CN113461550A - Compound and intermediate thereof, and application of compound and intermediate in organic electroluminescent device - Google Patents
Compound and intermediate thereof, and application of compound and intermediate in organic electroluminescent device Download PDFInfo
- Publication number
- CN113461550A CN113461550A CN202010241193.5A CN202010241193A CN113461550A CN 113461550 A CN113461550 A CN 113461550A CN 202010241193 A CN202010241193 A CN 202010241193A CN 113461550 A CN113461550 A CN 113461550A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- group
- organic electroluminescent
- electroluminescent device
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000002347 injection Methods 0.000 claims abstract description 41
- 239000007924 injection Substances 0.000 claims abstract description 41
- 230000005525 hole transport Effects 0.000 claims abstract description 29
- 239000010410 layer Substances 0.000 claims description 79
- -1 spirofluorenyl Chemical group 0.000 claims description 42
- 239000012044 organic layer Substances 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 10
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 9
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 9
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000005580 triphenylene group Chemical group 0.000 claims description 6
- XWSSEFVXKFFWLJ-UHFFFAOYSA-N 1-anthracen-1-ylanthracene Chemical group C1=CC=C2C=C3C(C=4C5=CC6=CC=CC=C6C=C5C=CC=4)=CC=CC3=CC2=C1 XWSSEFVXKFFWLJ-UHFFFAOYSA-N 0.000 claims description 5
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims description 4
- 125000005567 fluorenylene group Chemical group 0.000 claims description 4
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000006836 terphenylene group Chemical group 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 230000015572 biosynthetic process Effects 0.000 description 63
- 238000003786 synthesis reaction Methods 0.000 description 63
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 56
- 238000001514 detection method Methods 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000001704 evaporation Methods 0.000 description 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 230000008020 evaporation Effects 0.000 description 25
- 239000011521 glass Substances 0.000 description 25
- 238000001819 mass spectrum Methods 0.000 description 25
- 239000000758 substrate Substances 0.000 description 25
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 20
- 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 20
- 238000001308 synthesis method Methods 0.000 description 17
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 15
- 238000010898 silica gel chromatography Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 10
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- YDYIKNZEGGFAKG-UHFFFAOYSA-N 2-N,7-N-diethyl-9,9-dimethylfluorene-2,7-diamine Chemical compound CCNC(C=C1)=CC(C(C)(C)C2=C3)=C1C2=CC=C3NCC YDYIKNZEGGFAKG-UHFFFAOYSA-N 0.000 description 8
- 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 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- FSSYNTJUYWSXFS-UHFFFAOYSA-N n-ethyl-4-[4-(ethylamino)phenyl]aniline Chemical compound C1=CC(NCC)=CC=C1C1=CC=C(NCC)C=C1 FSSYNTJUYWSXFS-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ZEMODTUZIWTRPF-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(NCC)C=C1 ZEMODTUZIWTRPF-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- UKSZBOKPHAQOMP-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 UKSZBOKPHAQOMP-UHFFFAOYSA-N 0.000 description 4
- SQTLUXJWUCHKMT-UHFFFAOYSA-N 4-bromo-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 SQTLUXJWUCHKMT-UHFFFAOYSA-N 0.000 description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- WTAPZWXVSZMMDG-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WTAPZWXVSZMMDG-UHFFFAOYSA-N 0.000 description 3
- KCLWJZWBXNWRND-UHFFFAOYSA-N COCCOCCC(C=C(C=C1)N)=C1C(C=C1)=CC=C1N Chemical compound COCCOCCC(C=C(C=C1)N)=C1C(C=C1)=CC=C1N KCLWJZWBXNWRND-UHFFFAOYSA-N 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- LONBOJIXBFUBKQ-UHFFFAOYSA-N 2,7-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC(Br)=CC=C3C2=C1 LONBOJIXBFUBKQ-UHFFFAOYSA-N 0.000 description 2
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical group 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- QFUDENSTNNSGFG-UHFFFAOYSA-N 2,2',7'-tribromo-9,9'-spirobi[fluorene] Chemical compound C12=CC(Br)=CC=C2C2=CC=C(Br)C=C2C11C2=CC=CC=C2C2=CC=C(Br)C=C21 QFUDENSTNNSGFG-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- WNXNWOBGPRKOJF-UHFFFAOYSA-N 2-bromo-9,9-diphenylfluorene Chemical compound C12=CC(Br)=CC=C2C2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 WNXNWOBGPRKOJF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MTSOXHIGOUTMAK-UHFFFAOYSA-N N-[4-(4-bromophenyl)phenyl]-3-phenyl-N-(3-phenylphenyl)aniline Chemical compound BrC1=CC=C(C=C1)C1=CC=C(C=C1)N(C1=CC(=CC=C1)C1=CC=CC=C1)C1=CC=CC(=C1)C1=CC=CC=C1 MTSOXHIGOUTMAK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NNOBZUFIEWMDHW-UHFFFAOYSA-N n-[2-(2-methoxyethoxy)ethyl]aniline Chemical compound COCCOCCNC1=CC=CC=C1 NNOBZUFIEWMDHW-UHFFFAOYSA-N 0.000 description 1
- VBQIVFTUXFKGKW-UHFFFAOYSA-N n-[4-(4-bromophenyl)phenyl]-4-phenyl-n-(4-phenylphenyl)aniline Chemical compound C1=CC(Br)=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 VBQIVFTUXFKGKW-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005259 triarylamine group Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a compound and an intermediate thereof, and application of the compound in an organic electroluminescent device, wherein the compound has a structure shown in formula I, and the compound is applied to the organic electroluminescent device, particularly used as a hole transport layer material or a hole injection layer material, so that the device has higher luminous efficiency and lower driving voltage, and is further applied to a display panel and a display device.
