CN1066163C - 用作电致发光材料的含氮聚合物 - Google Patents
用作电致发光材料的含氮聚合物 Download PDFInfo
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- CN1066163C CN1066163C CN95195962A CN95195962A CN1066163C CN 1066163 C CN1066163 C CN 1066163C CN 95195962 A CN95195962 A CN 95195962A CN 95195962 A CN95195962 A CN 95195962A CN 1066163 C CN1066163 C CN 1066163C
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- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 4
- 125000005594 diketone group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 poly (p-phenylene vinylene) Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XWMGGPWBYNTWTD-UHFFFAOYSA-N (6-benzoyl-9-methylcarbazol-3-yl)-phenylmethanone Chemical compound C=1C=C2N(C)C3=CC=C(C(=O)C=4C=CC=CC=4)C=C3C2=CC=1C(=O)C1=CC=CC=C1 XWMGGPWBYNTWTD-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000006053 organic reaction Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000000214 vapour pressure osmometry Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229940122361 Bisphosphonate Drugs 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004663 bisphosphonates Chemical class 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZIZMDHZLHJBNSQ-UHFFFAOYSA-N 1,2-dihydrophenazine Chemical compound C1=CC=C2N=C(C=CCC3)C3=NC2=C1 ZIZMDHZLHJBNSQ-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- ADDBIFUIFFYIQN-UHFFFAOYSA-N 9-methylcarbazole-3,6-dicarbaldehyde Chemical compound O=CC1=CC=C2N(C)C3=CC=C(C=O)C=C3C2=C1 ADDBIFUIFFYIQN-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 description 1
- 241000271309 Aquilaria crassna Species 0.000 description 1
- FWDBZJBJTDRIIY-UHFFFAOYSA-N CC(C)(C)[K] Chemical compound CC(C)(C)[K] FWDBZJBJTDRIIY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000009619 Gattermann reaction Methods 0.000 description 1
