CN109096426A - Main polymer material and preparation method and application thereof - Google Patents
Main polymer material and preparation method and application thereof Download PDFInfo
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- CN109096426A CN109096426A CN201810836260.0A CN201810836260A CN109096426A CN 109096426 A CN109096426 A CN 109096426A CN 201810836260 A CN201810836260 A CN 201810836260A CN 109096426 A CN109096426 A CN 109096426A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002861 polymer material Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims description 99
- 238000006243 chemical reaction Methods 0.000 claims description 51
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 26
- 238000005859 coupling reaction Methods 0.000 claims description 24
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 19
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 claims description 18
- -1 tert-butyl sodium alkoxide Chemical class 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000011261 inert gas Substances 0.000 claims description 10
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 5
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000009471 action Effects 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
- 230000000694 effects Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 41
- 239000000463 material Substances 0.000 abstract description 25
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 112
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000002904 solvent Substances 0.000 description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000000921 elemental analysis Methods 0.000 description 20
- 239000003480 eluent Substances 0.000 description 20
- 239000012043 crude product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 239000012300 argon atmosphere Substances 0.000 description 17
- 230000001376 precipitating effect Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 13
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000011097 chromatography purification Methods 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 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 10
- 238000001914 filtration Methods 0.000 description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 230000005526 G1 to G0 transition Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 150000001716 carbazoles Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- UOKPYRQNIKRYMO-UHFFFAOYSA-N 9-(3-ethenylphenyl)carbazole Chemical compound C=CC1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 UOKPYRQNIKRYMO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- HKQZXQYDVVWKJA-UHFFFAOYSA-N 1,2,4,5-tetraphenyl-9h-carbazole-3,6-diamine Chemical class C=1C=CC=CC=1C1=C(N)C(C=2C=CC=CC=2)=C2C3=C(C=4C=CC=CC=4)C(N)=CC=C3NC2=C1C1=CC=CC=C1 HKQZXQYDVVWKJA-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000005977 Ethylene Substances 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Indole Compounds (AREA)
Abstract
The invention belongs to the technical field of organic photoelectric materials, and discloses a main polymer material, and a preparation method and application thereof. The structural formula of the main polymer material is shown in formula I, m is 1 or 2, and n is an integer larger than or equal to 2. The invention also discloses a preparation method of the main polymer material. The polymer main material has larger steric hindrance, excellent solubility, film forming property and film form stability, is beneficial to the injection and transmission of holes and electrons, and reduces the turn-on voltage of devices; moreover, the maximum lumen efficiency of a phosphorescent device taking the host polymer material as the host material can reach 22.6 candela per ampere. The main polymer material has excellent photoelectric properties, and the preparation method is simple and can be used for large-scale production. The polymer host material of the present invention is used in the field of organic light emitting diodes.
Description
Technical field
The invention belongs to organic photoelectrical material technical fields, and in particular to a kind of host polymer material and preparation method thereof
And application.
Background technique
The Forrest seminar of Princeton university in 1997 reports electroluminescent phosphor device for the first time
(PHPLEDs).The singlet exciton and triplet excitons ratio that electroexcitation generates are 1:3, and fluorescent device theoretically can only benefit
With singlet exciton, maximum external quantum efficiency is 25%；And phosphorescent devices can will be electrically excited generation by intersystem crossing (ISC)
Two kinds of excitons (singlet, triplet excitons) all use, and the maximum external quantum efficiency of theoretically PHPLEDs can reach
100%.On the other hand, the service life of phosphorescent emissions is longer than fluorescence.Between the advantage of phosphorescent devices, more and more researchers couple
Phosphorescent devices are furtherd investigate.The luminescent layer of phosphorescent devices mainly uses Subjective and Objective structure at present, usually in material of main part
The phosphorescent guest material of doping 1%~10%, reaches the maximization that exciton utilizes by the energy transfer of main body to object, with drop
The excitation state concentration of low-phosphorous luminescent material.Therefore, it is particularly significant to phosphorescent devices to develop outstanding material of main part.
As material of main part, need to meet following five conditions: (1) triplet is higher than phosphorescent guest, avoids energy
It is shifted from object to main body, while triplet excitons can be limited in luminescent layer；(2) emission spectrum of material of main part and object material
The absorption spectrum of material should have certain overlapping, be conducive to energy transfer；(3)
HOMO energy level and lumo energy should match with adjacent organic, to reduce the injection barrier in hole and electronics；
(4) luminescent spectrum red shift can be made due to increasing conjugate length, so the conjugate length of material of main part cannot be too long；(5) thermostabilization
Property it is good, thin film stability is good, can avoid plus the separation of thermogenetic phase, extends device lifetime.
Summary of the invention
In order to improve the performance of phosphorescent devices, develop new material of main part, the purpose of the present invention is to provide one kind
Host polymer material and its preparation method and application.Host polymer material of the invention is made of carbazole and its derivative,
Hole transporting unit is introduced, triplet can be improved, is applied to phosphorescent OLED material of main part, improves the photo electric of phosphorescent devices
Energy.
The purpose of the present invention is achieved through the following technical solutions:
A kind of host polymer material, structural formula are Formulas I:
M be 1 or 2, n >=2 and be integer.
Ar1Unit are as follows:Wherein * indicates Ar1With Ar2
Junction；
Ar2Unit is such as any one in flowering structure:
R in same structure is identical or different, and R is hydrogen, alkyl, substituted or unsubstituted aryl, and the alkyl is preferably
C1~C30Straight chain or branched alkyl, the substituted or unsubstituted aryl is preferably
R2=H, C1~C30Straight chain or branched alkyl.
