamine polymer luminescent material synthesis, purify convenient;
(2) containing three fluorenamine polymer luminescent materials, there is good solvability, film-forming properties and film morphology stability;
(3) containing three fluorenamine polymer luminescent materials, there is higher HOMO energy level and lower hole injection obstacle;
(4) bipolarity and the glow color of luminescent material can be regulated and controled by changing the chemical structure containing three fluorenamine polymer luminescent material side chains;
(5) containing three fluorenamine polymer luminescent materials, there is high photoluminescence and electroluminescent efficiency.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra of polymkeric substance in toluene solution prepared by embodiment 1 ~ 4.
Fig. 2 is the fluorescence spectrum of polymkeric substance in toluene solution prepared by embodiment 1 ~ 4.
Fig. 3 is the uv-visible absorption spectra of polymkeric substance under solid film state prepared by embodiment 1 ~ 4.
Fig. 4 is the fluorescence spectrum of polymkeric substance under solid film state prepared by embodiment 1 ~ 4.
Fig. 5 is the electroluminescent spectrum of polymkeric substance under solid film state prepared by embodiment 1 ~ 4.
Fig. 6 is the electroluminescent spectrum of polymkeric substance under solid film state (adding TPBI layer) prepared by embodiment 1 ~ 4.
Fig. 7 is the uv-visible absorption spectra of polymkeric substance in toluene solution prepared by embodiment 5 ~ 13.
Fig. 8 is the fluorescence spectrum of polymkeric substance in toluene solution prepared by embodiment 5 ~ 13.
Fig. 9 is the uv-visible absorption spectra of polymkeric substance under solid film state prepared by embodiment 5 ~ 13.
Figure 10 is the fluorescence spectrum of polymkeric substance under solid film state prepared by embodiment 5 ~ 13.
Figure 11 is the electroluminescent spectrogram of embodiment 10 ~ 13 polymkeric substance under solid film state.
Figure 12 is the electroluminescent spectrogram of embodiment 10 ~ 13 polymkeric substance under solid film state (adding TPBI layer).
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Step one: the preparation of 2-nitrofluorene
Fluorenes (33.2g, 0.2mol) is dissolved in 200ml glacial acetic acid, stirs, be heated to about 60 DEG C, with the dense HNO of constant pressure funnel instillation 15ml glacial acetic acid dilution
3(32ml, 0.464mol).After dropwising, then react 3 hours at 60 DEG C.Poured into by reaction mixture in frozen water, with dichloromethane extraction, the organic layer of gained washs 3 times with saturated common salt aqueous solution, merges organic phase, and uses anhydrous magnesium sulfate drying.Filtrate after suction filtration is under reduced pressure except desolventizing, and rear dehydrated alcohol recrystallization obtains khaki color solid 30.3g.Yield 71.6%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.71(s,1H),8.60-8.31(m,1H),7.91-7.88(m,2H),7.66-7.64(m,1H),7.48-7.46(m,2H),4.03(s,2H).
Step 2: the preparation of 2-nitro-99-dioctyl fluorene
Under nitrogen atmosphere, in 250ml there-necked flask, add 2-nitrofluorene (5.30g, 25mmol), Tetrabutyl amonium bromide (0.449g, 1.25mmol), and add 100ml toluene make it dissolve.Add n-Octyl Bromide (12.8g, 66.3mmol) with dropper, after about half an hour, add the 50%NaOH of 40ml, mixed solution becomes atropurpureus.8 hours are reacted at 60 DEG C.After naturally cooling, react with a certain amount of hydrochloric acid, and add the water of 100ml, be extracted with ethyl acetate, and have saturated brine It 3 times, gained organic over anhydrous dried over mgso.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and after moving phase used (pure sherwood oil, then to sherwood oil/methylene dichloride=1:6,1:4) is spin-dried for, vacuum-drying, obtains pale yellow oily liquid body 10.0g, yield 91.5%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.30-8.22(m,1H),8.20(m,1H),7.80-7.78(m,2H),7.43-7.38(m,3H),2.05-1.20(m,4H),1.28-1.03(m,20H),0.88-0.78(m,6H),0.59-0.52(m,4H).
Step 3: the preparation of 2-amido-9,9-dioctyl fluorene
Under argon atmosphere, in 50ml there-necked flask, add 2-nitro-9,9-dioctyl fluorene (4.38g, 10mmol), dehydrated alcohol 50ml, stir, dissolve.Add 5%Pd/C (1.05g, 0.5mmol) again, drip a hydrazine hydrate (2.4ml) with syringe needle, dripped off in 20 minutes.80 DEG C of reactions 10 hours.After naturally cooling, filter, obtain product 4.08g, yield is 100%.
1HNMR(300MHz,DMSO),δ(ppm):7.50(d,1H),7.40(d,1H),7.25(d,1H),7.19(t,1H),7.09(t,1H),6.55(s,1H),6.50(d,1H),5.19(s,2H),1.83(m,4H),1.22-0.91(m,20H),0.79(t,6H),0.51(m,4H).
