JP3711383B2 - Copolymer having 9-silafluorene-9,9-diyl skeleton, method for producing the same, and light emitting material comprising the same - Google Patents
Copolymer having 9-silafluorene-9,9-diyl skeleton, method for producing the same, and light emitting material comprising the same Download PDFInfo
- Publication number
- JP3711383B2 JP3711383B2 JP2001266311A JP2001266311A JP3711383B2 JP 3711383 B2 JP3711383 B2 JP 3711383B2 JP 2001266311 A JP2001266311 A JP 2001266311A JP 2001266311 A JP2001266311 A JP 2001266311A JP 3711383 B2 JP3711383 B2 JP 3711383B2
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- JP
- Japan
- Prior art keywords
- silafluorene
- group
- formula
- diyl
- general formula
- 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 - Lifetime
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- -1 9-silafluorene-9,9-diyl skeleton Chemical group 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000463 material Substances 0.000 title claims description 7
- 229920001577 copolymer Polymers 0.000 title description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000005568 organylene group Chemical group 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- ZJHMRPBTRSQNPI-UHFFFAOYSA-N benzo[b][1]benzosilole Chemical compound C1=CC=C2[Si]C3=CC=CC=C3C2=C1 ZJHMRPBTRSQNPI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 241000790917 Dioxys <bee> Species 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000002367 halogens Chemical group 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- IQURIBNOAPIFPZ-UHFFFAOYSA-N 5,5-dichlorobenzo[b][1]benzosilole Chemical compound C1=CC=C2[Si](Cl)(Cl)C3=CC=CC=C3C2=C1 IQURIBNOAPIFPZ-UHFFFAOYSA-N 0.000 description 4
- 0 CCS1(c2ccccc2-c2c1cccc2)O*C Chemical compound CCS1(c2ccccc2-c2c1cccc2)O*C 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229920006158 high molecular weight polymer Polymers 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 229920000548 poly(silane) polymer Polymers 0.000 description 4
- 150000004053 quinones Chemical class 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- PYWOMDDOXZOOJZ-UHFFFAOYSA-N [Li]C1=CC=C([Li])C=C1 Chemical compound [Li]C1=CC=C([Li])C=C1 PYWOMDDOXZOOJZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 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