The preparation method of the host polymer material, comprising the following steps:
(1) in atmosphere of inert gases and organic solvent, by compound Ar1-(Ar2)mWith bromstyrol in catalyst system
Effect is lower to occur C-N coupling reaction, and purifying obtains polymerized monomer M1；
(2) in atmosphere of inert gases and organic solvent, polymerized monomer M1 is subjected to free radical under the action of initiator
Polymerization reaction, purifying obtain host polymer material.
Compound Ar described in step (1)1-(Ar2)mFor
Organic solvent described in step (1) is toluene, and the catalyst system includes tert-butyl sodium alkoxide, palladium acetate and three tertiary fourths
Base phosphine；The temperature of reaction is 60~100 DEG C, and the time of reaction is 12~36h；
In step (1), the compound Ar1-Ar2, bromstyrol, tert-butyl sodium alkoxide and palladium acetate molar ratio be
(1~3): (1~3): (3~10): (0.02~0.1)；Palladium acetate and the molar ratio of tri-tert-butylphosphine are 1:(1~4).
In step (2), the molar ratio of the polymerized monomer M1 and initiator is 1:0.02~0.5；The purifying refers to
Gained reaction solution is cooled to room temperature, is precipitated in methyl alcohol, is filtered, dry that crude product, crude product are dissolved with toluene, column chromatography
Separation, concentration, precipitating in methyl alcohol, filters again, dry, successively uses methanol, acetone, tetrahydrofuran extracting, after concentration again
Precipitating in methyl alcohol, filters, dry, obtains target product.
Organic solvent described in step (2) is tetrahydrofuran, and the initiator is azodiisobutyronitrile AIBN, the temperature of reaction
30~90 DEG C of degree, the time of reaction are 24~48h.
Compound Ar in step (1)1-(Ar2)mPass through C-C coupling (Suzuki coupling reaction) or C-N coupling
(Buchwald-Hartwig coupling reaction) reaction obtains.
The C-C coupling reaction is divided into two kinds of situations:
The first situation: as Ar in host polymer material formula I1ForWhen, the specific steps of C-C coupling reaction are as follows: under atmosphere of inert gases and have
In solvent, Ar will be contained1The compound of unit and contain Ar2Suzuki coupling occurs under catalyst system for the compound of unit
Reaction obtains product Ar1-(Ar2)m；Contain Ar1The compound of unit is 3- (4,4,5,5- tetramethyl -1,3,2- dioxa boron
Alkane -2- base) -9H- carbazole or 3, bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- the base) -9H- carbazoles of 6- contain
Ar2The compound of unit is bromo Ar2Unit, that is, Ar2The bromide of unit；
In the first situation, the catalyst system includes wet chemical and tetrakis triphenylphosphine palladium, the reaction
Temperature is 60~100 DEG C, and the time of reaction is 12~36h；The organic solvent is tetrahydrofuran；
Second situation: as Ar in host polymer material formula I1ForWhen, C-C coupling reaction
Specific steps are as follows: in atmosphere of inert gases and organic solvent, Ar will be contained1The compound of unit and contain Ar2The chemical combination of unit
Suzuki coupling reaction occurs under catalyst system for object, obtains product Ar1-(Ar2)m；Contain Ar1The compound of unit is 4- bromine
Diphenylamines, bis- (4- bromobenzene) amine, 3- bromine carbazole or 3,6- dibromo carbazole are described to contain Ar2The compound of unit is Ar2Unit boron
Acid or borate, the Ar2Unit boric acid or borate are Ar2-B(OH)2Or
In second situation, the catalyst system includes wet chemical and tetrakis triphenylphosphine palladium, the reaction
Temperature is 60~100 DEG C, and the time of reaction is 12~36h；The organic solvent is toluene or tetrahydrofuran.
The first situation of C-C coupling reaction, the 3- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- base) -
9H- carbazole, bromo Ar2The molar ratio of unit, potassium carbonate and tetrakis triphenylphosphine palladium is 1:(1~3): (5~10): (0.02
~0.1), 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- base) -9H- carbazoles, bromo Ar2Unit, carbonic acid
The molar ratio of potassium and tetrakis triphenylphosphine palladium is 1:(2~6): (5~10): (0.02-0.1)；
The second situation of C-C coupling reaction, contains Ar1The compound of unit contains Ar2Compound, the potassium carbonate of unit
And the molar ratio of tetrakis triphenylphosphine palladium is 1:(1~3): (5~10): (0.02~0.1) contains Ar at this time1The change of unit
Conjunction object is 4- bromine diphenylamines, 3- bromine carbazole；
Ar1The compound of unit contains Ar2The molar ratio of the compound of unit, potassium carbonate and tetrakis triphenylphosphine palladium is
1:(2~6): (5~10): (0.02~0.1) contains Ar at this time1The compound of unit is bis- (4- bromobenzene) amine, 3,6- dibromo click
Azoles.
The C-N coupling reaction refers to bromine-containing compound and contains NH or NH2Compound by C-N coupling reaction, obtain
Compound Ar1-(Ar2)m。
The specific steps of the C-N coupling reaction are as follows:
In atmosphere of inert gases and organic solvent, Ar will be contained1The compound and Ar of unit2Unit compound is in catalytic body
System is lower to occur C-N coupling reaction, obtains product Ar1-(Ar2)m；It is described to contain Ar1The compound of unit is 4- bromine diphenylamines, double
(4- bromobenzene) amine, 3- bromine carbazole or 3,6- dibromo carbazole；The Ar2Unit compound is Ar2-H.It is urged described in C-N coupling reaction
Change system includes tert-butyl sodium alkoxide, palladium acetate and tri-tert-butylphosphine, and the temperature of the reaction is 60~100 DEG C, the time of reaction
For 12~36h；The organic solvent is toluene.