Step 4: the preparation of bromo-9, the 9-dioctyl fluorene of 2-nitro-7-
In 250ml three-necked flask, add 5.46g (12.5mmol) 2-nitro-9,9-dioctyl fluorene, 0.137g iron powder, then measure 50ml chloroform with graduated cylinder, pour in flask, stir under cryosel bath, lucifuge.Pipette 1.3ml (18.8mmol) bromine with 2ml transfer pipet, be added in 100ml constant pressure funnel, dropwise add in flask, the tail gas simultaneously produced enters saturated hypo solution by conduit.React 9 hours, with saturated hypo solution cancellation reaction, with dichloromethane extraction and with saturated sodium chloride solution washing, organic layer uses anhydrous magnesium sulfate drying again, is spin-dried for after suction filtration, then carries out column chromatography (sherwood oil/CH
2cl
2for 3:1), obtain faint yellow solid 5.42g after vacuum-drying, and use
1hNMR identifies.Productive rate is 84.0%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.28-8.24(m,1H),8.19-8.18(m,1H),7.75-7.63(m,2H),7.55-7.52(m,2H),2.08-1.92(m,4H),1.24-1.04(m,20H),0.84-0.79(t,6H),0.60-0.51(m,4H).
Step 5: the preparation of 2,7-dibromo fluorenes
The same step 4 of method, only need change 2-nitro-9,9-dioctyl fluorene into fluorenes (16.7g, 0.1mol), product is faint yellow solid.Yield 86.0%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.66(m,2H),7.62(s,1H),7.59(s,1H),7.52(m,1H),7.49-7.49(m,1H),3.87(s,2H).
The preparation of bromo-9, the 9-dioctyl fluorene of step 6: 2,7-bis-
In 500ml flask, add dibromo fluorenes (27.8g, 85.9mmol), 230ml dimethyl sulfoxide (DMSO), phase-transfer catalyst Tetrabutyl amonium bromide (0.252g, 0.78mmol), stir.Add 50%NaOH solution 20ml, mixed solution is atropurpureus.Stir 1 ~ 2 hour.Instill n-Octyl Bromide (35.7g, 185mmol) with constant pressure funnel, spend the night, react 18 hours.Add appropriate concentrated hydrochloric acid neutralization, and cool with frozen water.With dichloromethane extraction, organic layer strong brine washes three times, and with anhydrous magnesium sulfate drying, suction filtration, the filtrate of gained, under reduced pressure except desolventizing, obtains reddish-brown liquid.Be that moving phase crosses post with sherwood oil, and use ethanol as solvent recrystallization, obtain colorless solid 39.2g.Yield 83.2%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.50(m,1H),7.49-7.48(m,1H),7.46-7.46(m,1H),7.44-7.38(m,3H),1.93-1.88(m,4H),1.25-1.05(m,20H),0.85-0.80(t,6H),0.58-0.56(m,4H).
The preparation of step 7: 2,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy borine-2-)-9,9-dioctyl fluorene
Under an ar atmosphere, bromo-for 2,7-bis-9,9-dioctyl fluorene (20.1mmol, 11.0g) are added in the straight mouth three-necked flask of 250ml, sealing.After about 30 minutes, add with syringe needle and newly steam THF170ml, bromo-9, the 9-dioctyl fluorene of 2,7-bis-are fully dissolved, stirs 20 minutes.After cooled with liquid nitrogen extremely-78 DEG C, dropwise add n-Butyl Lithium (50mmol, 20ml) with syringe needle, reaction solution becomes orange-yellow, is colourless afterwards, stirs 2.5 hours at-78 DEG C, mixed solution is creamy white, and temperature is raised to-40 DEG C, adds after liquid nitrogen is cooled to-78 DEG C, add boric acid ester (10.5ml, 50mmol) fast with syringe needle, solution becomes orange-yellow, stir, mixed solution heats up gradually, is oyster white afterwards, spends the night.React 18 hours.Add appropriate water, stir, cancellation is reacted, and mixed solution color becomes clarification, is that extraction liquid extracts, takes off the colourless oil reservoir of layer, wash three times with strong brine with methylene dichloride.Merge the organic layer of gained, with anhydrous magnesium sulfate drying, suction filtration, obtain colourless permeate, under reduced pressure except desolventizing, obtain colorless solid.Make mixed solvent recrystallization 1 time with ethanol and methylene dichloride, obtain white solid 9.15g, yield 70.5%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.79(d,2H),7.74-7.73(m,3H),7.70(s,1H),2.00(m,4H),1.39(s,24H),1.30-1.01(m,20H),0.83-0.78(t,6H),0.55(m,4H)
Step 8: the preparation of two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(9,9-dioctyl fluorene-2-) amine
Under argon atmosphere, toward in 50ml there-necked flask, add bromo-9, the 9-dioctyl fluorene (2.23g, 4.77mmol) of 2,7-bis-, 2-amido-9,9-dioctyl fluorene (0.918g, 2.27mmol), dissolves with 20ml toluene.Add Pd again
2(dba)
3(0.576g, 0.0628mmol), DPPF (0.121g, 0.218mmol),
tbuONa (0.878g, 9.13mmol).React 40 hours at 110 DEG C.After naturally cooling, with dichloromethane extraction, and with saturated brine It 3 times, gained organic over anhydrous dried over mgso.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, the pure sherwood oil of moving phase used.After being spin-dried for, vacuum-drying, obtains product 2.14g, and yield is 80.0%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.62-7.41(m,9H),7.33-7.27(m,4H),7.24-7.23(m,3H),7.02-6.98(m,3H),1.96-1.78(m,12H),1.25-1.07(m,60H),0.87-0.81(t,18H),0.67(m,12H).