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- WMKGGPCROCCUDY-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one Chemical compound C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WMKGGPCROCCUDY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- KFCMUZONUPOPAC-UHFFFAOYSA-N C1=CC=C2[SiH2]C3=CC=CC=C3C2=C1 Chemical class C1=CC=C2[SiH2]C3=CC=CC=C3C2=C1 KFCMUZONUPOPAC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ODAJBJZSXXWXLB-UHFFFAOYSA-N [Li]C#C[Li] Chemical group [Li]C#C[Li] ODAJBJZSXXWXLB-UHFFFAOYSA-N 0.000 description 1
- TWJFKBDWCQSDLV-UHFFFAOYSA-N [Li]C1=CC=C([Li])O1 Chemical compound [Li]C1=CC=C([Li])O1 TWJFKBDWCQSDLV-UHFFFAOYSA-N 0.000 description 1
- VOTZHAZMXFYESM-UHFFFAOYSA-N [Li]C1=CC=CC([Li])=C1 Chemical compound [Li]C1=CC=CC([Li])=C1 VOTZHAZMXFYESM-UHFFFAOYSA-N 0.000 description 1
- CASDFPAHUXKYDO-UHFFFAOYSA-N [Li][C-]1C=CC=C1.[C-]1(C=CC=C1)[Li].[Fe+2] Chemical compound [Li][C-]1C=CC=C1.[C-]1(C=CC=C1)[Li].[Fe+2] CASDFPAHUXKYDO-UHFFFAOYSA-N 0.000 description 1
- RNUIRRIRPXUDDA-UHFFFAOYSA-N [Li]c1c2ccccc2c([Li])c2ccccc12 Chemical compound [Li]c1c2ccccc2c([Li])c2ccccc12 RNUIRRIRPXUDDA-UHFFFAOYSA-N 0.000 description 1
- UEPNOHZKMLHWNV-UHFFFAOYSA-N [Mg]CCCC[Mg] Chemical compound [Mg]CCCC[Mg] UEPNOHZKMLHWNV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical class Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical group C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、ケイ素原子で縮環した、９−シラフルオレン−９，９−ジイル骨格と、他の骨格との共重合体、それら共重合体の製造方法、及びその発光素子としての用途に関するものである。
【０００２】
【従来の技術】
９−シラフルオレン類は公知である。また、本発明者らの一部は、既に９−シラフルオレン−９，９−ジイル骨格のみを有するホモポリマーについて、Chem. Lett., 1997, 785、特開平１０−６７８５９、及び特開平１１−２２２５２５において開示した。しかし、９−シラフルオレン−９，９−ジイル骨格と、他の骨格との共重合体については、これまで知られていなかった。
【０００３】
【発明が解決しようとする課題】
本発明は、発光素子の構成材料として利用可能な、９−シラフルオレン−９，９−ジイル骨格と他の骨格との共重合体、及びそれら共重合体の製造方法を提供しようとするものである。
【０００４】
【課題を解決するための手段】
本発明者等は、上記課題を達成するために、鋭意努力を重ね、一般式（２）
【化１５】
【化１６】
【化１７】
【化１８】
【化１９】
【化２０】
【０００５】
即ち本発明によれば、
▲１▼一般式（１）
【化２１】
▲２▼一般式（３）
【化２２】
▲３▼一般式（４）
【化２３】
▲４▼一般式（７）
【化２４】
▲５▼上記の重合体類を構成要素とする蛍光材料。
▲６▼上記の重合体類を構成要素とする有機EL素子。
が提供される。
【０００６】
【発明の実施の形態】
本発明のポリ［オキシ（９−シラフルオレン−９，９−ジイル）］類を製造する原料である一般式（２）で表される９，９−ジハロ−９−シラフルオレンにおけるＸは、ハロゲンであるが、好ましくは塩素または臭素が例示される。
【０００７】
ポリ［オキシ（９−シラフルオレン−９，９−ジイル）］類は、オリゴマーから高分子量のポリマーまで作製することが可能であり、分子量には特に制限はないが、式（１）におけるｎが２以上、ポリマーとしての取扱易さを考えれば、１０，０００以下、より好ましくは２以上２，０００以下の正の整数であるものであり、９，９−ジハロ−９−シラフルオレンをホルムアミドと処理することにより、容易に得られる。本反応は通常溶媒を用いる。溶媒としてはハロシラン類と反応することなくこれを溶解するものであれば、特に制限はなく、これを例示すればトルエン等の炭化水素類、アセトン等のケトン類、酢酸エチル等のエステル類、クロロホルム等のハロゲン化炭化水素類が挙げられ、またこれらの混合溶媒を用いてもよい。９，９−ジハロ−９−シラフルオレンとホルムアミドとのモル比には特に制限はないが、１：２から１：５０、特に１：２から１：１０の間であることが特に好ましい。反応温度にも特に制限はないが、操作の容易さと反応速度とを考慮すれば、室温から１５０℃、より好ましくは５０℃〜１００℃で反応を行うのが好ましい。
【０００８】
