CN1295298C - Blue color electroluminescent macromolecular material and method for making same - Google Patents
Blue color electroluminescent macromolecular material and method for making same Download PDFInfo
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- CN1295298C CN1295298C CNB2004100113129A CN200410011312A CN1295298C CN 1295298 C CN1295298 C CN 1295298C CN B2004100113129 A CNB2004100113129 A CN B2004100113129A CN 200410011312 A CN200410011312 A CN 200410011312A CN 1295298 C CN1295298 C CN 1295298C
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- 238000000034 method Methods 0.000 title claims 2
- 239000000463 material Substances 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 38
- VHHWAUKXFGPSRM-UHFFFAOYSA-N 1-bromo-9h-fluorene Chemical class C12=CC=CC=C2CC2=C1C=CC=C2Br VHHWAUKXFGPSRM-UHFFFAOYSA-N 0.000 claims description 35
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 35
- -1 4-(phenylbenzene amido) phenyl Chemical group 0.000 claims description 33
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 239000004327 boric acid Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000002861 polymer material Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000012141 concentrate Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical class C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007818 Grignard reagent Substances 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 abstract description 2
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 abstract 5
- 239000002243 precursor Substances 0.000 abstract 2
- 238000005401 electroluminescence Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 150000002220 fluorenes Chemical class 0.000 description 13
- 239000013067 intermediate product Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 230000003252 repetitive effect Effects 0.000 description 10
- 238000005201 scrubbing Methods 0.000 description 10
- 239000002356 single layer Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 8
- 230000006698 induction Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 235000015320 potassium carbonate Nutrition 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- GWXQATMNIVLBQU-UHFFFAOYSA-N 1,4-dibromo-2-hexoxybenzene Chemical compound CCCCCCOC1=CC(Br)=CC=C1Br GWXQATMNIVLBQU-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 1
- VALXCIRMSIFPFN-UHFFFAOYSA-N 2,5-dibromobenzene-1,4-diol Chemical compound OC1=CC(Br)=C(O)C=C1Br VALXCIRMSIFPFN-UHFFFAOYSA-N 0.000 description 1
- APBIDAXJCGEEIS-UHFFFAOYSA-N 6-bromobenzo[de]isoquinoline-1,3-dione Chemical compound O=C1NC(=O)C2=CC=CC3=C2C1=CC=C3Br APBIDAXJCGEEIS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 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
- 230000005525 hole transport Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
The present invention relates to blue electroluminescent macromolecular material and a preparation method thereof. On the basis of the physical thought that a dark blue macromolecule can transfer effective energy to a blue light or blue green light fluorochrome molecules, blue light or blue green light fluorochrome molecular chemistry with high fluorescence quantum efficiency is grafted to a dark blue macromolecular precursor, the molecules are dispersed horizontally, the partial or complete energy transfer of the dark blue macromolecule to the blue light or blue green light fluorochrome molecule is realized by regulating the relative content of the blue light or blue green light fluorochrome molecule in the dark blue macromolecule precursor, theluminescence of the blue light or blue green light fluorochrome molecule is enhanced in order to realize the pure blue electroluminescence of the macromolecular material, and a class of molecule dispersion blue electroluminescent macromolecular material is constructed.
Description
Technical field
The present invention relates to blue electroluminescent polymer material and preparation method thereof.
Background technology
From nineteen ninety univ cambridge uk people such as Burroughs report the electro optical phenomenon of poly-(phenylenevinylene) first since, high molecule electroluminescent material and device since have technology simple, with low cost, be easy to realize that outstanding features such as large screen display and flexible demonstrations are subjected to the extensive concern of academia and industrial community and input competitively.In order to realize the panchromatic demonstration of macromolecular LED, press for the electroluminescent macromolecule material that exploitation can be launched red-green-blue.At present, ruddiness and green glow macromolecular material have reached the requirement of practicability, and every index of blue light macromolecular material, comprise chromaticity coordinates, efficient, life-span, from practicability bigger gap is arranged still, therefore, become one of main bottleneck of restriction macromolecular LED display screen industrialization.
Poly-fluorenes and derivative thereof are the high molecular typical case's representatives of blue light, have good light, heat and chemical stability, are considered to one of polymer blue light material that has most application potential.In order to improve poly-fluorenes and derivative EL efficiency thereof, take usually on the main chain of polymkeric substance or end group, to introduce the carrier transport unit, by realizing the carrier balance of electroluminescent device, reach the purpose that improves its electroluminescent efficiency.For example: U.S. Dow Chemical company is by introducing three arylamine unit with hole transport performance in the main chain of poly-fluorenes, having obtained electroluminescent efficiency is poly-fluorenes family macromolecule material (the Microelectronics Journal of blue light of 2.82cd/A, 35,343-348,2004).Germany U.Scherf research group prepares the unit terminated poly-fluorenes high-molecular luminous material of three arylamine, and its electroluminescent efficiency can reach 1.1cd/A (Advanced Materials 13,565-570,2001).
Summary of the invention
The purpose of this invention is to provide a class blue electroluminescent polymer material;
Another object of the present invention provides a kind of preparation method of blue electroluminescent polymer material.
The present invention is based on the mazarine polymer can be to the physical thought of blue light or the transfer of blue green light luminescent dye molecule generation useful energy, the blue light or the blue green light luminescent dye molecule chemical graft that will have high fluorescence quantum efficiency arrive mazarine polymer parent, realize that blue light or the blue green light luminescent dye molecule molecular level in mazarine polymer parent disperses, by regulating blue light or blue green light luminescent dye molecule relative content at mazarine polymer parent, realize that the mazarine polymer shifts to the partially or completely energy of blue light or blue green light luminescent dye molecule, it is luminous to strengthen blue light or blue green light luminescent dye molecule, then realize the pure blue electroluminescent of macromolecular material, construct molecule decentralized blue electroluminescent polymer material.
