CN100489008C - Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same - Google Patents
Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same Download PDFInfo
- Publication number
- CN100489008C CN100489008C CNB2006100433709A CN200610043370A CN100489008C CN 100489008 C CN100489008 C CN 100489008C CN B2006100433709 A CNB2006100433709 A CN B2006100433709A CN 200610043370 A CN200610043370 A CN 200610043370A CN 100489008 C CN100489008 C CN 100489008C
- Authority
- CN
- China
- Prior art keywords
- compound
- milliliters
- grams
- hours
- polymkeric substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 230000008878 coupling Effects 0.000 claims abstract description 9
- 238000010168 coupling process Methods 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- -1 alkyl silicon Chemical compound 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 93
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 92
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 12
- 238000004458 analytical method Methods 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- JYBJXKVJBAHQNF-UHFFFAOYSA-N 2-ethenylanthracene Chemical class C1=CC=CC2=CC3=CC(C=C)=CC=C3C=C21 JYBJXKVJBAHQNF-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000005055 short column chromatography Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 claims description 6
- RGPBQGGBWIMGMA-BJMVGYQFSA-N 5-[(e)-[5-(4-bromophenyl)-6-hydroxy-3,6-dihydro-1,3,4-oxadiazin-2-ylidene]methyl]-1h-pyrimidine-2,4-dione Chemical compound OC1O\C(=C\C=2C(NC(=O)NC=2)=O)NN=C1C1=CC=C(Br)C=C1 RGPBQGGBWIMGMA-BJMVGYQFSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005815 base catalysis Methods 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229940112822 chewing gum Drugs 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000011026 diafiltration Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000015320 potassium carbonate Nutrition 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001226 reprecipitation Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 4
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- PJGISJYVNVSSBU-UHFFFAOYSA-N 1-bromopentylbenzene Chemical group CCCCC(Br)C1=CC=CC=C1 PJGISJYVNVSSBU-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000005422 blasting Methods 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940125758 compound 15 Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- RYDMHGMXZHJUHB-UHFFFAOYSA-N lithium;cyclohexane;di(propan-2-yl)azanide Chemical compound [Li+].C1CCCCC1.CC(C)[N-]C(C)C RYDMHGMXZHJUHB-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 235000011182 sodium carbonates Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 12
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 8
- 229920000547 conjugated polymer Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 125000004663 dialkyl amino group Chemical group 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- 150000004982 aromatic amines Chemical class 0.000 abstract 2
- 125000005241 heteroarylamino group Chemical group 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 125000004414 alkyl thio group Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 46
- 239000000243 solution Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 230000027756 respiratory electron transport chain Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 0 CC*CC*C(*)C(C)CNC Chemical compound CC*CC*C(*)C(C)CNC 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to an electroluminescent material of poly(2,6) and poly(2,7)-anthryl vinylderivative and its process for preparing. The material is conjugated polymer constructed by 2,6 and 2,7-anthryl vinyl building block, in which Ar1, Ar2 and Ar of constitutional formula individually stand for arylamine or substituted arylamine with 6-46 carbon atoms, or individually stand for hetero arylamine or substituted hetero arylamine with 4-36 carbon atoms; or Ar1 and Ar2 individually stand for hydrogen atom, cyano-group, halogen atom, and alkoxylation catalyst, dialkylamino, alkyl silicon based or alkyl mercapto with 1-20 carbon atoms; R'and R' individually stand for hydrogen atom and cyano-group, or one stands for hydrogen atom and the other stands for cyano-group. The method consists of Gilch polymerization, Heck coupling or Wittg reaction catalyzed by alkali. The product is of good dissolving performance, efficiency and heat endurance, the illuminant color can be adjusted by introducing Ar1 and Ar2 and especially Ar group, and the other electrooptic property can be adjusted by introducing Ar, Ar1 or Ar2, which can be widely used in electroluminescent equipment.
Description
Technical field
The invention belongs to the electroluminescent material technical field, relate to more particularly that poly-(2,6-) and poly-2,7-anthryl ethene derivatives is as electroluminescent material and preparation method thereof.
Background technology
From (J.H.Burroughes such as nineteen ninety J.H.Burroughes, D.D.C.Bradley, A.R.Brown, R.N.Marks, K.Mackay, R.H.Friend, P.L.Burns, A.B.Holmes " Light-emitting diodes based on conjugated polymers ", Nature 347,539) deliver PPV and can be used as since the polymer electroluminescence material, the research and development of polymer electroluminescence material and device thereof becomes focus.Photodiode (LED) is the typical case representative of el light emitting device, it can be under the extra electric field effect visible emitting.At present, organic polymer and organic molecule have been used to make photodiode, the photodiode of organic materials manufacturing has the several advantages that are better than other technology, as the possibility of simple manufacturing process, low-work voltage and manufacturing big area, full color display more.Organic polymer can also provide the important processing advantage that is better than organic molecule, particularly for big area or deflection electroluminescent display, prepares high-quality polymeric film at an easy rate by solution casting method.
Conjugated polymers is the polymer that a class has stretching, extension π key conjugation to form along main polymer chain.Under light or electric field action, delocalization can take place or excite in their πDian Zi, and the energy that the electronics of generation and hole-recombination discharge can be converted into the form of light.In order to improve polymer dissolution, PPV such as MEH-PPV that dialkoxy replaces gather [2-methoxyl group-5-(2 '-ethyl is the oxygen base)-1,4-phenyl ethene] and are developed (F.Wudl et al., US Patent No.5 189 136 (1993)).In order to improve device performance, improved electroluminescent efficiency by device architecture, cathode material selection and materials chemistry and physically modified etc.Other conjugated polymers that has been studied mainly contains poly-diakyl fluorenes (Y.Ohmori et al., Jpn.J.Appl.Phys.Part 2,1991,20, L1941), Polythiophene (Y.Ohmori et al., SolidState Commun.1991,80,605), poly-to benzene (PPP) (G.Grem et al., Adv.Mater.1992,4,36) etc.