Step 9: the preparation of polymer P 4FN:
Under an argon atmosphere, in 50ml three-necked flask, add raw material two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(9,9-dioctyl fluorene-2-) amine (0.581g, 0.433mmol), 2,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy borine-2-)-9,9-dioctyl fluorene (0.281g, 0.433mmol), Et
4nOH1ml, and dilute with deionized water 1ml, catalyst P d (pph
3)
4(0.0065g, 0.00562mmol), leads to and is warming up to 90 ~ 100 DEG C gradually after Ar30 minute, react 48 hours.Naturally cooling, adds phenylo boric acid (0.137g, 1.12mmol), 2ml toluene, reacts 13 hours.After naturally cooling, add 1ml bromobenzene (9.6mmol), react 10 hours.Dissolve the dark blue-green dope of gained with toluene, and with methanol extraction, filtration is oyster, vacuum drying.Then methyl alcohol, acetone, THF extracting 24 hours are used respectively.Concentrated, precipitate in methyl alcohol, filter, vacuum-drying.Obtain 0.4235g, yield 58.0%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.90-7.80(m,2H),7.79-7.50(m,14H),7.43-7.31(m,5H),7.20-7.03(m,3H),2.30-1.75(m,16H),1.40-1.00(m,80H),0.99-0.50(m,40H).
The Absorption and fluorescence spectrum of this polymeric film is shown in Fig. 3, Fig. 4.
In order to characterize the electroluminescent properties of this polymkeric substance, making devices structure is the polymer electroluminescence diode component of ITO/PEDOT:PSS/Polymer (80nm)/CsF (1.5nm)/Al (120nm) and ITO/PEDOT:PSS/Polymer (80nm)/TPBI (30nm)/CsF (1.5nm)/Al (120nm) respectively, making processes is as follows: adopt the ito glass cleaned in advance to be anode, at this spin-on-glass one deck conducting polymer-polythiofuran derivative (PEDOT:PSS), and vacuum-drying 12 hours at 80 DEG C, then on PEDOT:PSS decorative layer, spin coating a layer thickness is the blue light conjugated polymers of 80nm, and 20min is heated at 80 DEG C.The TPBI (with not steaming comparing of TPBI) that evaporation 30nm is thick under a high vacuum again, the metallic aluminium that CsF and 120nm that 1.5nm is thick is thick.It is finally the encapsulation of device.Device performance is as follows: trigger voltage 3.0 volts, high-high brightness 747cd/m
2, maximum current efficiency is 0.48cd/A, maximum external quantum efficiency 0.59%, and chromaticity coordinates (CIE) is (0.165,0.123).The device performance not adding TPBI is as follows: trigger voltage 3.1 volts, high-high brightness 257cd/m
2, maximum current efficiency is 0.06cd/A, maximum external quantum efficiency 0.07%, and chromaticity coordinates (CIE) is (0.208,0.218).Its electroluminescent spectrum is shown in Fig. 5, Fig. 6.
Embodiment 2
The first seven the first seven walking with embodiment 1 of the present embodiment walks.
Step 8: the preparation of 2-cyano group-7-nitro-9,9-dioctyl fluorene
Under an argon atmosphere, 2-nitro-7-bromo-9 is added in 250ml three-necked flask, 9-dioctyl fluorene (2.05g, 4mmol), CuCN (0.389g, 4mmol), DMF (30ml), after stirring, is warming up to about 150 DEG C gradually, the lower reaction of backflow about 15 hours, in faint yellow.Spend the night, find aobvious orange red.With dichloromethane extraction, and wash three times with saturated common salt, the organic over anhydrous dried over mgso of gained.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and moving phase used is methylene dichloride/sherwood oil=1:6, and removing raw material point, methylene dichloride/sherwood oil=1:3, collects second point.Vacuum-drying obtains red brown solid 1.53g.Yield 83.2%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.32(d,1H),8.24(s,1H),7.89(d,2H),7.70(m,2H),2.08-2.01(m,4H),1.25-1.06(m,20H),0.88-0.80(t,6H),0.60-0.38(m,4H).
Step 9: the preparation of 2-amido-7-cyano group-9,9-dioctyl fluorene
The same step 3 of method, only need replace 2-nitro-9,9-dioctyl fluorene with 2-cyano group-7-nitro-9,9-dioctyl fluorene (1.13g, 2.2mmol), obtain orange-yellow viscous body 0.7637g, yield 72.3%.