本発明のポリ［（オルガニレン）（９−シラフルオレン−９，９−ジイル）］類は、オリゴマーから高分子量のポリマーまで作製することが可能であり、分子量には特に制限はないが、式（３）におけるｎが２以上、ポリマーとしての取扱易さを考えれば、１０，０００以下、より好ましくは２以上２，０００以下の正の整数であるものである。式（３）におけるオルガニレン基としては、対応する有機ジアニオン試薬が発生、または逐次的に発生させらるものであれば特に制限はないが、これを例示すれば、ｐ−フェニレン、ｍ−フェニレン、２，５−フリレン、２，５−チエニレン、１，１’−フェロセニレン、エチニレン、１，４−ブタジイニレン、９，１０−アントラセニレン、α，ω−アルキレン等を挙げることができる。これらポリ［（オルガニレン）（９−シラフルオレン−９，９−ジイル）］類は、一般式（２）で表される９，９−ジハロ−９−シラフルオレン（Ｘは、ハロゲンであるが、好ましくは塩素または臭素が例示される。）と、有機ジアニオン試薬とを反応させることによって、容易に製造される。
【０００９】
本発明の製造方法に用いられる有機ジアニオン試薬には特に制限はないが、これを例示すれば、ｐ−ジリチオベンゼン、ｍ−ジリチオベンゼン、二臭化ｐ−フェニレンジマグネシウム、２，５−ジリチオフラン、二臭化２，５−チオフェンジマグネシウム、１，１’−ジリチオフェロセン、１，２−ジリチオアセチレン、二臭化１，２−アセチレンジマグネシウム、１，４−ジリチオジアセチレン、９，１０−ジリチオアントラセン、二臭化１，４−ブチレンジマグネシウム等を挙げることができる。９，９−ジハロ−９−シラフルオレンと有機ジアニオン試薬との比率には特に制限はないが、生成物のポリ［（オルガニレン）（９−シラフルオレン−９，９−ジイル）］類の分子量を考慮すれば、１．３：１から１：１．３の間が好ましく、１．１：１から１：１．１の間がより好ましい。反応は通常溶媒を用いて行われ、ヘキサン、トルエン等の炭化水素、エーテル、ＴＨＦ等のエーテル類が好ましい。反応温度は−１００℃から＋５０℃、好ましくは、−８０℃から＋２５℃の範囲である。
【００１０】
本発明のポリ［（オルガニレンジオキシ）（９−シラフルオレン−９，９−ジイル）］類は、オリゴマーから高分子量のポリマーまで作製することが可能であり、分子量には特に制限はないが、式（４）におけるｎが２以上、ポリマーとしての取扱易さを考えれば、１０，０００以下、より好ましくは２以上２，０００以下の正の整数であるものである。式（４）におけるオルガニレンジオキシ基としては、対応するキノン類またはジオール類が入手可能なものであれば特に制限はないが、ｐ−フェニレンジオキシ基、１，４−ナフチレンジオキシ基、９，１０−フェナントリレンジオキシ基、９，１０−アントラセニレンジオキシ基、ｍ−フェニレンジオキシ基、α，α’−キシリレンジオキシ基、α，ω−アルキレンジオキシ基類、４，４’−ビフェニレンジオキシ基、４，４’−イソプロピリデンジフェニルジオキシ基等を挙げることができる。これらポリ［（オルガニレンジオキシ）（９−シラフルオレン−９，９−ジイル）］類は、９−シラフルオレンと、キノン類またはジオール類とを、パラジウム含有触媒の存在下に反応させることによって製造される。
【００１１】
本発明の製造方法に用いられるキノン類としては、特に制限はないが、これを例示すれば、ｐ−ベンゾキノン、１，４−ナフトキノン、９，１０−フェナントレンキノン、アントラキノン等を挙げることができる。また、本発明の製造方法に用いられるジオール類としては、特に制限はないが、これを例示すれば、ヒドロキノン、レゾルシン、α，α’−キシリレンジオール、α，ω−ジヒドロキシアルカン類、４，４’−ジヒドロキシビフェニル、ビスフェノールＡ等を挙げることができる。
【００１２】
９−シラフルオレンとキノン類またはジオール類とのモル比には特に制限はないが、生成するポリ［（オルガニレンジオキシ）（９−シラフルオレン−９，９−ジイル）］類の分子量を考慮すれば、５：１から１：５の間が好ましく、２：１から１：２の間がより好ましい。反応は通常溶媒を用いて行われ、トルエン、ベンゼン等の炭化水素類、塩化メチレン等のハロゲン化炭化水素類、エーテル、ＴＨＦ等のエーテル類が好ましい。反応温度は−２０℃から＋２００℃、好ましくは、０℃から１５０℃の範囲である。
【００１３】
パラジウム含有触媒としては、通常用いられるパラジウム金属、担持パラジウム触媒、種々のパラジウム塩、種々のパラジウム錯体、及びそれらの混合物またはそれらをふくむものを用いることができる。これらパラジウム含有触媒を例示すれば、パラジウム黒、パラジウムカーボン、酢酸パラジウム、塩化パラジウム、ビス（トリフェニルホスフィン）ジクロロパラジウム、ビス（トリエチルホスフィン）ジクロロパラジウム、ビス（トリシクロヘキシルホスフィン）パラジウム、テトラキス（トリフェニルホスフィン）パラジウム、トリス（トリエチルホスフィン）パラジウム、（テトラメチルエチレンジアミン）ジクロロパラジウム、アリルパラジウムクロリド二量体、ビス（ベンゾニトリル）ジクロロパラジウム、（１，５−シクロオクタジエン）ジクロロパラジウム、トリス（ジベンジリデンアセトン）ジパラジウム、ビス（アセチルアセトナト）パラジウム等を挙げることができる。
【００１４】
９−シラフルオレンとパラジウム含有触媒中のパラジウムとのモル比には特に制限はないが、収率を考慮すれば、２：１から１００，０００：１、好ましくは５：１から１０，０００：１の範囲から選ばれる。
【００１５】
本発明の一般式（７）
【化２５】
【００１６】
本発明の上記ポリシラン類の製造方法は、一般式（２）で表される９，９−ジハロ−９−シラフルオレンと、一般式（８）
【化２６】
【００１７】