- 238000006052 Horner reaction Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006828 Rosenmund reduction reaction Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000006007 Sommelet synthesis reaction Methods 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- GRTGGSXWHGKRSB-UHFFFAOYSA-N dichloromethyl methyl ether Chemical compound COC(Cl)Cl GRTGGSXWHGKRSB-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/285—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having unsaturation outside the six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
本发明涉及含有式(Ⅰ)结构单元的含氮聚合物，式中的符号和标记有下述含义：
Ar1、Ar2、Ar3相同或不同，为单核和/或多核的、必要时通过一个或多个桥连接的、和/或稠合的芳基和/或杂芳基，它们可任选被取代；
X为一个单键、-O-、-S-、-SO-、-SO2、NR3、-CR4R5-、-CO-、-CR6＝CR7、CR8R9-CR10R11或SiR12R13；
R1-R13为相同或不同，为H、一个有1-22个碳原子的烷基或Ar4，其中Ar4与Ar1相同或不同，有与Ar1相同的含义；
n为1、2或3。
Description
主要在显示元件、显示屏技术和照明领域的许多应用场合，对大面积的固态光源有高的工业需求。用任何一种现有技术目前还不能满足对这些光源提出的技术要求。
近一些时候以来，已利用电致发光(EL)材料和设备如发光二极管(LED)作为对常规显示元件和照明元件如白炽灯、气体放电管和不发光液晶显示元件的替代物。
DE-A 2545 784(对应于US-A 3 995299)公开了一种有发光源的电致发光设备，它由这样一层无定形或基本上无定形的聚合物材料，该材料有相当大的电荷移动性以及低的电离势，以及一种强电子供体、一种强电子受体和优选有至少一种发光添加物组成，组成物间有电连接，通过这些连接，电流可通过该层全厚度范围，并从该层激发出射线。
所用的聚合物材料包括共轭的聚合物如聚(对-亚苯基亚乙烯)(如参见WO-A 90/13148)，以及非共轭的聚合物(如参见I.Sokolik等，应用物理杂志，1993，74，3584)，共轭的聚合物材料通常有更高的电荷载体移动性的优点，因此有更高的效率和更低的阈电压。
除了基于聚合物的设备外，低分子量有机电致发光设备也已知道一些时候了。Saito等(应用物理通讯，1990，56，799)公开了这样的含三芳基胺芪作为发光层的设备。
虽然用这些材料得到了良好的结果，但这些化合物的性能仍有许多可改进的余地。
此外，因为电致发光材料、特别是那些基于聚合物的电致发光材料的开发到目前为止无论如何也不能认为已经完成，照明设备和显示设备的制造商仍对这种设备的各种各样电致发光材料感兴趣。
其原因之一是，只有发光材料与设备的其他组件的相互作用，才影响包括发光材料在内的质量。
所以，本发明的一个目的是提供这样一些新型的电致发光材料，它们适用于照明设备和显示设备，并改进这些设备的性能。
令人吃惊的是，现已发现，某些含氮的聚合物特别适合用作电致发光材料。
已知含三芳基单元的聚合物部分用作电子摄影法的光敏成分以及作为电光敏染料的感敏剂(US-A 4323203)，但是由此不能得知，有不同结构的新型聚合物通适用作电致发光材料。
所以，本发明涉及一种含有式(Ⅰ)结构单元的含氮聚合物式中的符号和标记有下述含义：
Ar1、Ar2、Ar3相同或不同，为单核和/或多核的、必要时通过一个或多个、优选一个桥连接的和/或稠合的芳基和/或杂环芳基，它们优选有4-400个碳原子、优选4-100、更优选4-20，必要时它们可被取代；
X为一单键、-O-、-S-、-SO-、-SO2、NR3、-CR4R5-、-CO-、-CR6=CR7、CR8R9-CR10R11或SiR12R13；R1-R13为相同或不同，为H、一个烃基，烃基必要时可被取代，也可含杂原子，优选O和/或F，烃基有1-22个碳原子，或为Ar4，Ar4可与Ar1相同或不同，有与Ar1相同的含义；
n为1、2或3、优选1或2、更优选1。
优选由式(Ⅰ)结构单元组成的聚合物。本发明的聚合物特别是具有低电致发光阈电压和高效率的特点。而且，它们特别适合作空穴导体材料。
对于本发明来说，这些材料称为电致发光材料，它们可用作电致发光设备的活性层。活性层指当施加电场时，该层能发光(发光层)和/或它能改进正电荷和/或负电荷的注入和/或转移(电荷注入层或电荷转移层)。