Description
Technical Field
The invention relates to the technical field of display, in particular to a compound and an intermediate thereof, and application of the compound in an organic electroluminescent device.
Background
Organic light-emitting diodes (OLEDs) attract the attention of many researchers due to the advantages of no need of backlight source for active light emission, high light-emitting efficiency, large visual angle, fast response speed, large temperature application range, relatively simple production and processing technology, low driving voltage, low energy consumption, lightness, thinness, flexible display and the like, and huge application prospects.
In the field of diodes, electron transport and hole transport are often involved, and the transport rates of hole transport and electron transport are generally different, which greatly affects the efficiency, lifetime, etc. of the diode.
In an OLED device, the choice of the carrier transport layer can greatly affect the performance of light emission efficiency, driving voltage, device lifetime, and the like. At present, the transmission performance of the hole transmission layer is far lower than that of the electron transmission layer, and the charge transmission balance of the device is difficult to realize. Also, the choice of the hole injection layer material is also crucial.
Therefore, there is a need in the art to develop a wider variety of higher performance OLED materials, particularly hole transporting materials and hole injecting materials, to improve device performance.
Disclosure of Invention
An object of the present invention is to provide a compound that can be used in an organic electroluminescent device, particularly a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material, and that can provide a device with high luminous efficiency and low driving voltage.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a compound, which has a structure shown in a formula I;
in the formula I, Ar is1The substituent of the arylene group of C6-C60 is selected from C1-C30 aliphatic alkyl or C1-C30 aliphatic alkoxy;
in the formula I, Ar is2、Ar3And Ar4Each independently selected from the group shown in formula II or substituted or unsubstituted C6-C60 aryl, wherein the substituent of the C6-C60 aryl is selected from C1-C30 aliphatic alkylOr C1-C30 aliphatic alkoxy;
in formula II, the wavy line represents the linkage of the group;
in the formula II, W is selected from C6-C60 arylene;
in the formula II, Ar is5And Ar6Each independently selected from C6-C60 aryl;
in the formula I, X, Y and Z are respectively and independently selected from any one of substituted or unsubstituted C1-C30 aliphatic alkyl, substituted or unsubstituted C3-C30 cycloalkyl and substituted or unsubstituted C1-C30 aliphatic alkoxy, and the substituent of the C1-C30 aliphatic alkyl, the C3-C30 cycloalkyl or the C1-C30 aliphatic alkoxy is selected from C6-C60 aryl;
in the formula I, n is 0 or 1;
any hydrogen atom in formula I is replaced or not replaced by deuterium.
On existing OLED analogous compounds, Ar1The invention provides a compound shown in formula I, wherein N atoms at two ends are substituted by aromatic compounds, belonging to triarylamine compounds1One substituent on the N atoms at two ends is changed into X and Y (or X, Y and Z) shown in the invention from an aromatic compound, so that the HOMO and LOMO energy levels of the material are improved, and the material provided by the invention is used as a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material and has higher luminous efficiency and lower driving voltage when being applied to an OLED (organic light emitting diode) device. And the structure is changed, and simultaneously, the dissolving performance of the material in an organic solvent, the film forming performance of the residual organic material after the solvent of the material solution is volatilized, and the viscosity property of the material in the organic solvent are correspondingly changed, so that the material is more suitable for being prepared by using a solution method when being used for preparing an OLED device.