９，９−ジハロ−９−シラフルオレン及びジハロシラン類におけるＸは、ハロゲンであるが、好ましくは塩素または臭素が例示される。ジハロシラン類のR及びR’は、アルキル基、アリール基、またはアラルキル基を示すが、これを例示すれば、メチル基、エチル基、イソプロピル基、ｓｅｃ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、２−エチルヘキシル基、デシル基、ドデシル基等のアルキル基、フェニル基、トリル基、ナフチル基、アニシル基、ビフェニリル基、フェノキシフェニル基等のアリール基、ベンジル基、α−フェネチル基、β−フェネチル基等のアラルキル基等を挙げることができる。
【００１８】
９，９−ジハロ−９−シラフルオレンとジハロシラン類とのモル比には特に制限はなく、製造されるポリシラン中における９−シラフルオレン−９，９−ジイルとシリレンとの比率との関連で、自由に決めることができる。重縮合反応におけるアルカリ金属としては、リチウム、ナトリウム、カリウム等を挙げることができる。また、重縮合反応は溶媒を用いて実施することができ、その溶媒を例示すれば、トルエン、キシレン等の炭化水素、エーテル、ＴＨＦ、ジオキサン等のエーテル類を挙げることができる。
反応温度は0℃から２００℃、より好ましくは２５℃から１５０℃の範囲で、これを実施することが出来る。
【００１９】
上記のポリ［オキシ（９−シラフルオレン−９，９−ジイル）］類、ポリ［（オルガニレン）（９−シラフルオレン−９，９−ジイル）］類、ポリ［（オルガニレンジオキシ）（９−シラフルオレン−９，９−ジイル）］類、及び一般式（７）
【化２７】
【００２０】
上記の重合体類は、いずれも膜及び溶液状態で蛍光を発する。即ち、蛍光材料として用いることができる。
【００２１】
上記の重合体類を発光層、電子輸送層、またはホール輸送層として、有機EL素子を構成することができる。
【００２２】
【実施例】
以下に本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。
【００２３】
実施例１
９，９−ジクロロ−９−シラフルオレン（３ｍｍｏｌ）とホルムアミド（２１ｍｍｏｌ）を酢酸エチル（９ｍｌ）中で３時間加熱環流した。塩化アンモニウムが沈殿するとともに、オリゴマーが有機層に浮遊した。大量の酢酸エチルで抽出し、水洗後、乾燥し、次いで溶媒を乾固した。収率８６％でポリ［オキシ（９−シラフルオレン−９，９−ジイル）］を得た。
【００２４】
このものは文献未収載の新規化合物である。２９ＳｉＮＭＲ（固体）−２７．６３ｐｐｍ。１３ＣＮＭＲ（ＣＰＭＡＳ）１２１．３，１２８．６，１３１．９，１４６．６ｐｐｍ。Ｔｄ５：４１８℃。元素分析：Ｃ３６Ｈ２６Ｓｉ３Ｏ４ としての計算値Ｃ７１．２５、 Ｈ４．３２％；実測値Ｃ７１．３７、Ｈ４．１４％。
【００２５】
実施例２
１，４−ジリチオベンゼン（１ｍｍｏｌ）のヘキサン（３ｍｌ）懸濁液を、−７８℃で、９，９−ジクロロ−９−シラフルオレン（１ｍｍｏｌ）のＴＨＦ（２ｍｌ）溶液に３０分かけて摘下した。−７８℃で３時間かくはん後、かくはんしながら徐々に室温にした。溶媒を乾固後、加水分解しエーテル抽出した。エーテル抽出液を乾燥後、乾固した。ＴＨＦ／イソプロピルアルコール＝１／１０から再沈し、ポリ［（１，４−フェニレン）（９−シラフルオレン−９，９−ジイル）］を５３％収率で得た。
【００２６】
このものは文献未収載の新規化合物である。１ＨＮＭＲ（ＴＨＦ−ｄ８）：７．１５−７．３５（broad、２Ｈ、ＡｒＨ）、７．４０−７．５５（broad、２Ｈ、ＡｒＨ）、７．５５−７．７０（broad、４Ｈ、ＡｒＨ）、７．７０−７．８５（broad、２Ｈ、ＡｒＨ）、７．８５−８．０（broad、２Ｈ、ＡｒＨ）ｐｐｍ。１３ＣＮＭＲ（ＴＨＦ−ｄ８）：１２２．０、１２８．５、１３１．６、１３４．７、１３５．６、１４９．７ｐｐｍ。２９ＳｉＮＭＲ（ＴＨＦ−ｄ８）：−１１．７１ｐｐｍ。Ｍｗ／Ｍｎ＝６９００／３４００。Ｔｄ５＝４０８℃。元素分析：Ｃ２２８Ｈ１５２Ｓｉ１３Ｃｌ２としての計算値Ｃ８２．２７、Ｈ４．６０％；実測値Ｃ８１．７３、Ｈ４．７５％。
【００２７】
実施例３
ｐ−ベンゾキノン（１．１ｍｍｏｌ）と９，９−ジクロロ−９−シラフルオレン（１．２ｍｍｏｌ）のベンゼン溶液にＰｄＣｌ２（ＰＥｔ３）２を０．０２０ｍｍｏｌ加え、窒素雰囲気で一晩加熱環流した。無色固体を濾別し、数回ベンゼンで洗浄して、ポリ［（１，４−フェニレンジオキシ）（９−シラフルオレン−９，９−ジイル）］を７４％収率で得た。
【００２８】
このものは文献未収載の新規化合物である。１ＨＮＭＲ（ＴＨＦ−ｄ８）：６．７０−６．８５（broad、４Ｈ、ＡｒＨ）、７．１５−７．２８（broad、２Ｈ、ＡｒＨ）、７．３５−７．４８（broad、２Ｈ、ＡｒＨ）、７．４８−７．６０（broad、２Ｈ、ＡｒＨ）、７．７８−７．９０（broad、２Ｈ、ＡｒＨ）ｐｐｍ。１３ＣＮＭＲ（ＴＨＦ−ｄ８）：１１９．２７、１１９．９４、１２７．０９、１２８．１５、１３１．４２、１３２．０８、１４５．９９，１４７．７１ｐｐｍ。２９ＳｉＮＭＲ（ＴＨＦ−ｄ８）：−２７．７９ｐｐｍ。Ｍｗ／Ｍｎ＝６９００／１５００。元素分析：Ｃ９０Ｈ６２Ｏ１１Ｓｉ５としての計算値Ｃ７４．０５、Ｈ４．２８％；実測値Ｃ７３．７９、Ｈ４．５９％。
【００２９】
実施例４
新たに作成したＮａディスパージョン９ｍｍｏｌをトルエン中で加熱環流させ、９，９−ジクロロ−９−シラフルオレン４ｍｍｏｌとジクロロジメチルシラン４ｍｍｏｌのトルエン４ｍｌ溶液を１０分間で加えた。その後加熱環流を３時間継続した。放冷後、エタノールを滴下してクエンチし、トルエンを追加した後、水洗した。不溶性固体を遠心分離した後、トルエン可溶分をＴＨＦ／メタノール＝１／８から再沈した。ポリ［（９，９−シラフルオレニレン）０．４４（ジメチルシリレン）０．５６］を収率４５％で得た。
【００３０】
