CN106046054A - Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods thereof - Google Patents
Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods thereof Download PDFInfo
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- CN106046054A CN106046054A CN201610343390.1A CN201610343390A CN106046054A CN 106046054 A CN106046054 A CN 106046054A CN 201610343390 A CN201610343390 A CN 201610343390A CN 106046054 A CN106046054 A CN 106046054A
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 6
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- DBWGAXVWWNKFNI-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 DBWGAXVWWNKFNI-UHFFFAOYSA-N 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 16
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- -1 alcohol ester Chemical class 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 3
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- XCQQWDCKLLORFE-UHFFFAOYSA-N [O].C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical group [O].C1(=CC=CC=C1)PC1=CC=CC=C1 XCQQWDCKLLORFE-UHFFFAOYSA-N 0.000 claims 1
- DHNRAGGXWCCERB-UHFFFAOYSA-N [O].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical group [O].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 DHNRAGGXWCCERB-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 229920005601 base polymer Polymers 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 abstract description 35
- 230000005525 hole transport Effects 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 208000035126 Facies Diseases 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- WTVUVLDLHBHZLT-UHFFFAOYSA-N BrC=1C=C(C=CC1)C=1C=CC=2NC3=CC=CC=C3C2C1 Chemical compound BrC=1C=C(C=CC1)C=1C=CC=2NC3=CC=CC=C3C2C1 WTVUVLDLHBHZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000144 PEDOT:PSS Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 238000003811 acetone extraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- YERGTYJYQCLVDM-UHFFFAOYSA-N iridium(3+);2-(4-methylphenyl)pyridine Chemical compound [Ir+3].C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1 YERGTYJYQCLVDM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 208000032825 Ring chromosome 2 syndrome Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DOGITMIOMQKEEM-UHFFFAOYSA-N [P].[O].C1=CC=CC=C1 Chemical compound [P].[O].C1=CC=CC=C1 DOGITMIOMQKEEM-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
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Abstract
The invention belongs to the field of photoelectric functional materials, and particularly relates to a vinyl polymer main body material with PVK respectively functionally modified by an electron donor group and an electron acceptor group, and based on a series of optical, electrical, electrochemical and other performance characterizations of the polymer, the polymer is applied to the field of organic luminescence, and a series of efficient luminescent devices are successfully prepared. The polymer host materials PTPACzPO and PVPPOK are taken as examples, the traditional hole transport materials PVK (polyvinyl carbazole) are taken as a framework, and the carrier transport performance better than that of the PVK is obtained through a series of molecular modification.
Description
Technical field
The invention belongs to field of organic electroluminescent materials.It is specifically related to some Suzuki coupled reactions, vinyl-based
The organic chemical reactionses such as the Raolical polymerizable of monomer, tie by adjusting polymer host material intramolecule electron donor-acceptor (EDA)
Structure, optimizes the electronic structure of material, thus obtains efficient device luminescent properties.
Background technology
Within 1987, Kodak's Tang research group opens organic light emission two based on small molecule fluorescent material
The research direction of pole pipe (OLEDs), nineteen ninety univ cambridge uk Dr.Friend teaches seminar and then opens polymeric material
Organic luminescent device (PLEDs) frontier (J.H.Burroughes, D.D.C.Bradley, A.R.Brown,
R.N.Marks, K.Mackay, R.H.Friend, P.L.Burns, A.B.Holmes, Nature, 1990,347,539.).Compare
In traditional inorganic semiconductor, organic semi-conductor uses and can be good at solving cost, processing, glow color regulation and control, visual angle
Etc. problem, and polymeric material can not only be greatly reduced processing cost, and its simple processing mode and large area become
Film meets now and the developing direction of following flat pannel display especially.Organic luminescent device is mainly used in flat pannel display at present
Device and solid light source, flat pannel display the most progressively replaces traditional lcd technology, solid light as third generation Display Technique
The research in source progressively attracts attention with its low energy consumption, the advantage such as high efficiency.At present, the carrier of novel stabilising is developed
Transmission material and luminescent material are still the key subjects of organic electronic research field.
Organic molecule is stimulated and according to the difference of absorption energy, can form list from ground state transition to excited state
Line state exciton and triplet excitons, learn according to statistical theory, and the formation ratio of singlet exciton and triplet excitons is 1:
3.Singlet exciton recombination radiation transition sends fluorescence, and triplet excitons radiation transistion is phosphorescent, sends out if only depending on fluorescence
Penetrating, organic molecule only up to reach the internal quantum efficiency of 25%, and the triplet excitons of 75% by concentration quenching or
Triplet state-triplet state (T1-T1) bury in oblivion and cause energy loss.The luminescent material of phosphorescence light emitting device mainly one class heavy metal is joined
Compound, arrives singletstate owing to heavy metal atom Effect of Spin-orbit Coupling makes this type organic can be only formed lowest triplet state
Transition such that it is able to reach the internal quantum efficiency of 100%.For avoiding triplet excitons to pass through concentration quenching or triplet state-three
Line state (T1-T1) bury in oblivion, this kind of organic coordination compound is doped in material of main part by the method generally using doping.
Polyvinyl carbazole (PVK) is a kind of wide variety of polymerization species photoelectric material, due to the spy of its molecular structure
Different property, its backbone structure passes through carbon atom SP3The mode of hydridization connects, and hinders electronics transmission on main chain, but due to
The stacking of complete (or the dislocation) of carbazole group so that hole can be piled up at carbazole and be moved by the way of jump in plane,
Therefore PVK is a kind of well hole mobile material, and due to the particularity of backbone structure, PVK has higher three simultaneously
Line state energy level (T1), thus PVK is widely used in PLEDs as material of main part.PVK derivant one based on PVK research
As there is the high hole transport performance of PVK, high triplet, and compared to PVK for, its derivant can be good
Factor (L.Li, T.Q.Hu, the C.R. such as the transmission balance of regulation and control carrier, electrochemically stable, thermodynamics and morphology stability
Yin, L.H.Xie, Y.Yang, C.Wang, J.Y.Lin, M.D.Yi, S.H.Ye, W.Huang, Polym.Chem.2015,6,
983.).Derivant research based on PVK is an important research direction of polymer host material.
