CN1330735C - Highly effective two-color white light high polymer material and method for making same - Google Patents
Highly effective two-color white light high polymer material and method for making same Download PDFInfo
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- CN1330735C CN1330735C CNB2005101190837A CN200510119083A CN1330735C CN 1330735 C CN1330735 C CN 1330735C CN B2005101190837 A CNB2005101190837 A CN B2005101190837A CN 200510119083 A CN200510119083 A CN 200510119083A CN 1330735 C CN1330735 C CN 1330735C
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- 239000002861 polymer material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 16
- MTVYKNXTXQBOLR-UHFFFAOYSA-N 4-methyl-N-[4-[4-[4-(N-(4-methylphenyl)anilino)phenyl]-2,1,3-benzothiadiazol-7-yl]phenyl]-N-phenylaniline Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C1=CC=C(C2=NSN=C21)C1=CC=C(C=C1)N(C1=CC=CC=C1)C1=CC=C(C=C1)C MTVYKNXTXQBOLR-UHFFFAOYSA-N 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- -1 4,7-bis(4-(N-(4-bromophenyl)-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole Chemical compound 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 4
- JKYPBYBOZSIRFW-UHFFFAOYSA-N 3-(4-chlorophenyl)oxolane-2,5-dione Chemical compound C1=CC(Cl)=CC=C1C1C(=O)OC(=O)C1 JKYPBYBOZSIRFW-UHFFFAOYSA-N 0.000 claims 3
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- GQTSHMNLOIRGSK-UHFFFAOYSA-N C(CCC)[Sn](C1=CC=C(C=C1)N(C1=CC=C(C=C1)C)C1=CC=CC=C1)(CCCC)CCCC Chemical compound C(CCC)[Sn](C1=CC=C(C=C1)N(C1=CC=C(C=C1)C)C1=CC=CC=C1)(CCCC)CCCC GQTSHMNLOIRGSK-UHFFFAOYSA-N 0.000 claims 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- SFLXUZPXEWWQNH-UHFFFAOYSA-K tetrabutylazanium;tribromide Chemical compound [Br-].[Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC SFLXUZPXEWWQNH-UHFFFAOYSA-K 0.000 claims 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 12
- 239000002356 single layer Substances 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 229920002098 polyfluorene Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 150000002220 fluorenes Chemical class 0.000 description 12
- 125000003368 amide group Chemical group 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WONCHGDEGMFLPR-UHFFFAOYSA-N [Cl-].[NH4+].CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC Chemical compound [Cl-].[NH4+].CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC WONCHGDEGMFLPR-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VHHWAUKXFGPSRM-UHFFFAOYSA-N 1-bromo-9h-fluorene Chemical class C12=CC=CC=C2CC2=C1C=CC=C2Br VHHWAUKXFGPSRM-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- ZMBCGFSFPFQLJE-UHFFFAOYSA-N C1(=CC=CC=C1)N(C1=CC=C(C=C1)CN)C1=CC=C(C=C1)[Sn] Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)CN)C1=CC=C(C=C1)[Sn] ZMBCGFSFPFQLJE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical group C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
本发明涉及高效双色白光高分子材料及其制备方法，属于发光材料技术领域。本发明的高效双色白光高分子材料的化学结构式如下：其中，x＝0.00001-0.5。该发光材料的制备方法是以聚芴为蓝光构造单元，4，7-二(4-(N-苯基-N-(4-甲基苯基)氨基)苯基)-2，1，3-苯并噻二唑为橙光构造单元，通过共聚合的方式，将橙光工作单元以化学键的形式引入到蓝光高分子主链中，制得高效双色白光高分子材料。其单层器件的流明效率达到8.99cd/A。可用于背景光源和照明光源。
The invention relates to a high-efficiency two-color white light polymer material and a preparation method thereof, belonging to the technical field of luminescent materials. The chemical structural formula of the high-efficiency two-color white light polymer material of the present invention is as follows: wherein, x=0.00001-0.5. The preparation method of the luminescent material uses polyfluorene as the blue light structural unit, 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3 - Benzothiadiazole is the orange light construction unit, and the orange light working unit is introduced into the main chain of the blue light polymer in the form of chemical bonds by means of copolymerization to prepare a high-efficiency two-color white light polymer material. The lumen efficiency of its single-layer device reaches 8.99cd/A. Can be used for background lighting and illumination lighting.
Description
Technical field
The invention belongs to highly effective two-color white light high polymer material and preparation method thereof.