このものは文献未収載の新規化合物である。１ＨＮＭＲ（Ｃ６Ｄ６）：−０．８〜０．９（very broad、６Ｈ、ＳｉＭｅ２、０．５６）、６．３〜７．８（very broad、８Ｈ、ＡｒＨ、０．４４）ｐｐｍ。１３ＣＮＭＲ（Ｃ６Ｄ６）：５．０、１２１．８、１２７．１、１２９．０、１３１．５、１３４．０、１４８．７ｐｐｍ。２９ＳｉＮＭＲ（Ｃ６Ｄ６）：−３３〜−３９、−３９〜−４４ｐｐｍ。Ｍｗ／Ｍｎ＝６００００／３７０００及び８９００／５３００、全体で３４０００／１１０００。元素分析：（Ｃ１２Ｈ８Ｓｉ）０．４４（Ｃ２Ｈ６Ｓｉ）０．５６としての計算値Ｃ６８．７０、Ｈ６．２０％；実測値Ｃ６８．５９、Ｈ６．０５％。
【００３１】
実施例５
実施例１〜４のポリマーのＵＶ吸収及び蛍光スペクトルを表１に示す。
【表１】
実施例６
実施例２のポリ［（１，４−フェニレン）（９−シラフルオレン−９，９−ジイル）］を発光・ホール輸送層に用い、Ａｌｑ３を電子輸送層に用いて、図１に示すような電界発光素子を作成した。このものは、図２に示すような輝度及び電流密度−電圧曲線を示し、最高１８カンデラ／ｍ２の発光強度を示した。従って、このものは電界発光材料として有効である。
【００３３】
【発明の効果】
以上のように、本発明により、蛍光素子、電界発光素子の構成要素として有用な９−シラフルオレン−９，９−ジイル骨格を有するポリマー及びその製造方法が提供される。
【図面の簡単な説明】
【図１】 本発明のポリマーを用いた電界発光素子の概念図
【図２】 電界発光素子の輝度及び電流密度−電圧曲線の説明図[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a copolymer of a 9-silafluorene-9,9-diyl skeleton fused with a silicon atom and another skeleton, a method for producing the copolymer, and its use as a light-emitting device. It is.
[0002]
[Prior art]
9-silafluorenes are known. In addition, some of the present inventors have already found that a homopolymer having only a 9-silafluorene-9,9-diyl skeleton is Chem. Lett., 1997, 785, JP-A-10-67859, and JP-A-11-11. Disclosed in 222225. However, a copolymer of 9-silafluorene-9,9-diyl skeleton and another skeleton has not been known so far.
[0003]
[Problems to be solved by the invention]
The present invention is intended to provide a copolymer of a 9-silafluorene-9,9-diyl skeleton and another skeleton that can be used as a constituent material of a light emitting device, and a method for producing the copolymer. is there.
[0004]
[Means for Solving the Problems]
In order to achieve the above-mentioned problems, the present inventors have made intensive efforts to achieve the general formula (2)
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[0005]
That is, according to the present invention,
(1) General formula (1)
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(2) General formula (3)
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(3) General formula (4)
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(4) General formula (7)
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(5) A fluorescent material comprising the above-mentioned polymers as constituent elements.
(6) An organic EL device comprising the above-described polymer as a constituent element.
Is provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
X in 9,9-dihalo-9-silafluorene represented by the general formula (2), which is a raw material for producing the poly [oxy (9-silafluorene-9,9-diyl)] s of the present invention, is halogen. Preferably, chlorine or bromine is exemplified.