Summary of the invention
The invention mainly includes the polymer green phosphorescent main body proposing a kind of novel bipolarity carrier transport
Material, and utilize this material of main part to carry out a series of application in organic luminescent device field.
The concrete synthetic route of described polyvinyl is as follows:
With N-bromo-succinimide under step (a) room temperature, it is dissolved in DMF solvent reaction.
At step (b) 100 DEG C, with diphenyl phosphorus oxygen palladium, dppf and TEA catalytic action under, compound is molten
Solution, in DMSO, reacts 3～4h.
At step (c) 90 DEG C, with connection pinacol borate palladium, dppf catalytic action under, compound dissolution exists
In Isosorbide-5-Nitrae-dioxane, react 15h.
At step (d) 100 DEG C, under the catalytic action of tetra-triphenylphosphine palladium and potassium carbonate and potassium fluoride, compound is molten
Solution, in Isosorbide-5-Nitrae-dioxane solvent with water, reacts 12h.
At step (e) 45～50 DEG C, in potassium carbonate, potassium hydroxide and phase transfer catalyst tetrabutyl ammonium bromide (TBAB)
Catalytic action under, compound dissolution is 1, in 2-dichloroethanes, react 3～5h.
At step (f) 85～90 DEG C, under the catalytic action of potassium hydroxide and hydroquinone, compound dissolution is at solvent
In the mixed solvent of isopropanol and toluene, reflux 2～3 days.
At step (g) 60 DEG C under azodiisobutyronitrile (AIBN) causes, monomer is dissolved in N-Methyl pyrrolidone (NMP)
In, polyreaction 2 days at 85～90 DEG C.
This material (PTPACzPO) is mainly used in organic electrophosphorescenpolymer light emitting diode, and device architecture is the most transparent
Anode/hole injection layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode.Polymeric material is with green
Phosphor material codope, polymer host material PTPACzPO is applied in luminescent layer and carrier blocking layers.
With N-bromo-succinimide under (a) room temperature, it is dissolved in DMF solvent reaction.
At (b) 100 DEG C, with diphenyl phosphorus oxygen at palladium, 1,1 '-bis-(diphenylphosphine) ferrocene (dppf), connection boric acid
Under the catalytic action of pinacol ester and potassium acetate, compound dissolution, in anaerobic dimethyl sulfoxide (DMSO), reacts one day.
C, at () 100 DEG C, with 1,3-dibromobenzene is dissolved in deoxygenated toluene and THF mixed solution, so at palladium, dppf
Rear addition anaerobic potassium carbonate and potassium fluoride mixed solution, react 15h.
At (d) 100 DEG C, with diphenyl phosphorus oxygen palladium, dppf and TEA catalytic action under, compound dissolution exists
In the DMSO of anaerobic, react 3～4h.
At (e) 45～50 DEG C, potassium carbonate, the urging of potassium hydroxide and phase transfer catalyst tetrabutyl ammonium bromide (TBAB)
Under change effect, compound dissolution is 1, in 2-dichloroethanes, reacts 3～5h.
F, at () 85～90 DEG C, under the catalytic action of potassium hydroxide and hydroquinone, compound dissolution is in solvent isopropyl
In the mixed solvent of alcohol and toluene, reflux 2～3 days.
G, at () 85～90 DEG C, monomeric compound is dissolved in the NMP under anhydrous and oxygen-free state, is simultaneously introduced monomer weight
Ratio is the polymerization initiator AIBN of 1%, reacts two days under the conditions of lucifuge.
This material (PVPPOK) is mainly used in organic electrophosphorescenpolymer light emitting diode, and device architecture is mainly transparent sun
Pole/hole injection layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode.Polymeric material and blue phosphorus
Luminescent material codope, polymer host material PVPPOK is applied in luminescent layer and carrier blocking layers.
Beneficial effect: characterized by nuclear magnetic resonance, NMR (NMR) etc., it is determined that polymer and the knot of each precursor material thereof
Structure；Additionally by ultra-violet absorption spectrum (UV), fluorescence emission spectrum (PL), electrochemical analyser (CV), thermogravimetric (DTG) and differential
Scanning calorimetric (DSC) etc. has carried out a series of property representation to polymeric material.Polymeric material heat analysis (TGA and
DSC) show excellent thermodynamics and morphology stability during, there is high heat decomposition temperature (Td) but there is no substantially
Glass Transition.Utilize the electrochemical profiles of cyclic voltammetry polymer host material, it is determined that its HOMO with
Lumo energy, can and device adjacent layer between level-density parameter.
This type of polymeric material can apply the every field with organic electronic and quasiconductor, such as organic electroluminescent two pole
Pipe, organic field effect tube etc..We devise a kind of polymer electro green phosphorescent based on PTPACzPO on this basis
Light emitting diode, device architecture is: glass substrate/ITO/PEDOT:PSS/PTPACzPO:Ir (mppy)3/TmPyPB/LiF/
Al.Polymeric material PTPACzPO is applied in device as material of main part and carrier transmission material, and PTPACzPO is with green
Phosphor material Ir (mppy)3Being blended according to a certain percentage, then film forming by the way of spin coating, little molecule and negative electrode are by true
The mode film forming of empty plated film.Test result indicate that, the green phosphorescent device that use polymer P TPACzPO does material of main part is permissible
Reaching device maximum brightness is 13166cd/m2Maximum current efficiency is 17.5cd/A and maximum power efficiency 7.7lm/W.Phase
Ratio is in PVK device, and PTPACzPO performance advantage is, it is ensured that the luminescent properties that device is excellent, greatly reduces device simultaneously and opens
Move and running voltage.It is 4.40V that the green device of PTPACzPO starts voltage, less than the startup voltage of PVK device 7.14V.