El light emitting device mainly is made up of negative electrode, anode and luminescent layer.Electron-hole pair is compound to be caused owing to negative electrode injected electrons and anode injected holes carry out in luminous material layer in electroluminescent.Light output had efficiently both depended on effectively and the high fluorescence material, and the high-molecular weight polymer that also depends on the preparation good solubility is to obtain high-quality polymeric film.Anthracene is the condensed-nuclei aromatics molecule of high fluorescence high thermal stability, Zheng's generation warblers etc. are with 9,10-diaryl anthracene organic molecule derivative prepares efficiency light output and high stability of operation el light emitting device (U.S. Pat-5 as luminescent material, 935,721 and US-5,972,247), in disclosed Chinese patent CN 1407054A in 2003, Zheng's generation warbler etc. carries out the Suzuki linked reaction by aromatic series hypoboric acid ester and aromatic series dibromide under palladium catalysis, prepared the el light emitting device of anthryl polymkeric substance (poly-anthracene) as luminescent material.As an analogy, these anthryl polymkeric substance are equivalent to the polyphenyl (PPP) in the phenyl polymer, anthryl polymkeric substance among the present invention then is equivalent to PPV and the MEH-PPV in the phenyl polymer, these anthryl polymkeric substance (poly-anthryl ethene) are to adopt Gilch polymerization or Heck coupling or Wittg prepared in reaction, and preferred Gilch polymerization process prepares high-molecular weight anthryl polymkeric substance.
Summary of the invention
Purpose of the present invention, be to provide a kind of poly-(2,6-) and poly-(2,7)-anthryl ethene derivatives as electroluminescent material and preparation method thereof.It not only provides the novel anthryl luminescence polymer material that is used for the polymer electroluminescence device, and the luminescence polymer of different band gaps is provided, and these gather 2,6-or 2,7-anthryl Alathon or contain the multipolymer of these anthryl ethene structural units can be launched the color gamut of broad.
Electroluminescent material provided by the present invention has lot of advantages such as the good solubility of comprising, efficient and thermostability.The glow color of polymkeric substance can be easily by introducing required Ar
1, Ar
2, particularly the Ar group is regulated.And other electro-optical properties also can be used the Ar group, comprises Ar
1, Ar
2The variation of group is regulated.Material of the present invention can be used for making el light emitting device, also can be as the material of main part of other photoelectric material.
In order to achieve the above object, the present invention poly-(2,6-) and poly-2,7-anthryl ethene derivatives is to contain 2,6 and 2 as electroluminescent material, and the conjugated polymers of 7-anthryl ethene structural unit has following structural formula I:
Structural formula I
Ar wherein
1, Ar
2With Ar be respectively the aryl or the substituted aryl of 6 to 46 carbon atoms separately; Perhaps Ar
1, Ar
2With Ar be respectively the heteroaryl or the substituted heteroaryl of 4 to 36 carbon atoms separately; Perhaps Ar
1, Ar
2Be respectively the silica-based or alkane sulfydryl of alkoxyl group, dialkylamino, alkane of hydrogen atom, cyano group, halogen atom, 1 to 20 carbon atom separately; R ' and R " be respectively hydrogen atom and cyano group separately, or one be hydrogen atom another be cyano group.
The Ar group comprises Ar
1, Ar
2The introducing of group has following feature: the solvability that further improves polymkeric substance; Obtain the compound of equilibrated electronics-hole injection and charged particle carrier; Improve the transmittability in electronics or hole; Improve the glow color of polymkeric substance.
Ar among the structural formula I
1, Ar
2Represent one of following structural or their combination separately:
Wherein: substituent R
1, R
2, R
3, R
4Can be hydrogen, cyano group, halogen atom; Perhaps the alkoxyl group of 1 to 20 carbon atom, dialkylamino, alkane sulfydryl or alkane are silica-based; Perhaps R
1, R
2, R
3Be the aryl or the substituted aryl of 6-36 carbon atom, the perhaps heteroaryl or the substituted heteroaryl of 4 to 36 carbon atoms.
Ar represents one of following structural or their combination among the structural formula I:
Wherein: substituent R
1, R
2, R
3, R
4Can be hydrogen, cyano group, halogen atom; Perhaps the alkoxyl group of 1 to 20 carbon atom, dialkylamino, alkane sulfydryl or alkane are silica-based; Perhaps R
1, R
2, R
3Be the aryl or the substituted aryl of 6-36 carbon atom, the perhaps heteroaryl or the substituted heteroaryl of 4 to 36 carbon atoms.
It is poly-that (2,6-) and poly-2,7-anthryl ethene derivatives can prepare with methods such as the Gilch polymerization under the base catalysis, Heck coupling or Wittg reactions as the preparation method of electroluminescent material.The synthetic technology route is:
Compound C 1 is by 1 in the formula, and 4-para benzoquinone 35 grams, 80 milliliters of isoprene and ethanol add in 1000 milliliters of single port flasks for 350 milliliters, and violent heated and stirred back flow reaction was cooled off in frozen water after 30-40 hour, filter white crystalline solid thing C1, yield 68%; Compound C 2 is obtained through the ethyl alcohol recrystallization secondary by C1; Compound C 3 is dissolved in behind the 4%KOH by C1 and is blasting under the air in 40-50 degree reaction 8 hours, product ethanol diafiltration, and drying provides, yield 91%; Compound C 4 is added in 200 milliliters of ammoniacal liquor by 15 grams of Compound C 3, add 0.05-0.15 gram copper sulfate and 10 gram zinc powders again, stir this mixture and be warming up to 80 degree reactions 6 hours, cold filtration and washing, solids leaches with acetone, adds the propyl alcohol dissolving behind the leaching liquid evaporate to dryness, the solution hcl acidifying, filtration is also used the methyl alcohol diafiltration, and drying obtains, productive rate 67%; Compound C 5 is by the preparation of Compound C 3 methods; Compound C 6 is by the preparation of Compound C 4 methods; Compound C 7 is dissolved in by 2.1 grams of Compound C 6 and is added drop-wise to behind 30 milliliters of methylene dichloride in 200 milliliters of methylene dichloride that contain 1.1 milliliter of 3.3 gram bromine, and the stirring at normal temperature reaction removes after 2 hours and desolvates, and adds the methyl alcohol agitation and filtration, and drying obtains 3.5 grams, yield 94%.