[0007]
Poly [oxy (9-silafluorene-9,9-diyl)] s can be prepared from oligomers to high molecular weight polymers, and the molecular weight is not particularly limited, but n in the formula (1) is 2 or more, considering the ease of handling as a polymer, it is a positive integer of 10,000 or less, more preferably 2 or more and 2,000 or less, and 9,9-dihalo-9-silafluorene and formamide It can be easily obtained by processing. This reaction usually uses a solvent. The solvent is not particularly limited as long as it dissolves without reacting with halosilanes. For example, hydrocarbons such as toluene, ketones such as acetone, esters such as ethyl acetate, chloroform And halogenated hydrocarbons such as these may be used, and a mixed solvent thereof may be used. The molar ratio of 9,9-dihalo-9-silafluorene to formamide is not particularly limited, but is particularly preferably 1: 2 to 1:50, particularly 1: 2 to 1:10. Although there is no restriction | limiting in particular also in reaction temperature, When the ease of operation and reaction rate are considered, it is preferable to react from room temperature to 150 degreeC, More preferably, it is 50 to 100 degreeC.
[0008]
The poly [(organylene) (9-silafluorene-9,9-diyl)] s of the present invention can be prepared from oligomers to high molecular weight polymers, and the molecular weight is not particularly limited. In consideration of the ease of handling as a polymer, n is 2 or more in 3), and is a positive integer of 10,000 or less, more preferably 2 or more and 2,000 or less. The organylene group in the formula (3) is not particularly limited as long as the corresponding organic dianion reagent is generated or sequentially generated. For example, p-phenylene, m-phenylene, Examples include 2,5-furylene, 2,5-thienylene, 1,1′-ferrocenylene, ethynylene, 1,4-butadienylene, 9,10-anthracenylene, α, ω-alkylene, and the like. These poly [(organylene) (9-silafluorene-9,9-diyl)] s are 9,9-dihalo-9-silafluorene represented by the general formula (2) (X is a halogen, Preferably, chlorine or bromine is exemplified.) And an organic dianion reagent is reacted with easily.
[0009]
There is no particular limitation on the organic dianion reagent used in the production method of the present invention, and examples thereof include p-dilithiobenzene, m-dilithiobenzene, p-phenylene diamagnesium dibromide, 2,5- Dilithiofuran, 2,5-thiophenedimesium dibromide, 1,1′-dilithioferrocene, 1,2-dilithioacetylene, 1,2-acetylenedimagnesium dibromide, 1,4-dilithiodiacetylene, Examples include 9,10-dilithioanthracene and 1,4-butylene dimagnesium dibromide. The ratio of 9,9-dihalo-9-silafluorene to the organic dianion reagent is not particularly limited, but the molecular weight of the product poly [(organylene) (9-silafluorene-9,9-diyl)] s is not limited. In consideration, it is preferably between 1.3: 1 and 1: 1.3, more preferably between 1.1: 1 and 1: 1.1. The reaction is usually carried out using a solvent, and hydrocarbons such as hexane and toluene, and ethers such as ether and THF are preferred. The reaction temperature is in the range of -100 ° C to + 50 ° C, preferably -80 ° C to + 25 ° C.
[0010]
The poly [(organylenedioxy) (9-silafluorene-9,9-diyl)] s of the present invention can be prepared from oligomers to high molecular weight polymers, and the molecular weight is not particularly limited. In the formula (4), n is 2 or more, and considering the ease of handling as a polymer, it is a positive integer of 10,000 or less, more preferably 2 or more and 2,000 or less. The organylene dioxy group in formula (4) is not particularly limited as long as the corresponding quinones or diols are available, but p-phenylenedioxy group, 1,4-naphthylene dioxy group, 9,10-phenanthrene dioxy group, 9,10-anthracenylene dioxy group, m-phenylene dioxy group, α, α′-xylylene dioxy group, α, ω-alkylenedioxy groups, 4,4 '-Biphenylenedioxy group, 4,4'-isopropylidene diphenyldioxy group and the like can be mentioned. These poly [(organylenedioxy) (9-silafluorene-9,9-diyl)] s are produced by reacting 9-silafluorene with quinones or diols in the presence of a palladium-containing catalyst. Manufactured.
[0011]
The quinones used in the production method of the present invention are not particularly limited, and examples thereof include p-benzoquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, and anthraquinone. In addition, the diols used in the production method of the present invention are not particularly limited. For example, hydroquinone, resorcin, α, α′-xylylenediol, α, ω-dihydroxyalkanes, 4, 4'-dihydroxybiphenyl, bisphenol A, etc. can be mentioned.
[0012]
The molar ratio of 9-silafluorene to quinones or diols is not particularly limited, but the molecular weight of the resulting poly [(organylenedioxy) (9-silafluorene-9,9-diyl)] s is considered. Thus, it is preferably between 5: 1 and 1: 5, more preferably between 2: 1 and 1: 2. The reaction is usually carried out using a solvent, and hydrocarbons such as toluene and benzene, halogenated hydrocarbons such as methylene chloride, ethers such as ether and THF are preferred. The reaction temperature is in the range of −20 ° C. to + 200 ° C., preferably 0 ° C. to 150 ° C.