In the present invention, "substituted or unsubstituted" means that the group may or may not be substituted with a substituent, for example, a substituted or unsubstituted C1-C30 aliphatic alkyl group, and means that the C1-C30 aliphatic alkyl group may or may not be substituted with a substituent. The selection range of the substituents is as described above, and the number of the substituents is not limited in the present invention as long as it is within the maximum substitutable number, and when two or more substituents are simultaneously substituted on the same group, the two or more substituents may be the same or different. The invention relates to the same expression mode and has the same meaning.
In the present invention, the number of carbon atoms in the arylene group having from C6 to C60 may be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, or the like; the number of carbon atoms of the aryl group of C6 to C60 may be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, or the like; the number of carbon atoms of the C1 to C30 aliphatic alkyl group may be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, or the like; the number of carbon atoms of the C1 to C30 aliphatic alkoxy group may be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, or the like; the number of carbon atoms of the C3 to C30 cycloalkyl group may be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, or the like.
Preferably, the compound has the structure shown in formula III;
in the formula III, the X, Y, Ar1、Ar2And Ar3Each independently has the same meaning as in formula I.
Preferably, Ar is1Selected from benzeneAny one of a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a 9, 9-dialkyl substituted fluorenyl group, a spirofluorenyl group, a carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, an indolocarbazolyl group, an indenocarbazolyl group, a biphenyl group, a binaphthyl group, a bianthryl group, a binaphthyl group, a terphenyl group, a triphenylene group, a fluoranthyl group, a benzophenanthryl group, or a hydrogenated benzanthracenyl group.
Preferably, Ar is2、Ar3And Ar4Each independently selected from the group shown in the formula II, or at least two of phenyl, naphthyl, anthryl, phenanthryl, 9-diphenyl substituted fluorenyl, 9-dialkyl substituted fluorenyl, biphenyl, binaphthyl, bianthryl, terphenyl, triphenylene, fluoranthenyl, benzophenanthryl or hydrogenated benzoanthryl.
Preferably, when n is 1, Ar is2、Ar3And Ar4At least one (e.g., one, two, three, or four, etc.) of the groups is selected from the group of formula II; when n is 0, Ar is2And Ar3At least one (e.g., one, two, three, or four, etc.) of which is selected from the group of formula II.
According to the invention, at least one arylamine group shown in the formula II is preferably selected, so that the compound at least contains three arylamine structures, the structure enables the conjugation of molecules to be enlarged, the Eg between the corresponding HOMO and LUMO to be reduced, and simultaneously the HOMO is improved, so that the energy level difference between the material serving as a hole injection material and ITO is reduced, and the hole injection is facilitated, therefore, the luminous efficiency of the device can be further improved, and the driving voltage is reduced.
Preferably, in formula III, Ar is2And Ar3At least one of them is selected from the group represented by formula II.
Preferably, W is selected from any one of phenylene, biphenylene, naphthylene, 9-diphenyl substituted fluorenylene or 9, 9-dialkyl substituted fluorenylene, spirobifluorenylene and terphenylene.
Preferably, Ar is5And Ar6Each independently selected from phenyl, naphthyl, anthryl, phenanthryl, 9-diAny one of phenyl-substituted fluorenyl, 9-dialkyl-substituted fluorenyl, biphenyl, binaphthyl, dianthranyl, binaphthyl, terphenyl, triphenylene, fluoranthryl, benzophenanthryl, or hydrogenated benzanthryl.
Preferably, X, Y and Z are each independently selected from a group of formula IV or a C3-C30 cycloalkyl group;
in the formula IV, L1Selected from C1-C10 (e.g. C2, C3, C4, C5, C6, C7, C8, C9, etc.) aliphatic alkyl, L2Selected from C1-C6 (e.g., C2, C3, C4, C5, C6) aliphatic alkyl groups;
in the formula IV, m is an integer of 0-6, such as 1, 2, 3, 4, 5 and the like;
in formula IV, the wavy line represents the bond of the group, i.e. formula IV in L1Is attached to the N atom in formula I.
Preferably, the compound has any one of the structures shown as P-1 to P-182 below:
ar in the compound shown as the formula I2、Ar3、Ar4When n is equal to 1, the synthesis pathway is represented as follows:
wherein Ar is1、Ar3X and Y are as defined in the description above, and Z represents chlorine, bromine, iodine.
V and M-2 are subjected to carbon-nitrogen coupling reaction to generate the compound shown in the formula I.
It is a second object of the present invention to provide an intermediate useful in the preparation of the compound of the first object, said intermediate having the structure:
in the formula V, the X, Y, Z and Ar1All toolsHave the same meaning as in formula I.
The invention also aims to provide application of the compound, which is applied to an organic electroluminescent device.
Preferably, the compound is used as a hole transport layer material or a hole injection layer material of an organic electroluminescent device.
It is a fourth object of the present invention to provide an organic electroluminescent device comprising an anode layer, a cathode layer and an organic layer interposed between the anode layer and the cathode layer, wherein the organic layer contains a compound according to one of the objects.