Molecule dispersion type blue electroluminescent polymer material provided by the present invention has a kind of in following two kinds of structures:
Wherein: R
1For hexyl, octyl group, carbonatoms is phenyl, 4-(phenylbenzene amido) phenyl of the alkyl replacement of 1-10; R
2For hydrogen or carbonatoms are alkyl or the alkoxyl group of 1-10;
Ar is the naphthalimide derivative primitive, has in the following structural unit one or both:
(I) class: 4 naphthalimide primitives that dialkyl amido replaces
Wherein, R
3For hydrogen or carbonatoms are the alkyl of 1-10, R
4For hydrogen, carbonatoms are the alkyl of 1-10, alkoxyl group, dialkyl amido, nitro, itrile group, amino or phenylbenzene amido;
(II) class: 4 naphthalimide primitives that ammonia diaryl base replaces
Wherein, X is Sauerstoffatom or sulphur atom;
(III) class: 4 naphthalimide primitives that carbon atom replaces
Wherein, 1≤p≤5;
(IV) class: 4 naphthalimide primitives that other heteroatomss replace
X is a naphthalimide primitive content, satisfies 0＜x≤1, m=1-20, n=1-300;
The preparation method of blue electroluminescent polymer material provided by the invention relates generally to three kinds of monomers and a kind of copolymerization:
(1) .2, the preparation of two bromo fluorenes of 7-and derivatives monomer thereof
2, the general structure of two bromo fluorenes of 7-and derivatives monomer thereof is:
2, two bromo fluorenes of 7-and derivatives monomer thereof comprise two classes: 9, and 9-dialkyl group-2, the two bromo fluorenes monomers and 9 of 7-, 9-diaryl-2, the two bromo fluorenes monomers of 7-, its preparation method is as follows respectively:
1) 9,9-dialkyl group-2, the two monomeric preparations of bromo fluorenes of 7-
With 2,7-two bromo fluorenes and excessive bromo alkane are dissolved in the toluene, add aqueous sodium hydroxide solution again, react under nitrogen protection, reaction product is poured in the water, separated organic phase, after the washed several times with water, dry, concentrated repeatedly, recrystallization obtains 9,9-dialkyl group-2,7-two bromo fluorenes;
2) 9,9-diaryl-2, the two monomeric preparations of bromo fluorenes of 7-
At first, with 2,7-two bromo Fluorenones are dissolved in the ether; add aryl grignard reagent under nitrogen protection, back flow reaction is prepared 9-hydroxyl-9-aryl-2; 7-two bromo fluorenes, with 9-hydroxyl-9-aryl-2,7-two bromo fluorenes slowly drip in the sulphuric acid soln of aromatic hydrocarbons; back flow reaction is poured reaction product in the water into, separates organic phase; after the washed several times with water, dry, concentrated repeatedly, recrystallization; obtain 9,9-diaryl-2,7-two bromo fluorenes.
(2) .2, the preparation of two boric acid ester fluorenes of 7-and derivatives monomer thereof
2, the general structure of two boric acid ester fluorenes of 7-and derivatives monomer thereof is:
2, the preparation method of two boric acid ester fluorenes of 7-and derivatives monomer thereof is as follows:
N-Butyl Lithium is joined 9 under-78-0 ℃, 9-two replaces-2, in the tetrahydrofuran solution of 7-two bromo fluorenes, stirring reaction,-the 78-0 ℃ excessive trimethyl borate of following adding, the stirring at room reaction is poured reaction mixture in the water into, separate organic phase, after the washed several times with water, dry, concentrated, the product that obtains dissolves with toluene repeatedly, add mol ratio again and be 2-3 doubly 1, ammediol refluxes, and reaction product is poured in the water, separate organic phase, after the washed several times with water, dry, concentrated repeatedly, ethyl alcohol recrystallization, obtain 2, two boric acid ester fluorenes of 7-and derivative thereof.
(3). the monomeric preparation of two naphthalene bromide imide derivatives
Two naphthalene bromide imide derivative monomers mainly comprise single naphthalimide derivative monomer of two bromobenzene and the two naphthalimide derivative monomers of two bromobenzene:
1) the single naphthalimide derivative monomer of two bromobenzene, its structure is as shown in the formula shown in the middle right formula
Wherein Ar is the naphthalimide derivative primitive;
Monomeric preparation method is as follows for the single naphthalimide derivative of two bromobenzene:
At first, 2-hydroxyl-5-is replaced-1,4-dibromobenzene and mol ratio are that 1-3 carbonatoms doubly is that two bromo alkane of m are dissolved in the dehydrated alcohol, in mol ratio is in the presence of the 1-10 potassium hydroxide doubly backflow 2-10 hour, 2-(m-bromo the alkoxyl group)-5-for preparing structure shown in levoform in the following formula replaces-1, the 4-dibromobenzene, naphthalimide derivative Ar is dissolved in the dimethyl sulfoxide (DMSO), adding mol ratio is 1-10 sodium hydroxide doubly, adding mol ratio then is that 0.5-5 2-(m-bromo alkoxyl group)-5-doubly replaces-1, and the 4-dibromobenzene is after reacting 1-24 hour under the 20-150 ℃ of temperature, the water termination reaction, separate organic phase, repeatedly after the washed several times with water, drying, concentrate, post separates, and obtains the single naphthalimide derivative monomer of two bromobenzene.