所以，本发明还涉及含有式(Ⅰ)结构单元的聚合物作为电致发光材料、特别是作为空穴导体材料的应用，以及涉及含有式(Ⅰ)结构单元的一种或多种聚合物的电致发光材料。
本发明的聚合物通常有2-1000、优选3-500、更优选4-300个重复单元。
这样一些含有式(Ⅰ)结构单元的聚合物是优选的，其中符号和标记有下述含义：
Ar1、Ar2相同或不同、优选相同的，为
Ar3与Ar1、Ar3相同或不同，有如Ar1相同的含义，但在每种情况下三个可能的键联点位中仅两个键联，或者为其中k为1-20、优选1、2或3；
这时，Ar1、Ar2、Ar3可相同或不同地被一个或多个R14取代；
X、Z相同或不同，为一个单键、-O-、-S-、-SO2-、-NR3-、-CR4R5-、-CO-、CR6=CR7-、-CR8R9-CR10R11-或-SiR12R13；
Y为-O-、-S-或-NR3-；
R1-R13为H；一个有1-22个碳原子的烷基直链的或支链的，其中一个或两个不相邻的CH2基可任选被-O-、-S-、-CO-、-CO-O-、-O-OC-或-Si(CH3)2-替代；为一个有3-10个碳原子的环烷基；或为Ar4，其中Ar4与Ar1-Ar3相同或不同，有与Ar1-Ar3相同的含义，但三个可能的键中只有一个键联，R4-R11也为F、CF3、O-CF3或CN；
R14为相同的或不同的，为H；一个有1-22个、优选1-12个碳原子的烷基，其中一个或2个不相邻的CH2也可任选被-O-、-S-、-CO-、-CO-O-、-O-OC-或Si(CH3)2-替代；或为-CF3、-Ph、-O-Ph、-S-Ph、-SO-Ph、-SO2-Ph、F、Cl、Br、I或-CN；n为1、2或3、优选1或2、更优选1。
特别优选的、含式(Ⅰ)结构单元的聚合物是这样一些聚合物，其中符号和标记有下述含义：
式中m为1-20、优选1、2或3、更优选1，
R1、R2与Ar3相同或不同，与Ar3有相同的含义，但对聚合物的两个可能的键联点位中，只有一个键联，或者为
或为H；一个有1-12个碳原子的直链或支链烷基，其中一个或二个不相邻CH2可任选被-O-、-S-、-CO-、-CO-O-、-O-OC-或-Si(CH3)2-替代；一个有3-6个碳原子的环烷基；或一个有7-11个碳原子的芳烷基；
R15-R21相同或不同，为F，Cl，一个有1-22、优选1-12个碳原子的直链或支链烷基或烷氧基；
R18-R21也可为氢。
特别优选这样的含有式(Ⅰ)结构单元的聚合物，其中Ar1和Ar2有相同的含义，以及特别优选这样的含式(Ⅰ)结构单元的聚合物，其中R2为H或Ar4。
本发明的聚合物可为均聚物或共聚物。共聚物含有不同的式(Ⅰ)结构单元和/或其他的可共轭或非共轭的结构单元，如1，4-亚苯基或α，ω-亚烷基。
本发明所用的新型聚合物的制备宜通过式(Ⅱ)的双醛或双酮
式中，Ar1、Ar2、R1、R2和X有式(Ⅰ)中规定的含义，与式(Ⅲ)的有机磷化合物缩合来实现，
式中，Ar2有式(Ⅰ)中规定的含义，Z为C1-C22烷氧基，优选乙氧基；或者芳基，优选苯基。
缩合在碱性缩合剂、优选叔丁醇钾或氢化钠作用下进行。
缩聚作用优选按这样的方式进行，使原料组分(Ⅱ)和(Ⅲ)的等摩尔混合物作为最初的物料送入溶剂中，然后在惰性气氛和搅拌下，将至少摩尔量缩合剂以溶液或悬浮液形式加入。
根据该法的另一变通方案，缩合剂本身也可作为最初的物料或与双酮一起作为最初的物料送入溶剂中，然后加入双磷组分。优选的溶剂是苯、甲苯、二甲苯或二甲基甲酰胺，反应温度优选为60-120℃，反应时间为0.1-20小时、优选0.1-5、更优选0.1-1。反应差不多为定量反应。
可通过加水，任选加酸如乙酸，然后分出有机反应相进行分离。为了纯化，可用如醇类或乙酸萃取制得的缩合产物，或者用非溶剂从溶液中沉积出来。
这种制备方法通常在下述文献中描述：DD84272，Horhold，H.-H.：化学杂志，12，41-52(1972)；Horhold，H.-H.；Bergmann，R.；Gottschaldt，J.；Drefahl.G.：匈牙利科学院化学学报，81，239-251；Horhold，H.-H.；Bergmann，R.：热稳定聚合物化学的进展，Warszawa，波兰科学出版社，29-48(1977)；Horhold，H.-H.；Helbig，M.：大分子化学，大分子文集，12，229-258(1987)和Horhold，H.-H.；Helbig，M.；Raabe，D.；Dpformann，J.；Scherf.U.；Stockmann，R.；WeiB，D.：化学杂志，27，126(1987)。