In C-N coupling reaction, contain Ar1When the compound of unit is 3- bromine carbazole or 4- bromine diphenylamines, contain Ar1Unit
Compound, Ar2The molar ratio of unit compound, tert-butyl sodium alkoxide (NaOBu) and palladium acetate is 1:(1~3): (4.1~
10): (0.02~0.1)；Contain Ar1When the compound of unit is 3,6- dibromo carbazole or bis- (4- bromobenzene) amine, contain Ar1Unit
Compound, Ar2The molar ratio of unit compound, tert-butyl sodium alkoxide and palladium acetate is 1:(2~6): (4.1~10): (0.02
~0.1)；Palladium acetate and the molar ratio of tri-tert-butylphosphine are 1:(1~4).
In the application of host polymer material of the invention in Organic Light Emitting Diode, especially phosphorus electroluminescence device
Using as material of main part.
The reaction equation of host polymer material of the invention are as follows:
Compound Ar1-(Ar2)mC-C be coupled preparation:
Compound Ar1-(Ar2)mC-N be coupled preparation:
The preparation of polymerized monomer M1:
Polymerized monomer M1 polymerization prepares host polymer material:
Compared with present technology, the beneficial effect of host polymer material (electroluminescent polymer) provided by the invention
Be: (1) polymer host material of the invention, preparation method is simple, and purification is easy, and can be mass-produced；(2) of the invention poly-
Close owner's body material space steric hindrance it is larger, have excellent dissolubility, film forming and film morphology stability, be conducive to hole and
The injection and transmission of electronics, reduce device opens bright voltage；(3) based on polymer host material of the invention material phosphorus
The maximum lumen efficiency of optical device can reach 22.6 every ampere of candelas.
Detailed description of the invention
Fig. 1 is thermogravimetic analysis (TGA) (TGA) spectrogram of host polymer material PH1；
Fig. 2 is current density-operating voltage-brightness relationship curve of host polymer material PH1 and PH5；
Fig. 3 is luminous efficiency-current density relation curve of host polymer material PH1 and PH5；
Fig. 4 is the electroluminescent curve of host polymer material PH1 and PH5.
Specific embodiment
Present invention is further described in detail with attached drawing combined with specific embodiments below, but embodiments of the present invention are not
It is limited to this.
The preparation of 1 polymer P H1 of embodiment
(1) N- (4- (9H- carbazole -3- base) phenyl) N- ([1,1 '-diphenyl] -4- base -9,9- dimethyl -9H- fluorenes -2-
The synthesis of amine: under argon atmosphere, N- ([1,1 '-diphenyl] -4- base)-N- (4- bromophenyl) 9,9- dimethyl -9H- fluorenes -2-
Amine (compound 1-1,7.25mmol), 3- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- base) -9H- carbazole (chemical combination
Object 1-2,6.05mmol), catalyst tetra-triphenylphosphine palladium (Pd (PPh3)4) (0.35g, 0.30mmol) be dissolved in tetrahydrofuran
In (80ml), it is heated to generating reflux, the K that then will now match2CO3Reaction system is added in aqueous solution (2mol/L, 60.5mmol),
It is reacted 24 hours under counterflow condition；Solvent is removed, is purified by silica gel column chromatography, eluent is petroleum ether/methylene chloride=3/1
(volume ratio) then recrystallizes in tetrahydrofuran/ethyl alcohol, obtains white powder (compound 1-3).1HNMR、13CNMR, MS and
The result shows that obtained compound is target product, preparation process chemical equation is as follows for elemental analysis:
(2) N- ([1,1 '-diphenyl] -4- base) -9,9- dimethyl-N-(4- (9- (3- vinyl phenyl) -9H- carbazole -3-
Base) phenyl) -9H- fluorenes -2- amine synthesis: under argon atmosphere, will between bromstyrol (2.5mol), N- (4- (9H- carbazole -3-
Base) phenyl) N- ([1,1 '-diphenyl] -4- base -9,9- dimethyl -9H- fluorenes -2- amine (compound 1-3,2.4mmol), tert-butyl
Sodium alkoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene are placed in container, heating stirring to 85
DEG C, tri-tert-butylphosphine (Bu is added3P toluene solution (0.24mmol, 2mol/L)) reacts 12h, after stopping reaction, is concentrated molten
Agent, for crude product by column Chromatographic purification, eluent is petroleum ether/methylene chloride=4/1 (volume ratio), obtains white solid eventually and (changes
Close object 1-4).1HNMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) synthesis of polymer P H1: under argon atmosphere, by N- ([1,1 '-diphenyl] -4- base) -9,9- dimethyl -
N- (4- (9- (3- vinyl phenyl) -9H- carbazole -3- base) phenyl) -9H- fluorenes -2- amine (compound 1-4,0.50mol), AIBN
(8.2mg, 0.05mmol) and 10ml solvents tetrahydrofurane are placed in container, and 50 DEG C are reacted 36 hours, and reaction is stopped, and are dropped to temperature
To room temperature, the precipitating in 300ml methanol, filtering is added dropwise in product, then crude product is dissolved in the toluene of 20mL, with 200~300
Mesh silica gel is stationary phase, is that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out in methyl alcohol come again, stirring, mistake
Filter, obtains polymer solids after vacuum drying；It is finally successively respectively extracted 24 hours, is removed small with methanol, acetone, tetrahydrofuran again
Molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the white polymer PH1 obtained after vacuum drying, yield
59%.1H NMR, GPC and elemental analysis are the result shows that obtained compound is target product, preparation process chemical reaction side
Formula is as follows:
Thermal weight loss (TG) curve of polymer P H1 is as shown in Figure 1.It can be seen that polymer P H1 is in entire heating process
In, only there is a thermal decomposition process, is the thermal decomposition process of conjugated main chain.When the Mass lost 5% of polymer P 1, institute is right
The temperature answered is 446 DEG C, i.e., the thermal decomposition temperature of polymer P H1 is 446 DEG C.Illustrate that polymer P H1 has excellent thermostabilization
Property.