With the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method, the synthetic technology route also can for:
Compound C 8 is added among 100 milliliters of DMF by pyrocatechol 11.1 grams, 2-ethylhexyl bromine 17.5 grams, salt of wormwood 20 grams in the formula, 80 degree stirring reaction are down used extracted with diethyl ether after 16 hours, wash three times, organic phase is removed after with dried over mgso and is desolvated, and drying obtains 15.2 grams; Compound C 9 is dissolved among 80 milliliters of DMF of exsiccant by 9.6 gram 43.2mmol of Compound C 8, NBS7.7 gram 43.2mmol is dissolved in 30 milliliters of DMF, and two solution are mixed in 0 degree, reacts to add entry after 2 hours, use extracted with diethyl ether, steam solvent after washing three times and obtain 12 grams; Compound C 10 is added among 70 milliliters of DMF by 8.3 grams, 2-ethylhexyl bromine 6.5 grams, salt of wormwood 7 grams of Compound C 9,80 degree stirring reaction are down used extracted with diethyl ether after 16 hours, wash three times, remove after the dried over mgso and desolvate, add the methyl alcohol agitation and filtration, drying obtains 9.7 grams; Compound C 11 is under nitrogen protection, 7.5 gram 18.2mmol of Compound C 10 are dissolved in anhydrous 50 milliliters of THF and place dry ice-propanone to bathe, drip 13 milliliters of n-Butyl Lithiums, stirring reaction adds 3 milliliters of trimethyl-boron acid esters after 1 hour, rise to room temperature after 10 minutes and continued stirring reaction 10 hours, use extracted with diethyl ether after adding 2M hydrochloric acid termination reaction again, wash three times, remove after the dried over mgso and desolvate, after column chromatography is separated with ethyl acetate/normal hexane, obtain 4.8 grams;
Compound C 12 is under nitrogen protection, add 50 milliliters and 60 milliliters 2M aqueous sodium carbonates of toluene with being equipped with in the twoport flask that Compound C 114.6 restrains, Compound C 71.82 restrains, four-triphenyl phosphorus palladium 0.82 restrains, the reflux stirring reaction was told organic layer after 24 hours, remove after the dried over mgso and desolvate, after column chromatography is separated with methylene dichloride/normal hexane, obtain 4.0 grams;
Compound C 13 is under nitrogen protection, 3.2 grams, NBS1.4 gram, the BP096 milligram of Compound C 12 are dissolved in 80 milliliters of tetracol phenixin, the backflow stirring reaction removes after 3 hours and desolvates, and resistates obtains 2.7 grams after short column chromatography separates with methylene dichloride/normal hexane; Compound C 14 adds 7 milliliters of triethoxy phosphorus P (OC by 1.5 grams of Compound C 13
2H
5)
3Middle back flow reaction removal of solvent under reduced pressure after 6 hours, crude product obtains 1.1 grams after short column chromatography separates with ethyl acetate/normal hexane;
The synthetic of polymkeric substance 4 places 250 milliliters of dry single port flasks by 0.48 gram of Compound C 13 with to 53 milligrams of tertiary butyl bromotoluenes, with anti-chewing-gum plug sealing back nitrogen replacement, importing 70 milliliters of anhydrous THF is placed in the ice-water bath, under agitation slowly add 4 milliliters of 1M potassium tert.-butoxide tetrahydrofuran solutions with syringe, stirring reaction after 4 hours mixture pour precipitation polymers in a large amount of methyl alcohol into, filter and with 2: 1 methanol, methyl alcohol is washed, vacuum drying polymkeric substance is dissolved in chloroform through methyl alcohol reprecipitation secondary, obtain 0.23 gram, gel osmoticing chromatogram analysis shows that the polymkeric substance weight-average molecular weight is 207000, polydispersity 4.3, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 385 ℃, does not observe second-order transition temperature before 385 ℃.
The synthetic technology route can also for:
Compound C 15 is by meta phenylene diamine 2.2 gram and excessive Tributyl phosphate ester PO (OC in the formula
4H
9)
3After 12 hours, this mixture obtains 5.4 grams through column chromatography with ethyl acetate/normal hexane separation 180 ℃ of back flow reaction; Compound C 16 is dissolved in behind distillatory DMF on the hydrolith by 3.5 grams of compound 15, slowly add 2.5 milliliters of phosphorus oxychloride, the stirring at normal temperature reaction added the entry dichloromethane extraction after 3 hours, wash three times, steam solvent after column chromatography with ethyl acetate/normal hexane separate 3.5 the gram;
The synthetic of polymkeric substance 20 is that 0.5001 gram of Compound C 14 and 0.1700 gram of Compound C 16 are placed two 50 milliliters of dry single port flasks respectively, with anti-chewing-gum plug sealing back nitrogen replacement, after each imports 10 milliliters of anhydrous THF, the single port flask that fills Compound C 14 is placed dry ice acetone bath, the LDA cyclohexane solution that under agitation slowly adds 0.7 milliliter of 1.5M with syringe, stirring reaction slowly added Compound C 16 solution with syringe after 1 hour, continue stirring reaction and be placed on room temperature reaction in 30 minutes 5 hours, added micro-Paradimethylaminobenzaldehyde afterreaction 2 hours again, stopping the back with less water extracts with methylene dichloride-water, the organic phase anhydrous sodium sulfate drying, pour in the methyl alcohol after the filtration and precipitate, three final vacuum dryings of reprecipitation obtain 0.46 gram polymkeric substance 20, gel osmoticing chromatogram analysis shows that the weight-average molecular weight of polymkeric substance and polydispersity are respectively 42000 and 1.95, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 370 degree, does not observe second-order transition temperature before 370 degree.
Polymerization process only is illustrative with the molecular weight that is used for resulting polymers of the present invention.Polymkeric substance can prepare with methods such as the Gilch polymerization under the base catalysis, Heck coupling and Wittg reactions.Exemplary polymkeric substance and monomer synthetic technology route and sign thereof are in an embodiment.These only are illustrative, can use as long as the polymkeric substance of preparation satisfies any monomer and the polymerization process of following general formula.
The invention provides and shown in structural formula I, contain 2,6-or 2,7-anthryl ethene structural unit also has good solubility and the anthryl luminescent conjugated polymers of thermostability, and the rigidity chromophore in the main polymer chain has increased the rigidity of polymer backbone, and has improved thermal characteristics.The polymkeric substance that contains these chromophores be high fluorescence and luminescent material efficiently.Polymkeric substance shown in the structural formula I is to adopt Gilch polymerization or Heck coupling or Wittg prepared in reaction.The preferred Gilch polymerization of 2,6 (2,7)-anthryl Alathons or its multipolymer.This also only is illustrative, can use as long as the polymkeric substance of preparation satisfies any monomer and the polymerization process of structure shown in the structural formula I.
The invention provides that a kind of poly-(2,6-) and poly-2,7-anthryl ethene derivatives is as electroluminescent material and preparation method thereof.Not only be provided for the novel anthryl luminescence polymer material of polymer electroluminescence device, and the luminescence polymer of different band gaps is provided, and these gather 2,6-or 2,7-anthryl Alathon or contain the multipolymer of these anthryl ethene structural units can be launched the color gamut of broad.