Preferably, the organic layer includes a hole injection layer containing the compound according to one of the objects.
Preferably, the organic layer includes a hole transport layer containing the compound according to one of the objects.
The fifth object of the present invention is to provide a display panel including the organic electroluminescent device of the fourth object.
It is a sixth object of the present invention to provide a display device including the organic electroluminescent device according to the fourth object or the display panel according to the fifth object.
Compared with the prior art, the invention has the following beneficial effects:
the compound provided by the invention can be applied to an organic electroluminescent device, particularly as a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material, can enable the device to have higher luminous efficiency and lower driving voltage, and is more suitable for being prepared by a solution method when being used for preparing an OLED device.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The following synthesis examples exemplarily provide methods for synthesizing specific compounds, but the present invention is not limited to the following specific synthesis methods, and a person skilled in the art can select a synthesis method according to the prior art.
Synthesis example 1 Synthesis of P-1
(1) Synthesis of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine
Adding 12.1 g (0.1mol) of N-ethylaniline, 300 ml of toluene and 27 g (0.1mol) of ferric chloride hexahydrate into a 500 ml three-neck flask, stirring and heating to 80 ℃ for reacting for 4 hours, cooling, adding water for separating liquid, washing an organic layer to be neutral, separating by silica gel column chromatography, adding petroleum ether: ethyl acetate ═ 9: 1 to obtain 8.6g of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine with the yield of 71.67 percent.
The obtained product N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine is subjected to mass spectrometric detection, and the molecular m/z is determined as follows: 240.
the obtained product N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine was subjected to nuclear magnetic detection, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.50(m，4H)，δ6.53(m，4H)，δ3.62(s，2H)，δ3.45(m，4H)，δ1.29(t，6H)。
(2) synthesis of P-1
A500 ml three-necked flask was charged with nitrogen, and 80 ml of dry toluene, 2.4 g (0.01mol) of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine, 3.45 g (0.022mol) of bromobenzene, 0.0575 g (0.0001mol) of Pd (dba)2(bis-dibenzylideneacetone palladium), 0.4 g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 2.3 g (0.024mol) of sodium tert-butoxide, heated to reflux for 4 hours, cooled, and then added with water to separate the liquidConcentrating the organic layer to be dry, separating by silica gel column chromatography, and mixing petroleum ether: ethyl acetate ═ 9: 1 (volume ratio) to obtain 3.6 g of a compound represented by P-1, with a yield of 91.8%.
Performing mass spectrum detection on the compound shown as the P-1, and determining that the molecular m/z is as follows: 392.
the nuclear magnetic detection is carried out on the compound shown as P-1, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.55(m，4H)，δ7.45～7.38(m，6H)，δ7.35(m，6H)，δ7.08(m，2H)，δ3.59～3.47(m，4H)，δ1.15(t，6H)。
synthesis example 2 Synthesis of P-5
The synthesis method is the same as that of P-1 in example 1, except that bromobenzene in the reaction mixture is replaced by 2-bromo-9, 9-diphenylfluorene in equal amount to obtain a compound P-5.
Performing mass spectrum detection on the compound shown in the P-5, and determining that the molecular m/z is as follows: 872.
the nuclear magnetic detection is carried out on the compound shown as P-5, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3):δ8.00(m，2H)，δ7.92(m，2H)，δ7.87(d，2H)，δ7.65(d，2H)，δ7.55(m，4H)，δ7.41～7.32(m，6H)，δ7.29～7.14(m，16H)，δ7.11(m，8H)，δ3.62～3.46(m，4H)，δ1.15(t，6H)。
synthesis example 3 Synthesis of P-15
The synthesis method is the same as that of P-1 in example 1, except that bromobenzene therein is replaced by the same amount of substance
To obtain the compound P-15.
Performing mass spectrum detection on the compound shown as the P-15, and determining that the molecular m/z is as follows: 896.
the nuclear magnetic detection is carried out on the compound shown as P-15, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ8.20(m，8H)，δ7.66(m，4H)，δ7.55(m，12H)，δ7.46～7.34(m，18H)，δ3.36～3.22(m，4H)，δ1.15(t，6H)。
synthesis example 4 Synthesis of P-19
The synthesis method was the same as that of P-1 in example 1, except that bromobenzene was replaced by 4-bromotriphenylamine in an equivalent amount to obtain compound P-19.