在Horner反应中生成的E/Z异构体以及由两个双键彼此可能的位置(反-反-反式、反-反-顺式、顺-反-反式，顺-反-顺式、顺-顺-反式、顺-顺-顺式)得到的异构体都在本发明涉及的范围内。
如果分别使用不同的双醛或双酮和/或双膦酸酯，那么可用简单的方式得到含有不同式(Ⅰ)结构单元的共聚物。在这些共聚物中，式(Ⅰ)中的R1基团必要时有不同的含义。此外，至少一种共聚单体的延迟加入提供了制备各种嵌段共聚物的可能性。
另一方面，含有式(Ⅰ)结构单元的聚合物的较小基团也可例如用FeCl3氧化聚合(参见P.Kovacic，N.B.Jones，化学通讯，1987，87，357-379；M.Weda，T.Abe，H.Awano，大分子，1992，25，5125)，或电化学聚合(参见如N.Saito，T.Kanbara，T.Sato，T.Yamamoto，聚合物通报，1993，30，285)，其中Ar1指Ar5-Ar5，Ar5为富电子的芳族化合物，优选噻吩-2，5-亚基，必要时它可被取代：
氧化聚合
同样，在Scholl反应条件下，芳族化合物氧化偶合也是可能的：
(例如参见J.March，高等有机化学，第3版，第484页及以下各页，McGraw Hill以及那里所引的文献)。
为了控制聚合过程中的摩尔质量，加入单官能的醛或酮，例如加入市售可得的N-乙基-3-咔唑羧基醛(由Aldrich，Milwaukee，USA得到)，或者加入下述化合物，它很容易由4-氟苯甲醛得到，以便生成规定的末端基团，这也是可能的，
如果2摩尔单官能的醛或酮与1摩尔式(Ⅲ)的有机磷化合物一起使用，可得到式(Ⅰa)的倍半链节，
其中符号和标记有式(Ⅰ)中给定的相同含义以及相同的优选含义。
这样的化合物、特别是与本发明聚合物的混合物同样适合用作电致发光材料。
有间位取代的结构单元的原料化合物的聚合可得到大环化合物。
所以，本发明的聚合物或按本发明使用的聚合物也可在与所述大环化合物的混合物中存在，后者的存在不影响作为电致发光材料的应用。
原料化合物(Ⅱ)和(Ⅲ)的制备可按从文献中已知的方法进行，如在有机合成的标准著作中描述的，例如Houben-Weyl，有机化学方法，Georg-Thieme-出版社，斯图加特。
所述的制备在已知的、并适合上述反应的反应条件下进行。也可利用本身已知的、而在这里未详细提到的各种变通方案。
需要的作为缩合组分的双(二苯基氧化膦)或双(膦酸酯)例如可通过Michaelis-Arbusov反应，由相应的双(卤代甲基)化合物与二苯基膦酸乙酯(C6H5)2P-O-C2H5或与亚磷酸三乙酯方便地制得。
式(Ⅱ)的双醛的合成可根据本专业的技术人员已知的各种反应类型来进行。
例如可用还原剂如三烷氧基阿兰酸锂或H2/Pd进行受控还原(“Rosenmund还原”)，由双羧酸衍生物来制得：
(参见如Fusoniu Patai，“羰基化学”，第1卷，第211-232页，Interscience，New York 1966)
(参见如Tylander，“在铂族金属上的催化加氢”，第398-404页，Academic Press，New York，1967)。
例如通过Sommelet反应，有可能由双(氯甲基)前体制得双醛：
(参见如Angyal，有机反应，1954，8，197)。
但是，优选的是，下面的胺(Ⅳ)和(Ⅴ)进行亲电子的芳族取代。
对此有许多方法是已知的，例如Gattermann-Koch反应： (参见如Grounise，有机反应，1949，5，290-300)；Gattermann反应：
(参见如Truce，有机反应，1957，9，37-72)；或芳族化合物与二氯甲基甲基醚的反应：
(参见如Rieche等，化学通讯，1960，93，88或Lewin等，有机制备过程(Org.Prep.Proced.Int.)，1978，10，201)。
但是，优选Vilsmeier反应(同样用DMF)：
(参见如Jutz，有机化学进展，第9卷，第1部分，第225--342页，Bohme，Viche编辑，Interscience，New York 1976，或Jackson，美国化学学会杂志，1981，103，533)。
如果式(Ⅰ)中的R1不为氢，那么双酮用作原料。
如果所用的酰胺不是甲酰胺，那么它们例如可通过上述Vilsmeier反应来制备。
双酮也可通过Friedel-Crafts酰化反应来制备：
(参见如Olah，弗瑞德-克来福特及相关的反应，第2卷，第979-1047页，Interscience，New York 1963-65)；或通过格利雅反应，用氰基芳烃来制备：
(参见如Kharasch和Rainmuth，非金属物质的格利雅反应，第767-845页，Prentice Hall，Eagle-Wood Clifrs，N.J.1954)。双醛和双酮的原料化合物是胺(Ⅳ)。它们用本专业的技术人员已知的方法来制备。