The preparation of 2 polymer P H2 of embodiment
(1) synthesis of bis- (4- (9H- carbazole -9- base) phenyl) amine: under argon atmosphere, by 4- (9H- carbazole -9- base) amine
(compound 2-1,10mmol), 9- (4- bromobenzene) -9H- carbazole (compound 2-2,11mmol), tert-butyl sodium alkoxide (7.67g,
80mmol), palladium acetate (113mg, 0.5mmol) and 200ml toluene are added in reaction vessel, and heating stirring is added to 85 DEG C
The toluene solution (1.0mmol, 2mol/L) of 0.5ml tri-tert-butylphosphine reacts 12h, after stopping reaction, concentrated solvent, and crude product
By column Chromatographic purification, eluent is petroleum ether/methylene chloride=3/1 (volume ratio), obtains white solid (compound 2-3) eventually.1HNMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.Reaction equation:
(2) synthesis of N, N- bis- (4- (9H- carbazole -9- base) phenyl) -3- vinyl amine: under argon atmosphere, the bromine by between
Styrene (0.44g, 2.5mmol), bis- (4- (9H- carbazole -9- base) phenyl) amine (compound 2-3,2.4mmol), tert-butyl alcohol
Sodium (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene are added in reaction vessel, heating stirring to 85
DEG C, 0.12ml tri-tert-butylphosphine (Bu is added3P toluene solution (0.24mmol, 2mol/L)) reacts 12h, after stopping reaction,
Concentrated solvent, for crude product by column Chromatographic purification, eluent is petroleum ether/methylene chloride=3/1 (volume ratio), is obtained eventually white solid
Body (compound 2-4).1HNMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(2) synthesis of polymer P H2: under argon atmosphere, by N, N- bis- (4- (9H- carbazole -9- base) phenyl) -3- ethylene
Base amine (compound 2-4,0.50mol), AIBN (8.2mg, 0.05mmol) and 10ml solvents tetrahydrofurane are added in reaction vessel,
50 DEG C are reacted 36 hours, are stopped reaction, are down to room temperature to temperature, and the precipitating in 300ml methanol is added dropwise in product, is filtered, then will
Crude product is dissolved in the toluene of 20mL, is that eluant, eluent carries out column chromatography, solvent with toluene using 200~300 mesh silica gel as stationary phase
Concentration separates out in methyl alcohol come again, stirs, and filtering obtains polymer solids after vacuum drying；First is finally successively used again
Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol,
The white polymer PH2 obtained after vacuum drying, yield 60%.1H NMR, GPC and elemental analysis are the result shows that obtainedization
Conjunction object is target product, and preparation process chemical equation is as follows:
The preparation of 3 polymer P H3 of embodiment
The synthesis of 3 ': 6 ', 9 "-three carbazoles: (1) 9 ' H-9 under argon atmosphere, in 100mL there-necked flask, is added 3,6-
Dibromo carbazole (0.40g, 2.4mmol), carbazole (1.63g, 5.0mmol), tert-butyl sodium alkoxide (1.84g, 19.2mmol), palladium acetate
0.12ml tri-tert-butylphosphine (Bu is added to 85 DEG C in (27mg, 0.12mmol) and 50ml toluene, heating stirring3P toluene solution)
(0.24mmol, 2mol/L) reacts 12h, and after stopping reaction, concentrated solvent, for crude product by column Chromatographic purification, eluent is stone
Oily ether/methylene chloride=3/1 (volume ratio) obtains white solid (compound 3-1) eventually.1HNMR、13CNMR, MS and elemental analysis knot
Fruit shows that obtained compound is target product.