2) the two naphthalimide derivative monomers of two bromobenzene, its structure is as shown in the formula shown in the middle right formula
Wherein Ar is the naphthalimide derivative primitive;
Two monomeric preparation methods of naphthalimide derivative are as follows for two bromobenzene:
At first, with 2,5-dihydroxyl-1,4-dibromobenzene and mol ratio are that 2-10 chain number doubly is that two bromo alkane of m are dissolved in the dehydrated alcohol, in mol ratio is in the presence of the 2-10 potassium hydroxide doubly backflow 2-10 hour, prepare 2 of shown in levoform in following formula structure, 5-two (m-bromo alkoxyl group)-1, the 4-dibromobenzene is dissolved in naphthalimide derivative Ar in the dimethyl sulfoxide (DMSO), adding mol ratio is 0.5-10 sodium hydroxide doubly, add mol ratio then and be 0.1-0.5 doubly 2,5-two (m-bromo alkoxyl group)-1,4-dibromobenzene are in reaction under the 20-150 ℃ of temperature after 1-5 days, the water termination reaction, separate organic phase, repeatedly after the washed several times with water, drying, concentrate, post separates, and obtains two bromobenzene naphthalimide derivative monomers.
(4) preparation of blue electroluminescent polymer material
The Suzuki polyreaction is adopted in the preparation of blue electroluminescent polymer material, and its preparation method is as follows:
With 2,2 of two bromobenzene naphthalimide derivative monomers of the two boric acid ester fluorene derivatives monomers of 7-, 0.00001-1 mol ratio, 0-1 mol ratio, the two bromo fluorene derivatives monomers of 7-are dissolved in the toluene, and adding mol ratio then is 2-10 2.0M wet chemical doubly.Under nitrogen protection and 50-100 ℃ of temperature; four (triphenylphosphines) that add the 0.0005-0.1 mol ratio close palladium; 0-0.5 the Aliquat 336 of mol ratio; react after 24-120 hour; through chloroform extraction, washing, drying, concentrated; methyl alcohol sedimentation, solvent extraction, vacuum-drying obtain the fibrous polymer material at last.
Figure of description
Fig. 1 is blue coloured electroluminous high molecular solid-state absorption spectrum and fluorescence emission spectrum.
Fig. 2 is based on blue coloured electroluminous high molecular single layer device, and structure is the electroluminescent spectrum of the blue coloured electroluminous polymer/Ca/Al of ITO/PEDOT/.
As can be seen from Figure 1, the maximum absorption wavelength of this material is at 392nm; Its fluorescence emission spectrum has three peaks, respectively at 430nm, and 450nm, 467nm, the intensity at these three peaks is basic identical; As can be seen from Figure 2, the peak value of the electroluminescent spectrum of this material is at 467nm, and 428nm also has an acromion.
Embodiment
Embodiment 1:2-(2-(4-amino-1, the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 2.12g (10mmol) 4-amino-1; the 8-naphthalimide is dissolved in 60 milliliters of dimethyl sulfoxide (DMSO); the potassium hydroxide that in solution, adds 0.56g (10mmol) powdered again; in 120 ℃ of reactions ten minutes, in system, add 4.59g (10mmol) 2-(2-bromine oxethyl)-5-hexyloxy-1 more gradually, the 4-dibromobenzene under the induction stirring; reacted 14 hours; repetitive scrubbing behind the chloroform extraction, drying is filtered; concentrate; the column chromatography separated product obtains pure intermediate product 2-(2-(4-amino-1, the oxyethyl group of 8-naphthalimide-9-)-1-)-5-hexyloxy-1; 4-dibromobenzene 3.59g, productive rate 61%.
Embodiment 2:2-(2-(4-dimethylamino-1, the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 0.590g (1mmol) 2-(2-(4-amino-1; the oxyethyl group of 8-naphthalimide-9-)-1-)-5-hexyloxy-1; the 4-dibromobenzene is dissolved in 30 milliliters of dimethyl sulfoxide (DMSO); the sodium hydride that in solution, adds 0.12g (3mmol) 60% again; in 60 ℃ of reactions 10 minutes, in system, add 2.840g (20mmol) methyl iodide then under the induction stirring, reacted 3 hours; repetitive scrubbing behind the chloroform extraction; drying is filtered the column chromatography separated product; obtain pure intermediate product 2-(2-(4-dimethylamino-1; the oxyethyl group of 8-naphthalimide-9-)-1-)-5-hexyloxy-1,4-dibromobenzene 0.506g, productive rate 82%.
Embodiment 3:2,5-two (6-(4-amino-1, the hexyloxy of 8-naphthalimide-9-))-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 1.06g (5mmol) 4-amino-1; the 8-naphthalimide is dissolved in 60 milliliters of methyl-sulphoxides; the potassium hydroxide that adds 0.84g (15mmol) powdered again in solution in 30 ℃ of reactions ten minutes, adds 1.366g (2.3mmol) 2 under the induction stirring more gradually in system; 5-two (6-bromine hexyloxy)-1; the 4-dibromobenzene reacted repetitive scrubbing behind the chloroform extraction 14 hours; dry; filter, the column chromatography separated product obtains pure intermediate product 2; 5-two (6-(4-amino-1; the hexyloxy of 8-naphthalimide-9-)-1-)-1,4-dibromobenzene 1.027g, productive rate 48%.