Technical background
Since nineteen ninety univ cambridge uk people such as Burroughs report the electro optical phenomenon of poly-phenylene vinylene (ppv) (PPV) first since, high molecule electroluminescent material and device (PLED) since have technology simple, with low cost, be easy to realize that outstanding features such as large screen display and flexible demonstrations have been subjected to people's extensive concern and input competitively.Up to the present, redness, green, blue high-molecular luminous material have reached the requirement of practicability; By contrast, every performance index of white high-molecular luminous material, comprise efficient, life-span, chromaticity coordinates etc., also have very big gap from practicability, and white high-molecular luminous material and device have boundless application prospect at aspects such as background light source, lighting source, panchromatic demonstrations.
Common white high molecule electroluminescent device is taked co-mixing system, the physical blending that mainly comprises two kinds of organic/polymer dyestuffs (blue light and orange photoinitiator dye) or three kinds of organic/polymer dyestuffs (blue light, green glow and red dye) is achieved, but has practical problemss such as color instability (color obviously depends on driving voltage) and luminous efficiency are lower by the white high molecule electroluminescent device that co-mixing system obtains.In previous research work, the contriver has proposed to realize by chemical doping (organic dye molecule disperses at the molecular level of high-molecular luminous material) new way of single polymer emission colour stable white light, promptly introduces the single white light high polymer system of a spot of orange luminescence unit structure molecule dispersion type in the blue light polymer.This breakthrough has promoted the further investigation and the practicalization of white light high polymer material and device.For example: by in the poly-fluorenes high-molecular luminous material of blue light, introducing a spot of orange light naphthalimide unit, obtained the highly stable white electroluminescent macromolecule of spectrum, the efficient of its single layer device reaches 3.8cd/A, chromaticity coordinates is (0.35,0.32), but its efficient from practicability still have very big distance (Chinese patent application number: 200410010770.0, Application No.: 11/042,193).
Summary of the invention
The objective of the invention is to bring into play the outstanding advantage that single polymer can be realized the colour stable white light emission, by improving orange photoinitiator dye luminous efficiency, overcome the lower shortcoming of white light high polymer material and device efficiency, molecule dispersion type two-color white light high polymer material of a kind of efficient, colour stable and preparation method thereof is provided.
A kind of highly effective two-color white light high polymer material of the present invention is to be the blue light tectonic element with poly-fluorenes, with 4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the 3-diazosulfide is orange light tectonic element, by the mode of copolymerization, the form of orange light tectonic element with chemical bond is incorporated in the blue light high polymer main chain, realize that the molecular level of orange light unit in the blue light polymer body disperses.By regulating the content of orange light tectonic element, realize that blue light polymer main body shifts to the unitary incomplete energy of orange light, and luminous when realizing blue light polymer main body and orange light tectonic element.By regulating the relative intensity of blue light and orange light, realize turning white look luminous highly effective two-color white light high polymer material then.
A kind of highly effective two-color white light high polymer material of the present invention is to be the blue light tectonic element with poly-fluorenes, with 4, and 7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the 3-diazosulfide is orange light tectonic element, its chemical structural formula is as follows:
Wherein, x=0.00001-0.5.