这样的方法例如在以下文献中描述：A.R.Katritzky和I.M.Lagowski，杂环化学原理，Methuen，London 1967或在A.Weissberger和E.C.Taylor(编辑)的“杂环化合物化学”系列中相关卷。
例如式(Ⅳ)的胺可由相应的二碘化合物制得：
这些化合物中有许多也可商购，例如咔唑、N-甲基咔唑、N-苯基咔唑、N-二苯基咔唑、二氢吩嗪、吖啶酮、吩噁嗪(二苯并噁嗪)、吩噻嗪(二苯并噻嗪)(所有的都由Aldrich，Steinheim，Germany得到)或9，9-二苯基-9，10-二氢-9-硅杂吖啶和9，9-二苄基-9，10-二氢-9-硅杂吖啶(由Salor，Steinheim，Germany得到)。
对于本发明用作电致发光材料的聚合物来说，它们通常用本专业的技术人员已知的方法如蘸涂或旋转涂法涂覆到基材上。
所以，本发明还涉及一种制备这样一种电致发光材料的方法，该法包括
a)使式(Ⅲ)的有机磷化合物
与式(Ⅱ)的双醛或双酮
在碱性缩合剂存在下缩合，生成含有式(Ⅰ)结构单元的聚合物，式中，符号和标记有下述含义：
Ar1、Ar2、Ar3相同或不同，为单核和/或多核的、必要时通过一个或多个、优选一个桥连接的、和/或稠合的芳基和/或杂芳基，它们优选有4-400、优选4-100、更优选4-20个碳原子，必要时可被取代；X为1个单键、-O-、-S-、-SO-、-SO2、NR3、-CR4R5、-CO-、-CR6=CR7、CR8R9-CR10R11或SiR12R13；
R1-R13相同或不同，为氢、一个有1-22个碳原子的烃基或Ar4，其中Ar4有与Ar1相同的含义；
n为1、2或3、优选1或2、更优选1；以及
b)将生成的含有式(Ⅰ)结构单元的聚合物作为薄膜涂覆到必要时已有其他层的基材上。
本发明还涉及一种含有一层或多层活性层的电致发光设备，所述的活性层中至少有一层含有本发明的一种或多种聚合物。活性层例如可为发光层和/或电荷转移层和/或电荷注入层。优选的是，它是发光层或空穴导体层。
这样的电致发光设备的一般结构如在US-A4539 507和US-A5151629中公开。含有聚合物的电致发光设备例如在WO-A90/13148或EP-A 0443861中公开。
它们通常在阴极和阳极之间有一电致发光层，电极中至少一个是透明的。另外，电子注入层和/或电子转移层可夹在电致发光层和阴极之间，和/或空穴注入层和/或空穴转移层可夹在电致发光层和阳极之间。金属和金属合金如Ca、Mg、Ag、In或Mg/Ag可作为阴极。在透明基材如玻璃或透明聚合物制成的基材上的金属如Au或其他金属导电材料如ITO(氧化铟/氧化锡)可用作阳极。
在操作过程中，阴极相对于阳极处于负电势。在这一方法中，电子从阴极注入电子注入层/电子转移层或直接注入发光层。同时，空穴从阳极注入空穴注入层/空穴转移层或直接注入发光层。
在施加的电压影响下，注入的电荷载体通过有效层相互运动。因此，在电荷转移层和发光层之间的界面处或在发光层内产生电子/空穴对，它们再组合，在这一过程中发光。发光的颜色可通过用作发光层的材料来改变。
电致发光设备例如用作照明显示元件如信号灯、字母数字显示、信息符号，以及用于光电偶合元件。
用实施例更详细地说明本发明，但不打算用这些实施例来限制本发明。
Tg：玻璃化转变温度，用差示扫描量热法测量
Mn：数均分子量
VPO：蒸汽压渗透压测定法(参见如Cherdron，Kern，Braun，实用大分子化学)
GPC：-凝胶渗透色谱法，聚苯乙烯作标准
实施例
实施例1
3，6-二苯甲酰基-9-甲基咔唑
3，6-二苯甲酰基-9-甲基咔唑(4)：将67.0克(0.37摩尔)9-甲基咔唑溶于400毫升干燥二氯乙烷中，然后将105.0克(0.79摩尔)AlCl3加入。在搅拌和用冰冷却下，将104.0克(0.74摩尔)苯甲酰氯滴入。在室温下继续搅拌3小时，然后用冰和盐酸分解反应混合物，用水和NaHCO3溶液洗涤有机相至中性。用共沸蒸馏法除去剩余的水。浓缩二氯乙烷溶液，同时使双酮结晶出来。从二氯乙烷中重结晶多次；熔点222℃(文献167：熔点219℃)，无色晶体。产量：114.2克(79.3％)。C27H19NO2(389.5)计算值C83.27 H4.92 N3.60测量值C83.45 H4.86 N3.50
实施例2
聚(9-甲基咔唑-3，6-二基-1-苯基-1，2-亚乙基-2，5-二辛氧基-1，4-亚苯基-2-苯基-1，2-亚乙基)
3，6-二苯甲酰基-9-甲基咔唑 [389.1]=1.83克(0.0047摩尔)
2，5-二辛氧基-对-二甲基-双
(磷酸二乙酯) [634.7]=3.00克(0.0047摩尔)