Embodiment 4:2,5-two (6-(4-didecyl amino-1, the hexyloxy of 8-naphthalimide-9-))-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 0.856g (1mmol) 2; 5-two (6-(4-amino-1; the 8-naphthalimide-9-) hexyloxy-1-)-1, the 4-dibromobenzene is dissolved in 30 milliliters of dimethyl sulfoxide (DMSO), adds the sodium hydride of 0.201g (5mmol) 60% again in solution; reacted 10 minutes in 60 ℃ under the induction stirring; in system, add 2.21g (10mmol) 1-bromo-decane then, reacted repetitive scrubbing behind the chloroform extraction 3 hours; dry; filter, the column chromatography separated product obtains pure intermediate product 2; 5-two (6-(4-didecyl amino-1; the hexyloxy of 8-naphthalimide-9-)-1-)-1,4-dibromobenzene 0.397g, productive rate 28%.
Embodiment 5:4-(9,9-dihexyl fluorenyl-2-)-1,8-naphthalimide synthetic
Under the nitrogen atmosphere protection; with 20.79g (55mmol) 9; 9-dihexyl fluorenyl-2-boric acid; 13.80g (50mmol) the 4-bromo-1; the 8-naphthalimide, 13.80g (100mmol) salt of wormwood, 50ml water; 200ml toluene; 0.231g (0.02mmol) four (triphenylphosphines) mixture that closes palladium is in 80 ℃ of stirring reactions 3 hours, repetitive scrubbing behind the chloroform extraction, drying; filter; remove the back of desolvating and use re-crystallizing in ethyl acetate, obtain pure intermediate product 4-(9,9-dihexyl fluorenyl-2-)-1; 8-naphthalimide 16.66g, productive rate 63%.
Embodiment 6:2-(6-(4-(9,9-dihexyl fluorenyl-2)-1, the hexyloxy of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 5.29g (10.00mmol) 4-(9; 9-dihexyl fluorenyl-2-)-1; the 8-naphthalimide is dissolved in 140 milliliters of dimethyl sulfoxide (DMSO); the potassium hydroxide that in solution, adds 5.6g (100.0mmol) powdered again; reacted ten minutes in 30 ℃ under the induction stirring; in system, add 2.376g (4.00mmol) 2-(6-bromine hexyloxy)-5-hexyloxy-1 more gradually; the 4-dibromobenzene reacted repetitive scrubbing behind the chloroform extraction 14 hours; dry; filter, the column chromatography separated product, ((4-(9 for 6-to obtain pure intermediate product 2-; 9-dihexyl fluorenyl-1)-1; the hexyloxy of 8-naphthalimide-9-)-1-)-5-hexyloxy-1,4-dibromobenzene 2.196g, productive rate 57%.
Embodiment 7:4-(carbazyl-N-)-1,8-naphthalimide synthetic
Under the nitrogen atmosphere protection, with 2.76g (10mmol) 4-bromo-1,8-naphthalimide; 5.01g (30mmol) carbazole, 4.14g (30mmol) Anhydrous potassium carbonate, 0.095g (0.5mmol) cuprous iodide; 0.03g 18-hat-6, the mixture of 3ml DMPU was 150 ℃ of stirring reactions 20 hours.The toluene extraction product, pickling, ammoniacal liquor is washed, washing repeatedly, drying is filtered, and removes the back of desolvating and uses the chloroform recrystallization, obtains pure intermediate product 4-(carbazyl-N-)-1,8-naphthalimide 0.869g, productive rate 24%.
Embodiment 8:2-(2-(4-(carbazyl-N-) 1, the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 0.362g (1mmol) 4-(carbazyl-N-)-1; the 8-naphthalimide is dissolved in 10 milliliters of methyl-sulphoxides; the potassium hydroxide that in solution, adds 0.414g (3.0mmol) powdered again; reacted ten minutes in 50 ℃ under the induction stirring; add 0.459g (1.0mmol) 2-(2-bromine oxethyl)-5-hexyloxy-1 again in system gradually, the 4-dibromobenzene reacted 14 hours; repetitive scrubbing behind the chloroform extraction; drying is filtered the column chromatography separated product; obtain pure intermediate product 2-(2-(4-(carbazyl-N-) 1; the oxyethyl group of 8-naphthalimide-9-))-and 5-hexyloxy-1,4-dibromobenzene 0.274g, productive rate 37%.
Embodiment 9:2-(2-(4-methoxyl group-1, the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 2.27g (10.0mmol) 4-methoxyl group-1; the 8-naphthalimide is dissolved in 60 milliliters of dimethyl sulfoxide (DMSO); the potassium hydroxide that in solution, adds 2.07g (15.0mmol) powdered again; reacted ten minutes in 50 ℃ under the induction stirring; add 2.754g (6.0mmol) 2-(2-bromine oxethyl)-5-hexyloxy-1 again in system gradually, the 4-dibromobenzene reacted 14 hours; repetitive scrubbing behind the chloroform extraction; drying is filtered the column chromatography separated product; obtain pure intermediate product 2-(2-(4-methoxyl group-1; the oxyethyl group of 8-naphthalimide-9-))-and 5-hexyloxy-1,4-dibromobenzene 2.58g, productive rate 71%.
Embodiment 10:4-(4-p-methoxy-phenyl)-1,8-naphthalimide synthetic
Under the nitrogen atmosphere protection; with 15.10g (100mmol) 4-anisole ylboronic acid; 24.80g (90mmol) the 4-bromo-1; the 8-naphthalimide; 41.4g (300mmol) salt of wormwood; 150ml water; the mixture that 300ml toluene, 2.31g (2.0mmol) four (triphenylphosphine) close palladium is at 50 ℃ of stirring reactions 3 hours, repetitive scrubbing behind the chloroform extraction; dry; filter, remove the back of desolvating and use re-crystallizing in ethyl acetate, obtain pure intermediate product 4-(4-p-methoxy-phenyl)-1; 8-naphthalimide 10.6g, productive rate 39%.