The preparation method of this two-color white light high polymer material is as follows:
(1) 9,9-dioctyl-2, the preparation of 7-dibromo fluorenes
In container, add 1 mole 2, the 1-bromooctane of 7-dibromo fluorenes, 2-10 mole, the Tetrabutyl amonium bromide of 0.02-0.10 mole and volume ratio are toluene and the water of 2-5,2, the quality of 7-dibromo fluorenes and the volume of toluene and water and ratio be 0.05-0.2g/ml; The sodium hydroxide that also adds the 3-50 mole, reaction is 12 hours under nitrogen protection, then reaction product is poured in the water, separates organic phase, and after the washed several times with water, dry, concentrated repeatedly, recrystallization obtains 9,9-dioctyl-2,7-dibromo fluorenes;
(2) .) 9,9-dioctyl-2, the preparation of 7-two (trimethylene boric acid ester group) fluorenes
Under nitrogen protection, 9,9-dioctyl-2, the preparation of 7-two (trimethylene boric acid ester group) fluorenes in container, add 1 mole 2,7-dibromo fluorenes and tetrahydrofuran (THF); 2, the ratio of the quality of 7-dibromo fluorenes and the volume of tetrahydrofuran (THF) is 0.05-0.2g/ml; Be cooled to-78 ℃, add the hexane solution of the n-Butyl Lithium of 2.0-2.5 mole then in the container; React after 1 hour, add the trimethyl borate of 2.0-3.0 mole again in the container; Room temperature reaction 15 hours; The dilute hydrochloric acid that adds the 2-10 mole then in the container; Room temperature reaction 1 hour.Reaction mixture is poured in the water, separated organic phase, after the washed several times with water, dry, concentrated, the solid that obtains dissolves with toluene repeatedly, and the volume ratio of solid quality and toluene is 0.05-0.20g/ml, adds 1 of 2-3 mole again, ammediol; Back flow reaction 12 hours obtains 9,9-dioctyl-2,7-two (trimethylene boric acid ester group) fluorenes
(3) 4,7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the preparation of 3-diazosulfide
Under nitrogen protection, in container, add 1 mole 4,7-two bromo-2,1, four (triphenylphosphines) of the tributyl of 3-diazosulfide, 2.0-3.0 mole (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl) tin, 0.01-0.02 mole close palladium and toluene; 4,7-two bromo-2,1, the quality of 3-diazosulfide and the volume ratio of toluene are 0.05-0.2g/ml; 100 ℃ were reacted 24 hours, and obtained 4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1,3-diazosulfide;
In container, add 1 mole 4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the tetrabutyl tribromide ammonium and the methylene dichloride of 3-diazosulfide, 0.05-1.0 mole; 4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the ratio of the quality of 3-diazosulfide and the volume of methylene dichloride is 0.02-0.10g/ml; Reacted 2 hours, and obtained 4,7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amino) phenyl)-2,1,3-diazosulfide.
(4) preparation of two-color white light high polymer material
Under nitrogen protection, in container, add 1 mole 9,9-dioctyl-2,9 of 7-two (trimethylene boric acid ester group) fluorenes, 0-0.99998 mole, 9-dioctyl-2,4 of 7-dibromo fluorenes, 0.00002-1 mole, 7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the wet chemical of methyl trioctylphosphine ammonium chloride, toluene and 2 mol of 3-diazosulfide, 0.03-0.1 mole: 9.9-dioctyl-2.7-two (the trimethylene boric acid ester group) quality of fluorenes and the volume ratio of toluene are 0.01-0.10g/ml; The volume ratio of toluene and wet chemical is 3-7; Nitrogen protection and 50-100 ℃, four (triphenylphosphines) that add the 0.0001-0.10 mole close palladium; Stirring reaction 24-120 hour, through chloroform extraction, washing, drying, concentrate, methyl alcohol sedimentation, solvent extraction and vacuum-drying, obtain fibrous two-color white light high polymer material at last.
The contriver selects 4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, and the 3-diazosulfide is orange light tectonic element, and poly-fluorenes is the blue light tectonic element, and the method by copolymerization has obtained high efficiency white light polymkeric substance.The present invention has improved the electroluminescent efficiency of white light polymkeric substance on the basis of the advantage of performance white light polymkeric substance spectrum-stable, individual layer electroluminescent device performance is as follows: trigger voltage 3.5V, high-high brightness 12300cd/m
2, electroluminescent maximum lumen efficient is 8.99cd/A, maximum power efficiency is 5.75lm/W.Make the efficient of white light polymer monolayers device reach the requirement of practicability substantially.The characteristics of this white light polymkeric substance are the electroluminescent efficiency height, and energy consumption is low, electroluminescent spectrum-stable, and device preparation technology is simple, and cost is low.Can share the full color that realizes the polymer electroluminescence diode with spectral filter and show, also can also can be used as illumination as the background light source material of liquid-crystal display.
Description of drawings
Fig. 1 is solid-state absorption spectrum and the fluorescence emission spectrum of two-color white light high polymer P1.
Fig. 2 is the luminous efficiency and the power efficiency (device architecture: ITO/PEDOT/P1/Ca/Al) of the single layer device of two-color white light high polymer P1.
Fig. 3. be the electroluminescent spectrum (device architecture: ITO/PEDOT/P1/Ca/Al) of standard single layer device under different driving voltage of two-color white light high polymer P1.