Electroluminescent material provided by the present invention has lot of advantages such as the good solubility of comprising, efficient and stability.The glow color of polymkeric substance can be easily by introducing required Ar
1, Ar
2, particularly the Ar group is regulated.And other electro-optical properties also can be used the Ar group, comprises Ar
1, Ar
2The variation of group is regulated.Material of the present invention also can be as the material of main part of other photoelectric material.
Anthryl polymkeric substance provided by the invention is used in the el light emitting device.This device places the polymer light-emitting layer between anode and the negative electrode to constitute by an anode, negative electrode and one.They can be multilayered structure, bilayer structure and single layer structure, as: an emission layer is arranged between transparent anode and metallic cathode, emission layer be electroluminescent medium also be the charged particle carrier layer, such el light emitting device is a single layer structure, can use polymkeric substance of the present invention to make emission layer.The bilayer structure el light emitting device comprises a hole transmission layer and the electron transfer layer near hole transmission layer near anode layer, and electron transfer layer also is to produce electroluminescent emission layer, and negative electrode is near electron transfer layer.Hole transmission layer and electron transfer layer constitute electroluminescent medium together, and this device can use polymkeric substance of the present invention to make emission layer.
The electroluminescent medium of multilayered structure el light emitting device is made of together hole transmission layer, emission layer and electron transfer layer, and hole transmission layer is near anode, and electron transfer layer has an emission layer near negative electrode between hole transmission layer and electron transfer layer.Emission layer produces electroluminescent, and this device can use polymkeric substance of the present invention to make emission layer.Said structure is described and only is used to illustrate the present invention, and the thickness of emission layer can change in 10-1000nm.
Description of drawings
Fig. 1 represents absorption, emission, the photoluminescence spectra of polymkeric substance 4.Fig. 2 represents absorption, emission, the photoluminescence spectra of polymkeric substance 20.Fig. 3 represents the electroluminescent spectrum by the individual layer el light emitting device of polymkeric substance 4 and polymkeric substance 20 manufacturings.Fig. 4 is the structural formula general formula of this electroluminescent material.
The embodiment example
Embodiment 1.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives is as electroluminescent material, the polymkeric substance 1 that its structural formula is listed as follows.
Polymkeric substance 1 polymkeric substance 2
Embodiment 2.A kind of poly-(2,6-) and poly-2, the electroluminescent material that 7-anthryl ethene derivatives constitutes, its structural formula is seen above-listed polymkeric substance 2.
Embodiment 3.A kind of poly-(2,6-) and poly-2, the electroluminescent material that 7-anthryl ethene derivatives constitutes, the polymkeric substance 3 that its structural formula is listed as follows.
Polymkeric substance 3 polymkeric substance 4
Embodiment 4.A kind of poly-(2,6-) and poly-2, the electroluminescent material that 7-anthryl ethene derivatives constitutes, its structural formula is seen above-listed polymkeric substance 4.
Embodiment 5.A kind of poly-(2,6-) and poly-2, the electroluminescent material that 7-anthryl ethene derivatives constitutes, the polymkeric substance 5 that its structural formula is listed as follows.
Polymkeric substance 5 polymkeric substance 6
Embodiment 6.A kind of poly-(2,6-) and poly-2, the electroluminescent material that 7-anthryl ethene derivatives constitutes, its structural formula is seen above-listed polymkeric substance 6.
Embodiment 7.A kind of poly-(2,6-) and poly-2, the electroluminescent material that 7-anthryl ethene derivatives constitutes, the polymkeric substance 7 that its structural formula is listed as follows.
Polymkeric substance 7 polymkeric substance 8
Embodiment 8.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, and its structural formula is seen above-listed polymkeric substance 8.
Embodiment 9.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 9 that its structural formula is listed as follows.
Polymkeric substance 9
Polymkeric substance 12
Embodiment 10.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, and its structural formula is seen above-listed polymkeric substance 12.
Embodiment 11.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 13 that its structural formula is listed as follows.
Polymkeric substance 13
Embodiment 12.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 15 that its structural formula is listed as follows.
Polymkeric substance 15 polymkeric substance 16
Embodiment 13.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, and its structural formula is seen above-listed polymkeric substance 16.
Embodiment 14.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 17 that its structural formula is listed as follows.
Polymkeric substance 17
Embodiment 15.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 18 that its structural formula is listed as follows.
Polymkeric substance 18
Embodiment 16.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 19 that its structural formula is listed as follows.
Polymkeric substance 19
Embodiment 17.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 20 that its structural formula is listed as follows.
Embodiment 18.It is a kind of that poly-(2,6-) and poly-2,7-anthryl ethene derivatives constitutes the electroluminescent material of luminescent layer, the polymkeric substance 21 that its structural formula is listed as follows.
Polymkeric substance 20 polymkeric substance 21
The foregoing description 1～21 can be widely used in making el light emitting device.Preferred el light emitting device structure is a single-shot photosphere structure, and it comprises an anode, negative electrode and individual layer electroluminescent medium.This electroluminescence layer is an emission layer, also can transmission electronic and hole.This layer can comprise one or more mixture of polymers in above embodiment 1～21 polymkeric substance; Or with one or more fluorescence dyes, phosphor material or the adulterated the present invention's of other luminescent material polymkeric substance.
The electroluminescent material of embodiment 1～21 has and comprises good solubility, high luminous efficiency and high lot of advantages such as thermostability.The glow color of polymkeric substance can be easily by introducing required Ar
1, Ar
2, particularly the Ar group is regulated.And other electro-optical properties also can be used the Ar group, comprises Ar
1, Ar
2The variation of group is regulated.Material of the present invention also can be as the material of main part of other photoelectric material.
Above mentioned polymkeric substance can be deposited as high-quality transparent film by the method for rotation coating or spray ink Printing polymers soln, preferably rotates paint-on technique and single electroluminescent medium layer.
Exemplary monomer and polymkeric substance synthetic route such as scheme 1-3 and explanation thereof:
Scheme 1
Compound C 1 is by 1 in the scheme 1,4-para benzoquinone 35 grams, 80 milliliters of isoprene and ethanol add in 1000 milliliters of single port flasks for 350 milliliters, violent heated and stirred back flow reaction was cooled off in frozen water after 30-40 hour, filter white crystalline solid thing C1, yield 68%.