Embodiment 11:2,5-two (10-(4-(4-p-methoxy-phenyl)-1, the oxygen base in the last of the ten Heavenly stems of 8-naphthalimide-9-))-1,4-dibromobenzene synthetic
Under the nitrogen atmosphere protection; with 0.606g (2.0mmol) 4-(4-p-methoxy-phenyl)-1; the 8-naphthalimide is dissolved in 5 milliliters of methyl-sulphoxides; the potassium hydroxide that in solution, adds 1.68g (3.0mmol) powdered again; in 50 ℃ of reactions ten minutes, in system, add 0.565g-(0.8mmol) 2 more gradually, 5-two (10-bromine oxygen in last of the ten Heavenly stems base)-1 under the induction stirring; the 4-dibromobenzene; reacted repetitive scrubbing behind the chloroform extraction, drying 14 hours; filter; the column chromatography separated product obtains pure intermediate product 2,5-two (10-(4-(4-p-methoxy-phenyl)-1; the oxygen base in the last of the ten Heavenly stems of 8-naphthalimide-9-))-1,4-dibromobenzene 0.16g. productive rate 17%.
Embodiment 12:
Under nitrogen protection; in reaction flask, add 0.2736g (0.499mmmol) 9; 9-dioctyl-2; 7-two bromo fluorenes, 0.2792g (0.5mmol) 9,9-dioctyl-2; 7-(trimethylene boric acid ester group) fluorenes; 0.0007g (0.001mmol) 2-(2-(4-dimethylamino-1, the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene; 0.4140g (3.0mmol) salt of wormwood; 1.5mL water, 7mL toluene, the mixture of 0.008g Aliquat 336; 80 ℃ of reactions ten minutes; in reaction flask, add 0.0115g (0.01mmol) four (triphenylphosphine) then and close palladium, 100 ℃ of stirring reactions 12 hours, reaction mixture dissolves with chloroform; ferric chloride aqueous solutions is washed once; wash repeatedly, drying concentrates; use the methyl alcohol sedimentation then three times; product is placed apparatus,Soxhlet's, with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid 0.253g, productive rate 65%.Product property is as follows: number-average molecular weight is 32,000, and weight-average molecular weight is that 62,000. film absorption spectrum and the fluorescence spectrums that this polymkeric substance spin coating on quartz substrate is become are seen Fig. 1.
(device architecture is: assembling condition ITO/PEDOT/Polymer/Ca/Al) is: adopt the ito glass that cleans in advance is anode to single layer device, and spin coating one deck conducting polymer-polythiofuran derivative (PEDOT) (50nm) subsequently.ITO after PEDOT modifies is 150 ℃ of following vacuum-dryings after 3 hours, is that the chloroformic solution of 10 mg/ml polymkeric substance is spin-coated on the ITO surface with concentration under the condition of 1500 rev/mins of rotating speeds.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: 3.8 volts of trigger voltages, high-high brightness 8700cd/m
2, maximum electroluminescent efficiency is 4.2cd/A, its electroluminescent spectrum is seen Fig. 2, its chromaticity coordinates (0.14,0.17).
Embodiment 13:
Under nitrogen protection, in reaction flask, add 0.2194g (0.4mmol) 9,9-dioctyl-2; 7-two bromo fluorenes, 0.2792g (0.5mmol) 9,9-dioctyl-2; 7-(trimethylene boric acid ester group) fluorenes; 0.0617g (0.1mmol) 2-(2-(4-dimethylamino-1, the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1,4-dibromobenzene; 0.138g (1.0mmol) salt of wormwood; 0.5ml water, 5ml toluene, the mixture of Aliquat 336; 80 ℃ of reactions ten minutes; in reaction flask, add 0.0230g (0.02mmol) four (triphenylphosphine) then and close palladium, back flow reaction 12 hours, reaction mixture dissolves with chloroform; the tindichloride aqueous solution is washed once; wash repeatedly, drying concentrates; use the methyl alcohol sedimentation then three times; product is placed apparatus,Soxhlet's, with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid 0.190g, productive rate 41%.Product property is as follows: number-average molecular weight is 32,000, and film ultraviolet maximum absorption is 392nm, and the solid state fluorescence emission peak is 485nm.
The single layer device assembling condition is as follows with embodiment 12. individual layer electroluminescent device performances: 11.6 volts of trigger voltages, high-high brightness 541cd/m
2, maximum electroluminescent efficiency is 0.68cd/A, chromaticity coordinates is (0.20,0.38).
Embodiment 14:
Under nitrogen protection; in reaction flask, add 0.2792g (0.5mmol) 9; 9-dioctyl-2,7-(trimethylene boric acid ester group) fluorenes, 0.3085g (0.5mmol) 2-(2-(4-dimethylamino-1; the oxyethyl group of 8-naphthalimide-9-))-5-hexyloxy-1; the 4-dibromobenzene, 0.138g (1.0mmol) salt of wormwood, 0.5ml water; 5ml toluene; the mixture of Aliquat 336 80 ℃ of reactions ten minutes, adds 0.0023g (0.002mmol) four (triphenylphosphine) then and closes palladium in reaction flask; back flow reaction 12 hours; reaction mixture dissolves with chloroform, and the tindichloride aqueous solution is washed once, and washing repeatedly; dry; concentrate, use the methyl alcohol sedimentation then three times, product is placed apparatus,Soxhlet's; with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid 0.1732g, productive rate 41%.Product property is as follows: number-average molecular weight is 22,000, and film ultraviolet maximum absorption is 392nm, and the solid state fluorescence emission peak is 515nm.