We devise a kind of polymer electro green phosphorescent light emitting diode based on PVPPOK simultaneously, and device architecture is:
Glass substrate/ITO/PEDOT:PSS/PVPPOK:FIrpic/TmPyPB/LiF/Al.Polymeric material PVPPOK is as main body material
Material and carrier transmission material are applied in device, and PVPPOK is blended according to a certain percentage with blue phosphor materials FIrpic, so
Film forming by the way of spin coating afterwards, little molecule and negative electrode film forming by the way of vacuum coating.Test result indicate that, use poly-
Compound PVPPOK makees the blue phosphorescent device of material of main part and can reach to match in excellence or beauty in the performance of PVK device, device luminescent layer simultaneously
Carrier transport efficiency raises significantly, it is achieved that bipolar transmission.
Application process: it is characterized in that target material is applied in polymer organic electro-phosphorescent luminescent device, device junction
Structure is: transparent anode/hole injection layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode.Luminescent layer
Material of main part be the polymer host material described by claims 2 and claims 3, the heavy metal of doping is joined
Compound is respectively green and blue phosphorescent luminescent material.
Accompanying drawing explanation
Above and other feature and the advantage of the present invention clearer will be understood in conjunction with drawings described below and detailed description, its
In:
Fig. 1 polymer P TPACzPO photophysical property figure；
Fig. 2 PTPACZPO antenna effect spectrogram；
Fig. 3 PTPACZPO electrochemical profiles；
Fig. 4 PTPACZPO thermal profile；
Fig. 5 is based on PTPACZPO green phosphorescent device property figure.
Fig. 6 polymer P VPPOK photophysical property figure；
Fig. 7 PVPPOK antenna effect spectrogram；
Fig. 8 PVPPOK electrochemical profiles；
Fig. 9 PVPPOK thermal profile；
Figure 10 is based on PVPPOK blue phosphorescent device property figure.
Detailed description of the invention:
Example 1: the synthesis of polymeric material PTPACzPO precursor compound
Compound 3, the synthesis of 6-dibromo carbazole (2):
Under the conditions of ice-water bath, will be dissolved with the N-N-dimethylformamide (DMF) (20ml) of carbazole (10g, 59.8mmol)
Solution constant pressure funnel is added dropwise over DMF (30ml) solution dissolved with N-bromo-succinimide (21.28g, 120mmol)
In.It is added dropwise to complete recession and removes ice-water bath, lucifuge reaction overnight under room temperature state.Then make to be washed with deionized reactant liquor, analysis
Go out after solid by solid sucking filtration out, use ethyl alcohol recrystallization to obtain product 2.Productivity: 47%.1H NMR (400MHz,
Chloroform-d) δ 8.13 (d, J=1.9Hz, 3H), 7.52 (dd, J=8.6,1.9Hz, 2H), 7.31 (d, J=8.6Hz,
2H).13C NMR (75MHz, Chloroform-d) δ 129.34,123.28,112.22.
The synthesis of compound 3-(diphenyl phosphorus oxygen)-6-bromine carbazole (4):
By compound 2 (0.488g, 1.5mmol) and diphenyl phosphorus oxygen (0.202g, 1mmol), palladium (0.01g,
0.05mmol), the DMSO (15ml) adding anaerobic after dppf (0.05g, 0.1mmol), TEA (0.12g, 1.2mmol) mixing is molten
Xie Hou, back flow reaction 3～4h under lucifuge and nitrogen guard mode.Reaction uses deionized water (3 × 50ml) and dichloro after terminating
Methane DCM (100ml) extracts organic facies.Using anhydrous magnesium sulfate to be dried organic facies, after filtration, rotation evaporates organic solution, uses
Column chromatography for separation method obtains product Compound 4.Productivity: 73%.1H NMR (500MHz, Chloroform-d) δ 10.49 (s,
1H), 8.19 (d, J=12.6Hz, 1H), 7.96 (d, J=1.8Hz, 1H), 7.72 (dd, J=12.0,7.6Hz, 4H), 7.60
(dd, J=11.2,8.4Hz, 1H), 7.54 (t, J=7.5Hz, 2H), 7.45 (td, J=7.7,2.8Hz, 4H), 7.40 (dd, J
=8.7,1.9Hz, 1H), 7.34 (dd, J=8.5,2.2Hz, 1H), 7.25 (d, J=6.0Hz, 1H).13C NMR (126MHz,
Chloroform-d) δ 142.46,139.01,133.43,132.60,132.26-131.92 (m), 129.4l-129.05 (m),
128.60 (d, J=11.9Hz), 125.16 (d, J=11.7Hz), 124.36,123.10,122.19 (d, J=14.6Hz),
121.67,120.79,112.83,112.59,111.57 (d, J=13.6Hz).
Compound N, the conjunction of N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxy boron penta ring-2-bases) aniline (5)
Become:
In two mouthfuls of flasks add compound 3 (4.86g, 15mmol), connection boric acid pinacol ester (4.95g, 19.5mmol),
Palladium (0.1g, 0.45mmol), dppf (0.5g, 0.9mmol), potassium acetate (4.42g, 45mmol), keep anaerobic ring in bottle
Under border, add the Isosorbide-5-Nitrae-dioxane (50ml) of anaerobic, back flow reaction 15h at 90 DEG C.Reaction terminate after with deionized water (3 ×
50ml) extracting with DCM (100ml), organic facies boils off DCM after drying through anhydrous magnesium sulfate, and column chromatography for separation method obtains product 5.
Productivity: 86%.1H NMR (500MHz, Chloroform-d) δ 7.73 (d, J=8.1Hz, 2H), 7.31 (t, J=7.7Hz,
4H), 7.16 (d, J=7.9Hz, 4H), 7.10 (t, J=8.0Hz, 4H), 1.39 (s, 12H).13C NMR (126MHz,
Chloroform-d) δ 150.64,147.46,135.89,129.31,125.02,123.38,121.85,83.57.