Performing mass spectrum detection on the compound shown as P-19, and determining that the molecular m/z is as follows: 726.
the nuclear magnetic detection is carried out on the compound shown as P-19, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.57(m，4H)，δ7.38(m，4H)，δ7.26(m，8H)，δ7.15(s，8H)，δ7.06(m，8H)，δ7.00(m，4H)，δ3.63～3.48(m，4H)，δ1.15(t，6H)。
synthesis example 5 Synthesis of P-23
The synthesis method is the same as that of P-1 in example 1, except that bromobenzene therein is replaced by the same amount of substance
Compound P-23 is obtained.
Performing mass spectrum detection on the compound shown as the P-23, and determining that the m/z of the molecule is as follows: 958.
the nuclear magnetic detection is carried out on the compound shown as P-23, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.88(d，4H)，δ7.56(m，4H)，δ7.49(m，4H)，δ7.38(m，4H)，δ7.28～7.16(m，12H)，δ7.11(m，8H)，δ7.02(m，4H)，δ3.61～3.52(m，4H)，δ1.70(s，12H)，δ1.15(t，6H)。
synthesis example 6 Synthesis of P-34
The synthesis method comprises the following steps:
(1) 3.52 g (0.01mol) of 2, 7-dibromo-9, 9-dimethylfluorene, 4.5 g (0.1mol) of ethylamine, 20 ml of toluene, 50 ml of N, N-dimethylformamide, 0.1 g of cuprous iodide, 5.52 g (0.04mol) of potassium carbonate are added into a 250 ml autoclave, after nitrogen replacement, the autoclave is sealed and heated to 100 ℃ for reaction for 8 hours, the temperature is reduced, water is added for liquid separation, an organic layer is washed to be neutral, the organic layer is concentrated to be dry, silica gel column chromatography separation is carried out, and petroleum ether: ethyl acetate ═ 9: 1 to obtain 1.61 g of N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine with the yield of 57%.
Mass spectrum detection is carried out on the obtained product N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the molecular m/z is determined as follows: 280.
the obtained product N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was subjected to nuclear magnetic resonance examination, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.77(d，2H)，δ6.91(d，2H)，δ6.66(m，2H)，δ3.66(s，2H)，δ3.45(m，4H),δ1.71(s，6H)，δ1.28(t，6H)。
(2) a250 ml three-necked flask was charged with 100 ml of dry toluene under nitrogen protection, 2.8 g (0.01mol) of N2 represented by the formula P-34-2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, 3.45 g (0.022mol) of bromobenzene, 0.0575 g (0.0001mol) of Pd (dba)2(bis-dibenzylideneacetone palladium), 0.4 g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 2.3 g (0.024mol) of sodium tert-butoxide, reflux reaction for 8 hours under heating, cooling, adding water to separate the liquid, washing the organic layer with water to neutrality, separating by silica gel column chromatography, petroleum ether: ethyl acetate ═ 9: 1 (volume ratio) to obtain 3.5 g of a compound represented by P-34 with a yield of 81%.
Performing mass spectrum detection on the compound shown as the P-34, and determining that the m/z of the molecule is as follows: 432.
the nuclear magnetic detection is carried out on the compound shown as P-34, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.88(d，2H)，δ7.40(m，6H)，δ7.35(m，4H)，δ7.15(m，2H)，δ7.09(m，2H)，δ3.60～3.47(m，4H)，δ1.70(s，6H)，δ1.15(t，6H)。
synthesis example 7 Synthesis of P-52
The procedure was as described for the synthesis of P-34 in example 6 except that bromobenzene was replaced by 4-bromo-triphenylamine in an equivalent amount to obtain compound P-52.
Performing mass spectrum detection on the compound shown as P-52, and determining that the m/z of the molecule is as follows: 766.
the nuclear magnetic detection is carried out on the compound shown as P-52, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.80(d，2H)，δ7.33(d，2H)，δ7.15(m，8H)，δ7.06(m，10H)，δ7.03(m，8H)，δ6.95(m，4H)，δ3.60～3.44(m，4H)，δ1.68(s，6H)，δ1.14(t，6H)。
synthesis example 8 Synthesis of P-55
Synthesis method for P-34 in synthetic example 6, except that bromobenzene therein is replaced by equivalent amount of substance
To obtain the compound P-55.
Performing mass spectrum detection on the compound shown as P-55, and determining that the molecular m/z is as follows: 918.
the nuclear magnetic detection is carried out on the compound shown as P-55, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.88(d，2H)，δ7.55(m，8H)，δ7.45(d，2H)，δ7.39(m，8H)，δ7.26(m，8H)，δ7.17(d，2H)，δ7.11(m，8H)，δ7.02(m，4H)，δ3.64～3.53(m，4H)，δ1.70(s，6H)，δ1.14(t，6H)。
synthesis example 9 Synthesis of P-67
(1) Synthesis of N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine
Synthesis method with reference to the synthesis of N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine in example 6, the ethylamine was replaced with an equivalent amount of benzylamine to obtain N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine.