Compound C 3 is dissolved in behind the 4%KOH by C1 and is blasting under the air in 40-50 ℃ of degree reaction 8 hours, product ethanol diafiltration, and drying provides, yield 91%,
1H-NMR (300MHz, CDCl
3), δ (ppm): 8.18 (d, 2H, J=9.0Hz), 8.08 (s, 2H), 7.58 (d, 2H, J=9.0Hz), 2.53 (s, 6H);
Compound C 4 is added in 200 milliliters of ammoniacal liquor by 15 grams of Compound C 3, adds 0.05-0.15 gram copper sulfate and 10 gram zinc powders again, stirs this mixture and is warming up to 80 ℃ of reactions 6 hours.Cold filtration and washing, solids leaches with acetone, adds the propyl alcohol dissolving behind the leaching liquid evaporate to dryness, the solution hcl acidifying, filtration is also used the methyl alcohol diafiltration, and drying obtains, productive rate 67%,
1H-NMR (300MHz, CDCl
3), δ (ppm): 8.33 (s, 1H), 8.27 (s, 2H), 8.21 (s, 1H), 7.89 (d, 4H, J=9.0Hz), 7.73 (d, 4H, J=9.0Hz), 7.28 (dd, 4H, J
1=9.0Hz, J
2=3.0Hz), 2.54 (s, 12H);
Compound C 5 prepares by Compound C 3 methods,
1H-NMR (300MHz, CDCl
3), δ (ppm): 818 (d, 2H, J=9.0Hz), 8.08 (s, 2H), 7.58 (d, 2H, J=9.0Hz), 2.53 (s, 6H);
Compound C 6 prepares by Compound C 4 methods,
1H-NMR (300MHz, CDCl
3), δ (ppm): 8.27 (s, 2H); 7.88 (d, 2H, J=9.0Hz), 7.73 (d, 2H, J=9.0Hz), 7.28 (d, 2H, J=9.0Hz), 2.54 (s, 6H);
Compound C 7 is restrained by 2.1 of Compound C 6 and is added drop-wise in 200 milliliters of methylene dichloride that contain 1.1 milliliter of 3.3 gram (20.6) bromine after (10.2mmol) is dissolved in 30 milliliters of methylene dichloride, the stirring at normal temperature reaction removes after 2 hours and desolvates, add the methyl alcohol agitation and filtration, drying obtains (yield 94%) 3.5 grams
1H-NMR (300MHz, CDCl
3), δ (ppm): 8.42 (d, 2H, J=9.0Hz), 8.28 (s, 2H), 7.42 (d, 2H, J=9.0Hz), 2.60 (s, 6H).
Compound C 8 in the scheme 2: pyrocatechol 11.1 grams, 2-ethylhexyl bromine 17.5 grams, salt of wormwood 20 grams add among 100 milliliters of DMF, 80 ℃ of following stirring reactions were used extracted with diethyl ether after 16 hours, wash three times, organic phase is removed after with dried over mgso and is desolvated, drying obtains (containing di-substituted on a small quantity, yield 73%) 15.2 grams
1H-NMR (300MHz, CDCl
3), δ (ppm): 6.94 (d, 2H, J=9.0Hz), 6.85 (m, 3H), 5.61 (s, 1H), 3.93 (d, 2H, J=6.0Hz), 1.77 (m, 1H), 1.48 (m, 4H), 1.33 (m, 4H), 0.94 (m, 6H);
Compound C 9 is dissolved among 80 milliliters of DMF of exsiccant by 9.6 grams (43.2mmol) of Compound C 8, NBS7.7 gram (43.2mmol) is dissolved in 30 milliliters of DMF, two solution are mixed in 0 ℃, react and add entry after 2 hours, use extracted with diethyl ether, steam solvent after washing three times and obtain (yield 92%) 12 grams
1H-NMR (300MHz, CDCl
3), δ (ppm): 6.97 (m, 2H), 6.80 (d, 1H, J=9.0Hz), 5.54 (s, 1H), 3.90 (d, 2H, J=6.0Hz), 1.77 (m, 1H), 1.45 (m, 4H), 1.33 (m, 4H), 0.94 (m, 6H);
Compound C 10 is added among 70 milliliters of DMF by 8.3 grams, 2-ethylhexyl bromine 6.5 grams, salt of wormwood 7 grams of Compound C 9, and 80 ℃ of following stirring reactions were used extracted with diethyl ether after 16 hours, washed three times, remove after the dried over mgso and desolvate, add the methyl alcohol agitation and filtration, drying obtains (yield 85%) 9.7 grams
1H-NMR (300MHz, CDCl
3), δ (ppm): 6.80 (d, 1H, J=9.0Hz), 6.72 (s, 1H), 6.68 (d, 1H, J=9.0Hz), 3.85 (m, 4H), 2.54 (t, 2H, J=7.5Hz), 1.75 (m, 2H), 1.50 (m, 8H), 1.34 (m, 8H), 0.94 (m, 12H);
Compound C 11: under nitrogen protection; 7.5 grams with Compound C 10; (18.2mmol) be dissolved in anhydrous 50 milliliters of THF and place dry ice-propanone to bathe; drip 13 milliliters of n-Butyl Lithiums; (1.6M hexane solution); stirring reaction adds 3 milliliters of trimethyl-boron acid esters after 1 hour; rise to room temperature after 10 minutes and continued stirring reaction 10 hours; use extracted with diethyl ether after adding 2M hydrochloric acid termination reaction again; wash three times; remove after the dried over mgso and desolvate; through column chromatography; (ethyl acetate/normal hexane) obtains after separating; (yield 71%) 4.8 grams
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.82 (d, 1H, J=9.0Hz), 7.68 (s, 1H), 6.90 (d, 1H, J=9.0Hz), 4.01 (d, 2H, J=6.0Hz), 3.96 (d, 2H, J=6.0Hz), 1.81 (m, 4H), 1.52 (m, 8H), 1.36 (m, 8H), 0.94 (m, 12H).
