CN109312025A - 用于制备有机电荷传输膜的方法 - Google Patents
用于制备有机电荷传输膜的方法 Download PDFInfo
- Publication number
- CN109312025A CN109312025A CN201680086531.4A CN201680086531A CN109312025A CN 109312025 A CN109312025 A CN 109312025A CN 201680086531 A CN201680086531 A CN 201680086531A CN 109312025 A CN109312025 A CN 109312025A
- Authority
- CN
- China
- Prior art keywords
- base
- phenyl
- xenyl
- fluorenes
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical class C* 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 73
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 41
- 239000010408 film Substances 0.000 description 35
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 16
- 238000004587 chromatography analysis Methods 0.000 description 16
- 229920001519 homopolymer Polymers 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical class C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 12
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 8
- 238000000137 annealing Methods 0.000 description 8
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 benzyl carbon Chemical compound 0.000 description 3
- KOCXMMTWVKMODE-UHFFFAOYSA-N bromobenzene;phosphane Chemical compound P.BrC1=CC=CC=C1 KOCXMMTWVKMODE-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VNXNRYYBAVLABR-UHFFFAOYSA-N C(C=CC)CC(C)(C)P(C(C)(C)C)C(C)(C)C.[Cl] Chemical compound C(C=CC)CC(C)(C)P(C(C)(C)C)C(C)(C)C.[Cl] VNXNRYYBAVLABR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- SAFCVUUJRXNLHG-UHFFFAOYSA-N (1-methylnaphthalen-2-yl) acetate Chemical compound C1=CC=CC2=C(C)C(OC(=O)C)=CC=C21 SAFCVUUJRXNLHG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 description 1
- RQBRSIVAHJCTSL-UHFFFAOYSA-N 1-methyl-9H-fluoren-2-amine Chemical compound NC1=C(C=2CC3=CC=CC=C3C2C=C1)C RQBRSIVAHJCTSL-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- DJJCELUIFUBEJJ-UHFFFAOYSA-N C(Cl)Cl.[Si]=O Chemical compound C(Cl)Cl.[Si]=O DJJCELUIFUBEJJ-UHFFFAOYSA-N 0.000 description 1
- ATXGJIQZZNBZHJ-UHFFFAOYSA-N CN1C2=CC=CC=C2C(=C1C3=CC=CC=C3)C4=CC=C(C=C4)N Chemical compound CN1C2=CC=CC=C2C(=C1C3=CC=CC=C3)C4=CC=C(C=C4)N ATXGJIQZZNBZHJ-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- YNUQMJWCWFDJJQ-UHFFFAOYSA-N NS(=O)(=O)C1=CC=CC=C1OB(O)O Chemical compound NS(=O)(=O)C1=CC=CC=C1OB(O)O YNUQMJWCWFDJJQ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PRHDLIFXDPJWCJ-UHFFFAOYSA-N [O]Cc1ccc(C=C)cc1 Chemical compound [O]Cc1ccc(C=C)cc1 PRHDLIFXDPJWCJ-UHFFFAOYSA-N 0.000 description 1
- GWJBEJFEFFWFBI-UHFFFAOYSA-N acenaphthylen-1-ylmethanol Chemical group C1=CC(C(CO)=C2)=C3C2=CC=CC3=C1 GWJBEJFEFFWFBI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TWJVNKMWXNTSAP-UHFFFAOYSA-N azanium;hydroxide;hydrochloride Chemical compound [NH4+].O.[Cl-] TWJVNKMWXNTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- H10K85/115—Polyfluorene; Derivatives thereof
-
- 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
- C08F12/00—Homopolymers and copolymers 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
-
- 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
-
- 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
- C08F12/00—Homopolymers and copolymers 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/26—Nitrogen
-
- 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
- C08F12/00—Homopolymers and copolymers 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- 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
- C08F12/00—Homopolymers and copolymers 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
- C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers 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; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- H10K50/15—Hole transporting layers
-
- 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
-
- 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