Mass spectrum detection is carried out on the obtained product N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the molecular m/z is determined as follows: 404.
nuclear magnetic detection was performed on the obtained product N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.83(d，2H)，δ7.34～7.29(m，10H)，δ6.97(d，2H)，δ6.70(m，2H)，δ4.33(s，4H)，δ3.95(s，2H),δ1.71(s，6H)。
(2) synthesis of P-67
Synthesis method with reference to the synthesis method of P-34 in example 6, except that N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was replaced with an equivalent amount of N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and bromobenzene was replaced with an equivalent amount of N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine
To obtain the compound shown as the formula P-67.
Performing mass spectrum detection on the compound shown as P-67, and determining that the m/z of the molecule is as follows: 1082.
the nuclear magnetic detection is carried out on the compound shown as P-67, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.79(d，4H)，δ7.72(d，2H)，δ7.52(d，2H)，δ7.50～7.43(m，6H)，δ7.39(m，2H)，δ7.33(m，4H)，δ7.26～7.14(m，18H)，δ7.03(m，8H)，δ6.95(m，4H)，δ4.35(s，2H),δ4.21(s，2H)，,δ1.71(s，12H)。
synthesis example Synthesis of P-82
(1) Synthesis of N1, N4-diethylbenzene-1, 4-diamine
Synthesis method referring to the synthesis of N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine in example 6, except that 2, 7-dibromo-9, 9-dimethylfluorene therein was replaced with an equivalent amount of p-dibromobenzene to obtain N1, N4-diethylbenzene-1, 4-diamine.
The obtained product N1, N4-diethylbenzene-1, 4-diamine is subjected to mass spectrum detection, and the molecular m/z is determined as follows: 164.
the obtained product N1, N4-diethylbenzene-1, 4-diamine was subjected to nuclear magnetic resonance analysis, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3)：δ6.59(s，4H)，δ3.47(m，4H)，δ2.83(s，2H)，δ1.29(t，6H)。
(2) synthesis of P-82
Synthesis method with reference to the synthesis method of P-34 in example 6, except that N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was replaced with an equivalent amount of N1, N4-diethylbenzene-1, 4-diamine, and bromobenzene was replaced with an equivalent amount of bromobenzene
To obtain the compound shown as the formula P-82.
Performing mass spectrum detection on the compound shown as the P-82, and determining that the molecular m/z is as follows: 1034.
the nuclear magnetic detection is carried out on the compound shown as P-82, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ8.11(m，2H)，δ7.91(m，2H)，δ7.87(d，2H)，δ7.54～7.49(m，4H)，δ7.45～7.36(m，10H)，δ7.35～7.29(m，4H)，δ7.25(m，2H)，δ7.17～7.11(m，14H)，δ7.09(m，4H)，δ3.39(m，2H)，δ3.33(m，2H)，δ1.70(s，12H)，δ1.15(t，6H)。
synthesis example 11 Synthesis of P-91
(1) Synthesis of N1, N3, N5-triethylbenzene-1, 3, 5-triamine
3.15 g (0.01mol) of 1,3, 5-tribromobenzene, 5.4 g (0.2mol) of ethylamine, 20 ml of toluene, 50 ml of N, N-dimethylformamide, 0.1 g of cuprous iodide, 8.28 g (0.06mol) of potassium carbonate are added into a 250 ml autoclave, after nitrogen replacement, the autoclave is sealed and heated to 100 ℃ for reaction for 8 hours, the temperature is reduced, water is added for liquid separation, an organic layer is washed to be neutral, the organic layer is concentrated to be dry, silica gel column chromatography separation is carried out, and petroleum ether: ethyl acetate ═ 9: 1 to obtain 1.11 g of product N1, N3, N5-triethyl benzene-1, 3, 5-triamine with 53.6 percent of yield.
The obtained products N1, N3, N5-triethyl benzene-1, 3,5 triamine are subjected to mass spectrum detection, and the molecular m/z is determined as follows: 207.
the obtained products N1, N3, N5-triethyl benzene-1, 3, 5-triamine were subjected to nuclear magnetic detection, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3)：δ5.26(s，3H)，δ3.47(m，6H)，δ3.35(s，3H)，δ1.29(t，9H)。
(2) synthesis of the Compound represented by P-91:
a250 ml three-necked flask was charged with 100 ml of dry toluene under nitrogen protection, 2.07 g (0.01mol) of N1, N3, N5-triethylbenzene-1, 3, 5-triamine, 12.96 g (0.04mol) of 4-bromo-N, N-diphenylaniline, 0.115 g (0.0002mol) of Pd (dba)2(bis (dibenzylideneacetone palladium)), 0.8 g (0.0004mol) of a toluene solution containing 10% tri-tert-butylphosphine, 3.46 g (0.036mol) of sodium tert-butoxide, reflux-heating for 8 hours, cooling, adding water for separating liquid, washing the organic layer with water to neutrality, separating by silica gel column chromatography, petroleum ether: ethyl acetate: dichloromethane ═ 9: 0.5: elution with 0.5 (by volume) gave 5.6 g of the compound P-91 in 59.8% yield.