1HNMR(300MHz,DMSO),δ(ppm):7.64(s,1H),7.55(s,2H),7.53(d,1H),5.53(s,2H),2.00-1.75(m,4H),1.22-0.99(m,20H),0.78(t,6H),0.51-0.49(m,4H).
Step 10: the preparation of two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(7-cyano group-9,9-dioctyl fluorene-2-) amine
Under argon atmosphere, toward in 50ml there-necked flask, add bromo-9, the 9-dioctyl fluorene (2.30g, 4.18mmol) of 2,7-bis-, 2-amido-7-cyano group-9,9-dioctyl fluorene (0.360g, 0.837mmol), dissolves with 20ml toluene.Add Pd again
2(dba)
3(0.0164g, 0.021mmol), DPPF (0.0399g, 0.0837mmol),
tbuONa (0.390g, 3.48mmol).React 24 hours at 110 DEG C.After naturally cooling, be extracted with ethyl acetate, and have saturated brine It 3 times, gained organic over anhydrous dried over mgso.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and moving phase used is sherwood oil/methylene dichloride=1:6,1:3.Vacuum-drying, obtain product brown color viscous body 0.900g, yield is 78.8%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.68-7.60(m,2H),7.60-7.50(m,6H),7.50-7.46(m,4H),7.46-7.43(m,2H),7.07-7.00(m,4H),2.07-1.81(m,12H),1.27-1.09(m,60H),0.89(m,18H),0.84-0.69(m,12H).
Step 11: the preparation of polymer P 4FNCN
Under an argon atmosphere, in 50ml three-necked flask, add raw material two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(7-cyano group-9,9-dioctyl fluorene-2-) amine (0.755g, 0.55mmol), 2,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy borine-2-)-9,9-dioctyl fluorene (0.358g, 0.55mmol), Et
4nOH2ml, and dilute with deionized water 2ml, catalyst P d (pph
3)
4(8.4mg, 0.0073mmol), toluene 10ml.Lead to and be warming up to 90 ~ 100 DEG C gradually after Ar30 minute, react 48 hours.Naturally cooling, adds phenylo boric acid (11.2mg, 0.0918mmol), toluene 3ml, reacts 12 hours.After naturally cooling, add 1ml bromobenzene (9.6mmol), react 12 hours.Dissolve dope with toluene, and with methanol extraction, filter, vacuum drying.Then methyl alcohol, acetone, THF extracting 24 hours are used respectively.Concentrated, precipitate in methyl alcohol, filter, vacuum-drying.Obtain 0.770g, yield 79.6%.
1HNMR(300MHz,CDCl
3),δ(ppm):7.88-7.78(m,2H),7.77-7.52(m,15H),7.37-7.27(m,4H),7.17-7.02(m,3H),2.30-1.75(m,16H),1.40-1.00(m,80H),0.99-0.48(m,40H).
The Absorption and fluorescence spectrum of this polymeric film is shown in Fig. 3, Fig. 4.
Device implementation step is with embodiment 1.Device performance is as follows: trigger voltage 3.5 volts, high-high brightness 1133cd/m
2, maximum current efficiency is 1.16cd/A, maximum external quantum efficiency 1.21%, and chromaticity coordinates (CIE) is (0.173,0.245).The device performance not adding TPBI is as follows: trigger voltage 3.5 volts, high-high brightness 1265cd/m
2, maximum current efficiency is 0.71cd/A, maximum external quantum efficiency 0.74%, and chromaticity coordinates (CIE) is (0.226,0.284).Its electroluminescent spectrum is shown in Fig. 5, Fig. 6.
Embodiment 3
The first seven the first seven walking with embodiment 1 of the present embodiment walks.
Step 8: the preparation of 2-carbazole-7-nitro-9,9-dioctyl fluorene
By 3,5-under an argon atmosphere, adds bromo-9, the 9-dioctyl fluorene (1.03g of 2-nitro-7-in 50ml three-necked flask, 2mmol), carbazole (0.334g, 2mmol), salt of wormwood (0.849g, 6mmol), dimethyl sulfoxide (DMSO) 30ml, copper powder (5g, 78mmol).After stirring, be warming up to 150 DEG C of reactions 12 hours.After cooling, with dichloromethane extraction, and wash three times with saturated common salt, the organic over anhydrous dried over mgso of gained.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and moving phase used is methylene dichloride/sherwood oil=1:8, and removing raw material point, methylene dichloride/sherwood oil=1:4, collects second point.Obtain yellow-brown solid 0.320g.Yield 26.7%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.36-8.34(m,1H),8.28(s,1H),8.20(d,2H),8.04-8.02(m,1H),7.91-7.88(m,1H),7.67-7.63(m,2H),7.45(s,4H),7.37-7.32(m,2H),2.09(m,4H),1.28-1.12(m,20H),0.85-0.80(t,6H),0.74(m,4H).
Step 10: the preparation of 2-amido-7-carbazole-9,9-dioctyl fluorene
The same step 3 of method, only need replace 2-nitro-9,9-dioctyl fluorene with 2-carbazole-7-nitro-9,9-dioctyl fluorene (0.32g, 0.53mmol), obtain bluish yellow look viscous body 0.179g, yield 58.9%.