- H10K85/151—Copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
一种聚合物,其Mn为至少4,000并且包含式NAr1Ar2Ar3的化合物的聚合单元,其中Ar1、Ar2和Ar3独立地为C6‑C40芳香族取代基;Ar1、Ar2和Ar3共同含有不超过一个氮原子,并且Ar1、Ar2和Ar3中的至少一个含有与芳环连接的乙烯基。
Description
技术领域
本发明涉及一种用于制备有机电荷传输膜(charge transporting film)的方法。
背景技术
需要一种制造用于平板有机发光二极管(OLED)显示器的有机电荷传输膜的有效方法。溶液加工是用于通过将OLED溶液沉积到衬底上以形成薄膜然后进行交联和聚合反应来制造大型平板OLED显示器的主要技术之一。目前,可溶液加工的聚合材料是可交联的有机电荷传输化合物。例如,US7037994公开了一种抗反射膜形成制剂,其包含至少一种含有乙酰氧基甲基萘或羟甲基苊烯重复单元的聚合物和在溶剂中的热或光酸产生剂(TAG,PAG)。然而,这篇参考文献并没有公开本文所描述的制剂。
发明内容
本发明提供了一种聚合物,其Mn为至少4,000并且包含式NAr1Ar2Ar3的化合物的聚合单元,其中Ar1、Ar2和Ar3独立地为C6-C45芳香族取代基;Ar1、Ar2和Ar3共同含有不超过一个氮原子,并且Ar1、Ar2和Ar3中的至少一个含有与芳环连接的乙烯基。
具体实施方式
除非另有规定,否则百分比是重量百分比(wt%)并且温度是以℃为单位。除非另有规定,否则操作在室温(20-25℃)下进行。沸点是在大气压(约101kPa)下测量。分子量是以道尔顿为单位并且聚合物的分子量通过尺寸排阻色谱法使用聚苯乙烯标准物来测定。
如本文所用,术语“芳香族取代基”是指具有至少一个芳环,优选至少两个芳环的取代基。含有两个或多个稠合环的环状部分被认为是单个芳环,条件是环状部分中的所有环原子都是芳香族体系的一部分。例如,萘基、咔唑基和吲哚基被认为是单芳环,但芴基被认为含有两个芳环,因为芴的9位碳原子不是芳香族体系的一部分。
优选地,式NAr1Ar2Ar3的化合物不含芳基甲氧基键。芳基甲氧基键是具有两个与氧原子连接的苄基碳原子的醚键。苄基碳原子是不是芳环的一部分并且与具有5至30个碳原子(优选5至20)的芳环(优选苯环)的环碳连接的碳原子。优选地,该化合物不含有仅有一个与氧原子连接的苄基碳原子的键。优选地,芳基甲氧基键是醚、酯或醇。优选地,式NAr1Ar2Ar3的化合物不具有醚键,其中碳是苄基碳,优选根本没有醚键。
优选地,式NAr1Ar2Ar3的化合物含有总共4至12个芳环;优选至少5个,优选至少6个;优选不超过10个,优选不超过9个,优选不超过8个。优选地,Ar1、Ar2和Ar3中的每一个独立地含有至少10个碳原子,优选至少12个;优选不超过42个,优选不超过40个,优选不超过35个,优选不超过30个,优选不超过25个,优选不超过20个。脂肪族碳原子,例如C1-C6烃基取代基或非芳环碳原子(例如,芴的9-碳),包括在Ar取代基中的碳原子总数中。Ar基团可含有杂原子,优选N、O或S;优选地Ar基团不含除氮以外的杂原子。优选地,在式NAr1Ar2Ar3的化合物中仅存在一个乙烯基。优选地,该化合物在稠环体系统不具有乙烯基,例如芴基、咔唑基或吲哚基。优选地,Ar基团由联苯基、芴基,亚苯基、咔唑基和吲哚基中的一种或多种组成。在本发明的优选实施例中,Ar1、Ar2和Ar3中的两个通过至少一个共价键连接。这方面的一个实例是下面示出的结构
当一个芳基取代基中的氮原子是三芳基胺氮原子时,Ar1、Ar2和Ar3基团可以用不同的方式定义,这取决于哪个氮原子被认为是NAr1Ar2Ar3中的氮原子。在这种情况下,氮原子和Ar基团应解释为满足权利要求的限制。
“有机电荷传输化合物”是能够接收电荷并传输其通过电荷传输层的材料。电荷传输化合物的实例包括“电子传输化合物”(能够接收电子并传输其通过电荷传输层的电荷传输化合物)和“空穴传输化合物”(能够传输正电荷通过电荷传输层的电荷传输化合物)。优选是有机电荷传输化合物。优选地,有机电荷传输化合物具有至少50wt%芳环(以所有芳环的分子量除以总分子量测量;在所述芳环的分子量中包括与芳环稠合的非芳环),优选至少60%、优选至少70%、优选至少80%、优选至少90%。优选地,聚合物包含有机电荷传输化合物。
在本发明的优选实施例中,所使用的一些或全部材料(包括溶剂和树脂)富含超过氘天然同位素丰度的氘。本文中所出现的所有化合物名称和结构意欲包括所有部分或完全氘化的类似物。
优选地,聚合物的Mn为至少6,000,优选至少8,000,优选至少10,000,优选至少20,000;优选不大于10,000,000,优选不大于1,000,000,优选不大于500,000,优选不大于300,000,优选不大于200,000。优选地,聚合物包含至少60%(优选至少80%、优选至少95%)含有至少五个芳环、优选至少六个芳环的聚合单体;不具有这种特征的其它单体也可能存在。
如在固体基础上通过液相色谱/质谱(LC/MS)所测量,聚合物的纯度优选是至少99%、优选至少99.5%、优选至少99.7%。本发明的制剂优选含有不超过10ppm金属,优选不超过5ppm。
可用于本发明的优选聚合物包括例如以下结构。
不必一定是电荷传输化合物的交联剂也可以包括在制剂中。这些交联剂优选具有至少60wt%芳环(如先前所定义)、优选至少70wt%、优选至少75wt%。交联剂优选具有三到五个可聚合基团,优选三或四个。优选地,可聚合基团是连接到芳环的乙烯基。下面示出了优选的交联剂
优选地,如通过气相色谱-质谱(GC/MS)测量,制剂中使用的溶剂具有至少99.8%的纯度,优选至少99.9%。优选地,溶剂具有相对于聚合物小于1.2、优选小于1.0的RED值(根据汉森(Hansen)溶解度参数计算的相对能量差),使用CHEMCOMP v2.8.50223.1计算优选的溶剂包括芳烃和芳香族-脂肪族醚,优选具有六至二十个碳原子的那些。苯甲醚、二甲苯和甲苯是特别优选的溶剂。
优选地,用于制备膜的制剂的固体百分比,即聚合物相对于制剂总重量的百分比为0.5到20wt%;优选至少0.8wt%,优选至少1wt%,优选至少1.5wt%;优选不超过15wt%,优选不超过10wt%,优选不超过7wt%,优选不超过4wt%。优选地,一种或多种溶剂的量为80到99.5wt%;优选至少85wt%,优选至少90wt%,优选至少93wt%,优选至少94wt%;优选不超过99.2wt%,优选不超过99wt%,优选不超过98.5wt%。
优选地,式NAr1Ar2Ar3的化合物通过已知方法使用自由基引发剂聚合,所述自由基引发剂为例如偶氮化合物、过氧化物或具有结构R1R2R3C-CR4R5R6的烃基引发剂,其中R1至R6独立地为氢或C1-C20烃基(优选C1-C12),其中不同的R基团可以连接在一起形成环结构,条件是R1、R2和R3中的至少一个为芳基,并且R4、R5和R6中的至少一个为芳基。当使用烃基引发剂时,优选聚合温度为20-100℃。
本发明进一步涉及包含本发明的聚合物的有机电荷传输膜和用于制备其的方法,所述方法是通过将制剂涂布在表面上,优选是另一种有机电荷传输膜,以及氧化铟锡(ITO)玻璃或硅晶片。通过以下来形成膜:将制剂涂布在表面上,在50至150℃(优选80至120℃)的温度下预烘焙,优选少于五分钟,然后在120至280℃;优选至少140℃,优选至少160℃,优选至少170℃;优选不大于230℃,优选不大于215℃的温度下进行热退火。
优选地,根据本发明制备的聚合物膜的厚度是1nm到100微米,优选至少10nm、优选至少30nm,优选不大于10微米、优选不大于1微米、优选不大于300nm。旋涂膜厚度主要由溶液中的固体含量和旋转速率来确定。例如,在2000rpm的旋转速率下,2wt%、5wt%、8wt%和10wt%的聚合物配制的溶液分别使膜厚是30nm、90nm、160nm和220nm。在烘烤和退火后,湿膜收缩5%或更少。
实例