Compound C 12: under nitrogen protection; to be equipped with in the twoport flask of Compound C 114.6 gram (12mmol), Compound C 71.82 gram (5mmol), four-(triphenyl phosphorus) palladiums 0.82 gram (0.71mmol) and add 50 milliliters and 60 milliliters 2M aqueous sodium carbonates of toluene; the reflux stirring reaction was told organic layer after 24 hours; remove after the dried over mgso and desolvate; after separating, column chromatography (methylene dichloride/normal hexane) obtains (yield 92%) 4.0 grams
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.66 (d, 2H, J=9.0Hz), 7.50 (s, 2H), 7.17 (d, 2H, J=9.0Hz), 7.11 (d, 2H, J=9.0Hz), 6.97 (m, 4H), 4.04 (d, 4H, J=6.0Hz), 3.85 (d, 4H, J=6.0Hz), 2.41 (s, 6H), 1.88 (m, 2H), 1.78 (m, 2H), 1.48 (m, 16H), 1.33 (m, 16H), 0.97 (m, 24H);
Compound C 13: under nitrogen protection; 3.2 grams (3.6mmol), NBS1.4 gram (7.9mmol), the BPO96 milligram (0.4mmol) of Compound C 12 are dissolved in 80 milliliters of tetracol phenixin; the backflow stirring reaction removes after 3 hours and desolvates; resistates obtains (yield 73%) 2.7 grams after short column chromatography (methylene dichloride/normal hexane) separates
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.78 (d, 2H, J=9.0Hz), 7.72 (s, 2H), 7.36 (d, 2H, J=9.0Hz), 7.10 (d, 2H, J=9.0Hz), 6.94 (m, 4H), 4.56 (s, 4H), 4.04 (d, 4H, J=6.0Hz), 3.85 (d, 4H, J=6.0Hz), 1.88 (m, 2H), 1.78 (m, 2H), 1.51 (m, 16H), 1.37 (m, 16H), 0.97 (m, 24H).
Compound C 14 adds 7 milliliters of triethoxy phosphorus (P (OC by 1.5 grams of Compound C 13
2H
5)
3) in back flow reaction removal of solvent under reduced pressure after 6 hours, crude product obtains (yield 68%) 1.1 grams after short column chromatography (ethyl acetate/normal hexane) separates,
1H-NMR (300MHz, CDCl
3), δ (ppm): 8.44 (d, 2H, J=9.0Hz), 8.30 (s, 2H), 7.78 (d, 2H, J=9.0Hz), 7.37 (d, 2H, J=9.0Hz), 6.64 (m, 4H), (s, 4H).4.14(m，8H)，4.07(m，8H)，3.32(d，4H，J＝21.0Hz)，1.88(m，2H)，1.78(m，2H)，1.51(m，16H)，1.37(m，16H)，1.30(t，12H，J＝6.0Hz)，0.97(m，24H)；
The synthetic of polymkeric substance 4 places 250 milliliters of dry single port flasks by 0.48 gram (0.47mmol) of Compound C 13 with to tertiary butyl bromotoluene 53 milligrams (0.24mmol), with anti-chewing-gum plug sealing back nitrogen replacement, importing about 70 milliliters of anhydrous THF is placed in the ice-water bath, under agitation slowly add 4 milliliters of 1M potassium tert.-butoxide tetrahydrofuran solutions with syringe, stirring reaction after 4 hours mixture pour precipitation polymers in a large amount of methyl alcohol into, filter and with methanol (2: 1), methyl alcohol is washed, vacuum drying polymkeric substance is dissolved in chloroform through methyl alcohol reprecipitation secondary, obtain 0.23 gram, gel permeation chromatography (GPC, eluent THF, standard substance is a polystyrene) analysis revealed polymkeric substance weight-average molecular weight is 207000, polydispersity 4.3, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 385 ℃, does not observe second-order transition temperature before 385 ℃.
Scheme 3
Compound C 15 is by meta phenylene diamine 2.2 gram and excessive Tributyl phosphate ester (PO (OC in the scheme 3
4H
9)
3) 180 ℃ of back flow reaction after 12 hours, this mixture separates through column chromatography (ethyl acetate/normal hexane) and obtains (yield 80%) 5.4 grams,
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.01 (t, 1H, J=7.5Hz), 6.05 (d, 2H, J=9.0Hz), 6.01 (s, 1H), 3.16 (t, 8H, J=6.0Hz), 1.84 (m, 8H), 1.45 (m, 8H), 0.92 (t, 12H, J=7.5Hz);
Compound C 16 is dissolved in behind distillatory DMF on the hydrolith by 3.5 grams of compound 15, slowly add 2.5 milliliters of phosphorus oxychloride, the stirring at normal temperature reaction is after 3 hours, add the entry dichloromethane extraction, wash three times, steam solvent and obtain (yield 85%) 3.5 grams after column chromatography (ethyl acetate/normal hexane) is separated
1H-NMR (300MHz, CDCl
3), δ (ppm) 9.80 (s, 2H), 8.11 (s, 1H), 6.28 (s, 1H), 3.21 (t, 8H, J=6.0Hz), 1.88 (m, 8H), 1.47 (m, 8H), 0.92 (t, 12H, J=7.5Hz);
Synthesizing of polymkeric substance 20: 0.5001 gram (0.4372mmol) of Compound C 14 and 0.1700 gram (0.4372mmol) of Compound C 16 are placed two 50 milliliters of dry single port flasks respectively, with anti-chewing-gum plug sealing back nitrogen replacement, after each imports about 10 milliliters of anhydrous THF, the single port flask that fills Compound C 14 is placed dry ice acetone bath, the LDA cyclohexane solution that under agitation slowly adds 0.7 milliliter of 1.5M with syringe, stirring reaction slowly added Compound C 16 solution with syringe after 1 hour, continue stirring reaction and be placed on room temperature reaction in 30 minutes 5 hours, added micro-Paradimethylaminobenzaldehyde afterreaction 2 hours again, stopping the back with less water extracts with methylene dichloride-water, the organic phase anhydrous sodium sulfate drying, pour in the methyl alcohol after the filtration and precipitate, three final vacuum dryings of reprecipitation obtain 0.46 gram polymkeric substance 20, gel permeation chromatography (GPC, eluent THF, standard substance is a polystyrene) weight-average molecular weight and the polydispersity of analysis revealed polymkeric substance be respectively 42000 and 1.95, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 370 degree, does not observe second-order transition temperature before 370 degree.
The el light emitting device of single polymeric film luminescent layer of the present invention makes up according to following procedure:
After the glass matrix that scribbles indium-tin-oxide (ITO) is washed with washing composition, distilled water and ethanol successively, be exposed to several minutes in UV-light and the ozone.The rotation of PEDOT+PSS (Bayer) aqueous dispersions is coated in ITO and goes up formation 100nm thickness film, and drying is 10 minutes under 105 ℃.Then will apply the polymeric film that forms the about 80nm of thickness in the above through the filtering polymers soln of 0.25 μ m PTFE strainer (chloroformic solutions of 6 mg/ml) rotation.On polymeric film in 5 * 10
-4The about 200nmBa of heat deposition under the Pa, heat deposition 150nm Al again, device architecture such as ITO/PEDOT+PSS/ polymeric film/Ba/Al.Test job is at room temperature carried out in common environment.