叔丁基钾 [112.2]=2.00克
溶剂：甲苯 (0.0178摩尔)
在搅拌下和惰性气体下，将双酮和双膦酸酯溶于少量的沸腾甲苯中，然后将固体叔丁醇钾一次加入。混合物突然变粘稠。10分钟后，将约20毫升甲苯加入，使搅拌变得容易。继续搅拌2小时后，汽提出溶剂，将残留物吸收在氯仿中，随后在异丙醇中沉淀。用甲醇萃取得到的黄色絮状物5小时，并多次沉淀(氯仿/甲醇)。干燥后，得到黄色粉末，产率为68％。分析数据：
-玻璃化转变温度Tg：90℃
-荧光λ最大发射=505纳米θ=30％
-UV/VIS=λ最大吸收=400.8纳米1gε=4.5
-EOX-1=0.91伏对Ag/AgCl
-Mn(VPO)=4500
-Mn(GPC)=5200Mw(GPC)=11300
实施例3
原料3，6-二甲酰基-N-甲基-咔唑用Vilsmeier反应来制备。进一步的合成按类似实施例2的方式进行。
Mw＞10000
ΦPL75％，聚合物溶于氯苯，而很少溶于氯仿。
实施例4
电致发光设备
在氮气下，将实施例2得到的聚合物的2％(重量)溶液用旋转涂覆法在500转/分下涂覆在用ITO(氧化铟锡)涂覆过的玻璃载体上(结构化的2毫米宽的条)。玻璃载体保持在惰性气氛下，通过一锁合装置转移到高真空蒸汽沉积系统中。在2×10-5毫巴下，将Ca条(2毫米宽，230纳米厚)横过ITO条蒸汽沉积到聚合物层上，其中使用一掩模。将如此制得的设备即ITO/聚合物/Ca放在一简单的电极夹中，电极通过弹簧接点与电源相连，ITO条连接到正极端，而Ca条连接到负极端。如果施加足够高的电压，在相应的基质元件上得到绿色的电致发光。
阈电压：7.0伏
最大效率：0.032％
最大亮度：120新烛光/米2(在13伏和7毫安/4毫米2下)
Claims (13)
1．一种含有式(Ⅰ)结构单元的聚合物，
式中，各符号和标记有下述含义：
Ar1、Ar2、Ar3相同或不同，为单核和/或多核的、未被或被一个或多个桥连接的、和/或稠合的芳基和/或杂芳基，碳原子，它们未被取代或被取代；
X为一个单键、-O-、-S-、-SO-、-SO2、NR3、-CR4R5-、-CO-、-CR6=CR7、CR8R9-CR10R11或SiR12R13；
R1-R13相同或不同，为H、一个可被取代的有1-22个碳原子的烃基，它还可含有杂原子；或Ar4，其中Ar4与Ar1相同或不同，有与Ar1相同的含义；
n为1、2或3。
2．根据权利要求1的聚合物，其特征在于，它由式(Ⅰ)的结构单元组成。
3．根据权利要求1的聚合物，其特征在于，它有2-1000个重复单元。
4．根据权利要求1-3中任一项的聚合物，其特征在于，它为共聚物的形式。
5．根据权利要求4的聚合物，其特征在于，它含有式(Ⅰ)的不同结构单元。
6．根据权利要求1-3中任一项的聚合物，其特征在于，其中式(Ⅰ)中的符号和标记有下述含义：
Ar3与Ar1、Ar3相同或不同，有与Ar1相同的含义，但在每一情况下三个可能的键联点位中只有两个键联，或者为
Ar1、Ar2、Ar3这时可相同或不同，并可被一个或多个R14基取代；
X、Z相同或不同，为一个单键、-O-、-S-、-SO-、-SO2-、-NR3、-CR4R5-、-CO-、CR6=CR7、CR8R9-CR10R11或SiR12R13；
Y为-O-、-S-或-NR3-；
R1-R13为H；一个有1-22个碳原子的直链或支链烷基，其中一个或两个不相邻的CH2基可被-O-、-S-、-CO-、-CO-O-、-O-OC-或Si(CH3)2-替代；一个有3-10个碳原子的环烷基，或Ar4，其中Ar4与Ar1～Ar2相同或不同，有Ar1、Ar3相同的含义，但三个可能的键联点位中只有一个键联；R4-R11也为F、CF3、O-CF3或CN；R14相同或不同，为H，有1-22个碳原子的烷基，其中一个或两个不相邻的CH2基可被-O-、-S-、-CO-、-CO-O-、-O-OC-或Si(CH3)2-替代，-CF3、-Ph、-O-Ph、-S-Ph、-SO-Ph、-SO2-Ph、F、Cl、Br、I或-CN；
n为1、2或3。
7．根据权利要求1-3中任一项的聚合物，其特征在于，式(Ⅰ)中的符号和标记有下述含义： 
式中，m为1-20、优选1、2或3，
R1、R2与Ar3相同或不同，有与Ar3相同的含义，但两个可能的键联点位中只有一个键联连接到聚合物上；或者为
或为H；一个有1-12个碳原子的直链或支链的烷基，其中一个或两个不相邻的CH2基可被-O-、-S-、-CO-、-CO-O-、-O-OC-或Si(CH3)2-替代；一个有3-6个碳原子的环烷基；或有7-11个碳原子的芳烷基；
R5-R21相同或不同，为F、Cl、一个有1-22个碳原子的直链或支链的烷基，