1HNMR(300MHz,DMSO),δ(ppm):8.24(m,2H),7.76(m,1H),7.52(m,2H),7.41(m,3H),7.30(m,4H),6.60(m,2H),5.30(s,2H),2.10-1.75(m,4H),1.40-0.90(m,20H),0.90-0.500(m,10H).
The preparation of step 11: two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(7-(9-carbazole)-9,9-dioctyl fluorene-2-) amine
Under argon atmosphere, toward in 50ml there-necked flask, add bromo-9, the 9-dioctyl fluorene (0.966g, 1.75mmol) of 2,7-bis-, 2-amido-7-carbazole-9,9-dioctyl fluorene (0.179g, 0.35mmol), dissolves with 15ml toluene.Add Pd again
2(dba)
3(0.0090g, 0.00875mmol), DPPF (0.0214g, 0.035mmol),
tbuONa (0.390g, 3.48mmol).React 24 hours at 110 DEG C.After naturally cooling, be extracted with ethyl acetate, and have saturated brine It 3 times, gained organic over anhydrous dried over mgso.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and moving phase used is sherwood oil/methylene dichloride=1:6,1:3.Vacuum-drying, obtain the orange-yellow viscous body 0.325g of product, yield is 68.9%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.19-8.16(m,2H),7.80(m,1H),7.63-7.60(m,1H),7.54-7.42(m,12H),7.32-7.26(m,4H),7.26-7.25(m,3H),7.05-7.03(m,3H).1.88(m,12H),1.25-1.09(m,60H),0.86-0.68(m,30H).
Step 12: the preparation of polymer P 4FNCz
Under an argon atmosphere, in 50ml three-necked flask, add raw material two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(7-(9-carbazole)-9,9-dioctyl fluorene-2-) amine (0.246g, 0.163mmol), 2,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy borine-2-)-9,9-dioctyl fluorene (0.106g, 0.163mmol), Et
4nOH1ml, and dilute with deionized water 1ml, add catalyst P d (pph
3)
4(0.0048g, 0.00415mmol), toluene 5ml, leads to and is warming up to 90 ~ 100 DEG C gradually after Ar30 minute, react 48 hours.Naturally cooling, adds phenylo boric acid (11.2mg, 0.0918mmol), toluene 2ml, reacts 12 hours.After naturally cooling, add 1ml bromobenzene (9.6mmol), react 12 hours.Dissolve the dope of gained with toluene, and with methanol extraction, dry.Then methyl alcohol, acetone, tetrahydrofuran (THF) extracting 24 hours are used respectively, concentrated, precipitate in methyl alcohol, filter, vacuum-drying.Obtain 0.233g, yield 75.5%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.20-8.16(m,2H),7.90-7.75(m,4H),7.74-7.57(m,12H),7.56-7.48(m,3H),7.47-7.37(m,5H),7.36-7.27(m,4H),7.20-6.90(m,2H),2.30-1.80(m,16H),1.40-1.00(m,80H),0.99-0.50(m,40H).
The Absorption and fluorescence spectrum of this polymeric film is shown in Fig. 3, Fig. 4.
Device implementation step is with embodiment 1.The performance of this device is as follows: trigger voltage 3.0 volts, high-high brightness 1265cd/m
2, maximum current efficiency is 1.34cd/A, maximum external quantum efficiency 1.67%, and chromaticity coordinates (CIE) is (0.164,0.125).The device performance not adding TPBI is as follows: trigger voltage 3.0 volts, high-high brightness 1241cd/m
2, maximum current efficiency is 0.49cd/A, maximum external quantum efficiency 0.62%, and chromaticity coordinates (CIE) is (0.192,0.220).Its electroluminescent spectrum is shown in Fig. 5, Fig. 6.
Embodiment 4
Front ten steps of the present embodiment are with ten steps before embodiment 2.
The preparation of step 11: two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(7-(2-oxadiazoles (5-benzene))-9,9-dioctyl fluorene-2-) amine
Under argon atmosphere, two (the 7-bromo-9 newly steaming DMF dissolving with 30ml are added in 50ml there-necked flask, 9-dioctyl fluorene-2-)-(7-cyano group-9,9-dioctyl fluorene-2-) amine (0.7397g, 0.542mmol), sodium azide (0.224g, 3.45mmol), ammonium chloride (0.1953g, 3.65mmol).After stirring, react 36 hours at 100 DEG C.Naturally cooling, adds hydrochloric acid to acid, has solid to separate out.Suction filtration, finds that the filtrate of gained also has product.So, select extraction into ethyl acetate, and have saturated brine It 3 times, gained organic over anhydrous dried over mgso.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and after moving phase (sherwood oil/methylene dichloride=1:6 removes raw material and reclaims, and 1:4 obtains product point) used is spin-dried for, vacuum-drying, obtains intermediate tetrazolium 0.3652g.In 50ml there-necked flask, under argon atmosphere, dissolved by tetrazolium (0.342g, 0.24mmol) 40ml anhydrous pyridine, drip Benzoyl chloride (2ml, 4.26mmol), color becomes orange-yellow, refluxes 3 days.Naturally cooling, is extracted with ethyl acetate, and with saturated brine It 3 times, gained organic over anhydrous dried over mgso.Suction filtration, the filtrate of gained is under reduced pressure except desolventizing.Post is separated, and moving phase: sherwood oil/methylene dichloride=10:1,8:1,6:1,5:1,4:1, be spin-dried for, vacuum-drying obtains 0.413g, and two-step reaction average yield is 51.4%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.20-8.17(m,2H),8.11-8.09(m,2H),7.75-7.72(m,1H),7.61-7.43(m,11H),7.27-7.26(m,2H),7.25-7.24(m,2H),7.04-7.01(m,3H),2.07-1.80(m,12H),1.43-1.08(m,60H),0.99-0.69(m,30H).