[0013]
As the palladium-containing catalyst, generally used palladium metal, supported palladium catalyst, various palladium salts, various palladium complexes, and mixtures thereof or those containing them can be used. Examples of these palladium-containing catalysts include palladium black, palladium carbon, palladium acetate, palladium chloride, bis (triphenylphosphine) dichloropalladium, bis (triethylphosphine) dichloropalladium, bis (tricyclohexylphosphine) palladium, tetrakis (triphenyl). Phosphine) palladium, tris (triethylphosphine) palladium, (tetramethylethylenediamine) dichloropalladium, allylpalladium chloride dimer, bis (benzonitrile) dichloropalladium, (1,5-cyclooctadiene) dichloropalladium, tris (dibenzylidene) Acetone) dipalladium, bis (acetylacetonato) palladium and the like.
[0014]
The molar ratio of 9-silafluorene to palladium in the palladium-containing catalyst is not particularly limited, but considering the yield, 2: 1 to 100,000: 1, preferably 5: 1 to 10,000: A range of 1 is selected.
[0015]
General formula (7) of the present invention
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[0016]
The method for producing the polysilanes of the present invention comprises 9,9-dihalo-9-silafluorene represented by the general formula (2) and the general formula (8).
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[0017]
X in 9,9-dihalo-9-silafluorene and dihalosilanes is a halogen, preferably chlorine or bromine. R and R ′ of dihalosilanes represent an alkyl group, an aryl group, or an aralkyl group. For example, methyl group, ethyl group, isopropyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group , Cyclohexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group and other alkyl groups, phenyl group, tolyl group, naphthyl group, anisyl group, biphenylyl group, phenoxyphenyl group and other aryl groups, benzyl group, α- Examples thereof include aralkyl groups such as phenethyl group and β-phenethyl group.
[0018]
The molar ratio of 9,9-dihalo-9-silafluorene to dihalosilanes is not particularly limited, and is related to the ratio of 9-silafluorene-9,9-diyl to silylene in the produced polysilane. You can decide freely. Examples of the alkali metal in the polycondensation reaction include lithium, sodium, and potassium. The polycondensation reaction can be carried out using a solvent. Examples of the solvent include hydrocarbons such as toluene and xylene and ethers such as ether, THF and dioxane.
This can be carried out at a reaction temperature ranging from 0 ° C. to 200 ° C., more preferably from 25 ° C. to 150 ° C.
[0019]
Poly [oxy (9-silafluorene-9,9-diyl)] s, poly [(organylene) (9-silafluorene-9,9-diyl)] s, poly [(organylene dioxy) (9 -Silafluorene-9,9-diyl)] and general formula (7)
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[0020]
All of the above polymers emit fluorescence in a film and a solution state. That is, it can be used as a fluorescent material.
[0021]
An organic EL device can be formed by using the above polymers as a light emitting layer, an electron transport layer, or a hole transport layer.
[0022]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[0023]
Example 1
9,9-Dichloro-9-silafluorene (3 mmol) and formamide (21 mmol) were heated to reflux in ethyl acetate (9 ml) for 3 hours. As ammonium chloride precipitated, oligomers floated in the organic layer. Extracted with a large amount of ethyl acetate, washed with water and dried, and then the solvent was evaporated. Poly [oxy (9-silafluorene-9,9-diyl)] was obtained with a yield of 86%.
[0024]
This is a novel compound not yet published in the literature. 29 Si NMR (solid)-27.63 ppm. 13 C NMR (CPMAS) 121.3, 128.6, 131.9, 146.6 ppm. T d5 : 418 ° C. Elemental analysis: C 36 H 26 Si 3 O as 4 Calculated C71.25, H4.32%; Found C71.37, H4.14%.
[0025]
Example 2
A suspension of 1,4-dilithiobenzene (1 mmol) in hexane (3 ml) was excised at −78 ° C. with 9,9-dichloro-9-silafluorene (1 mmol) in THF (2 ml) over 30 minutes. I gave it. After stirring at -78 ° C for 3 hours, the mixture was gradually brought to room temperature while stirring. The solvent was dried and then hydrolyzed and extracted with ether. The ether extract was dried and then solidified. Reprecipitation from THF / isopropyl alcohol = 1/10 gave poly [(1,4-phenylene) (9-silafluorene-9,9-diyl)] in 53% yield.