R8-R21也可为氢。
8．根据权利要求1-3中任一项的聚合物，其特征在于，其中Ar1和Ar2为相同的。
9．一种制备按上述权利要求中任一项的聚合物的方法，其特征在于，使式(Ⅱ)的双醛或双酮
式中，Ar1、Ar2、R1、R2和X有式(Ⅰ)中规定的含义，与式(Ⅲ)的有机磷化合物缩合，
式中，Ar3有式(Ⅰ)中规定的含义，Z为C1-C22烷氧基。
10．权利要求1-8中任一项的聚合物作为电致发光材料的应用。
11．一种含有权利要求1-8中任一项的一种或多种聚合物的电致发光材料。
12．一种制备权利要求11的电致发光材料的方法，其特征在于，该方法包括
a)使式(Ⅲ)的有机磷化合物
与式(Ⅱ)的双醛或双酮在碱性缩合剂存在下缩合，生成含式(Ⅰ)结构单元的聚合物，
式中，符号和标记有下述含义：
Ar1、Ar2、Ar3相同或不同，为单核和/或多核的、未被或被一个或多个桥连接的、和/或稠合的芳基和/或杂芳基，碳原子，它们未被取代或被取代；
X为一个单键、-O-、-S-、-SO-、-SO2、NR3、-CR4R5-、-CO-、-CR6=CR7、CR8R9-CR10R11或SiR12R13；
R1-R13为相同或不同，为H、一个有1-22个碳原子的烃基或Ar4，其中Ar4与Ar1相同或不同，有与Ar1相同的含义；
n为1、2或3；以及
b)将生成的含有式(Ⅰ)结构单元的聚合物以膜的形式涂覆到必要时已有其他层的基材上。
13．一种有一层或多层活性层的电致发光设备，所述的活性层中至少一层含有权利要求1-8中任一项的一种或多种聚合物。
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| DEP4435047.3 | 1994-09-30 | ||
| DE4435047A DE4435047A1 (de) | 1994-09-30 | 1994-09-30 | Poly(paraphenylenvinylen)-Derivate und ihre Verwendung als Elektrolumineszenzmaterialien |
| DE19505416.4 | 1995-02-17 | ||
| DE19505416A DE19505416A1 (de) | 1995-02-17 | 1995-02-17 | Poly(paraphenylenvinylen)-Derivate und ihre Verwendung als Elektrolumineszenzmaterialien |
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| CN1162323A CN1162323A (zh) | 1997-10-15 |
| CN1066163C true CN1066163C (zh) | 2001-05-23 |
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| CN95195962A Expired - Fee Related CN1066163C (zh) | 1994-09-30 | 1995-09-28 | 用作电致发光材料的含氮聚合物 |
| CN95195330A Expired - Fee Related CN1122696C (zh) | 1994-09-30 | 1995-09-28 | 聚(对亚苯基亚乙烯基)衍生物及其作为场致发光材料的用途 |
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| US (1) | US5874179A (zh) |
| EP (2) | EP0783541B1 (zh) |
| JP (2) | JPH10506426A (zh) |
| CN (2) | CN1066163C (zh) |
| AT (1) | ATE175695T1 (zh) |
| DE (2) | DE59504835D1 (zh) |
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| JP5691177B2 (ja) | 2009-01-29 | 2015-04-01 | 住友化学株式会社 | 高分子化合物及びそれを用いる発光素子 |
| EP2492988B1 (en) | 2009-10-22 | 2018-12-26 | Sumitomo Chemical Company, Limited | Organic electroluminescent element |