The synthesis of compound (3-diphenyl phosphorus oxygen-6-(4-(hexichol amido) phenyl))-9H-carbazole (6):
There-necked flask adds compound 4 (1.566g, 3.5mmol), compound 5 (1.69g, 4.5mmol), four triphenyls
Phosphine palladium (81mg, 0.07mmol), keeps oxygen-free environment in there-necked flask, adds the Isosorbide-5-Nitrae-dioxane of 50ml anaerobic, and dissolving completes
Rear use Dropping funnel adds anaerobic potassium carbonate and the potassium fluoride mixed solution (1: 1) of the 2mol/L of 3.5ml, refluxes at 100 DEG C
Cancellation reaction after reaction 12h.Reaction extracts with DCM (100ml) with deionized water (3 × 50ml) after terminating, and organic facies is through anhydrous
Magnesium sulfate boils off DCM after drying, and column chromatography for separation method obtains product 6.Productivity: 54%.1H NMR (500MHz, Chloroform-
D) δ 8.41 (dd, J=12.0,6.0Hz, 1H), 8.13 (s, 2H), 7.73 (dt, J=11.9,6.6Hz, 7H), 7.55-7.49
(m, 4H), 7.49-7.44 (m, 11H), 7.29-7.23 (m, 3H), 7.16-7.10 (m, 2H), 7.02 (t, J=7.2Hz, 1H)
.13C NMR (126MHz, Chloroform-d) δ 147.85,146.67,142.24,133.28,132.29,132.21,
131.80,130.52,129.27,128.55,128.46,127.92,126.66,125.90,125.20,124.36,124.28,
123.36,122.79,120.65,120.19,118.54,111.30,111.05.
The synthesis of compound (3-diphenyl phosphorus oxygen-6-(4-(hexichol amido) phenyl))-9-chloroethyl-carbazole (7):
At 45～50 DEG C, by compound 6 (0.503g, 0.8mmol), potassium hydroxide (KOH) (0.37g, 6.4mmol), carbon
Acid potassium (K2CO3) (2.27g, 16mol), tetrabutyl ammonium bromide (TBAB) (25.79mg, 0.08mmol) is dissolved in 1,2-dichloroethanes
(100ml) in single port flask, react 3～5h in.Reaction removes solid in solution after terminating, use deionized water (50ml) with
DCM (100ml) extracts, MgSO4Being dried organic facies, the method that uses column chromatography after removing organic solvent obtains compound 7.Productivity:
88%.1H NMR (500MHz, Chloroform-d) δ 8.48 (d, J=11.9Hz, 1H), 8.21 (s, 1H), 7.73 (d, J=
9.1Hz, 6H), 7.58-7.43 (m, 10H), 7.28 (d, J=7.8Hz, 4H), 7.15 (t, J=8.8Hz, 6H), 7.03 (t, J=
7.4Hz, 2H), 4.68 (t, J=6.9Hz, 2H), 3.91 (t, J=6.7Hz, 2H).13C NMR (126MHz, Chloroform-d)
δ 147.81,146.88,135.60,133.77,131.84,129.30,128.57,127.94,126.05,122.89,
118.91,109.14,45.10,41.15.
The synthesis of compound (3-diphenyl phosphorus oxygen-6-(4-(hexichol amido) phenyl))-9-vinyl-carbazole (8):
Compound 7 (0.71g, 1mmol) and KOH (0.41g, 7mmol), hydroquinone (0.01mg, 0.1mmol), toluene
(10ml) and isopropanol (40ml) refluxes 2～3h at 85～90 DEG C.Reaction is spin-dried for toluene and isopropanol after terminating, and spend from
Sub-water (50ml) and DCM (3 × 50ml) extractive reaction liquid, MgSO4It is spin-dried for after drying, makes the method that uses column chromatography obtain compound
8.Productivity: 92%.1H NMR (500MHz, Chloroform-d) δ 9.84 (q, J=2.9Hz, 1H), 8.42 (d, J=12.5Hz,
1H), 7.78 (dt, J=10.8,5.4Hz, 8H), 7.58 (rd, J=8.3,2.7Hz, 5H), 7.50 (dd, J=7.7,2.6Hz,
7H), 7.32 (d, J=7.7Hz, 2H), 7.19 (d, J=8.0Hz, 4H), 7.09-7.06 (m, 4H), 5.34 (s, 1H).13C NMR
(126MHz, Chloroform-d) δ 147.76,139.37,133.64,133.10,132.27,132.19,131.90,
131.84,129.29,129.17,128.60,128.56,128.51,128.47,127.89,126.21,125.84,125.18,
125.08,124.38,124.24,123.24,122.90,122.76,118.52,111.42.
Compound poly-((3-diphenyl phosphorus oxygen-6-(4-(hexichol amido) phenyl))-9-vinyl-carbazole) (PTPACzPO)
(9) synthesis:
The reaction tube processed adds monomeric compound 8 (0.3g, 0.5mmol) and monomer weight ratio is the polymerization of 1%
Initiator azodiisobutyronitrile (3mg, 0.018mmol), keeps anhydrous and oxygen-free environment in reaction tube, adds at except water deoxygenation
The N-Methyl pyrrolidone (NMP) (0.9ml) of reason, after in the complete solvent of monomer with solution, under the conditions of lucifuge, 60 DEG C are caused poly-
Close reaction.After polymerization initiation completes, system is placed at 85～90 DEG C reaction two days.Reaction uses a small amount of methanol cancellation after terminating
Reaction, then settles reactant liquor in petroleum ether, and obtains polymer 9 with acetone extraction.Polymer P TPACzPO number is divided equally
Son amount Mn is 8798, and weight average molecular weight Mw is 14867, and polydispersity index PDI is 1.69.Productivity: 89%.1H NMR (300MHz,
Chloroform-d) δ 6.34-8.65 (br, ArH), 2.18 (s, CH), 1.27 (s, CH2).13C NMR (75MHz,
Chloroform-d) δ 131.97,129.29,128.49,124.31,122.93.