Embodiment
Embodiment 1:4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amino) phenyl)-2,1, the preparation of 3-diazosulfide
Under the nitrogen atmosphere protection, with 4,7-two bromo-2; 1, and the 3-diazosulfide (1.47g, 5.0mmol); tributyl (4-(N-phenyl-N-(4-aminomethyl phenyl) amido)-phenyl) tin (6.03g; 11mmol), four (triphenylphosphines) close palladium (0.057g, 0.05mmol); the mixture of toluene (100ml) reacted 30 hours down at 100 ℃; then reaction mixture is poured in the potassium fluoride aqueous solution, chloroform extraction is washed three times then; dry; concentrate, post separates, and obtains pure intermediate product 4; 7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amido)-phenyl-)-2; 1,3-diazosulfide 2.340g, productive rate 72%.
Embodiment 2:4,7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amido)-phenyl-)-2,1,3-diazosulfide synthetic
Under the nitrogen atmosphere protection; with 4,7-two (4-(N-phenyl-N-(4-aminomethyl phenyl) amido)-phenyl-)-2,1; 3-diazosulfide (0.651g; 1mmol) be dissolved in the chloroform, add aluminum chloride, repeatedly add tetrabutyl tribromide ammonium (1.446g then in batches; 3mmol); added afterreaction 30 minutes, with reaction mixture with the aqueous solution of sodium bisulfite washing once, washing repeatedly then; dry; concentrate, post separates, and obtains pure intermediate product 4; 7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amido)-phenyl-)-2; 1,3-diazosulfide 0.751g, productive rate 93%.
Embodiment 3: two-color white light high polymer material P1's (structural formula is as follows) is synthetic
Under nitrogen protection, in reaction flask, add 9,9-dioctyl-2; 7-two bromo fluorenes (0.2740g; 0.4997mmol), 9,9-dioctyl-2; 7-(trimethylene boric acid ester group) fluorenes (0.2792g; 0.5mmol), 4,7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amido)-phenyl-)-2; 1; the 3-diazosulfide (0.0005g, 0.0006mmol), 2M wet chemical (2mL); toluene (10mL); the mixture of methyl trioctylphosphine ammonium chloride (0.13g) 80 ℃ of reactions ten minutes, adds four (triphenylphosphines) then and closes palladium in reaction flask; 90 ℃ of stirring reactions 48 hours, 60 ℃ of stirring reactions are 24 hours then.Reaction mixture dissolved with chloroform, washes repeatedly, and drying concentrates, and uses the methyl alcohol sedimentation then three times, and product is placed apparatus,Soxhlet's, with acetone extracting 24 hours.With the chloroform dissolving, sedimentation in methyl alcohol, product vacuum-drying get faint yellow polymer P 1 0.257g, productive rate 65% then.Product property is as follows: number-average molecular weight is 26,000, weight-average molecular weight 46,000.Film absorption spectrum and fluorescence spectrum that this polymkeric substance spin coating on quartz substrate is become are seen Fig. 1.
Embodiment 4: two-color white light high polymer material P2's (structural formula is as follows) is synthetic
Under nitrogen protection; in reaction flask, add 9,9-dioctyl-2,7-two bromo fluorenes (0.2742g; 0.49999mmol); 9,9-dioctyl-2,7-(trimethylene boric acid ester group) fluorenes (0.2792g; 0.5mmol); 4,7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amido)-phenyl-)-2,1; 3-diazosulfide (0.000008g; 0.00001mmol), 2M wet chemical (10mL), toluene (10mL); the mixture of methyl trioctylphosphine ammonium chloride (0.13g); 80 ℃ of reactions ten minutes, in reaction flask, add four (triphenylphosphines) then and close palladium, 90 ℃ of stirring reactions 48 hours.Reaction mixture dissolved with chloroform, washes repeatedly, and drying concentrates, and uses the methyl alcohol sedimentation then three times, and product is placed apparatus,Soxhlet's, with acetone extracting 24 hours.With the chloroform dissolving, sedimentation in methyl alcohol, product vacuum-drying get faint yellow polymer P 20.268g, productive rate 69% then.
Embodiment 5: two-color white light high polymer material P3's (structural formula is as follows) is synthetic
Under nitrogen protection; in reaction flask, add 9; 9-dioctyl-2; 7-(trimethylene boric acid ester group) fluorenes (0.2792g; 0.5mmol); 4,7-two (4-(N-(4-bromophenyl)-N-(4-aminomethyl phenyl) amido)-phenyl-)-2,1; 3-diazosulfide (0.4043g; 0.5mmol) 2M wet chemical (2mL), toluene (10mL), the mixture of methyl trioctylphosphine ammonium chloride (0.013g); 80 ℃ of reactions ten minutes; in reaction flask, add four (triphenylphosphines) then and close palladium, 90 ℃ of stirring reactions 48 hours, 60 ℃ of stirring reactions are 24 hours then.Reaction mixture dissolved with chloroform, washes repeatedly, and drying concentrates, and uses the methyl alcohol sedimentation then three times, and product is placed apparatus,Soxhlet's, with acetone extracting 24 hours.With the chloroform dissolving, sedimentation in methyl alcohol, product vacuum-drying get faint yellow polymer P 30.280g, productive rate 54% then.