Fig. 1 is polymkeric substance 4 emmission spectrum under absorption and emmission spectrum and the membrane stage in toluene solution.
Fig. 2 is polymkeric substance 20 emmission spectrum under absorption and emmission spectrum and the membrane stage in toluene solution.
Fig. 3 is the electroluminescent spectrum of the single layer device of polymkeric substance 4 and 20.
Claims (3)
1. one kind is gathered 2, and 6-reaches and gathers 2, and 7-anthryl ethene derivatives is characterized in that as the preparation method of electroluminescent material the synthetic technology route is with the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method:
Compound C 1 is by 1 in the formula, and 4-para benzoquinone 35 grams, 80 milliliters of isoprene and ethanol add in 1000 milliliters of single port flasks for 350 milliliters, and violent heated and stirred back flow reaction was cooled off in frozen water after 30-40 hour, filter white crystalline solid thing C1, yield 68%;
Compound C 2 is obtained through the ethyl alcohol recrystallization secondary by C1; Compound C 3 is dissolved in behind the 4%KOH by C1 and is blasting under the air in 40-50 degree reaction 8 hours, product ethanol diafiltration, and drying provides, yield 91%; Compound C 4 is added in 200 milliliters of ammoniacal liquor by 15 grams of Compound C 3, add 0.05-0.15 gram copper sulfate and 10 gram zinc powders again, stir this mixture and be warming up to 80 degree reactions 6 hours, cold filtration and washing, solids leaches with acetone, adds the propyl alcohol dissolving behind the leaching liquid evaporate to dryness, the solution hcl acidifying, filtration is also used the methyl alcohol diafiltration, and drying obtains, productive rate 67%;
Compound C 5 is by the preparation of Compound C 3 methods; Compound C 6 is by the preparation of Compound C 4 methods;
Compound C 7 is dissolved in by 2.1 grams of Compound C 6 and is added drop-wise to behind 30 milliliters of methylene dichloride in 200 milliliters of methylene dichloride that contain 1.1 milliliter of 3.3 gram bromine, and the stirring at normal temperature reaction removes after 2 hours and desolvates, and adds the methyl alcohol agitation and filtration, and drying obtains 3.5 grams, yield 94%.
2. one kind is gathered 2, and 6-reaches and gathers 2, and 7-anthryl ethene derivatives is characterized in that as the preparation method of electroluminescent material the synthetic technology route is with the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method:
Compound C 8 is added among 100 milliliters of DMF by pyrocatechol 11.1 grams, 2-ethylhexyl bromine 17.5 grams, salt of wormwood 20 grams in the formula, 80 degree stirring reaction are down used extracted with diethyl ether after 16 hours, wash three times, organic phase is removed after with dried over mgso and is desolvated, and drying obtains 15.2 grams;
Compound C 9 is dissolved among 80 milliliters of DMF of exsiccant by 9.6 gram 43.2mmol of Compound C 8, NBS7.7 gram 43.2mmol is dissolved in 30 milliliters of DMF, and two solution are mixed in 0 degree, reacts to add entry after 2 hours, use extracted with diethyl ether, steam solvent after washing three times and obtain 12 grams;
Compound C 10 is added among 70 milliliters of DMF by 8.3 grams, 2-ethylhexyl bromine 6.5 grams, salt of wormwood 7 grams of Compound C 9,80 degree stirring reaction are down used extracted with diethyl ether after 16 hours, wash three times, remove after the dried over mgso and desolvate, add the methyl alcohol agitation and filtration, drying obtains 9.7 grams;
Compound C 11 is under nitrogen protection, 7.5 gram 18.2mmol of Compound C 10 are dissolved in anhydrous 50 milliliters of THF and place dry ice-propanone to bathe, drip 13 milliliters of n-Butyl Lithiums, stirring reaction adds 3 milliliters of trimethyl-boron acid esters after 1 hour, rise to room temperature after 10 minutes and continued stirring reaction 10 hours, use extracted with diethyl ether after adding 2M hydrochloric acid termination reaction again, wash three times, remove after the dried over mgso and desolvate, after column chromatography is separated with ethyl acetate/normal hexane, obtain 4.8 grams;
Compound C 12 is under nitrogen protection, add 50 milliliters and 60 milliliters 2M aqueous sodium carbonates of toluene with being equipped with in the twoport flask that Compound C 114.6 restrains, Compound C 71.82 restrains, four-triphenyl phosphorus palladium 0.82 restrains, the reflux stirring reaction was told organic layer after 24 hours, remove after the dried over mgso and desolvate, after column chromatography is separated with methylene dichloride/normal hexane, obtain 4.0 grams;
Compound C 13 is under nitrogen protection, 3.2 grams, NBS1.4 gram, the BP096 milligram of Compound C 12 are dissolved in 80 milliliters of tetracol phenixin, the backflow stirring reaction removes after 3 hours and desolvates, and resistates obtains 2.7 grams after short column chromatography separates with methylene dichloride/normal hexane; Compound C 14 adds 7 milliliters of triethoxy phosphorus P (OC by 1.5 grams of Compound C 13
2H
5)
3Middle back flow reaction removal of solvent under reduced pressure after 6 hours, crude product obtains 1.1 grams after short column chromatography separates with ethyl acetate/normal hexane;
The synthetic of polymkeric substance 4 places 250 milliliters of dry single port flasks by 0.48 gram of Compound C 13 with to 53 milligrams of tertiary butyl bromotoluenes, with anti-chewing-gum plug sealing back nitrogen replacement, importing 70 milliliters of anhydrous THF is placed in the ice-water bath, under agitation slowly add 4 milliliters of 1M potassium tert.-butoxide tetrahydrofuran solutions with syringe, stirring reaction after 4 hours mixture pour precipitation polymers in a large amount of methyl alcohol into, filter and with 2: 1 methanol, methyl alcohol is washed, vacuum drying polymkeric substance is dissolved in chloroform through methyl alcohol reprecipitation secondary, obtain 0.23 gram, gel osmoticing chromatogram analysis shows that the polymkeric substance weight-average molecular weight is 207000, polydispersity 4.3, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 385 ℃, does not observe second-order transition temperature before 385 ℃.