The single layer device assembling condition is as follows with embodiment 12. individual layer electroluminescent device performances: 9.6 volts of trigger voltages, high-high brightness 1032cd/m
2, maximum electroluminescent efficiency is 0.99cd/A, chromaticity coordinates is (0.26,0.62).
Embodiment 15:
Under nitrogen protection, in reaction flask, add 0.2714g (0.49mmol) 9,9-dioctyl-2; 7-two bromo fluorenes; 0.2792g (0.5mmol) 9,9-dioctyl-2,7-(trimethylene boric acid ester group) fluorenes; 0.0153g (0.01mmol) 2; 5-two (6-(4-didecyl amino-1, the hexyloxy of 8-naphthalimide-9-))-1,4-dibromobenzene; the 2mL2M wet chemical; 6ml toluene, the mixture of 0.008g Aliquat 336 was 80 ℃ of reactions ten minutes; in reaction flask, add 0.0230g (0.02mmol) four (triphenylphosphine) then and close palladium; 50 ℃ of stirring reactions 120 hours, reaction mixture dissolves with chloroform, and washing is repeatedly; dry; concentrate, use the methyl alcohol sedimentation then three times, product is placed apparatus,Soxhlet's; with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid 0.208g, productive rate 53%.Product property is as follows: number-average molecular weight is 18,000, and film ultraviolet maximum absorption is 380nm, and the solid state fluorescence emission peak is 450nm.
The single layer device assembling condition is as follows with embodiment 12. individual layer electroluminescent device performances: 5.2 volts of trigger voltages, high-high brightness 13500cd/m
2, maximum electroluminescent efficiency is 3.9cd/A, chromaticity coordinates is (0.17,0.17).
Embodiment 16:
Under nitrogen protection; in reaction flask, add 0.2715g (0.495mmol) 9; 9-dioctyl-2; 7-two bromo fluorenes, 0.2792g (0.5mmol) 9,9-dioctyl-2; 7-(trimethylene boric acid ester group) fluorenes; 0.0048g (0.005mmol) 2-(6-(4-(9,9-dihexyl fluorenyl-2)-1, the hexyloxy of 8-naphthalimide-9-))-5-hexyloxy-1; the 4-dibromobenzene; the 2mL2M wet chemical, 10mL toluene, the mixture of 0.13g Aliquat 336; 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.Dissolve with chloroform then, sedimentation in methyl alcohol, product vacuum-drying gets faint yellow solid 0.2068g, productive rate 55%.Product property is as follows: number-average molecular weight is 28,000, and film ultraviolet maximum absorption is 392nm, and the solid state fluorescence emission peak is 434nm.
The single layer device assembling condition is as follows with embodiment 12. individual layer electroluminescent device performances: 3.4 volts of trigger voltages, high-high brightness 1430cd/m
2, maximum electroluminescent efficiency is 0.9cd/A, chromaticity coordinates is (0.16,0.10).
Embodiment 17
Under nitrogen protection, in reaction flask, add 0.2467g (0.4498mmol) 9,9-dioctyl-2; 7-two bromo fluorenes; 0.2792g (0.5mmol) 9,9-dioctyl-2,7-(trimethylene boric acid ester group) fluorenes; 0.0002g (0.0002mmol) 2-(2-(4-(carbazyl-N-) 1; the oxyethyl group of 8-naphthalimide-9-))-and 5-hexyloxy-1,4-dibromobenzene, 1.38g (10mmol) salt of wormwood; 5mL water; 5mL toluene, the mixture of 0.0005g Aliquat 336 was 80 ℃ of reactions ten minutes; in reaction flask, add four (triphenylphosphines) then and close palladium; 90 ℃ of stirring reactions 96 hours, reaction mixture dissolves with chloroform, and washing is repeatedly; dry; concentrate, use the methyl alcohol sedimentation then three times, product is placed apparatus,Soxhlet's; with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid, productive rate.Product property is as follows: number-average molecular weight is 28,000, and film ultraviolet maximum absorption is 392nm, and the solid state fluorescence emission peak is 460nm.
The single layer device assembling condition is as follows with embodiment 12. individual layer electroluminescent device performances: 3.5 volts of trigger voltages, high-high brightness 6660cd/m
2, maximum electroluminescent efficiency is 3.00cd/A, chromaticity coordinates is (0.14,0.19).
Embodiment 18:
Under nitrogen protection, in reaction flask, add 0.2731g (0.498mmol) 9,9-dioctyl-2; 7-two bromo fluorenes; 0.2792g (0.5mmol) 9,9-dioctyl-2,7-(trimethylene boric acid ester group) fluorenes; 0.0012g (0.002mmol) 2-(2-(4-methoxyl group-1; the oxyethyl group of 8-naphthalimide-9-))-and 5-hexyloxy-1,4-dibromobenzene, 0.414g (3.0mmol) salt of wormwood; 1.5mL water; 7mL toluene, the mixture of 0.005g Aliquat 336 was 80 ℃ of reactions ten minutes; in reaction flask, add four (triphenylphosphines) then and close palladium; 90 ℃ of stirring reactions 72 hours, reaction mixture dissolves with chloroform, and washing is repeatedly; dry; concentrate, use the methyl alcohol sedimentation then three times, product is placed apparatus,Soxhlet's; with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid 0.163g, productive rate 42%.Product property is as follows: number-average molecular weight is 21,000, and film ultraviolet maximum absorption is 392nm, and the solid state fluorescence emission peak is 468nm.
The single layer device assembling condition is as follows with embodiment 12. individual layer electroluminescent device performances: 3.8 volts of trigger voltages, high-high brightness 7230cd/m
2, maximum electroluminescent efficiency is 3.20cd/A, chromaticity coordinates is (0.15,0.19).