合成4-(3-(4-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛:向圆底烧瓶中装入N-(4-(9H-咔唑-3-基)苯基)-N-([1,1'-联苯基]-4-基)-9,9-二甲基-9H-芴-2-胺(2.00g,3.32mmol,1.0当量)、4-溴苯甲醛(0.737g,3.98mmol,1.2当量)、CuI(0.126g,0.664mmol,0.2当量)、碳酸钾(1.376g,9.954mmol,3.0当量)和18-冠-6(86mg,10mol%)。将烧瓶用氮气冲洗并连接到回流冷凝器。添加10.0mL干燥、脱气的1,2-二氯苯,并将混合物回流48小时。将冷却的溶液用饱和NH4Cl水溶液淬灭,用二氯甲烷萃取。将合并的有机级分干燥,并通过蒸馏除去溶剂。在硅胶上通过色谱法(己烷/氯仿梯度)纯化粗残余物,得到产物,为亮黄色固体(2.04g,87%)。1H NMR(500MHz,CDCl3)δ10.13(s,1H),8.37(d,J=2.0Hz,1H),8.20(dd,J=7.7,1.0Hz,1H),8.16(d,J=8.2Hz,2H),7.83(d,J=8.1Hz,2H),7.73–7.59(m,7H),7.59–7.50(m,4H),7.50–7.39(m,4H),7.39–7.24(m,10H),7.19–7.12(m,1H),1.47(s,6H)。13C NMR(126MHz,CDCl3)δ190.95,155.17,153.57,147.21,146.98,146.69,143.38,140.60,140.48,139.28,138.93,135.90,135.18,134.64,134.46,133.88,131.43,128.76,127.97,127.81,126.99,126.84,126.73,126.65,126.54,126.47,125.44,124.56,124.44,124.12,123.98,123.63,122.49,120.96,120.70,120.57,119.47,118.92,118.48,110.05,109.92,46.90,27.13。
合成(4-(3-(4-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑9-基)苯基)甲醇。在氮气的覆盖之下,向圆底烧瓶中装入4-(3-(4-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛(4.36g,6.17mmol,1.00当量)。将该材料溶于40mL 1:1THF/EtOH中。分批添加硼氢化钠(0.280g,7.41mmol,1.20当量),将该材料搅拌3小时(通过TLC指示起始材料的消耗)。用1M HCl小心地淬灭反应混合物,用部分二氯甲烷萃取产物。将合并的有机级分用饱和碳酸氢钠水溶液洗涤,用MgSO4干燥并浓缩成粗残余物。通过色谱法(己烷/二氯甲烷梯度)纯化该材料,得到产物,为白色固体(3.79g,85%)。1H NMR(500MHz,CDCl3)δ8.35(s,1H),8.19(dt,J=7.8,1.1Hz,1H),7.73–7.56(m,11H),7.57–7.48(m,2H),7.48–7.37(m,6H),7.36–7.23(m,9H),7.14(s,1H),4.84(s,2H),1.45(s,6H)。13C NMR(126MHz,CDCl3)δ155.13,153.56,147.24,147.02,146.44,141.27,140.60,140.11,140.07,138.94,136.99,136.33,135.06,134.35,132.96,128.73,128.44,127.96,127.76,127.09,126.96,126.79,126.62,126.48,126.10,125.15,124.52,123.90,123.54,123.49,122.46,120.66,120.36,120.06,119.43,118.82,118.33,109.95,109.85,64.86,46.87,27.11。
合成N-([1,1'-联苯基]-4-基)-9,9-二甲基-N-(4-(9-(4-(((4-乙烯基苄基)氧基)甲基)苯基)-9H-咔唑-3-基)苯基)-9H-芴-2-胺(比较单体):在氮气填充的手套箱中,向100mL圆底烧瓶中装入(4-(3-(4-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯基)甲醇(4.40g,6.21mmol,1.00当量)和35mLTHF。分批添加氢化钠(0.224g,9.32mmol,1.50当量),并将混合物搅拌30分钟。连接回流冷凝器,将该单元密封并从手套箱中取出。注入4-乙烯基苄基氯(1.05mL,7.45mmol,1.20当量),并将混合物回流直至消耗起始材料(TLC)。冷却反应混合物(冰浴)并用异丙醇小心地淬灭。添加饱和NH4Cl水溶液,并用乙酸乙酯萃取产物。将合并的有机级分用盐水洗涤,用MgSO4干燥,过滤,浓缩,并在二氧化硅上通过色谱法(己烷/乙酸乙酯梯度)纯化,得到产物,为白色固体(3.49g,67%)。1H NMR(400MHz,CDCl3)δ8.35(s,1H),8.18(dt,J=7.8,1.0Hz,1H),7.74–7.47(m,14H),7.47–7.35(m,11H),7.35–7.23(m,9H),7.14(s,1H),6.73(dd,J=17.6,10.9Hz,1H),5.76(dd,J=17.6,0.9Hz,1H),5.25(dd,J=10.9,0.9Hz,1H),4.65(s,4H),1.45(s,6H)。13CNMR(101MHz,CDCl3)δ155.13,153.56,147.25,147.03,146.43,141.28,140.61,140.13,138.94,137.64,137.63,137.16,137.00,136.48,136.37,135.06,134.35,132.94,129.21,128.73,128.05,127.96,127.76,126.96,126.94,126.79,126.62,126.48,126.33,126.09,125.14,124.54,123.89,123.54,123.48,122.46,120.66,120.34,120.04,119.44,118.82,118.31,113.92,110.01,109.90,72.33,71.61,46.87,27.11。
合成3-(3-(4-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛:在圆底烧瓶中装入咔唑(9.10g,15.1mmol,1.0当量)、3-溴苯甲醛(2.11mL,18.1mmol,1.2当量)、CuI(0.575g,3.02mmol,0.2当量)、碳酸钾(6.26g,45.3mmol,3.0当量)和18-冠-6(399mg,10mol%)。将烧瓶用氮气冲洗并连接到回流冷凝器。添加55mL干燥、脱气的1,2-二氯苯,并将混合物加热至180℃过夜。14小时后仅发现部分转化。再添加2.1mL 3-溴苯甲醛,再继续加热24小时。将溶液冷却并过滤以除去固体。浓缩滤液并吸附在二氧化硅上,通过色谱法(0至60%二氯甲烷的己烷溶液)纯化,得到产物,为浅黄色固体(8.15g,74%)。1H NMR(500MHz,CDCl3)δ10.13(s,1H),8.39–8.32(m,1H),8.20(dd,J=7.8,1.0Hz,1H),8.13(t,J=1.9Hz,1H),7.99(d,J=7.5Hz,1H),7.91–7.86(m,1H),7.80(t,J=7.7Hz,1H),7.70–7.58(m,7H),7.56–7.50(m,2H),7.47–7.37(m,6H),7.36–7.22(m,9H),7.14(ddd,J=8.2,2.1,0.7Hz,1H),1.46(s,6H)。13C NMR(126MHz,CDCl3)δ191.24,155.15,153.57,147.22,146.99,146.60,140.93,140.60,139.75,138.93,138.84,138.17,136.07,135.13,134.42,133.53,132.74,130.75,128.75,128.49,127.97,127.79,127.58,126.97,126.82,126.64,126.51,126.36,125.36,124.47,124.20,123.94,123.77,123.60,122.47,120.68,120.60,120.54,119.45,118.88,118.48,109.71,109.58,46.88,27.12。