[0026]
This is a novel compound not yet published in the literature. 1 HNMR (THF-d 8 ): 7.15-7.35 (broad, 2H, ArH), 7.40-7.55 (broad, 2H, ArH), 7.55-7.70 (broad, 4H , ArH), 7.70-7.85 (broad, 2H, ArH), 7.85-8.0 (broad, 2H, ArH) ppm. 13 C NMR (THF-d 8 ): 122.0, 128.5, 131.6, 134.7, 135.6, 149.7 ppm. 29 Si NMR (THF-d 8 ): -111.71 ppm. Mw / Mn = 6900/3400. T d5 = 408 ° C. Elemental analysis: C 228 H 152 Si 13 Calculated C82.27 as Cl 2, H4.60%; Found C81.73, H4.75%.
[0027]
Example 3
0.020 mmol of PdCl 2 (PEt 3 ) 2 was added to a benzene solution of p-benzoquinone (1.1 mmol) and 9,9-dichloro-9-silafluorene (1.2 mmol), and the mixture was heated and refluxed overnight in a nitrogen atmosphere. The colorless solid was filtered off and washed several times with benzene to give poly [(1,4-phenylenedioxy) (9-silafluorene-9,9-diyl)] in 74% yield.
[0028]
This is a novel compound not yet published in the literature. 1 HNMR (THF-d 8 ): 6.70-6.85 (broad, 4H, ArH), 7.15-7.28 (broad, 2H, ArH), 7.35-7.48 (broad, 2H , ArH), 7.48-7.60 (broad, 2H, ArH), 7.78-7.90 (broad, 2H, ArH) ppm. 13 C NMR (THF-d 8 ): 119.27, 119.94, 127.09, 128.15, 131.42, 132.08, 145.999, 147.71 ppm. 29 Si NMR (THF-d 8 ): −27.79 ppm. Mw / Mn = 6900/1500. Elemental analysis: C 90 H 62 O 11 Si 5 as Calculated C74.05, H4.28%; Found C73.79, H4.59%.
[0029]
Example 4
9 mmol of newly prepared Na dispersion was heated and refluxed in toluene, and 4 ml of toluene in which 4 mmol of 9,9-dichloro-9-silafluorene and 4 mmol of dichlorodimethylsilane were added over 10 minutes. Heating reflux was then continued for 3 hours. After cooling, ethanol was added dropwise to quench, and toluene was added, followed by washing with water. After the insoluble solid was centrifuged, the toluene-soluble component was reprecipitated from THF / methanol = 1/8. Poly [(9,9-silafluorenylene) 0.44 (dimethylsilylene) 0.56 ] was obtained with a yield of 45%.
[0030]
This is a novel compound not yet published in the literature. 1 HNMR (C 6 D 6 ): −0.8 to 0.9 (very broad, 6H, SiMe 2 , 0.56), 6.3 to 7.8 (very broad, 8H, ArH, 0.44) ppm. 13 C NMR (C 6 D 6 ): 5.0, 121.8, 127.1, 129.0, 131.5, 134.0, 148.7 ppm. 29 Si NMR (C 6 D 6 ): −33 to −39, −39 to −44 ppm. Mw / Mn = 60000/37000 and 8900/5300, 34,000 / 11000 in total. Elemental analysis: (C 12 H 8 Si) 0.44 (C 2 H 6 Si) as 0.56 Calculated C68.70, H6.20%; Found C68.59, H6.05%.
[0031]
Example 5
Table 1 shows the UV absorption and fluorescence spectra of the polymers of Examples 1-4.
[Table 1]
Example 6
As shown in FIG. 1, poly [(1,4-phenylene) (9-silafluorene-9,9-diyl)] of Example 2 was used for the light-emitting / hole transport layer and Alq 3 was used for the electron transport layer. An electroluminescent element was prepared. This showed a luminance and current density-voltage curve as shown in FIG. 2, and showed an emission intensity of up to 18 candela / m 2 . Therefore, this is effective as an electroluminescent material.
[0033]
【The invention's effect】
As described above, the present invention provides a polymer having a 9-silafluorene-9,9-diyl skeleton useful as a component of a fluorescent element and an electroluminescent element, and a method for producing the same.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of an electroluminescent device using the polymer of the present invention. FIG. 2 is an explanatory diagram of luminance and current density-voltage curves of the electroluminescent device.
Claims (10)
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| KR20080096585A (en) * | 2006-02-16 | 2008-10-30 | 유니버시티 오브 코넥티컷 | Conductive polymers from precursor polymers, method of making, and use thereof |
| JP5154957B2 (en) * | 2007-02-28 | 2013-02-27 | 国立大学法人東京工業大学 | New fluorene skeleton-containing polymer |
| JP5154958B2 (en) * | 2007-02-28 | 2013-02-27 | 国立大学法人東京工業大学 | Method for producing silicon-containing polymer having fluorene skeleton |
| CN101885835B (en) * | 2010-07-21 | 2012-07-18 | 华南理工大学 | Soluble poly-(9, 9'-aryl 2, 7-silicon fluorine), preparation method and application thereof |
| CN102093565B (en) * | 2011-01-20 | 2012-11-28 | 华南师范大学 | Novel polysilane containing silafluorene |
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