Polymeric material PTPACZPO ultra-violet absorption spectrum and the mensuration of photoluminescence spectra:
PTPAC is prepared in cuvetteZThe toluene solution of PO, concentration is about 10-5Mol/L, uses Shimadzu (Shimadzu)
UV-1750 ultraviolet-visual spectrometer and Hitachi (Hitachi) F-4600 fluorescence spectrophotometer carry out absorption spectrum and emission spectrum is surveyed
Fixed.For the absorption spectrum of PTPACzPO, its peak changes less for PVK, but PTPACzPO
Absorption near 332nm is very strong, and this is incorporated in carbazole structure mainly due to trianilino group, substantially increases carbazole and puts down
The cloud density in face, so that it is provided with stronger absorption.And the solution emission peak positions of PTPACzPO compares
π-π * the transition energy occurred between carbazole plane in the obvious red shift of PVK (about 47nm), this explanation PTPACzPO molecule is differential
Shorten, it can thus be appreciated that PTPACzPO has narrower in the band gap of PVK.Meanwhile, the most single in the emission spectrum of PTPACzPO
Peak, thus it is recognised that PVK modified by triphenylamine and phosphorus oxygen base can hinder PVK intramolecular or the heap of intermolecular carbazole group
Folded effect, it is to avoid the excimer emission under filminess.Absorption-the emission spectrum of PTPACzPO Yu PVK under filminess
Display, the change of PTPACzPO absorption spectrum is less, but in emission spectrum, PTPACzPO has close with PVK transmitting main peak
Emission peak (417nm), compared with PTPACzPO solution emission peak 419nm before, the emission peak positions base under filminess
This does not changes, and the transmitting of PTPACzPO still only one of which.Therefore, we understand under filminess, intramolecular
Portion is due to the existence of stacking effect, and molecular emission is still shown that unimolecule and launches, and concrete condition refers to accompanying drawing 1.
Display, the emission peak of the PTPACzPO under filminess and green phosphorescent material Ir (mppy) in accompanying drawing 1 (c)3's
Absworption peak is the most overlapping again, and this has turned out and can form good energy transfer process between material of main part and guest materials.
Accompanying drawing 1 (d) is the green phosphorescent material Ir (mppy) of material of main part doping different proportion3The thin film made, it can be seen that along with
The rising of doping ratio, obvious energy transmission between Subjective and Objective material.
The mensuration of polymeric material PTPACzPO electrochemical properties:
The electrochemical properties electrochemical cyclic voltammetry (CV) of this material of main part measures, and experimental apparatus is occasion China
CHI660E electrochemical workstation, this instrument uses three-electrode system, including glass carbon working electrode, Ag/Cl reference electrode with
And platinum filament is to electrode.Polymer electrochemical measures the acetonitrile that the solvent used generally is dried, and electrolyte is the hexafluoro phosphorus tetrabutyl
Ammonium (Bu4NPF6), concentration is 0.1M；Test environment needs nitrogen to protect.The speed of instrument scanning is 0.1V/s, and primary standard substance is two
Cyclopentadienyl ferrum (FOC), calculates HOMO and the lumo energy of this material respectively by measuring the beginning voltage of oxidation and reduction process.
The electrochemical profiles of PTPACzPO Yu PVK such as accompanying drawing 3, through calculating this polymer host material PTPACzPO's
HOMO energy level is-5.28eV, and lumo energy is-2.19eV；The HOMO energy level obtaining PVK as comparative measurements is-5.64eV,
Lumo energy is-1.95eV.
The mensuration of polymeric material PTPACzPO thermodynamic stability:
The differential scanning calorimetric analysis (DSC) of this polymeric material is to be surveyed by Shimadzu Corporation (Shimadzu) DSC-60A
Examination instrument measures, and first sample is heated to the state less than decomposition temperature with the speed of 10 DEG C/min, then, under the conditions of liquid nitrogen
Cooling returns to initial temperature, and second time scans with the ramp of 10 DEG C/min again.Thermogravimetric analysis (TGA) is to pass through Shimadzu Corporation
(Shimadzu) DTG-60H thermogravimetric analyzer is tested, and heat scan speed is 10 DEG C/min, protects the stream of air-flow nitrogen simultaneously
Speed is 20cm3/min。
The preparation of polymeric material PTPACzPO green phosphorescent device and sign:
PTPACzPO is that the structure of the green phosphorescent device of main body is: ITO/PEDOT:PSS (40nm)/PTPACzPO:Ir
(mppy)3(95∶5w/w)(100nm)/TmPyPB(20nm)/LiF(0.8nm)/Al(100nm).Its Anodic is the oxidation of indium stannum
Thing, interface-modifying layer is PEDOT:PSS, and hole blocking layer is TmPyPB, and negative electrode is Al electrode.From accompanying drawing 5, PTPACzPO
Device startup voltage for material of main part is 4.4V, and high-high brightness is 13166cd/m2, maximum current efficiency is 17.5cd/A,
Power efficiency is 7.7lm/W；PVK be material of main part device start voltage be 7.6V, high-high brightness is 10401cd/m2,
Big current efficiency is 25.03cd/A, and maximum power efficiency is 6.6lm/W.Triphenylamine and phosphorus-oxygen groups modify PVK at PVK molecule
On the basis of improve its carrier transmission performance, it is ensured that the balance of main body luminescent layer carrier transport in device, therefore
The startup voltage of PTPACzPO device significantly reduces, and carrier high efficiency of transmission improves the luminous efficiency of device simultaneously.
Example 2: the synthesis of polymeric material PVPPOK precursor compound
The synthesis of compound 3-bromine carbazole (2):
Under the conditions of ice-water bath, will be dissolved with the N-N-dimethyl formyl of N-bromo-succinimide (10.64g, 59.8mol)
Amine (DMF) (20ml) solution constant pressure funnel is added dropwise over DMF (20ml) solution dissolved with carbazole (10g, 59.8mol)
In.It is added dropwise to complete recession and removes ice-water bath, lucifuge reaction overnight under room temperature state.Then make to be washed with deionized reactant liquor, analysis
Going out after solid by solid sucking filtration out, ethyl alcohol recrystallization obtains product 2.Productivity: 47%.1H-NMR (400MHz, CDCl3) δ
8.19 (d, J=1.9Hz, 1H), 8.09 (d, J=6.9Hz, 1H), 8.05-8.01 (m, 1H), 7.50 (dd, J=8.6,1.9Hz,
1H), 7.46-7.43 (m, 2H), 7.31 (d, J=8.6Hz, 1H), 7.28-7.22 (m, 1H).13C-NMR (75MHz, CDC13) δ
128.55,126.61,123.12,120.50,119.94,111.99,110.79.