合成N-([1,1'-联苯基]-4-基)-9,9-二甲基-N-(4-(9-(3-乙烯基苯基)-9H-咔唑-3-基)苯基)-9H-芴-2-胺(A单体):在氮气的覆盖之下,向圆底烧瓶中装入甲基三苯基溴化鏻(14.14g,39.58mmol,2.00当量)和80mL无水THF。一次性添加叔丁醇钾(5.55g,49.48mmol,2.50当量),并将混合物搅拌15分钟。将乙醛(13.99g,19.79mmol,1.00当量)添加在8mL无水THF中。将浆液在室温下搅拌过夜。将溶液用二氯甲烷稀释,并通过二氧化硅塞过滤。用几份二氯甲烷冲洗垫。将滤液吸附在二氧化硅上,并通过色谱法纯化两次(10至30%二氯甲烷的己烷溶液),其得到产物,为白色固体(9.66g,67%)。通过反相色谱法将纯度提高至99.7%。1H NMR(400MHz,CDCl3)δ8.35(d,J=1.7Hz,1H),8.18(dt,J=7.7,1.0Hz,1H),7.68–7.39(m,19H),7.34–7.23(m,9H),7.14(dd,J=8.1,2.1Hz,1H),6.79(dd,J=17.6,10.9Hz,1H),5.82(d,J=17.6Hz,1H),5.34(d,J=10.8Hz,1H),1.45(s,6H)。13C NMR(101MHz,CDCl3)δ155.13,153.57,147.26,147.03,146.44,141.29,140.61,140.13,139.55,138.95,137.99,136.36,135.98,135.06,134.36,132.96,130.03,128.74,127.97,127.77,126.96,126.79,126.63,126.49,126.31,126.11,125.34,125.16,124.67,124.54,123.90,123.55,123.49,122.46,120.67,120.36,120.06,119.44,118.83,118.33,115.27,110.01,109.90,46.87,27.12。实验室笔记本参考EXP-15-BD3509。
合成N-(4'-(1,3-二氧戊环-2-基)-[1,1'-联苯基]-4-基)-9,9-二甲基-N-苯基-9H-芴-2-胺:在500mL圆底烧瓶中装入9,9-二甲基-N-苯基-9H-芴-2-胺(9.91g,34.7mmol,1.00当量)、2-(4'-溴-[1,1'-联苯基]-4-基)-1,3-二氧戊环(3.10g,7.78mmol,1.00当量)、叔丁醇钾(1.31g,11.68mmol,1.50当量)和Pd(巴豆基)(PtBu3)Cl(0.062g,0.16mmol,2mol%)。将烧瓶连接到回流冷凝器,并置于氮气气氛下。添加40mL干燥的氮气喷射的甲苯,并将溶液在120℃下搅拌过夜。将溶液冷却并通过二氧化硅垫过滤。用几份二氯甲烷冲洗二氧化硅垫。将滤液吸附在二氧化硅上并通过色谱法(10至80%二氯甲烷的己烷溶液)纯化,得到产物,为白色固体(13.69g,73%)。1H NMR(500MHz,CDCl3)δ7.64(d,J=7.3Hz,1H),7.62–7.56(m,3H),7.52(d,J=8.3Hz,2H),7.48(d,J=8.8Hz,2H),7.38(d,J=7.4Hz,1H),7.33–7.21(m,5H),7.20–7.14(m,4H),7.09–7.00(m,2H),5.85(s,1H),4.21–3.97(m,4H),1.42(s,6H)。13C NMR(126MHz,CDCl3)δ155.07,153.52,147.73,147.46,147.00,141.53,138.89,136.27,134.43,134.36,129.26,127.76,126.94,126.86,126.58,126.48,124.36,123.62,123.57,122.90,122.44,120.62,119.42,118.85,103.63,65.30,46.81,27.06
合成N-(4'-(1,3-二氧戊环-2-基)-[1,1'-联苯基]-4-基)-N-(4-溴苯基)-9,9-二甲基-9H-芴-2-胺:在圆底烧瓶中装入N-(4'-(1,3-二氧戊环-2-基)-[1,1'-联苯基]-4-基)-9,9-二甲基-N-苯基-9H-芴-2-胺(13.7g,26.8mmol,1.00当量)。将固体溶于130mL二氯甲烷中。剧烈搅拌混合物,并在30分钟内分批添加N-溴代琥珀酰亚胺(4.77g,26.8mmol,1.00当量)。将混合物搅拌24小时,并通过TLC判断反应完成。将溶液用1M NaOH洗涤,用MgSO4干燥并浓缩。通过色谱法(30至90%二氯甲烷的己烷溶液)纯化残余物,得到产物,为浅黄色固体(15.49g,95%)。1H NMR(400MHz,CDCl3)δ7.64(ddd,J=7.4,1.4,0.7Hz,1H),7.62–7.56(m,3H),7.56–7.51(m,2H),7.51–7.46(m,2H),7.41–7.19(m,6H),7.15(d,J=6.7Hz,2H),7.07–7.00(m,3H),5.84(s,1H),4.19–3.99(m,4H),1.42(s,6H)。13C NMR(101MHz,CDCl3)δ155.23,153.52,146.93,146.91,146.48,141.36,138.71,136.45,135.04,134.85,132.20,127.91,126.98,126.88,126.66,126.61,125.37,123.92,123.71,122.46,120.75,119.50,119.01,115.01,103.59,65.30,46.85,27.05。
合成N-(4'-(1,3-二氧戊环-2-基)-[1,1'-联苯基]-4-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-9H-芴-2-胺:在圆底烧瓶中装入N-(4'-(1,3-二氧戊环-2-基)-[1,1'-联苯基]-4-基)-N-(4-溴苯基)-9,9-二甲基-9H-芴-2-胺(15.1g,25.7mmol,1.00当量)、(9-苯基-9H-咔唑-3-基)硼酸(9.58g,33.4mmol,1.30当量)、碳酸钾(10.6g,77.0mmol,3.00当量)和Pd(PPh3)4(0.593g,0.513mmol,2mol%)。将烧瓶连接到回流冷凝器,并置于氮气气氛下。添加130mL氮气喷射的4:1THF:水,并将溶液在70℃搅拌过夜。将溶液冷却并用水和二氯甲烷稀释。用几份二氯甲烷萃取产物,并用MgSO4干燥合并的有机级分。通过色谱法(25至100%二氯甲烷的己烷溶液)纯化残余物,得到产物,为黄色固体(17.21g,82%)。1HNMR(500MHz,CDCl3)δ8.39–8.31(m,1H),8.18(dt,J=7.7,1.1Hz,1H),7.66–7.56(m,11H),7.56–7.48(m,4H),7.48–7.38(m,5H),7.33–7.22(m,8H),7.13(dd,J=8.2,2.1Hz,1H),5.85(s,1H),4.20–3.98(m,4H),1.45(s,6H)。13CNMR(126MHz,CDCl3)δ155.13,153.56,147.43,146.96,146.36,141.55,141.29,140.14,138.92,137.64,136.45,136.29,134.50,134.40,132.89,129.87,127.97,127.81,127.44,127.01,126.96,126.88,126.60,126.49,126.07,125.12,124.61,123.88,123.74,123.59,123.45,122.46,120.67,120.33,120.01,119.44,118.86,118.31,109.99,109.88,103.64,65.31,46.87,27.11。
合成4'-((9,9-二甲基-9H-芴-2-基)(4-(9-苯基-9H-咔唑-3-基)苯基)氨基)-[1,1'-联苯基]-4-甲醛:向圆底烧瓶中装入N-(4'-(1,3-二氧戊环-2-基)-[1,1'-联苯基]-4-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-9H-芴-2-胺(17.21g,22.92mmol,1.00当量)。添加115mL四氢呋喃,然后添加HCl水溶液(1.00M,45.8mL,2.00当量)。将烧瓶连接到回流冷凝器,并在70℃下搅拌5小时。将溶液冷却,用三份二氯甲烷萃取产物。将合并的有机级分用水洗涤,然后饱和NaHCO3水溶液洗涤。将溶液用MgSO4干燥,并吸附在二氧化硅上,通过色谱法纯化,得到产物,为黄色固体(16.0g,95%)。通过反相色谱法可以获得更高纯度(>99.5%)材料。1H NMR(400MHz,CDCl3)δ10.02(s,1H),8.36(dd,J=1.8,0.6Hz,1H),8.18(dt,J=7.7,1.0Hz,1H),7.92(d,J=8.3Hz,2H),7.75(d,J=8.3Hz,2H),7.69–7.53(m,11H),7.51–7.38(m,5H),7.36–7.21(m,8H),7.15(dd,J=8.1,2.1Hz,1H),1.46(s,6H)。13CNMR(101MHz,CDCl3)δ191.82,155.24,153.58,148.50,146.62,146.57,146.03,141.32,140.21,138.81,137.63,136.97,134.88,134.65,132.77,132.71,130.33,129.89,128.08,128.04,127.49,127.02,126.85,126.67,126.12,125.12,124.99,123.97,123.90,123.43,123.14,122.50,120.77,120.32,120.05,119.53,119.26,118.36,110.03,109.92,46.90,27.11。