(2) 9 '-(3- vinyl phenyl) -9 ' H-9, the synthesis of 3 ': 6 ', 9 "-three carbazoles: under argon atmosphere, in 100mL tri-
In mouth bottle, bromstyrol (0.44g, 2.5mmol), 9H-9 between addition, 3 ': 6 ', 9 "-three carbazoles (compound 3-1,2.4mmol),
Tert-butyl sodium alkoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene, heating stirring add to 85 DEG C
Enter 0.12ml tri-tert-butylphosphine (Bu3P toluene solution (0.24mmol, 2mol/L)) reacts 12h, after stopping reaction, is concentrated molten
Agent, for crude product by column Chromatographic purification, eluent is petroleum ether/methylene chloride=3/1 (volume ratio), obtains white solid eventually and (changes
Close object 3-2).1HNMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) under argon atmosphere, in 50mL two-mouth bottle, 9 '-(3- vinyl phenyls) -9 ' synthesis of polymer HP3: are added
H-9,3 ': 6 ', 9 "-three carbazoles (compound 3-2,0.50mol), AIBN (8.2mg, 0.05mmol) and 10ml solvent tetrahydro furan
It mutters, 50 DEG C are reacted 36 hours, are stopped reaction, are down to room temperature to temperature, and the precipitating in 300ml methanol is added dropwise in product, is filtered, then
Crude product is dissolved in the toluene of 20mL, is that eluant, eluent carries out column chromatography with toluene using 200~300 mesh silica gel as stationary phase, it is molten
Agent concentration, separates out in methyl alcohol come again, stirs, and filtering obtains polymer solids after vacuum drying；First is finally successively used again
Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol,
The white polymer PH3 obtained after vacuum drying, yield 63%.1H NMR, GPC and elemental analysis are the result shows that obtainedization
Conjunction object is target product, and preparation process chemical equation is as follows:
The preparation of 4 polymer P H4 of embodiment
(1)N3,N3,N6,N6The synthesis of tetraphenyl -9H- carbazole -3,6- diamines: under argon atmosphere, at tri- mouthfuls of 100mL
In bottle, 3,6- dibromo carbazole (2.4mmol), diphenylamines (5.0mmol), tert-butyl sodium alkoxide (1.84g, 19.2mmol), vinegar is added
0.12ml tri-tert-butylphosphine (Bu is added to 85 DEG C in sour palladium (27mg, 0.12mmol) and 50ml toluene, heating stirring3P toluene)
Solution (0.24mmol, 2mol/L) reacts 12h, and after stopping reaction, concentrated solvent, crude product passes through column Chromatographic purification, eluent
For petroleum ether/methylene chloride=4/1 (volume ratio), white solid (i.e. compound 4-1) is obtained eventually.1HNMR、13CNMR, MS and element
Analysis is the result shows that obtained compound is target product.
(2)N3,N3,N6,N6The synthesis of tetraphenyl -9 '-(3- vinyl phenyl) -9H- carbazole -3,6- diamines: in argon atmospher
Under enclosing, in 100mL there-necked flask, bromstyrol (2.5mmol), compound 4-1 (2.4mmol), tert-butyl sodium alkoxide between addition
0.12ml tri- is added to 85 DEG C in (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene, heating stirring
Tert-butyl phosphine (Bu3P toluene solution (0.24mmol, 2mol/L)) reacts 12h, after stopping reaction, concentrated solvent, and crude product
By column Chromatographic purification, eluent is petroleum ether/methylene chloride=3/1 (volume ratio), obtains white solid (compound 4-2) eventually.1HNMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) under argon atmosphere, in 50mL two-mouth bottle, compound 4-2 the synthesis of polymer P H4: is added
(0.50mol), AIBN (8.2mg, 0.05mmol) and 10ml solvents tetrahydrofurane, 50 DEG C are reacted 36 hours, stop reaction, to temperature
Degree is down to room temperature, the precipitating in 300ml methanol, filtering is added dropwise in product, then crude product is dissolved in the toluene of 20mL, with 200
~300 mesh silica gel are stationary phase, are that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out in methyl alcohol come again, stirs
It mixes, filters, obtain polymer solids after vacuum drying；Finally successively respectively extracted 24 hours with methanol, acetone, tetrahydrofuran again,
Remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the white polymer obtained after vacuum drying
PH4, yield 58%.1H NMR, GPC and elemental analysis are the result shows that obtained compound is target product, preparation process
It is as follows to learn reaction equation:
The preparation of 5 polymer P H5 of embodiment
(1) 9,9 '-diphenyl -9H, 9 ' H, 9 " H-3,3 ': 6 ', the synthesis of 3 " -4- carbazoles: in closed, logical argon gas condition
Under, by 3,6- dibromo carbazole (1.97g, 6.05mmol), 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -
2- yl) -9H- carbazole (2.13g, 15.15mmol), catalyst tetra-triphenylphosphine palladium (Pd (PPh3)4) (0.70g, 0.61mmol) molten
In tetrahydrofuran (80ml), it is heated to generating reflux, the K that then will now match2CO3Aqueous solution (2mol/L, 60.5mmol) is added
Reaction system is reacted 48 hours under counterflow condition, and solvent is rotated, and carries out column chromatography, eluent be petroleum ether/methylene chloride=
3/1 (volume ratio), then recrystallizes in tetrahydrofuran/ethyl alcohol, obtains white powder (compound 5-1), yield 88%.1H
NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation process chemical equation
It is as follows:
(2) 9,9 '-diphenyl -9 '-(3- vinyl phenyl) -9H, 9 ' H, 9 " H-3,3 ': 6 ', 3 "-three carbazoles (compound 5-
2) synthesis: under argon atmosphere, in 100mL there-necked flask, bromstyrol (1.24g, 5.5mol), 9,9 '-hexichol between addition
Base -9H, 9 ' H, 9 " H-3,3 ': 6 ', 3 " -4- carbazole (compound 5-1,5.0mmol), tert-butyl sodium alkoxide (1.84g,
19.2mmol), 0.12ml tri-tert-butylphosphine is added to 85 DEG C in palladium acetate (27mg, 0.12mmol) and 50ml toluene, heating stirring