Step 12: the preparation of polymer P 4FNOXDPh
Under an ar atmosphere, in 50ml three-necked flask, add raw material two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(7-(2-oxadiazoles (5-benzene))-9,9-dioctyl fluorene-2-) amine (0.2986g, 0.20mmol), 2,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy borine-2-)-9,9-dioctyl fluorene (0.1306g, 0.20mmol), Et
4nOH1.5ml, and dilute with deionized water 1.5ml, catalyst acetic acid palladium 1.9mg, thricyclohexyl phosphorus 4.0mg toluene 7ml.Lead to and be warming up to 90 ~ 100 DEG C gradually after Ar30 minute.React 48 hours.Naturally cooling, adds phenylo boric acid (0.0107g, 0.0088mmol), toluene 2ml, reacts 10 hours.Naturally cooling, adds bromobenzene (0.5ml, 4.8mmol), reacts 10 hours.Naturally cooling, with methanol extraction, filter, vacuum-drying, then uses methyl alcohol, acetone, THF extracting 24 hours respectively, concentrated, with methanol extraction, filters, vacuum-drying.Obtain 246.3mg, yield 65.4%.
1HNMR(300MHz,CDCl
3),δ(ppm):8.24-8.04(m,4H),7.87-7.50(m,18H),7.40-7.27(m,4H),7.16-7.03(m,3H),2.30-1.76(m,16H),1.40-1.00(m,80H),0.99-0.43(m,40H).
The Absorption and fluorescence spectrum of this polymeric film is shown in Fig. 3, Fig. 4.
Device implementation step is with embodiment 1.The performance of this device is as follows: trigger voltage 2.9 volts, high-high brightness 4824cd/m
2, maximum current efficiency is 4.1cd/A, maximum external quantum efficiency 2.8%, and chromaticity coordinates (CIE) is (0.181,0.301).The device performance not adding TPBI is as follows: trigger voltage 3.0 volts, high-high brightness 4456cd/m
2, maximum current efficiency is 1.05cd/A, maximum external quantum efficiency 0.66%, and chromaticity coordinates (CIE) is (0.193,0.352).Its electroluminescent spectrum is shown in Fig. 5, Fig. 6.
Embodiment 5
The first eight the first eight walking with embodiment 1 of the present embodiment walks.
Step 9: the preparation of polymer P SFOFN5
Under an ar atmosphere, in 50ml three-necked flask, add raw material two (bromo-9, the 9-dioctyl fluorene-2-of 7-)-(9,9-dioctyl fluorene-2-) amine (0.0671g, 0.05mmol), 2,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy borine-2-)-9,9-dioctyl fluorene (0.3239g, 0.50mmol), bromo-9, the 9-dioctyl fluorene (0.1912g of 2,7-bis-, 0.35mmol), 2,7-dibromo dibenzothiophene-S, S-dioxy (0.0383mg, 0.10mmol), Et
4nOH1.7ml, and dilute with deionized water 1.7ml, catalyst acetic acid palladium 1.8mg, thricyclohexyl phosphorus 6.4mg, toluene 8ml.Lead to and be warming up to 90 ~ 100 DEG C gradually after Ar30 minute.React 48 hours.Naturally cooling, adds phenylo boric acid (0.0157g, 0.0129mmol), toluene 2ml, reacts 10 hours.Naturally cooling, adds bromobenzene (0.5ml, 4.8mmol), reacts 10 hours.Naturally cooling, with methanol extraction, filter, vacuum-drying, then uses methyl alcohol, acetone, THF extracting 24 hours respectively, concentrated, with methanol extraction, filters, vacuum-drying.Obtain 219.2mg.
1HNMR(300MHz,CDCl
3),δ(ppm):8.20-7.90(m,4H),7.89-7.79(m,7H),7.78-7.50(m,14H),2.12(m,16H),1.33-1.03(m,80H),0.96-0.50(m,40H).
The Absorption and fluorescence spectrum of this polymeric film is shown in Fig. 9, Figure 10 respectively.
Embodiment 6
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3), (ppm):7.83(m,7H),7.72-7.61(m,16H),7.49-7.47(m,1H),7.38-7.28(m,1H),2.11(m,16H),1.25-0.96(m,80H),0.84-0.50(m,40H).