合成9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-N-(4'-乙烯基-[1,1'-联苯基]-4-基)-9H-芴-2-胺(C单体):在氮气的覆盖之下,向圆底烧瓶中装入甲基三苯基溴化鏻(16.17g,45.27mmol,2.00当量)和100mL无水THF。一次性添加叔丁醇钾(6.35g,56.6mmol,2.50当量),并将混合物搅拌15分钟。将4'-((9,9-二甲基-9H-芴-2-基)(4-(9-苯基-9H-咔唑-3-基)苯基)氨基)-[1,1'-联苯基]-4-甲醛(16.00g,22.63mmol,1.00当量)添加在50mL无水THF中。将浆液在室温下搅拌过夜。将溶液用1mL水淬灭,并将混合物通过二氧化硅垫过滤。用几份二氯甲烷冲洗垫。将滤液吸附到二氧化硅上,并通过色谱法(30%二氯甲烷的己烷溶液)纯化,得到产物,为白色固体(10.18g,63%)。反相色谱法使纯度达到99.5%。1H NMR(500MHz,CDCl3)δ8.35(d,J=1.7Hz,1H),8.18(dd,J=7.8,1.0Hz,1H),7.67–7.55(m,11H),7.54–7.50(m,2H),7.48–7.37(m,7H),7.33–7.21(m,8H),7.13(dd,J=8.1,2.0Hz,1H),6.74(dd,J=17.6,10.9Hz,1H),5.77(dd,J=17.6,0.9Hz,1H),5.25(dd,J=10.9,0.8Hz,1H),1.45(s,6H)。13C NMR(126MHz,CDCl3)δ155.14,153.56,147.31,146.98,146.38,141.30,140.15,139.97,138.93,137.65,136.44,136.08,134.46,134.39,132.90,129.88,127.98,127.56,127.45,127.02,126.97,126.64,126.63,126.50,126.08,125.12,124.59,123.89,123.82,123.57,123.47,122.47,120.68,120.34,120.02,119.45,118.84,118.31,113.56,110.00,109.89,46.87,27.12。
合成4'-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)-[1,1'-联苯基]-4-甲醛在装有热电偶、带有N2入口的冷凝器和隔膜的500mL的3颈圆底烧瓶中装入N-([1,1'-联苯基]-4-基)-N-(4-溴苯基)-9,9-二甲基-9H-芴-2-胺(18g,34.6mmol,1当量)、4-甲酰基苯基硼酸(5.75g,38.3mmol,1当量)、四氢呋喃(285mL)和2M K2CO3水溶液(52mL)。搅拌混合物并用N2喷射30分钟。添加Pd(dppf)Cl2(0.51g,0.70mmol,0.02当量),并将反应物加热至回流21小时。蒸馏除去四氢呋喃,并将反应物用水(300mL)稀释,并用二氯甲烷(2×300mL)萃取。将合并的有机相用MgSO4干燥,过滤并浓缩到二氧化硅上。使用梯度洗脱剂(1柱体积己烷,增加至1:1己烷:二氯甲烷超过8柱体积,然后保持1:1比率,10柱体积)对该材料进行色谱分离。将合并的级分浓缩,得到亮黄色固体(7.41g,纯度99.6%;7.24g,纯度98.9%,合并收率:77%)。1H NMR(400MHz,C6D6)δ9.74(s,1H),7.61(2H,dd,J=8Hz,2Hz),7.55(2H,dd,J=20Hz,2.4Hz),7.50–7.46(5H,多重峰),7.37–7.11(15H,多重峰),1.28(s,6H)。13C NMR(101MHz,C6D6)δ190.64,155.70,153.83,148.64,147.24,147.05,146.04,140.76,139.10,136.52,135.61,135.38,133.68,130.22,129.01,128.43,128.36,127.39,127.18,127.12,126.95,126.94,124.93,124.44,123.82,122.74,121.29,119.88,119.61,46.95z,26.93。
合成N-([1,1'-联苯基]-4-基)-9,9-二甲基-N-(4'-乙烯基-[1,1'-联苯基]-4-基)-9H-芴2-胺(B单体)在装有热电偶、带有N2入口的冷凝器和隔膜的250mL圆底烧瓶3颈圆底烧瓶中装入甲基三苯基溴化鏻(5.3g,5.28mmol,2当量)和无水四氢呋喃(34mL)。添加叔丁醇钾(2.08g,18.4mmol,2.5当量),并将混合物搅拌15分钟。4'-([1,1'-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)-[1,1'-联苯基]-4-甲醛(3.94g,7.3mmol,1当量)溶于无水四氢呋喃(17mL)中,并添加到甲基三苯基溴化鏻溶液中。将反应物在室温下搅拌16小时。添加水(0.5mL),并将混合物通过二氧化硅垫过滤。将垫用二氯甲烷冲洗,并将滤液吸附到二氧化硅上并通过色谱法使用梯度洗脱剂(1柱体积己烷增加至80:20己烷:二氯甲烷超过19柱体积,然后保持80:20比率,10柱体积)纯化。将合并的级分浓缩,得到为白色固体(分离2.62g,纯度为99.8%,67%收率)。1H NMR(400MHz,C6D6)δ7.55-7.43(多峰,11H),7.33-7.10(多峰13H),6.63(1H,dd,J=20Hz,12Hz)5.66(1H,dd,J=20Hz,1.2Hz),5.11(1H,dd,J=12Hz,1.2Hz),1.27(s,6H)。13C NMR(101MHz,C6D6)δ155.61,153.85,147.66,147.57,147.39,140.91,140.28,139.25,136.82,136.51,136.04,135.41,135.19,128.98,128.28,128.02,127.78,127.34,127.04,127.02,126.98,126.94,124.60,124.52,124.15,122.71,121.23,119.81,119.30,113.42,46.93,26.94。
合成N-(4-(9-苯基-9H-咔唑-3-基)苯基)-[1,1'-联苯基]-4-胺在N2-吹扫的手套箱中,在带有涂有特氟龙(Teflon)的搅拌棒的500mL圆底烧瓶中装入3-(4-溴苯基)-9-苯基-9H-咔唑(9.50g,23.9mmol)、[1,1'-联苯基]-4-胺(4.04g,23.9mmol)、叔丁醇钠(3.44g,35.8mmol)、氯(巴豆基)(三叔丁基膦)钯(II)(0.19g,0.48mmol)和300mL干燥、脱气的甲苯。连接回流冷凝器,将混合物加热至110℃并搅拌16小时。将混合物冷却至室温,然后用水(150mL)和乙酸乙酯(150mL)稀释。分离各层,水层用另外两份150mL乙酸乙酯萃取。将合并的有机层用MgSO4干燥并减压浓缩。所得材料通过硅胶色谱法用0-50%v/v乙酸乙酯和己烷的混合物洗脱来纯化。通过反相色谱法用乙腈洗脱进一步纯化该材料,得到所需产物,为白色固体(2.82g,24.3%收率,99.8%纯度)。1H NMR(400MHz,氯仿-d)δ8.35(d,J=1.7Hz,1H),8.21(dt,J=7.7,1.1Hz,1H),7.69–7.57(m,9H),7.57–7.51(m,2H),7.51–7.39(m,6H),7.35–7.27(m,2H),7.24–7.16(m,3H),5.84(s,1H)。
合成N-([1,1'-联苯基]-4-基)-7-(1,3-二氧戊环-2-基)-9,9-二甲基-N-(4-(9-苯基-9H)的-咔唑-3-基)苯基)-9H-芴-2-胺在N2-吹扫的手套箱中,在带有涂有特氟龙的搅拌棒的250mL圆底烧瓶中装入2-(7-溴-9,9-二甲基-9H-芴-2-基)-1,3-二氧戊环(1.08g,3.12mmol)、N-(4-(9-苯基-9H-咔唑-3-基)苯基)-[1,1'-联苯基]-4-胺(1.52g,3.12mmol)、叔丁醇钠(0.45g,4.69mmol)、氯(巴豆基)(三叔丁基膦)钯(II)(0.025g,0.06mmol)和100mL干燥、脱气的甲苯。连接回流冷凝器,将混合物加热至110℃并搅拌16小时。将混合物冷却至室温并用水(50mL)和乙酸乙酯(50mL)稀释。分离各层,水层用另外两份50mL乙酸乙酯萃取。将合并的有机层用MgSO4干燥并减压浓缩。得到浅橙色固体,不经纯化或表征用于下一步骤,未测定产率。