The synthesis of 3-(4,4,5,5-tetramethyl-1,3,2-dioxy boron pentane-2-bases)-9H-carbazole (3):
Two mouthfuls of flasks add compound 2 (4.92g, 20mmol), connection boric acid pinacol ester (6.6g, 26mmol), acetic acid
Palladium (0.134g, 0.6mmol), dppf (0.66g, 1.2mmol), potassium acetate (5.88g, 60mmol), keep oxygen-free environment in bottle
Under, add anaerobic DMSO (50ml), back flow reaction 24h at 90 DEG C.Reaction uses deionized water (3 × 50ml) and DCM after terminating
(100ml) extraction, organic facies boils off DCM after drying through anhydrous magnesium sulfate, and column chromatography for separation method obtains product 3.Productivity: 64%.1H NMR (300MHz, Chloroform-d) δ 8.52 (s, 1H), 8.08-8.00 (m, 2H), 7.80 (dd, J=8.2,1.2Hz,
1H), 7.36-7.27 (m, 3H), 7.16 (tt, J=5.3,2.9Hz, 1H), 1.33 (s, 12H).13C NMR (75MHz,
Chloroform-d) δ 141.72,139.45,132.34,127.76,125.86,123.48,123.09,120.54,119.81,
110.59,110.00,83.64,25.03,24.95.
The synthesis of 3-(3-bromophenyl)-9H-carbazole (4):
In there-necked flask add compound 3 (0.29g, 1mmol), 1,3-dibromobenzene (0.35g, 1.5mmol), palladium
(6.7mg, 0.03mmol), dppf (33.2mg, 0.06mmol), keep oxygen-free environment in there-necked flask, adds 50ml deoxygenated toluene
With THF mixed solution (1: 1), after having dissolved, use the 2molL that Dropping funnel adds 1.5ml-1Anaerobic potassium carbonate and fluorination
Potassium mixed solution (1: 1), cancellation reaction after back flow reaction 12h at 100 DEG C.Reaction terminate after with deionized water (3 × 50ml) with
DCM (l00ml) extracts, and organic facies boils off DCM after drying through anhydrous magnesium sulfate, and column chromatography for separation method obtains product 4.Productivity:
56%.1H NMR (300MHz, Chloroform-d) δ 8.17 (d, J=1.7Hz, 1H), 8.05 (d, J=8.0Hz, 2H), 7.77
(t, J=1.9Hz, 1H), 7.55 (dd, J=8.3,1.7Hz, 2H), 7.46-7.33 (m, 4H), 7.22-7.16 (m, 1H).13C
NMR (75MHz, Chloroform-d) δ 130.30,130.23,129.36,126.23,125.88,125.28,120.44,
119.78,118.93,110.90,110.77.
The synthesis of (3-(9H-carbazole-3-base) phenyl) diphenyl phosphorus oxygen (5):
Two-mouth bottle adds compound 4 (0.193g, 0.6mmol), diphenyl phosphorus oxygen (0.1g, 0.5mmol), palladium
(5.6mg, 0.25mmol), dppf (27.7mg, 0.5mmol), keep oxygen-free environment in two-mouth bottle, be subsequently adding TEA (0.06g,
0.6mmol), and with anaerobic DMSO (10ml) dissolve, back flow reaction 3～4h at 100 DEG C.Reaction terminate after with deionized water (3 ×
50ml) extracting with DCM (100ml), organic facies boils off DCM after drying through anhydrous magnesium sulfate, and column chromatography for separation method obtains product 5.
Productivity: 63%.1H NMR (300MHz, Chloroform-d) δ 8.76 (s, 1H), 8.16-7.95 (m, 2H), 7.79 (d, J=
7.2Hz, 1H), 7.68 (dd, J=12.1,7.3Hz, 3H), 7.51-7.34 (m, 13H), 7.21-7.10 (m, 2H).13C NMR
(75MHz, Chloroform-d) δ 132.25,132.12,132.03,131.99,131.43,131.31,130.85,130.80,
130.77,130.72,129.95,129.81,128.87,128.67,128.51,126.04,125.23,120.37,119.49,
118.93,111.06.110.89.
The synthesis of (3-(9-(2-chloroethyl)-9H-carbazole-3-base) phenyl) diphenyl phosphorus oxygen (6):
At 45～50 DEG C, by compound 5 (4.43g, 0.01mol), potassium hydroxide (KOH) (3.93g, 0.07mol), carbon
Acid potassium (K2CO3) (27.6g, 0.20mol), tetrabutyl ammonium bromide (TBAB) (0.097g, 0.0003mol) is dissolved in 1,2-bis-chloroethene
Alkane (100ml) reacts in single port flask 3～5h.React and after terminating, remove solid in solution, use deionized water (3 ×
50ml) extracting with DCM (100ml), MgSO4 is dried organic facies, and the method that uses column chromatography after removing organic solvent obtains compound
6.Productivity: 91%.1H NMR (300MHz, Chloroform-d) δ 8.20 (d, J=1.7Hz, 1H), 8.05 (dd, J=10.2,
6.8Hz, 2H), 7.83-7.78 (m, 1H), 7.70 (d, J=1.4Hz, 1H), 7.68-7.65 (m, 2H), 7.64 (d, J=
1.6Hz, 1H), 7.60 (dd, J=8.5,1.8Hz, 1H), 7.52-7.44 (m, 3H), 7.41 (dt, J=6.8,2.5Hz, 5H),
7.37 (d, J=2.5Hz, 2H), 7.23-7.17 (m, 2H), 4.57 (t, J=7.0Hz, 2H), 3.79 (t, J=6.9Hz, 2H)
.13C NMR (75MHz, Chloroform-d) δ 132.24,132.11,131.99,131.95,131.75,130.84,130.77,
130.72,130.17,130.03,128.93,128.76,128.63,128.47,126.31,125.38,120.68,119.89,
119.24,108.88,108.66,44.87,41.07.