3. one kind is gathered 2, and 6-reaches and gathers 2, and 7-anthryl ethene derivatives is characterized in that as the preparation method of electroluminescent material the synthetic technology route is with the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method:
Compound C 14 adds 7 milliliters of triethoxy phosphorus P (OC by 1.5 grams of Compound C 13 in the formula
2H
5)
3Middle back flow reaction removal of solvent under reduced pressure after 6 hours, crude product obtains 1.1 grams after short column chromatography separates with ethyl acetate/normal hexane;
Compound C 15 is by meta phenylene diamine 2.2 gram and excessive Tributyl phosphate ester PO (OC
4H
9)
3After 12 hours, this mixture obtains 5.4 grams through column chromatography with ethyl acetate/normal hexane separation 180 ℃ of back flow reaction;
Compound C 16 is dissolved in behind distillatory DMF on the hydrolith by 3.5 grams of compound 15, slowly add 2.5 milliliters of phosphorus oxychloride, the stirring at normal temperature reaction added the entry dichloromethane extraction after 3 hours, wash three times, steam solvent after column chromatography is separated with ethyl acetate/normal hexane and obtain 3.5 grams;
The synthetic of polymkeric substance 20 is that 0.5001 gram of Compound C 14 and 0.1700 gram of Compound C 16 are placed two 50 milliliters of dry single port flasks respectively, with anti-chewing-gum plug sealing back nitrogen replacement, after each imports 10 milliliters of anhydrous THF, the single port flask that fills Compound C 14 is placed dry ice acetone bath, the LDA cyclohexane solution that under agitation slowly adds 0.7 milliliter of 1.5M with syringe, stirring reaction slowly added Compound C 16 solution with syringe after 1 hour, continue stirring reaction and be placed on room temperature reaction in 30 minutes 5 hours, added micro-Paradimethylaminobenzaldehyde afterreaction 2 hours again, stopping the back with less water extracts with methylene dichloride-water, the organic phase anhydrous sodium sulfate drying, pour in the methyl alcohol after the filtration and precipitate, three final vacuum dryings of reprecipitation obtain 0.46 gram polymkeric substance 20, gel osmoticing chromatogram analysis shows that the weight-average molecular weight of polymkeric substance and polydispersity are respectively 42000 and 1.95, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 370 degree, does not observe second-order transition temperature before 370 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100433709A CN100489008C (en) | 2006-03-28 | 2006-03-28 | Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100433709A CN100489008C (en) | 2006-03-28 | 2006-03-28 | Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844302A CN1844302A (en) | 2006-10-11 |
| CN100489008C true CN100489008C (en) | 2009-05-20 |
Family
ID=37063271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100433709A Expired - Fee Related CN100489008C (en) | 2006-03-28 | 2006-03-28 | Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100489008C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102049973B1 (en) | 2012-12-27 | 2019-11-28 | 엘지디스플레이 주식회사 | Blue fluorescence compounds and organic light emitting diode devices using the same |
| CN111217660B (en) * | 2018-11-27 | 2021-06-01 | 中国科学院大连化学物理研究所 | Method for preparing 2, 6-dimethylanthracene from isoprene and 1, 4-benzoquinone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807974A (en) * | 1996-05-16 | 1998-09-15 | Korea Institute Of Science And Technology | Fluorene-based alternating copolymers for electroluminescence element and electroluminescence element using such copolymers as light emitting materials |
| CN1407054A (en) * | 2001-08-28 | 2003-04-02 | 伊斯曼柯达公司 | Electroluminescent device containing diaryl anthramine polymer |
-
2006
- 2006-03-28 CN CNB2006100433709A patent/CN100489008C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807974A (en) * | 1996-05-16 | 1998-09-15 | Korea Institute Of Science And Technology | Fluorene-based alternating copolymers for electroluminescence element and electroluminescence element using such copolymers as light emitting materials |
| CN1407054A (en) * | 2001-08-28 | 2003-04-02 | 伊斯曼柯达公司 | Electroluminescent device containing diaryl anthramine polymer |
Non-Patent Citations (2)
| Title |
|---|
| 可溶性聚蒽基乙烯的合成及其光电特性初步研究. 王晓燕，王声媛，陈宁等.2005年全国高分子学术论文报告会论文摘要集. 2005 |
| 可溶性聚蒽基乙烯的合成及其光电特性初步研究. 王晓燕，王声媛，陈宁等.2005年全国高分子学术论文报告会论文摘要集. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1844302A (en) | 2006-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100425671C (en) | Electroluminescent device containing diaryl anthramine polymer | |
| CN101024633B (en) | Tricyclic arylamine monomer and polymers and devices thereof | |
| CN102060982B (en) | Organic semiconductor material containing naphthalene [1, 2-c: 5, 6-c] di [1, 2, 5] thiadiazole and application thereof | |
| CN103270077B (en) | Macromolecular compound and organic el element using same | |
| CN1835986B (en) | Conjugated polymers containing dihydrophenanthrene units and use thereof | |
| CN103270111B (en) | Compositions and block type copolymer | |
| CN1322019C (en) | Light-emitting polymer and organoelectroluminescent display using the same | |
| CN1974709B (en) | Electroluminescent conjugated polymer containing polar radical and its application | |
| CN101321801A (en) | Copolymer and polymer light emitting devices made by using the same | |
| JP5341973B2 (en) | Novel production of useful monomers for semiconductor polymer products | |
| CN1166854A (en) | Conjugated polymers with hetero-spiroatoms and the use of such polymers as electroluminescent materials | |
| JP2001504533A (en) | Regular poly (arylene-vinylene) terpolymers, their preparation and their use as electroluminescent materials | |
| WO2016115726A1 (en) | Hyperbranched white light conjugated polymer and preparation method and use thereof | |
| CN103270079A (en) | High-molecular compound and light-emitting element using same | |
| CN1995097A (en) | Blue electroluminescent polymer, method of preparing blue electroluminescent polymer, and organic electroluminescent device employing the same | |
| CN103539737B (en) | A kind of azepine phenanthro- fluorene kind derivative, preparation method and electroluminescent fluorescent luminescent device | |
| CN101148508B (en) | Tricarbazole ultra-branching polymer | |
| CN100489008C (en) | Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same | |
| CN102295743A (en) | Fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application | |
| CN101389685A (en) | Block copolymer | |
| CN103547611B (en) | The light-emitting component of macromolecular compound and its formation of use | |
| CN113493564B (en) | Organic polymer luminescent material with D-sigma-A structure, and preparation method and application thereof | |
| CN109776768A (en) | A kind of blue light conjugated polymer and the preparation method and application thereof based on triphenylamine and sulphur dibenzofuran unit | |
| CN102127207B (en) | Polyfluorene/poly p-divinyl benzene and synthetic method thereof | |
| CN101654399B (en) | Phenanthrene benzene derivative and polymer thereof, copolymer containing phenanthrene benzene derivative and luminous material composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090520 Termination date: 20100328 |