合成7-([1,1'-联苯基]-4-基(4-(9-苯基-9H-咔唑-3-基)苯基)氨基)-9,9-二甲基-9H-芴-2-甲醛向带有涂有特氟龙的搅拌棒的50mL圆底烧瓶中装入粗N-([1,1'-联苯基]-4-基)-7-(1,3-二氧戊环-2-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-9H-芴-2-胺(2.3g,3.06mmol,理论值)、30mL THF和7.7mL 1.0M HCl(7.7mmol)。连接回流冷凝器并将混合物加热至回流并搅拌过夜。将混合物冷却至室温并添加10mL水。分离各层,然后用三份20mL二氯甲烷萃取水层。将合并的有机层用50mL饱和碳酸氢钠水溶液洗涤,然后用MgSO4干燥并减压浓缩。残留物在硅胶上通过快速色谱法纯化,用70%v/v二氯甲烷和己烷的混合物洗脱。得到所需产物,为黄色固体(2.02g,收率93.3%,纯度99.6%)。1HNMR(400MHz,氯仿-d)δ10.02(s,1H),8.36(d,J=1.8Hz,1H),8.18(dd,J=7.8,1.1Hz,1H),7.92(d,J=1.4Hz,1H),7.83(dd,J=7.8,1.5Hz,1H),7.75(d,J=7.8Hz,1H),7.68–7.63(m,4H),7.63–7.58(m,6H),7.58–7.52(m,3H),7.51–7.39(m,6H),7.36–7.25(m,7H),7.16(dd,J=8.3,2.1Hz,1H),1.48(s,7H)。13CNMR(101MHz,氯仿-d)δ192.03,154.14,148.84,146.84,146.03,141.35,140.49,137.13,135.87,134.70,132.76,132.02,130.83,129.91,128.79,128.13,127.94,127.51,127.05,126.98,126.69,126.14,125.16,125.13,124.61,123.93,123.45,122.82,122.00,120.33,120.06,119.44,118.39,117.59,110.05,109.94,46.94,26.88。
合成N-([1,1'-联苯基]-4-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-7-乙烯基-9H-芴-2-胺(E单体)在N2-吹扫的手套箱中,在带有涂有特氟龙的搅拌棒的经烘箱干燥的100mL广口瓶中装入甲基三苯基溴化鏻(2.04g,5.72mmol)和50mL干燥、脱气的THF。添加叔丁醇钾(0.80g,7.14mmol)并将混合物搅拌15分钟。将7-([1,1'-联苯基]-4-基(4-(9-苯基-9H-咔唑-3-基)苯基)氨基)-9,9-二甲基-9H-芴-2-甲醛(2.02g,2.86mmol)的溶液添加在10mL THF中,将得到的浆液在室温下搅拌16小时。通过添加水淬灭混合物并用三份50mL二氯甲烷萃取。合并有机层,用MgSO4干燥并减压浓缩。残留物在硅胶上通过快速色谱法纯化,用55%v/v二氯甲烷和己烷的混合物洗脱。得到所需产物,为黄色固体(1.56g,收率77.4%,纯度99.5%)。1H NMR(400MHz,氯仿-d)δ8.35(d,J=1.7Hz,1H),8.18(dd,J=7.8,1.0Hz,1H),7.68–7.56(m,11H),7.55–7.50(m,2H),7.48–7.40(m,7H),7.37(dd,J=7.9,1.6Hz,1H),7.34–7.25(m,7H),7.13(dd,J=8.2,2.1Hz,1H),6.79(dd,J=17.6,10.9Hz,1H),5.79(dd,J=17.6,1.0Hz,1H),5.27–5.20(m,1H),1.46(s,6H)。13C NMR(101MHz,氯仿-d)δ155.47,153.93,147.22,147.11,146.40,141.33,140.62,140.17,138.89,137.68,137.25,136.48,135.99,135.15,129.88,128.75,127.99,127.79,127.45,127.03,126.81,126.64,126.09,125.64,125.14,124.62,123.98,123.91,123.49,120.70,120.34,120.08,120.03,119.47,118.69,118.33,112.81,110.01,109.90,46.81,27.14。
合成4'-((9,9-二甲基-9H-芴-2-基)(4-(1-甲基-2-苯基-1H-吲哚-3-基)苯基)氨基)-[1,1'-联苯基]-4-甲醛(2):将N-(4-溴苯基)-9,9-二甲基-N-(4-(1-甲基-2-苯基-1H-吲哚-3-基)苯基)-9H-芴-2-胺(1)(12.9g,20mmol)、(4-甲酰基苯基)硼酸(1.07g,30mmol)、Pd(PPh3)4(693mg,1155,3%)、2M K2CO3(4.14g,30mmol,15mL H2O)和45mL THF中的混合物在80℃下在氮气气氛下加热12小时。冷却到室温后,在真空下除去溶剂并且用二氯甲烷萃取残余物。冷却到室温后,在真空下除去溶剂,然后添加水。用CH2Cl2萃取混合物。收集有机层,并且用无水硫酸镁干燥。过滤后,蒸发滤液以除去溶剂并且在硅胶上通过柱色谱法纯化残余物以得到白色固体(产率:75%)。MS(ESI):671.80[M+H]+。1H-NMR(CDCl3,400MHz,TMS,ppm):δ10.03(s,1H),7.94(d,2H),7.75(d,2H),7.64(m,2H),7.55(d,2H),7.41(m,9H),7.23(m,8H),7.09(m,3H),3.69(s,3H),1.43(s,6H)。
合成(4'-((9,9-二甲基-9H-芴-2-基)(4-(1-甲基-2-苯基-1H-吲哚-3-基)苯基)氨基)-[1,1'-联苯基]-4-基)甲醇(3):在氮气气氛下向在40℃下的(2)(10g,15mmol)在50mL THF和50mL乙醇中的溶液添加NaBH4(2.26g,60mmol)。使溶液在室温下搅拌2小时。然后,添加盐酸水溶液直至pH为5,并将添加物再保持30分钟。在真空下除去溶剂,残余物用二氯甲烷萃取。然后通过除去溶剂得到产物,不经进一步纯化用于下一步(产率:95%)。MS(ESI):673.31[M+H]+。
合成9,9-二甲基-N-(4-(1-甲基-2-苯基-1H-吲哚-3-基)苯基)-N-(4'-(((4-乙烯基苄基)氧基)甲基)-[1,1'-联苯基]-4-基)-9H-芴-2-胺(F单体):向(3)(9.0g,13.4mmol)在50mL无水DMF中的溶液添加NaH(482mg,20.1mmol),然后将混合物在室温下搅拌1小时。用注射器将4-乙烯基苄基氯(3.05g,20.1mmol)添加上述溶液中。将混合物加热到50℃持续24小时。用水淬灭后,将混合物倒入水中以除去DMF。过滤残余物并用二氯甲烷溶解所得固体,接着用水洗涤。在真空下除去溶剂并用二氯甲烷萃取残余物。接着在硅胶上通过柱色谱法获得产物(产率:90%)。MS(ESI):789.38[M+H]+。1H-NMR(CDCl3,400MHz,TMS,ppm):δ7.59(d,4H),7.48(m,2H),7.40(m,18H),7.22(m,8H),6.71(dd,1H),5.77(d,1H),5.25(d,1H),4.58(s,4H),3.67(s,3H),1.42(s,6H)。
电荷传输单体自由基聚合的一般方案:
在手套箱中,将电荷传输单体(1.00当量)溶解在苯甲醚(电子级,0.25M)中。将混合物加热至70℃,并注入AIBN溶液(0.20M,在甲苯中,5mol%)。搅拌混合物直至完全消耗单体,至少24小时(可添加2.5mol%份的AIBN溶液以完成转化)。用甲醇(苯甲醚的10倍体积)沉淀聚合物并通过过滤分离。用另外份的甲醇冲洗过滤的固体。将过滤的固体重新溶解在苯甲醚中,并将沉淀/过滤顺序重复两次。将分离的固体置于50℃的真空烘箱中过夜以除去残留的溶剂。
电荷传输聚合物的分子量数据:
凝胶渗透色谱法(GPC)研究进行如下。将2mg电荷传输聚合物溶解于1mL THF中。将溶液通过0.20μm聚四氟乙烯(PTFE)注射器过滤器过滤,并将50μl滤液注射到GPC系统上。使用以下分析条件:泵:WatersTMe2695分离模块,标称流动速率为1.0mL/分钟;洗脱剂:飞世尔科技公司(Fisher Scientific)HPLC级别THF(经稳定的);注射器:Waters e2695分离模块;柱:来自聚合物实验室公司(Polymer Laboratories Inc)的两个5μm混合C柱,保持在40℃下;检测器:昭和(Shodex)RI-201差异折射率(DRI)检测器;校准:来自聚合物实验室公司的17种聚苯乙烯标准材料,在3,742kg/mol到0.58kg/mol范围内拟合3阶多项式曲线。
单体 | M<sub>n</sub> | M<sub>w</sub> | M<sub>z</sub> | M<sub>z+1</sub> | M<sub>w</sub>/M<sub>n</sub> |