Performing mass spectrum detection on the compound shown as P-91, and determining that the m/z of the molecule is as follows: 936.
the nuclear magnetic detection is carried out on the compound shown as P-91, and the data analysis is as follows:
1HNMR(500MHz，CDCl3)：δ7.26(m，12H)，δ7.13(s，12H)，δ7.09(m，12H)，δ7.02(m，6H)，δ6.51(s，3H)，δ3.59(m，3H)，δ3.53(m，3H)，δ1.15(t，9H)。
synthesis example 12 Synthesis of P-107
Synthesis method reference was made to the synthesis of P-55 in Synthesis example 8 except that in (1) the ethylamine was changed to N-butylamine therein to give N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine.
Mass spectrum detection is carried out on the obtained product N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the molecular m/z is determined to be: 336.
nuclear magnetic detection was performed on the obtained product N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.79(d，2H)，δ6.91(d，2H)，δ6.66(m，2H)，δ3.70(s，2H)，δ3.31(m，4H),δ1.71(s，6H)，δ1.49(m，4H),δ1.31(m，4H),δ0.90(t，6H)。
in the step (2), the procedure of the step (2) of Synthesis example 8 was repeated except that N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was changed to N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine
Change to
The compound shown as P-107 is obtained.
Performing mass spectrum detection on the compound shown as P-107, and determining that the m/z of the molecule is as follows: 1126.
the nuclear magnetic detection is carried out on the compound shown as P-107, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.88(d，2H)，δ7.77(m，8H)，δ7.56(m，8H)，δ7.51(m，8H)，δ7.43(m，4H)，δ7.38(m，8H)，δ7.17(s，8H)，δ6.53(d，2H)，δ6.15(m，2H)，δ3.95(t，4H)，δ1.70(s，6H)，δ1.49(m，4H)，δ1.32(m，4H)，δ0.91(t，6H)。
synthesis example 13 Synthesis of P-150
(1) Synthesis of N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine
A500 ml three-necked flask was charged with nitrogen, and 80 ml of dry toluene, 2.4 g (0.01mol) of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine, 1.57 g (0.01mol) of bromobenzene, 0.0575 g (0.0001mol) of Pd (dba)2(palladium bis (dibenzylideneacetone)), 0.4 g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 1.44 g (0.015mol) of sodium tert-butoxide, heated to 60 ℃ to react for 4 hours, cooled, added with water to separate the liquid, the organic layer concentrated to dryness, separated by silica gel column chromatography, petroleum ether: ethyl acetate 15: 1 (volume ratio) to obtain N4, N4 '-diethyl-N4-phenyl- [1,1' -biphenyl]1.22 g of (E) -4,4' -diamine, yield 38.6%.
Mass spectrometry detection is carried out on N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine, and the molecular m/z is determined as follows: 316.
nuclear magnetic resonance analysis was performed on N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine, and the data was resolved as follows:
1HNMR(500MHz，CDCl3):δ7.57(m，2H)，δ7.51(m，2H)，δ7.44～7.30(m，6H)，δ7.07(m，1H)，δ6.52(m，2H)，δ3.60～3.49(m，3H)，δ3.47(m，2H)，δ1.29(t，3H)，δ1.15(t，3H)。
(2) synthesis of P-150
500 ml three-mouth bottle, nitrogen gasTo this solution, 200 ml of dry toluene and 3.16 g (0.01mol) of N4, N4 '-diethyl-N4-phenyl- [1,1' -biphenyl were added]4,4 '-diamine, 5.52 g (0.01mol) N, N-bis ([1,1' -biphenyl)]-4-yl) -4 '-bromo- [1,1' -biphenyl]-4-amine, 0.0575 g (0.0001mol) Pd (dba)2(palladium bis (dibenzylideneacetone)), 0.4 g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 1.44 g (0.015mol) of sodium tert-butoxide, heated to reflux for 8 hours, cooled, added with water to separate the liquid, the organic layer concentrated to dryness, separated by silica gel column chromatography, petroleum ether: ethyl acetate ═ 9: 1 (volume ratio) to obtain 5.92 g of a compound represented by P-150 with a yield of 75.1%.