Embodiment 6: the purposes of two-color white light high polymer material P1
The luminescent layer that is used for the individual layer electroluminescent device with the polymer P 1 of embodiment 3 preparations as luminescent material, (device architecture is: assembling condition ITO/PEDOT/Polymer/Ca/Al) is: adopt the ito glass that cleans in advance is anode to the individual layer electroluminescent device, and spin coating one deck conducting polymer one polythiofuran derivative (PEDOT) (50nm) subsequently.ITO after PEDOT modifies after 3 hours, is that 10 grams per liters high molecular chloroformic solution under the condition of rotating speed 1500 rev/min be spin-coated on ITO surface with concentration 150 ℃ of following vacuum-dryings.Subsequently, under the condition of high vacuum, the calcium metal of evaporation 10nm and the metallic aluminium of 100nm.Individual layer electroluminescent device performance is as follows: trigger voltage 3.5V, and high-high brightness 12300cd/m2, electroluminescent maximum lumen efficient is 8.99cd/A, maximum power efficiency is 5.75lm/W.Its luminous efficiency and energy efficiency are seen Fig. 2.The electroluminescent spectrum of this device under different driving voltage seen Fig. 3, and their chromaticity coordinates is (0.35,0.34).
Embodiment 7: the purposes of two-color white light high polymer material P2
Be used for the luminescent layer of individual layer electroluminescent device with the polymer P 2 of embodiment 4 preparation as luminescent material, the assembling condition of individual layer electroluminescent device is as described in the embodiment 6.Individual layer electroluminescent device performance is as follows: trigger voltage 3.0V, high-high brightness 2600cd/m
2, electroluminescent maximum lumen efficient is 0.91cd/A, maximum power efficiency is (0.20,0.12) for the 0.63lm/W. chromaticity coordinates.
Embodiment 8: the purposes of two-color white light high polymer material P3
Be used for the luminescent layer of individual layer electroluminescent device with the polymer P 3 of embodiment 5 preparation as luminescent material, the assembling condition of individual layer electroluminescent device is as described in the embodiment 6.Individual layer electroluminescent device performance is as follows: trigger voltage 9.0V, high-high brightness 4320cd/m
2, electroluminescent maximum lumen efficient is 1.26cd/A, maximum power efficiency is (0.55,0.40) for the 0.33lm/W. chromaticity coordinates.
Claims (2)
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| US5876864A (en) * | 1996-12-31 | 1999-03-02 | Korea Institute Of Science And Technology | Fluorene-based alternating polymers containing acetylene group and electroluminescence element using the same |
| CN1337987A (en) * | 1999-02-04 | 2002-02-27 | 陶氏化学公司 | Fluorene copolymers and devices made therefrom |
| US6512083B1 (en) * | 1995-07-28 | 2003-01-28 | Dow Global Technologies Inc. | Fluorene-containing polymers and compounds useful in the preparation thereof |
| JP2003142268A (en) * | 2001-08-23 | 2003-05-16 | Tdk Corp | Organic el element |
| CN1580179A (en) * | 2004-03-29 | 2005-02-16 | 中国科学院长春应用化学研究所 | White electroluminescent polymer material and its preparing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6512083B1 (en) * | 1995-07-28 | 2003-01-28 | Dow Global Technologies Inc. | Fluorene-containing polymers and compounds useful in the preparation thereof |
| US5876864A (en) * | 1996-12-31 | 1999-03-02 | Korea Institute Of Science And Technology | Fluorene-based alternating polymers containing acetylene group and electroluminescence element using the same |
| CN1337987A (en) * | 1999-02-04 | 2002-02-27 | 陶氏化学公司 | Fluorene copolymers and devices made therefrom |
| JP2003142268A (en) * | 2001-08-23 | 2003-05-16 | Tdk Corp | Organic el element |
| CN1580179A (en) * | 2004-03-29 | 2005-02-16 | 中国科学院长春应用化学研究所 | White electroluminescent polymer material and its preparing method |
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