比较 | 17,845 | 38,566 | 65,567 | 95,082 | 2.161 |
A | 23,413 | 88,953 | 176,978 | 266,718 | 3.799 |
C | 22,348 | 93,724 | 196,464 | 302,526 | 4.194 |
B | 22,175 | 58,355 | 101,033 | 148,283 | 2.632 |
D | 15,704 | 61,072 | 124,671 | 227,977 | 3.889 |
E | 25,139 | 59,034 | 108,767 | 163,606 | 2.348 |
F,低MW | 4,606 | 8,233 | 13,254 | 22,789 | 1.79 |
F,高Mw | 27,171 | 59,262 | 104,762 | 157,817 | 2.18 |
HTL均聚物薄膜研究-溶剂正交性:
1)HTL均聚物溶液的制备:将电荷传输均聚物固体粉末直接溶解在苯甲醚中以制备2wt%的储备溶液。将溶液在80℃下在N2中搅拌5至10分钟,以为完全溶解。
2)制备热退火HTL均聚物膜:在使用之前,将Si晶片用紫外-臭氧预处理2分钟。将数滴上述过滤溶液沉积到预处理的Si晶片上。通过以500rpm旋涂5秒然后以2000rpm旋涂30秒来获得薄膜。然后将所得膜转移到N2吹扫箱中。在100℃下预烘烤“湿”膜1分钟以除去大部分残余的苯甲醚。随后,将膜在160至235℃下热退火10至20分钟。
3)在热退火HTL均聚物膜上的剥离测试:热退火HTL膜的“初始”厚度使用M-2000D椭偏仪(JA Woollam公司(J.A.Woollam Co.,Inc.))测量。然后,将数滴邻二甲苯或苯甲醚添加到膜上以形成水坑。90秒后,以3500rpm离心邻二甲苯/苯甲醚溶剂30秒。使用椭偏仪立即测量膜的“剥离”厚度。然后将膜转移到N2吹扫箱中,随后在100℃下后烘烤1分钟以除去膜中的任何溶胀的溶剂。使用椭偏仪测量“最终”厚度。使用柯西(Cauchy)模型测定膜厚度,并对1cm×1cm区域中的9=3×3点进行平均。
“-剥离”=“剥离”-“初始”:由于溶剂剥离导致的初始膜损失
“-PSB”=“最终”-“剥离”:溶胀溶剂的进一步膜损失
“-总”=“-剥离”+“-PSB”=“最终”-“初始”:由于溶剂剥离和溶胀导致的总膜损失
应用剥离测试来研究HTL均聚物正交溶解度。对于完全耐溶剂的HTL膜,溶剂剥离后的总膜损失应<1nm,优选<0.5nm。
比较的高MW低MW F均聚物膜与邻二甲苯不正交。高MW F均聚物膜仅在低的热退火温度(例如180℃)下与邻二甲苯正交。高MW A和C、中等MWB和E均聚物膜均与邻二甲苯正交。高MW C均聚物膜在接近其Tg的退火温度下与苯甲醚正交。其它测试的HTL均聚物膜均未与苯甲醚正交。
汇总表:高MW A均聚物剥离试验结果(邻二甲苯作为剥离溶剂)
汇总表:中等MW B均聚物剥离试验结果(邻二甲苯作为剥离溶剂)
汇总表:高MW均聚物F剥离试验结果(邻二甲苯作为剥离溶剂)
汇总表:高MW C均聚物剥离试验结果(邻二甲苯和苯甲醚作为剥离溶剂)
汇总表:高MW E均聚物剥离试验结果(邻二甲苯作为剥离溶剂)
发光装置的制备
按顺序用溶剂乙醇、丙酮和异丙醇清洁氧化铟锡(ITO)玻璃衬底(2*2cm),且接着用UV臭氧清洁剂处理15分钟。在手套箱中将来自Plextronics公司的空穴注入层(HIL)材料PlexcoreTMOC AQ-1200从水溶液旋涂到ITO衬底上且在150℃下退火20分钟。其后,对于比较性蒸发性HTL,N-([1,1'-联苯基]-4-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-9H-芴-2-胺,将衬底转移到热蒸发器中以便沉积HTL、发射材料层(EML)、电子转移层(ETL)和阴极;对于溶液法的本发明HTL,从苯甲醚溶液沉积HTL材料(可溶的共聚物)且在150℃下退火10分钟以除去有机溶剂。此后,聚合HTL的交联可在手套箱中在205℃下在加热板上进行10分钟。然后,按顺序沉积后续磷光绿色(Ph-Green)EML、ETL和阴极。最终这些装置在测试之前密封。
OLED装置的电流-电压-亮度(J-V-L)特征,即,驱动电压(V)、亮度效率(Cd/A)和1000尼特和50mA/cm2亮度下的国际照明委员会(international commission onillumination,CIE)数据以及15000尼特持续10小时的寿命用KeithlyTM238高电流源测量单元和柯尼卡美能达公司(Konica Minolta Company)的CS-100A颜色和亮度仪进行且在表2中列出。通过经校准的CCD摄谱收集OLED装置的电致发光(EL)光谱且对于所有四个OLED装置实例都固定在516nm下。
HTL材料 | 10mA/cm<sup>2</sup>下的电压 | 100mA/cm<sup>2</sup>下的电压 |
比较 | 1.6V | 2.9V |
A | 2.5V | 4.2V |
B | 3.0V | 4.5V |
Claims (9)
1.一种聚合物,其Mn为至少4,000并且包含式NAr1Ar2Ar3的化合物的聚合单元,其中Ar1、Ar2和Ar3独立地为C6-C40芳香族取代基;Ar1、Ar2和Ar3共同含有不超过一个氮原子,并且Ar1、Ar2和Ar3中的至少一个含有与芳环连接的乙烯基。
2.根据权利要求1所述的聚合物,其Mn为6,000至1,000,000。
3.根据权利要求2所述的聚合物,其中所述式NAr1Ar2Ar3的化合物含有总共4至12个芳环。
4.根据权利要求3所述的聚合物,其中Ar1、Ar2和Ar3中的每一个独立地含有10至32个碳原子。
5.根据权利要求4所述的聚合物,其中Ar基团不含氮以外的杂原子。
6.根据权利要求5所述的聚合物,其中在所述式NAr1Ar2Ar3的化合物中仅存在一个乙烯基。
7.根据权利要求6所述的聚合物,其中Ar基团由联苯基、芴基、亚苯基、咔唑基和吲哚基中的一种或多种组成。
8.一种电子装置,其包含根据权利要求1所述的一种或多种聚合物。
9.一种发光装置,其包含根据权利要求1所述的一种或多种聚合物。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2016/087408 WO2018000175A1 (en) | 2016-06-28 | 2016-06-28 | Process for making an organic charge transporting film |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109312025A true CN109312025A (zh) | 2019-02-05 |
Family
ID=60785014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201680086531.4A Pending CN109312025A (zh) | 2016-06-28 | 2016-06-28 | 用于制备有机电荷传输膜的方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20190207115A1 (zh) |
JP (1) | JP2019518845A (zh) |
KR (1) | KR20190020069A (zh) |
CN (1) | CN109312025A (zh) |
WO (1) | WO2018000175A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109096426B (zh) * | 2018-07-26 | 2021-03-16 | 华南协同创新研究院 | 一类主体聚合物材料及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030164678A1 (en) * | 2002-02-25 | 2003-09-04 | Yasuhiko Shirota | Vinyl polymer and organic electroluminescent device |
WO2006101018A1 (en) * | 2005-03-23 | 2006-09-28 | Semiconductor Energy Laboratory Co., Ltd. | Composite material, material for light-emitting element, light-emitting element, light-emitting device and electronic device |