Embodiment 7
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):7.89-7.78(m,7H),7.77-7.55(m,16H),7.52-7.47(m,1H),7.40-7.28(m,1H),2.11(m,16H),1.30-0.98(m,80H),0.96-0.50(m,40H).
Embodiment 8
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):7.88-7.80(m,6H),7.79-7.52(m,16H),7.45-7.29(m,3H),2.27(m,16H),1.35-1.02(m,80H),0.98-0.50(m,40H).
Device implementation step is with embodiment 1.The performance of this device is as follows: trigger voltage 3.2 volts, high-high brightness 2465cd/m
2, maximum current efficiency is 3.36cd/A, maximum external quantum efficiency 4.64%, and chromaticity coordinates (CIE) is (0.152,0.102).The device performance not adding TPBI is as follows: trigger voltage 3.2 volts, high-high brightness 7695cd/m
2, maximum current efficiency is 1.68cd/A, maximum external quantum efficiency 1.97%, and chromaticity coordinates (CIE) is (0.182,0.198).
Embodiment 9
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):8.20-7.95(m,3H),7.94-7.77(m,7H),7.76-7.54(m,15H),2.11(m,16H),1.33-1.03(m,80H),0.96-0.50(m,40H).
Embodiment 10
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):7.89-7.77(m,5H),7.76-7.51(m,15H),7.40-7.27(m,3H),7.19-6.81(m,2H),2.10(m,16H),1.33-1.01(m,80H),0.93-0.50(m,40H).
Embodiment 11
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):7.90-7.76(m,5H),7.75-7.51(m,14H),7.41-7.28(m,4H),7.17-6.95(m,2H),2.10(m,16H),1.32-1.01(m,80H),0.95-0.50(m,40H).
Embodiment 12
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):7.91-7.75(m,4H),7.74-7.53(m,15H),7.42-7.29(m,4H),7.23-7.07(m,2H),2.08(m,16H),1.31-1.01(m,80H),0.92-0.50(m,40H).
Embodiment 13
This implementation step is with embodiment 5, and the proportioning of monomer used sees table 1.
1HNMR(300MHz,CDCl
3),δ(ppm):7.89-7.76(m,3H),7.75-7.51(m,14H),7.41-7.29(m,5H),7.18-6.97(m,3H),2.08(m,16H),1.32-1.01(m,80H),0.95-0.50(m,40H).
Table 1
As can be seen from Fig. 1, Fig. 2, four kinds of polymer P 4FN, P4FNCN, P4FNCz, the P4FNOXDPh maximum absorption band in toluene solution is all at about 410nm, and its fluorescence spectrum main peak is all in blue light region.As can be seen from Fig. 7, Fig. 8, the maximum absorption band of polymer P SFOFN1 ~ PSFOFN50 in toluene solution is at about 390nm, its fluorescence spectrum main peak is in blue light region, and along with the increase of three fluorenamine compounds contents in polymkeric substance, Absorption and fluorescence spectrum all shows certain red shift.As can be seen from Fig. 3, Fig. 4, the maximum absorption band of these four kinds of polymkeric substance under solid film state is all at about 220nm, and its fluorescence spectrum main peak is all in blue light region.And find out from Fig. 9, Figure 10, under solid film state, along with the increase of three fluorenamine compounds contents in polymer P SFOFN1 ~ PSFOFN50, its maximum absorption band changes to about 220nm from about 390nm, present certain regularity, its fluorescence spectrum main peak is in blue light region.As can be seen from Fig. 5, Fig. 6, Figure 11, Figure 12, the electroluminescent spectrum main peak of this series polymer is all in blue light region.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (14)
1. the preparation method of three fluorenamine polymer luminescent materials, is characterized in that, comprise the steps:
Suzuki linked reaction is adopted to prepare polymkeric substance, 9 are added in nitrogen or argon gas atmosphere downhill reaction bottle, 2 of 9-dialkyl fluorene, the two boric acid ester of 7-, three fluorenamine compounds, when adding y part three fluorenamine compound, 0 < y≤0.5, then add 0.5 part 9, 2 of 9-dialkyl fluorene, the two boric acid ester of 7-and (0.5-y) part 2, 7-bis-bromo-9, 9-dioctyl fluorene is dissolved in the toluene of 30 ~ 150 times that are equivalent to above-mentioned reactant mole total amount, add again and be equivalent to the tetraethyl ammonium hydroxide aqueous solution of above-mentioned reactant mole total amount 1 ~ 10 times and the catalyzer of 1% ~ 10%, stirring reaction 12 ~ 48 hours under reflux, after naturally cooling, then carry out end capping, reaction terminates, and naturally cooling, goes out polymkeric substance with methanol extraction, and dried product uses methyl alcohol, acetone, tetrahydrofuran (THF) extracting 24 hours respectively, concentrated extract, and precipitate in methyl alcohol, final product is dry under vacuo, obtained luminescent material,
The chemical structure of described three fluorenamine compounds is as follows:
Wherein: R
1be alkyl or the alkoxyl group of lyotropy, carbonatoms is 1 ~ 20; The structure of X is as follows:
h,
or-CN.