(Bu3P toluene solution (0.24mmol, 2mol/L)) reacts 12h, and after stopping reaction, concentrated solvent, crude product passes through column layer
Analysis purification, eluent are petroleum ether/methylene chloride=2/1 (volume ratio), obtain green solid (compound 5-2) eventually.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product, and preparation process chemical equation is such as
Under:
(3) under argon atmosphere, in 50mL two-mouth bottle, compound 5-2 the synthesis of polymer P H5: is added
(0.50mol), AIBN (8.2mg, 0.05mmol) and 10ml solvents tetrahydrofurane, 50 DEG C are reacted 36 hours, stop reaction, to temperature
Degree is down to room temperature, the precipitating in 300ml methanol, filtering is added dropwise in product, then crude product is dissolved in the toluene of 20mL, with 200
~300 mesh silica gel are stationary phase, are that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out in methyl alcohol come again, stirs
It mixes, filters, obtain polymer solids after vacuum drying；Finally successively respectively extracted 24 hours with methanol, acetone, tetrahydrofuran again,
Remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the white polymer obtained after vacuum drying
PH5, yield 62%.1H NMR, GPC and elemental analysis are the result shows that obtained compound is target product, preparation process
It is as follows to learn reaction equation:
The preparation of 6 polymer P H6 of embodiment
(1) 9,9 '-diphenyl -9H, 9 ' H, 9 " H-3,3 ': 6 ', the synthesis of 3 " -4- carbazoles (compound 6-2): it is closed,
Under the conditions of logical argon gas, by 3,6- dibromo carbazole (6.05mmol), N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxy
Miscellaneous borine -2- base) amine (compound 6-1,15.15mmol), catalyst tetra-triphenylphosphine palladium (Pd (PPh3)4) (0.61mmol) molten
In tetrahydrofuran (80ml), it is heated to generating reflux, the K that then will now match2CO3Aqueous solution (2mol/L, 60.5mmol) is added
Reaction system is reacted 48 hours under counterflow condition, and solvent is rotated, and carries out column chromatography, eluent be petroleum ether/methylene chloride=
4/1 (volume ratio), then recrystallizes in tetrahydrofuran/ethyl alcohol, obtains white powder, yield 88%.1H NMR、13CNMR、MS
With elemental analysis the result shows that obtained compound is target product, preparation process chemical equation is as follows:
The synthesis of (2) 4,4 '-(9- (3- vinyl benzene) -9H- carbazole -3,6- diyl) bis- (N, N- diphenylamines): in argon gas
Under atmosphere, in 100mL there-necked flask, bromstyrol (2.4mol), compound 6-2 (5.0mmol), tert-butyl sodium alkoxide between addition
0.12ml tri- is added to 85 DEG C in (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene, heating stirring
Tert-butyl phosphine (Bu3P toluene solution (0.24mmol, 2mol/L)) reacts 12h, after stopping reaction, concentrated solvent, and crude product
By column Chromatographic purification, eluent is petroleum ether/methylene chloride=1/1 (volume ratio), obtains green solid (compound 6-3) eventually.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation process chemical reaction side
Formula is as follows:
(3) under argon atmosphere, in 50mL two-mouth bottle, 4,4 '-(9- (3- vinyl the synthesis of polymer P H6: are added
Benzene) -9H- carbazole -3,6- diyl) bis- (N, N- diphenylamines) (compound 6-3,0.50mol), AIBN (8.2mg, 0.05mmol) and
10ml solvents tetrahydrofurane, 50 DEG C are reacted 36 hours, are stopped reaction, are down to room temperature to temperature, and product is added dropwise in 300ml methanol
Middle precipitating, filtering, then crude product is dissolved in the toluene of 20mL, it is elution with toluene using 200~300 mesh silica gel as stationary phase
Agent carries out column chromatography, and solvent concentration separates out in methyl alcohol come again, stirs, and it is solid to obtain polymer for filtering after vacuum drying
Body；It is finally successively respectively extracted 24 hours with methanol, acetone, tetrahydrofuran again, removes small molecule；Tetrahydrofuran after concentration is molten
Drop enters precipitating in methanol, the white polymer PH6 obtained after vacuum drying, yield 64%.1H NMR, GPC and elemental analysis
The result shows that obtained compound is target product, preparation process chemical equation is as follows:
The preparation of 7 polymer P H7 of embodiment
(1) under argon atmosphere, in 100mL there-necked flask, 4,4 '-dibromo diphenylamines the synthesis of compound 7-2: are added
(2.4mmol), compound 7-1 (5.0mmol), catalyst tetra-triphenylphosphine palladium (Pd (PPh3)4) (0.12mmol) be dissolved in tetrahydro furan
It mutters in (60ml), is heated to generating reflux, the K that then will now match2CO3Reaction system is added in aqueous solution (2mol/L, 24mmol),
It is reacted 48 hours under counterflow condition, rotates solvent, carry out column Chromatographic purification, eluent is petroleum ether/methylene chloride=3/1
(volume ratio) then recrystallizes in tetrahydrofuran/ethyl alcohol, obtains white solid (compound 7-2) eventually.1H NMR、13CNMR、MS
With elemental analysis the result shows that obtained compound is target product.
(2) synthesis of compound 7-3: under argon atmosphere, in 100mL there-necked flask, bromstyrol between addition
(2.4mmol), compound 7-2 (2.6mmol), tert-butyl sodium alkoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol)
And 0.12ml tri-tert-butylphosphine (Bu is added to 85 DEG C in 50ml toluene, heating stirring3P toluene solution (0.24mmol, 2mol/)
L), react 12h, after stopping reaction, concentrated solvent, crude product by column Chromatographic purification, eluent be petroleum ether/methylene chloride=
1/1 (volume ratio) obtains white solid eventually.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is mesh
Mark product.