The synthesis of (3-(9-vinyl-9H-carbazole-3-base) phenyl) diphenyl phosphorus oxygen (7): compound 6 (0.51g,
1mmol) exist with KOH (0.22g, 4mmol), hydroquinone (3.03mg, 0.03mmol), toluene (10ml) and isopropanol (50ml)
Backflow 2～3h at 85 DEG C.Reaction is spin-dried for toluene and isopropanol after terminating, and extracts with DCM (3 × 50ml) with deionized water (50ml)
Extract reaction solution, be dried after being spin-dried for and make the method that uses column chromatography obtain compound 7.Productivity: 93%.1H NMR (300MHz,
Chloroform-d) δ 9.71 (m, J=2.9Hz, 1H), 8.21-8.13 (m, 1H), 8.10-7.95 (m, 2H), 7.85-7.74
(m, 1H), 7.68 (dd, J=12.4,6.8Hz, 4H), 7.57 (d, J=9.1Hz, 1H), 7.52-7.34 (m, 10H), 7.31 (d,
J=5.8Hz, 1H), 5.48 (d, J=15.9Hz, 1H), 5.11 (d, J=9.2Hz, 1H), 4.98-4.79 (m, 1H).13C NMR
(75MHz, Chloroform-d) δ 132.23 (d, J=1.9Hz), 132.10 (d, J=2.0Hz), 131.97 (d, J=
2.7Hz), 130.79 (d, J=5.3Hz), 130.70,130.22 (d, J=10.9Hz), 129.88 (d, J=10.5Hz),
128.94,128.86,128.77,128.68,128.63,128.47,126.67 (d, J=11.9Hz), 126.01,125.67
(d, J=11.1Hz), 125.18,120.91,120.68,120.36 (d, J=3.0Hz), 119.45,119.15,118.91,
29.69.
The synthesis of poly-((3-(9-vinyl-9H-carbazole-3-base) phenyl) diphenyl phosphorus oxygen) (PVPPOK) (8): processed
Reaction tube in add monomeric compound 7 (0.17g, 0.36mmol) and polymerization initiator azo two that monomer weight ratio is 1%
Isopropyl cyanide (1.7mg, 0.010mmol), keeps anhydrous and oxygen-free environment in reaction tube, adds the toluene through processing except water deoxygenation
(0.7 ml), after in the complete solvent of monomer with solution, 60 DEG C of initiated polymerizations under the conditions of lucifuge.After polymerization initiation completes,
System is placed at 85～90 DEG C reaction two days.Reaction uses a small amount of methanol cancellation to react, then by reactant liquor at stone after terminating
Oil ether settles, and obtains polymer 8 with acetone extraction.Polymer P VPPOK number-average molecular weight Mn is 11088, weight average molecular weight
Mw is 15941, and polydispersity index PDI is 1.44.Productivity: 78%.1H NMR (300MHz, Chloroform-d) δ 5.14-9.11
(br, ArH), 2.27 (s, CH), 1.75 (s, CH2).13C NMR (75MHz, Chloroform-d) δ 132.02,130.49,
128.55.
Polymeric material PVPPOK ultra-violet absorption spectrum and the mensuration of photoluminescence spectra:
Preparing the toluene solution of PVPPOK in cuvette, concentration is about 10-5Mol/L, uses Shimadzu (Shimadzu) UV-
1750 ultraviolet-visual spectrometers and Hitachi (Hitachi) F-4600 fluorescence spectrophotometer carry out absorption spectrum and emission spectrometry.
The absorption of PVPPOK is more weak, and absworption peak 291nm and a very weak peak bag that only one of which is stronger are positioned at 348nn, thus
Visible three absworption peaks (293,330,343nm) with PVK keep unanimously on peak position substantially；But, in PL spectrum I
It will be seen that the peak (386nm) of PVPPOK under solution state there occurs obvious red shift relative to PVK (372nm).This
Redshift effect makes the reaction force attenuation between polymer molecular chain mainly due to the introducing of benzene phosphorus oxygen base, carbazole in original molecule
The completely overlapped conformation of surface-to-surface of group is broken, then defines substantial amounts of part stacked state, thus it is dual to change PVK
The PL characteristic at peak, connects on the base of side simultaneously and has conjugation group, so spectrum generation red shift.It is similar with solution UV-fluorescence spectrum,
The peak position of the ultra-violet absorption spectrum of PVPPOK is the most similar to PVK, and in the spectrum under PVK filminess, main peak becomes
415nm, and the main peak under its solution state has reduced to secondary peak, this most directly illustrates molecule aggregation under PVK filminess
Clearly, under aggregation state, the ratio that intramolecule or intermolecular carbazole group occur complete surface-to-surface overlapping exceedes
The ratio of limit-face stacking；PVPPOK fluorescence spectrum under filminess also there occurs the red shift of about 12nm, and this is mainly
Owing to there is quenching effect under coherent condition.
Polymer is dissolved in toluene under 77K and recording, by with PVK's by the antenna effect spectrum of PVPPOK in advance
Antenna effect spectrum contrasts, it has been found that PVPPOK has higher triplet (ET=2.95eV), higher than blue phosphorescent
The triplet (ET=2.65eV) of material of main part FIrpic, therefore can be used to the material of main part as blue PhPLEDs.
The mensuration of polymeric material PVPPOK electrochemical properties:
The electrochemical properties electrochemical cyclic voltammetry (CV) of this material of main part measures, and experimental apparatus is occasion China
CHI660E electrochemical workstation, this instrument uses three-electrode system, including glass carbon working electrode, Ag/Cl reference electrode with
And platinum filament is to electrode.Polymer electrochemical measures the acetonitrile that the solvent used generally is dried, and electrolyte is the hexafluoro phosphorus tetrabutyl
Ammonium (Bu4NPF6), concentration is 0.1M；Test environment needs nitrogen to protect.The speed of instrument scanning is 0.1V/s, and primary standard substance is two
Cyclopentadienyl ferrum (FOC), calculates HOMO and the lumo energy of this material respectively by measuring the beginning voltage of oxidation and reduction process.
The electrochemical profiles of PVPPOK Yu PVK such as accompanying drawing 8, through calculating the HOMO energy level of this polymer host material PVPPOK for-
5.68eV, lumo energy is-2.15eV, close with PVK energy level.