Embodiment 19:
Under nitrogen protection, in reaction flask, add 0.2192g (0.4mmol) 9,9-dioctyl-2; 7-two bromo fluorenes, 0.2792g (0.5mmol) 9,9-dioctyl-2; 7-(trimethylene boric acid ester group) fluorenes; 0.1151g (0.1mmol) 2,5-two (10-(4-(4-p-methoxy-phenyl)-1, the oxygen base in the last of the ten Heavenly stems of 8-naphthalimide-9-))-1; the 4-dibromobenzene; 0.414g (3mmol) salt of wormwood, 1.5mL water, 5mL toluene; 0.08g the mixture of Aliquat 336; 80 ℃ of reactions ten minutes, in reaction flask, add 0.115g (0.01mmol) four (triphenylphosphine) then and close palladium, 90 ℃ of stirring reactions 12 hours; reaction mixture dissolves with chloroform; wash repeatedly, drying concentrates; use the methyl alcohol sedimentation then three times; product is placed apparatus,Soxhlet's, with acetone extracting 24 hours, then with chloroform dissolving back sedimentation in methyl alcohol.Product vacuum-drying gets faint yellow solid 0.323g, productive rate 72%.Product property is as follows: number-average molecular weight is 26,000, and film ultraviolet maximum absorption is 392nm, and the solid state fluorescence emission peak is 498nm.
The single layer device assembling condition is as follows with embodiment 16. individual layer electroluminescent device performances: 3.8 volts of trigger voltages, high-high brightness 2230cd/m
2, maximum electroluminescent efficiency is 1.40cd/A, chromaticity coordinates is (0.25,0.47).
Claims (2)
1. a class blue electroluminescent polymer material is characterized in that having a kind of in following two kinds of structures:
Wherein: R
1For hexyl, octyl group, carbonatoms is phenyl, 4-(phenylbenzene amido) phenyl of the alkyl replacement of 1-10; R
2For hydrogen or carbonatoms are alkyl or the alkoxyl group of 1-10;
Ar is the naphthalimide derivative primitive, has in the following structural unit one or both:
(I) class: 4 naphthalimide primitives that dialkyl amido replaces
Wherein, R
3For hydrogen or carbonatoms are the alkyl of 1-10, R
4For hydrogen, carbonatoms are the alkyl of 1-10, alkoxyl group, dialkyl amido, nitro, itrile group, amino or phenylbenzene amido; (II) class: 4 naphthalimide primitives that ammonia diaryl base replaces
Wherein, X is Sauerstoffatom or sulphur atom;
(III) class: 4 naphthalimide primitives that carbon atom replaces
Wherein, 1≤p≤5;
(IV) class: 4 naphthalimide primitives that other heteroatomss replace
X is the content of naphthalimide derivative primitive, satisfies 0＜x≤1, m=1-20, n=1-300.
2. prepare the method for blue electroluminescent polymer material according to claim 1, relate to three kinds of monomers and a kind of copolymerization:
(1) .2, the preparation of two bromo fluorenes of 7-and derivatives monomer thereof
2, the general structure of two bromo fluorenes of 7-and derivatives monomer thereof is:
2, two bromo fluorenes of 7-and derivatives monomer thereof comprise two classes: 9, and 9-dialkyl group-2, the two bromo fluorenes monomers and 9 of 7-, 9-diaryl-2, the two bromo fluorenes monomers of 7-, its preparation method is as follows respectively:
1) 9,9-dialkyl group-2, the two monomeric preparations of bromo fluorenes of 7-
With 2,7-two bromo fluorenes and excessive bromo alkane are dissolved in the toluene, add aqueous sodium hydroxide solution again, react under nitrogen protection, reaction product is poured in the water, separated organic phase, after the washed several times with water, dry, concentrated repeatedly, recrystallization obtains 9,9-dialkyl group-2,7-two bromo fluorenes;
2) 9,9-diaryl-2, the two monomeric preparations of bromo fluorenes of 7-
At first, with 2,7-two bromo Fluorenones are dissolved in the ether, add aryl grignard reagent under nitrogen protection, back flow reaction is prepared 9-hydroxyl-9-aryl-2,7-two bromo fluorenes, with 9-hydroxyl-9-aryl-2,7-two bromo fluorenes slowly drip in the sulphuric acid soln of aromatic hydrocarbons, back flow reaction is poured reaction product in the water into, separates organic phase, after the washed several times with water, dry, concentrated repeatedly, recrystallization, obtain 9,9-diaryl-2,7-two bromo fluorenes;
(2) .2, the preparation of two boric acid ester fluorenes of 7-and derivatives monomer thereof
2, the general structure of two boric acid ester fluorenes of 7-and derivatives monomer thereof is:
2, the preparation method of two boric acid ester fluorenes of 7-and derivatives monomer thereof is as follows:
N-Butyl Lithium is joined 9 under-78-0 ℃, 9-two replaces-2, in the tetrahydrofuran solution of 7-two bromo fluorenes, stirring reaction,-the 78-0 ℃ excessive trimethyl borate of following adding, the stirring at room reaction is poured reaction mixture in the water into, separate organic phase, after the washed several times with water, dry, concentrated, the product that obtains dissolves with toluene repeatedly, add mol ratio again and be 2-3 doubly 1, ammediol refluxes, and reaction product is poured in the water, separate organic phase, after the washed several times with water, dry, concentrated repeatedly, ethyl alcohol recrystallization, obtain 2, two boric acid ester fluorenes of 7-and derivative thereof;
(3). the monomeric preparation of two naphthalene bromide imide derivatives