(3) synthesis of polymer P H7: under argon atmosphere, in the reaction vessel, addition compound 7-3 (0.50mol),
AIBN (8.2mg, 0.05mmol) and 10ml solvents tetrahydrofurane, 50 DEG C are reacted 36 hours, are stopped reaction, are down to room to temperature
Product is added dropwise the precipitating in 300ml methanol, filtering, then crude product is dissolved in the toluene of 20mL by temperature, with 200~300 mesh silicon
Glue is stationary phase, is that eluant, eluent carries out column chromatography with toluene, and solvent concentration separates out in methyl alcohol come again, is stirred, filtering,
Polymer solids are obtained after vacuum drying；It is finally successively respectively extracted 24 hours with methanol, acetone, tetrahydrofuran again, removes small point
Son；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the white polymer PH7 obtained after vacuum drying, yield
53%.1H NMR, GPC and elemental analysis are the result shows that obtained compound is target product, preparation process chemical reaction side
Formula:
The preparation of 8 electroluminescent device of embodiment
(1) ito glass substrate the cleaning of ITO electro-conductive glass: is sequentially placed into acetone, isopropanol, dish washing liquid, deionized water
It is cleaned by ultrasonic in isopropanol, removing ito glass substrate surface may remaining spot (such as photoresist) and improvement
Interfacial contact is put into vacuum drying oven dry after having cleaned；
(2) ITO is placed in oxygen plasma etch instrument, is carried out 20 minutes using oxygen plasma (O2Plasma)
Bombardment thoroughly removes the possible remaining organic matter of ito glass substrate surface；
(3) on ITO 40 nanometer thickness of spin coating hole injection layer PEDOT:PSS (Baytron P4083), then in vacuum
It is 12 hours dry at 80 DEG C in baking oven；
(4) in the glove box of nitrogen atmosphere, by polymer host material PH1 (embodiment 1) or PH5 (embodiment 5) with
Phosphorescent guest is blended with the mass ratio of 94:6, and solvent is dimethylbenzene, and compound concentration is the solution of 20mg/mL, at PEDOT:PSS layers
After the active layer film of one layer of 80 nanometer thickness of upper spin coating, heating anneal 20 minutes at 80 DEG C on warm table are molten to remove residual
Agent and the pattern for improving the tunic that shines；
(5) one layer 40 is first deposited on active layer film under the vacuum degree lower than 3 × 10-4Pa in vacuum evaporation storehouse
Electron transport material 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBI) of nanometer thickness, then be deposited one layer 1.0 and receive
The thick lithium fluoride (LiF) of rice, is finally deposited the aluminium cathode (Al) of one layer of 90 nanometer thickness, wherein lithium fluoride and aluminium layer are by mask plate
It carries out vacuum-deposited.
The effective area of device is 0.09cm2.With the thickness of quartz crystal monitoring thickness gauge measurement organic layer.Device preparation
Polarity solidification and encapsulation in ultraviolet light with epoxy resin and thin layer of glass afterwards.Electroluminescent (EL) spectrogram passes through Photo
Research PR705 type optical analyser measures.The characteristic of current density and brightness and driving voltage passes through Keithley respectively
2400 source measuring units and Konica Minolta chromascope CS-200 are measured.External quantum efficiency assumes that Lambertian points
Cloth, by brightness, current density and EL spectrum are calculated.The device architecture of preparation is ITO/PEDOT:PSS/host:IrO2=
94:6/TML/LiF/Al。
Wherein, the structural formula of phosphorescent guest (IrO2) are as follows:
Electron transport material structure are as follows:
Photoelectric properties test is carried out respectively to obtained electroluminescent device, test result is as shown in table 1.
The photoelectric properties of 1 electroluminescent device of table
Fig. 2 is current density-operating voltage-brightness relationship curve of host polymer material PH1 and PH5；
Fig. 3 is luminous efficiency-current density relation curve of host polymer material PH1 and PH5.
For the data from Fig. 2 and Fig. 3 performance chart and table 1 it is found that based on polymer P H1, PH5, IrO2 is object
Electroluminescent device have excellent photoelectric properties.Phosphorescent devices open bright voltage (brightness be every square metre of 1 candela when
Voltage) it is only 2.6 volts, with report in periodical " organic electronic " (Organic Electronics 57 (2018), 178-185)
With classical material of main part CBP, object is that the minimum of the device of IrO2 opens bright voltage 4.1V and compare, with polymer in the present invention
Device based on PH1, PH5 to open bright voltage obviously much lower.Illustrate under identical voltage conditions, device brightness of the present invention
Height has a clear superiority.Their maximum current efficiency respectively reaches 22.6,21.8 every ampere of candelas.With above-mentioned document report
The phosphorescent devices in road basically reach same level.
In order to study the luminous situation of the above phosphorescent devices, the electroluminescent spectrum of the above device is acquired, such as Fig. 4 institute
Show.Fig. 4 is the electroluminescent curve of host polymer material PH1 and PH5.It can be seen from the figure that the spectrum and object of device
Photic spectrum it is almost the same, illustrate, in the above device, electrons and holes can effective luminescent layer it is compound, and complete energy
Transfer from main body to object, and then object is excited to shine.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other are any to should be without departing from spirit of the invention and changes, modifications, substitutions, combinations, simplifications made under principle
Equivalent substitute mode, is included within the scope of the present invention.