2. preparation method according to claim 1, is characterized in that, described Ar has following structure:
3. preparation method according to claim 2, is characterized in that, the preparation method of described three fluorenamine compounds, comprises the steps:
2-amido-9 is added in argon atmosphere downhill reaction bottle, 9-dioctyl fluorene inductor and be equivalent to 2-amido-9,5 times of 9-dioctyl fluorene inductor molar weight 2,7-bis-bromo-9,9-dioctyl fluorene, and with toluene dissolve, then add be equivalent to 2-amido-9,9-dioctyl fluorene inductor molar weight 1/40 Pd
2(dba)
3the t-BuONa of DPPF and 10 times of 1/10, reacts 24 ~ 36 hours under reflux, and reaction terminates rear naturally cooling, be extracted with ethyl acetate, and with saturated brine It, gained organic over anhydrous dried over mgso, suction filtration, the filtrate of gained is under reduced pressure except desolventizing, be separated by chromatographic column, steam and desolventize and vacuum-drying, obtain three fluorenamine compounds.
4. the preparation method according to claim 1 or 2 or 3, is characterized in that, described catalyzer is the mixing of one or more that four (triphenyl phosphorus) close in palladium, palladium and thricyclohexyl phosphorus.
5. the preparation method of three fluorenamine polymer luminescent materials, is characterized in that, comprise the steps:
Suzuki linked reaction is adopted to prepare polymkeric substance, 9 are added in nitrogen or argon gas atmosphere downhill reaction bottle, 2 of 9-dialkyl fluorene, the two boric acid ester of 7-, three fluorenamine compounds, dibromo dibenzothiophene-S, S-dioxy and 2, 7-bis-bromo-9, 9-dioctyl fluorene is dissolved in the toluene of 30 ~ 150 times that are equivalent to above-mentioned reactant mole total amount, when adding y part three fluorenamine compound, 0 < y < 0.5, z part dibromo dibenzothiophene-S, S-dioxy, 0 < z < 0.5, y+z≤0.5, then add 0.5 part 9, 2 of 9-dialkyl fluorene, the two boric acid ester of 7-and (0.5-y-z) part 2, 7-bis-bromo-9, 9-dioctyl fluorene, add again and be equivalent to the tetraethyl ammonium hydroxide aqueous solution of above-mentioned reactant mole total amount 1 ~ 10 times and the catalyzer of 1% ~ 10%, stirring reaction 12 ~ 48 hours under reflux, after naturally cooling, then carry out end capping, reaction terminates, and naturally cooling, goes out polymkeric substance with methanol extraction, and dried product uses methyl alcohol, acetone, tetrahydrofuran (THF) extracting 24 hours respectively, concentrated extract, and precipitate in methyl alcohol, final product is dry under vacuo, obtained luminescent material,
The chemical structure of described three fluorenamine compounds is as follows:
Wherein: R
1be alkyl or the alkoxyl group of lyotropy, carbonatoms is 1 ~ 20; The structure of X is as follows:
h,
or-CN.
6. preparation method according to claim 5, is characterized in that, described Ar has following structure:
7. preparation method according to claim 6, is characterized in that, the preparation method of described three fluorenamine compounds, comprises the steps:
2-amido-9 is added in argon atmosphere downhill reaction bottle, 9-dioctyl fluorene inductor and be equivalent to 2-amido-9,5 times of 9-dioctyl fluorene inductor molar weight 2,7-bis-bromo-9,9-dioctyl fluorene, and with toluene dissolve, then add be equivalent to 2-amido-9,9-dioctyl fluorene inductor molar weight 1/40 Pd
2(dba)
3the t-BuONa of DPPF and 10 times of 1/10, reacts 24 ~ 36 hours under reflux, and reaction terminates rear naturally cooling, be extracted with ethyl acetate, and with saturated brine It, gained organic over anhydrous dried over mgso, suction filtration, the filtrate of gained is under reduced pressure except desolventizing, be separated by chromatographic column, steam and desolventize and vacuum-drying, obtain three fluorenamine compounds.
8. the preparation method according to claim 5 or 6, is characterized in that, described catalyzer is the mixing of one or more that four (triphenyl phosphorus) close in palladium, palladium and thricyclohexyl phosphorus.
9. the three fluorenamine polymer luminescent materials prepared of Claims 1 to 4 any one method.
10. three fluorenamine polymer luminescent materials according to claim 9, it is characterized in that, this material has following chemical structure:
Wherein: R
2various substituted radicals, n=10 ~ 1000, R
3for alkyl.
The 11. three fluorenamine polymer luminescent materials prepared according to any one of claim 5 ~ 8 method.
12. three fluorenamine polymer luminescent materials according to claim 11, it is characterized in that, this material has following chemical structure:
Wherein: R
2various substituted radicals; N=10 ~ 1000, R
3for alkyl.
13., according to luminescent material described in claim 12, is characterized in that, as 0.01≤y < 0.5, and z=0.1; Described R
2for H.
14. application of luminescent material according to any one of claim 9 ~ 13, it is characterized in that, this materials application is in polymer electroluminescence LED lighting layer.
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