The mensuration of polymeric material PVPPOK thermodynamic stability:
The differential scanning calorimetric analysis (DSC) of this polymeric material is to be surveyed by Shimadzu Corporation (Shimadzu) DSC-60A
Examination instrument measures, and first sample is heated to the state less than decomposition temperature with the speed of 10 DEG C/min, then, in liquid nitrogen condition
Borehole cooling returns to initial temperature, and second time scans with the ramp of 10 DEG C/min again.Thermogravimetric analysis (TGA) is public by Shimadzu
Department's (Shimadzu) DTG-60H thermogravimetric analyzer test, heat scan speed is 10 DEG C/min, protects air-flow nitrogen simultaneously
Flow velocity is 20cm3/min；Test result is as shown in Figure 9.
The preparation of polymeric material PVPPOK blue phosphorescent device and sign:
PVPPOK is that the structure of the blue phosphorescent device of main body is: ITO/PEDOT:PSS (40nm)/PVPPOK:FIrpic
(90:10w/w) (100nm)/TmPyPB (20nm)/LiF (0.8nm)/Al (100nm).Its Anodic is indium tin oxide, interface
Decorative layer is PEDOT:PSS, and hole blocking layer is TmPyPB, and negative electrode is Al electrode.From accompanying drawing 10, PVPPOK is main body material
It is 7.52V that the device of material starts voltage, and high-high brightness is 6164cd/m2, maximum current efficiency is 9.70cd/A, and peak power is imitated
Rate is 3.61lm/W.
Claims (5)
1. a base polymer material of main part, be primarily characterized in that on C3 and the C6 position of carbazole group modify respectively to electronics and
Electron withdraw group, concrete structure is as follows:
Wherein, R1For carbazole, aniline or hydrogen atom, R2For diphenyl phosphorus oxygen, azoles, imidazoles, triazine, pyridine, indole；N be 1～
Any number of 10000.
2. the preparation method of the polymer host material as described by claims 1, it is characterised in that carbazole group
Carry out respectively on C3 and C6 position modifying triphenylamine and diphenylphosphine oxygen groups, specifically comprise the following steps that
(1) under room temperature with N-bromo-succinimide, be dissolved in DMF solvent reaction.
At (2) 100 DEG C, with diphenyl phosphorus oxygen at palladium, 1,1 '-bis-(diphenylphosphine) ferrocene (dppf) and triethylamine
(TEA), under catalytic action, compound dissolution, in dimethyl sulfoxide (DMSO), reacts 3～4h.
At (3) 90 DEG C, with connection pinacol borate palladium, dppf catalytic action under, compound dissolution is at Isosorbide-5-Nitrae-dioxy
In six rings, react 15h.
At (4) 100 DEG C, under the catalytic action of tetra-triphenylphosphine palladium and potassium carbonate and potassium fluoride, compound dissolution Isosorbide-5-Nitrae-
In dioxane solvent and water, reaction overnight.
At (5) 45～50 DEG C, the catalysis in potassium carbonate, potassium hydroxide and phase transfer catalyst tetrabutyl ammonium bromide (TBAB) is made
Under with, compound dissolution is 1, in 2-dichloroethanes, reacts 3～5h.
At (6) 85～90 DEG C, under the catalytic action of potassium hydroxide and hydroquinone, compound dissolution at solvent isopropanol and
In the mixed solvent of toluene, backflow 2～3h.
At (7) 85～90 DEG C, in the N-Methyl pyrrolidone (NMP) that monomeric compound is dissolved under anhydrous and oxygen-free state, simultaneously
Add the polymerization initiator azodiisobutyronitrile (AIBN) that monomer weight ratio is 1%, react two days under the conditions of lucifuge.
3. the preparation method of the polymer host material as described by claims 1, it is characterised in that carbazole group
Modify triphenyl phosphorus oxygen groups on C6 position, specifically comprise the following steps that
(1) under room temperature with N-bromo-succinimide, be dissolved in DMF solvent reaction.
At (2) 100 DEG C, with diphenyl phosphorus oxygen palladium, 1,1 '-bis-(diphenylphosphine) ferrocene (dppf), connection boric acid frequency that
Under the catalytic action of alcohol ester and potassium acetate, compound dissolution, in anaerobic dimethyl sulfoxide (DMSO), reacts one day.
At (3) 100 DEG C, with 1,3-dibromobenzene is dissolved in deoxygenated toluene and THF mixed solution at palladium, dppf, then adds
Enter anaerobic potassium carbonate and potassium fluoride mixed solution, react 15h.
At (4) 100 DEG C, with diphenyl phosphorus oxygen palladium, dppf and TEA catalytic action under, compound dissolution is in anaerobic
DMSO in, react 3～4h.
At (5) 45～50 DEG C, the catalysis in potassium carbonate, potassium hydroxide and phase transfer catalyst tetrabutyl ammonium bromide (TBAB) is made
Under with, compound dissolution is 1, in 2-dichloroethanes, reacts 3～5h.
At (6) 85～90 DEG C, under the catalytic action of potassium hydroxide and hydroquinone, compound dissolution at solvent isopropanol and
In the mixed solvent of toluene, backflow 2～3h.
At (7) 85～90 DEG C, monomeric compound is dissolved in the NMP under anhydrous and oxygen-free state, is simultaneously introduced monomer weight ratio and is
The polymerization initiator AIBN of 1%, reacts two days under the conditions of lucifuge.
4. according to the application process of the polymer host material described by claims 2, it is characterised in that this material of main part should
For polymer light emitting devices, device architecture is: transparent anode/hole injection layer/luminescent layer/hole blocking layer/electronics
Transport layer/electron injecting layer/negative electrode.Material of main part and guest materials layer are luminescent layer, with material of main part and heavy metal
Thing doping forms, and the material of main part of luminescent layer is the polymer host material described by claims 2, the heavy metal of doping
Coordination compound is green phosphorescent luminescent material.
5. according to the application process of the polymer host material described by claims 3, it is characterised in that this material of main part should
For polymer light emitting devices, device architecture is: transparent anode/hole injection layer/luminescent layer/hole blocking layer/electronics
Transport layer/electron injecting layer/negative electrode.Material of main part and guest materials layer are luminescent layer, with material of main part and heavy metal
Thing doping forms, and the material of main part of luminescent layer is the polymer host material described by claims 3, the heavy metal of doping
Coordination compound is blue phosphorescent luminescent material.
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