| JP5710994B2 (ja) | 2010-01-28 | 2015-04-30 | 住友化学株式会社 | 高分子化合物及びそれを用いてなる発光素子 |
| US20140017762A1 (en) * | 2011-03-28 | 2014-01-16 | Hitachi Chemical Research Center, Inc. | Network conjugated polymers with enhanced solubility |
| EP3681889A1 (en) * | 2017-09-13 | 2020-07-22 | Merck Patent GmbH | Organic semiconducting compounds |
| CN112701238B (zh) * | 2021-01-06 | 2022-11-11 | 长春海谱润斯科技股份有限公司 | 一种包含覆盖层及密封层的有机发光器件 |
| CN113307953B (zh) * | 2021-05-26 | 2022-07-22 | 齐鲁工业大学 | 一种固相聚咔唑衍生物电致发光体系及其构建方法和应用 |
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- 1995-09-28 JP JP8511384A patent/JPH10506426A/ja not_active Ceased
- 1995-09-28 EP EP95933436A patent/EP0783555B1/de not_active Expired - Lifetime
- 1995-09-28 US US08/809,772 patent/US5874179A/en not_active Expired - Fee Related
- 1995-09-28 WO PCT/EP1995/003836 patent/WO1996010598A1/de active IP Right Grant
- 1995-09-28 DE DE59504835T patent/DE59504835D1/de not_active Expired - Fee Related
- 1995-09-28 CN CN95195962A patent/CN1066163C/zh not_active Expired - Fee Related
- 1995-09-28 DE DE59510507T patent/DE59510507D1/de not_active Expired - Fee Related
- 1995-09-28 WO PCT/EP1995/003835 patent/WO1996010617A1/de active IP Right Grant
- 1995-09-28 CN CN95195330A patent/CN1122696C/zh not_active Expired - Fee Related
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- 1995-09-28 JP JP8511385A patent/JPH11501955A/ja active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH10506426A (ja) | 1998-06-23 |
| CN1159204A (zh) | 1997-09-10 |
| CN1162323A (zh) | 1997-10-15 |
| EP0783541B1 (de) | 1999-01-13 |
| ATE175695T1 (de) | 1999-01-15 |
| DE59504835D1 (de) | 1999-02-25 |
| DE59510507D1 (de) | 2003-01-23 |
| EP0783555B1 (de) | 2002-12-11 |
| WO1996010598A1 (de) | 1996-04-11 |
| US5874179A (en) | 1999-02-23 |
| EP0783555A1 (de) | 1997-07-16 |
| WO1996010617A1 (de) | 1996-04-11 |
| CN1122696C (zh) | 2003-10-01 |
| JPH11501955A (ja) | 1999-02-16 |
| EP0783541A1 (de) | 1997-07-16 |
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