Claims (10)
1. a kind of host polymer material, it is characterised in that: its structural formula is Formulas I:
M be 1 or 2, n >=2 and be integer；
Ar1Unit are as follows:
Wherein * indicates Ar1With Ar2Junction；
Ar2Unit is such as any one in flowering structure:
R in same structure is identical or different, and R is hydrogen, alkyl, substituted or unsubstituted aryl.
2. host polymer material according to claim 1, it is characterised in that: the alkyl is C1~C30Straight chain or branch
Alkyl group, the substituted or unsubstituted aryl areR2=H, C1~C30Straight chain or
Branched alkyl.
3. the preparation method of any one host polymer material according to claim 1~2, it is characterised in that: including following
Step:
(1) in atmosphere of inert gases and organic solvent, by compound Ar1-(Ar2)mWith bromstyrol catalyst system effect
Lower generation C-N coupling reaction, purifying obtain polymerized monomer M1；
(2) in atmosphere of inert gases and organic solvent, polymerized monomer M1 is subjected to free radical polymerization under the action of initiator
Reaction, purifying obtain host polymer material；
Compound Ar described in step (1)1-(Ar2)mFor Ar2, m is as defined in claim 1.
4. the preparation method of host polymer material according to claim 3, it is characterised in that: be catalyzed described in step (1)
System includes tert-butyl sodium alkoxide, palladium acetate and tri-tert-butylphosphine；The temperature of reaction is 60~100 DEG C, time of reaction is 12~
36h；
Initiator described in step (2) is azodiisobutyronitrile, and 30~90 DEG C of the temperature of reaction, the time of reaction is 24~48h.
5. the preparation method of host polymer material according to claim 4, it is characterised in that: in step (1), the chemical combination
Object Ar1-(Ar2)m, bromstyrol, tert-butyl sodium alkoxide and palladium acetate molar ratio be (1~3): (1~3): (3~10):
(0.02~0.1)；Palladium acetate and the molar ratio of tri-tert-butylphosphine are 1:(1~4)；
In step (2), the molar ratio of the polymerized monomer M1 and initiator is 1:(0.02~0.5).
6. the preparation method of host polymer material according to claim 3, it is characterised in that: compound Ar in step (1)1-
(Ar2)mIt is obtained by C-C coupling or C-N coupling reaction.
7. the preparation method of host polymer material according to claim 6, it is characterised in that: the C-C coupling reaction point
For two kinds of situations:
The first situation: as Ar in host polymer material formula I1For
When, the specific steps of C-C coupling reaction are as follows: under atmosphere of inert gases and in organic solvent, Ar will be contained1The compound of unit with
Contain Ar2Suzuki coupling reaction occurs under catalyst system for the compound of unit, obtains product Ar1-(Ar2)m；Contain Ar1It is single
The compound of member is 3- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- base) -9H- carbazole or the bis- (4,4,5,5- of 3,6-
Tetramethyl -1,3,2- dioxaborinate -2- base) -9H- carbazole, contains Ar2The compound of unit is bromo Ar2Unit, that is, Ar2It is single
The bromide of member；
Second situation: as Ar in host polymer material formula I1ForWhen, C-C coupling reaction
Specific steps are as follows: in atmosphere of inert gases and organic solvent, Ar will be contained1The compound of unit and contain Ar2The chemical combination of unit
Suzuki coupling reaction occurs under catalyst system for object, obtains product Ar1-(Ar2)m；Contain Ar1The compound of unit is 4- bromine
Diphenylamines, bis- (4- bromobenzene) amine, 3- bromine carbazole or 3,6- dibromo carbazole are described to contain Ar2The compound of unit is Ar2Unit boron
Acid or borate, the Ar2Unit boric acid or borate are Ar2-B(OH)2Or
8. the preparation method of host polymer material according to claim 6, it is characterised in that: the C-N coupling reaction is
Refer to bromine-containing compound and contains NH or NH2Compound by C-N coupling reaction, obtain compound Ar1-(Ar2)m。
9. the preparation method of host polymer material according to claim 8, it is characterised in that: the C-N coupling reaction
Specific steps are as follows:
In atmosphere of inert gases and organic solvent, Ar will be contained1The compound and Ar of unit2Unit compound is under catalyst system
C-N coupling reaction occurs, obtains product Ar1-(Ar2)m；It is described to contain Ar1The compound of unit is 4- bromine diphenylamines, bis- (4- bromines
Benzene) amine, 3- bromine carbazole or 3,6- dibromo carbazole；The Ar2Unit compound is Ar2-H。
10. application of any one host polymer material in Organic Light Emitting Diode according to claim 1~2.
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| CN112661887A (en) * | 2020-12-04 | 2021-04-16 | 华南理工大学 | Non-conjugated electroluminescent polymer with high exciton utilization rate and preparation method and application thereof |
| WO2021203663A1 (en) * | 2020-04-10 | 2021-10-14 | 华南理工大学 | Electroluminescent polymer based on phenanthroimidazole units, preparation method therefor, and use thereof |
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| KR20210033929A (en) * | 2019-09-19 | 2021-03-29 | 주식회사 엘지화학 | Polymer, monomer, coating compositions comprising same, organic light emitting device using same and method of manufacturing of organic light emitting device using same |
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| CN112661887A (en) * | 2020-12-04 | 2021-04-16 | 华南理工大学 | Non-conjugated electroluminescent polymer with high exciton utilization rate and preparation method and application thereof |
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