CN102725875A (zh) * | 2009-11-17 | 2012-10-10 | 通用电气公司 | 可用于光电子器件的材料的制造方法、材料和光电子器件 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2334959A (en) * | 1998-03-05 | 1999-09-08 | Secr Defence | Conducting polymers |
US20060142520A1 (en) * | 2004-12-27 | 2006-06-29 | 3M Innovative Properties Company | Hole transport layers for organic electroluminescent devices |
JP5008324B2 (ja) * | 2005-03-23 | 2012-08-22 | 株式会社半導体エネルギー研究所 | 複合材料、発光素子用材料、発光素子、発光装置及び電子機器。 |
JP2010150425A (ja) * | 2008-12-25 | 2010-07-08 | Idemitsu Kosan Co Ltd | 新規重合性単量体とその重合体、それを用いた有機デバイス用材料、及び有機エレクトロルミネッセンス素子 |
WO2010103765A1 (ja) * | 2009-03-11 | 2010-09-16 | 出光興産株式会社 | 新規重合性単量体及びその重合体(高分子化合物)を用いた有機デバイス用材料、正孔注入輸送材料、有機エレクトロルミネッセンス素子用材料及び有機エレクトロルミネッセンス素子 |
US9644048B2 (en) * | 2009-10-27 | 2017-05-09 | Samsung Electronics Co., Ltd | Composition for anode buffer layer, high-molecular weight compound for anode buffer layer, organic electroluminescence element, and production process and uses of the same |
TWI421279B (zh) * | 2011-02-01 | 2014-01-01 | Eternal Chemical Co Ltd | 可固化材料及其應用 |
JP2016119320A (ja) * | 2013-03-01 | 2016-06-30 | 出光興産株式会社 | 重合性単量体、その重合体を含む有機デバイス用材料、正孔注入輸送材料、及び有機エレクトロルミネッセンス素子用材料、並びに有機エレクトロルミネッセンス素子 |
-
2016
- 2016-06-28 JP JP2018564283A patent/JP2019518845A/ja active Pending
- 2016-06-28 WO PCT/CN2016/087408 patent/WO2018000175A1/en active Application Filing
- 2016-06-28 CN CN201680086531.4A patent/CN109312025A/zh active Pending
- 2016-06-28 KR KR1020197001623A patent/KR20190020069A/ko active IP Right Grant
- 2016-06-28 US US16/311,874 patent/US20190207115A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030164678A1 (en) * | 2002-02-25 | 2003-09-04 | Yasuhiko Shirota | Vinyl polymer and organic electroluminescent device |
WO2006101018A1 (en) * | 2005-03-23 | 2006-09-28 | Semiconductor Energy Laboratory Co., Ltd. | Composite material, material for light-emitting element, light-emitting element, light-emitting device and electronic device |
CN102725875A (zh) * | 2009-11-17 | 2012-10-10 | 通用电气公司 | 可用于光电子器件的材料的制造方法、材料和光电子器件 |
Also Published As
Publication number | Publication date |
---|---|
JP2019518845A (ja) | 2019-07-04 |
KR20190020069A (ko) | 2019-02-27 |
US20190207115A1 (en) | 2019-07-04 |
WO2018000175A1 (en) | 2018-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI683835B (zh) | 聚合電荷轉移層及含有其的有機電子裝置 | |
CN106554771B (zh) | 用于有机光电子器件的组合物、包含其的有机光电子器件及显示设备 | |
WO2016026266A1 (en) | Polymeric charge transfer layer and organic electronic device containing the same | |
WO2017107117A1 (en) | Polymeric layer and organic electronic device comprising same. | |
US20230247902A1 (en) | Heterocyclic compound, organic light-emitting device comprising same, and composition for organic layer of organic light-emitting device | |
WO2017031622A1 (en) | Polymeric charge transfer layer and organic electronic device containing same | |
WO2016026451A1 (en) | Compositions comprising oxygen substituted benzocyclobutenes and dienophiles, and electronic devices containing same | |
CN107118334B (zh) | 单一白光聚合物及有机电致发光材料和有机电致发光器件及其制备方法 | |
TW201035281A (en) | Electronic devices having long lifetime | |
CN105339365A (zh) | 新型化合物和使用其的有机电致发光元件 | |
CN106575705A (zh) | 用于电子器件的衍生自氧取代的苯并环丁烯的组合物 | |
CN107926094A (zh) | 有机半导体元件用油墨组合物和使用其的有机半导体元件 | |
CN109690802A (zh) | 用来制备有机电荷传输膜的方法 | |
CN109315047A (zh) | 用于制备有机电荷传输膜的方法 | |
CN109312025A (zh) | 用于制备有机电荷传输膜的方法 | |
CN109312229A (zh) | 用于制备有机电荷传输膜的方法 | |
CN109891617A (zh) | 聚合电荷转移层和包含其的有机电子装置 | |
TWI689493B (zh) | 聚合電荷轉移層及含有其的有機電子裝置 | |
JP7427317B2 (ja) | 新規な高分子およびこれを用いた有機発光素子 | |
CN109348733A (zh) | 用于制造有机电荷传输膜的方法 | |
WO2019090462A1 (en) | Polymeric charge transfer layer and organic electronic device comprising the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190205 |
|
WD01 | Invention patent application deemed withdrawn after publication |