Two naphthalene bromide imide derivative monomers mainly comprise single naphthalimide derivative monomer of two bromobenzene and the two naphthalimide derivative monomers of two bromobenzene;
1) the single naphthalimide derivative monomer of two bromobenzene, its structure is as shown in the formula shown in the middle right formula
Wherein Ar is the naphthalimide derivative primitive;
Monomeric preparation method is as follows for the single naphthalimide derivative of two bromobenzene:
At first, 2-hydroxyl-5-is replaced-1,4-dibromobenzene and mol ratio are that 1-3 carbonatoms doubly is that two bromo alkane of m are dissolved in the dehydrated alcohol, in mol ratio is in the presence of the 1-10 potassium hydroxide doubly backflow 2-10 hour, 2-(m-bromo the alkoxyl group)-5-for preparing structure shown in levoform in the following formula replaces-1, the 4-dibromobenzene, naphthalimide derivative Ar is dissolved in the dimethyl sulfoxide (DMSO), adding mol ratio is 1-10 sodium hydroxide doubly, adding mol ratio then is that 0.5-5 2-(m-bromo alkoxyl group)-5-doubly replaces-1, and the 4-dibromobenzene is after reacting 1-24 hour under the 20-150 ℃ of temperature, the water termination reaction, separate organic phase, repeatedly after the washed several times with water, drying, concentrate, post separates, and obtains the single naphthalimide derivative monomer of two bromobenzene;
2) the two naphthalimide derivative monomers of two bromobenzene, its structure is as shown in the formula shown in the middle right formula
Wherein Ar is the naphthalimide derivative primitive;
Two monomeric preparation methods of naphthalimide derivative are as follows for two bromobenzene:
At first, with 2,5-dihydroxyl-l, 4-dibromobenzene and mol ratio are that 2-10 chain number doubly is that two bromo alkane of m are dissolved in the dehydrated alcohol, in mol ratio is in the presence of the 2-10 potassium hydroxide doubly backflow 2-10 hour, prepare 2 of shown in levoform in following formula structure, 5-two (m-bromo alkoxyl group)-l, the 4-dibromobenzene is dissolved in naphthalimide derivative Ar in the dimethyl sulfoxide (DMSO), adding mol ratio is 0.5-10 sodium hydroxide doubly, add mol ratio then and be 0.1-0.5 doubly 2,5-two (m-bromo alkoxyl group)-1,4-dibromobenzene are in reaction under the 20-150 ℃ of temperature after 1-5 days, the water termination reaction, separate organic phase, repeatedly after the washed several times with water, drying, concentrate, post separates, and obtains the two naphthalimide derivative monomers of two bromobenzene;
(4) preparation of blue electroluminescent polymer material
The Suzuki polyreaction is adopted in the preparation of blue electroluminescent polymer material, and its preparation method is as follows:
With 2,2 of two bromobenzene naphthalimide derivative monomers of the two boric acid ester fluorene derivatives monomers of 7-, 0.00001-1 mol ratio, 0-l mol ratio, the two bromo fluorene derivatives monomers of 7-are dissolved in the toluene, and adding mol ratio then is 2-10 2.0M wet chemical doubly; Under nitrogen protection and 50-100 ℃ of temperature; four (triphenylphosphines) that add the 0.0005-0.1 mol ratio close palladium; 0-0.5 the Aliquat 336 of mol ratio; react after 24-120 hour; through chloroform extraction, washing, drying, concentrated; methyl alcohol sedimentation, solvent extraction, vacuum-drying obtain the fibrous polymer material at last.
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| CN101942211B (en) * | 2010-09-21 | 2013-08-14 | 大连理工大学 | Naphthalimide fluorescent dichroic dye containing aromatic ester group and application thereof |
| CN101942210B (en) * | 2010-09-21 | 2013-05-08 | 大连理工大学 | 4-amido-1,8-naphthalimide derivative fluorescent dichroic dye and application thereof |
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| CN1275604A (en) * | 1999-05-31 | 2000-12-06 | 三星Sdi株式会社 | Blue light emission compound and indicator adopting same as developer |
| KR20020013222A (en) * | 2000-08-12 | 2002-02-20 | 강승구 | Blue electroluminescence polymeric flurophores |
| CN1381543A (en) * | 2002-04-28 | 2002-11-27 | 中国科学院长春应用化学研究所 | High-molecular luminous material with energy-transfer main chain and its preparing process |
| CN1421470A (en) * | 2001-11-30 | 2003-06-04 | 中国科学院化学研究所 | Conjugated polymer containing oxdiazole and its application |
| JP2003221579A (en) * | 2002-02-01 | 2003-08-08 | Toppan Printing Co Ltd | Organic luminescent material |
| CN1551694A (en) * | 2002-12-24 | 2004-12-01 | ����Sdi��ʽ���� | Blue light-emitting polymer and organic el element using the same |
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| CN1275604A (en) * | 1999-05-31 | 2000-12-06 | 三星Sdi株式会社 | Blue light emission compound and indicator adopting same as developer |
| KR20020013222A (en) * | 2000-08-12 | 2002-02-20 | 강승구 | Blue electroluminescence polymeric flurophores |
| CN1421470A (en) * | 2001-11-30 | 2003-06-04 | 中国科学院化学研究所 | Conjugated polymer containing oxdiazole and its application |
| JP2003221579A (en) * | 2002-02-01 | 2003-08-08 | Toppan Printing Co Ltd | Organic luminescent material |
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| CN1551694A (en) * | 2002-12-24 | 2004-12-01 | ����Sdi��ʽ���� | Blue light-emitting polymer and organic el element using the same |
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