Performing mass spectrum detection on the compound shown as P-150, and determining that the m/z of the molecule is as follows: 787.
the nuclear magnetic detection is carried out on the compound shown as P-150, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.73(m，4H)，δ7.53(m，12H)，δ7.47(m，5H)，δ7.40～7.29(m，17H)，δ7.03(m，1H)，δ3.61～3.47(m，4H)，δ1.15(t，6H)。
synthesis example 14 Synthesis of P-160
(1) Synthesis of N1- ([1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine
Synthesis method referring to the synthesis of N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine in example 13, except that N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine therein was changed to N1, N4-diethylbenzene-1, 4-diamine and bromobenzene therein was changed to 4-bromobiphenyl to obtain N1- ([1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine.
Mass spectrometry detection is carried out on N1- ([1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine, and the molecular m/z is determined as follows: 316.
nuclear magnetic resonance analysis was performed on N1- ([1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.77(m，2H)，δ7.57(m，2H)，δ7.51(m，2H)，δ7.41(m，1H)，δ7.36(m，2H)，δ7.08(m，2H)，δ6.95(m，2H)，δ3.59～3.41(m，4H)，δ3.21(s，1H)，δ1.29(t，3H)，δ1.15(t，3H)。
(2) synthesis of P-160
Synthesis method referring to the synthesis of P-150 in example 13, except that N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine was changed to N1- ([1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine, and N, N-bis ([1,1' -biphenyl ] -4-yl) -4' -bromo- [1,1' -biphenyl ] -4-amine was changed to N- ([1,1' -biphenyl ] -3-yl) -N- (4' -bromo- [1,1' -biphenyl ] -4-yl) - [1,1' -biphenyl ] -3-amine, the compound shown as P-160 is obtained.
Performing mass spectrum detection on the compound shown as P-160, and determining that the molecular m/z is as follows: 787.
the nuclear magnetic detection is carried out on the compound shown as P-160, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.77(m，6H)，δ7.59～7.39(m，17H)，δ7.36(m，6H)，δ7.29(t，2H)，δ7.18(m，4H)，δ7.16(s，4H)，δ3.60～3.48(m，4H)，δ1.15(t，6H)。
synthesis example 15 Synthesis of P-170
(1) Synthesis of N4, N4 '-bis (4-bromophenyl) -N4, N4' -diethyl- [1,1 '-biphenyl ] -4,4' -diamine
A250 ml three-necked flask was charged with 100 ml of dry toluene, 2.4 g (0.01mol) of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine, 18.9 g (0.08mol) of p-dibromobenzene, 0.115 g (0.0002mol) of Pd (dba)2(bis-dibenzylideneacetone palladium), 0.8 g (0.0004mol) of a toluene solution containing 10% tri-tert-butylphosphine, 3.84 g (0.04mol) of sodium tert-butoxide, heated to 60 ℃ and reacted for 4 hoursCooling, adding water to separate liquid, washing organic layer to neutrality, silica gel column chromatographic separation, petroleum ether elution to obtain N4, N4' -bis (4-bromophenyl) -N4, N4' -diethyl- [1,1' -biphenyl]1.9 g of (E) -4,4' -diamine, yield 34.5%.
p-N4, N4' -bis (4-bromophenyl) -N4, N4' -diethyl- [1,1' -biphenyl]Mass spectrometric detection of the 4,4' -diamine, determining the molecular m/z as: 550, determining the molecular formula as C28H26Br2N2。
(2) Synthesis of P-170-1
A 500 ml three-neck flask, protected by nitrogen, 200 ml of dry toluene, 5.5 g (0.01mol) of N4, N4' -bis (4-bromophenyl) -N4, N4' -diethyl- [1,1' -biphenyl]4,4' -diamine, 6.77 g (0.04mol) 4-phenylaniline, 0.115 g (0.0002mol) Pd (dba)2(bis (dibenzylideneacetone palladium)), 0.8 g (0.0004mol) of a toluene solution containing 10% tri-tert-butylphosphine and 3.84 g (0.04mol) of sodium tert-butoxide, heating to 60 ℃ to react for 6 hours, cooling, adding water to separate the liquid, washing the organic layer to neutrality, separating by silica gel column chromatography, eluting with petroleum ether to obtain 1.1 g of a compound represented by P-170-1, wherein the yield is 15.13%.
Performing mass spectrum detection on the compound shown as P-170-1, and determining that the molecular m/z is as follows: 726.
the nuclear magnetic detection is carried out on the compound shown as P-170-1, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.75(m，4H)，δ7.59～7.41(m，14H)，δ7.38(m，8H)，δ7.15(s，8H)，δ5.65(s，2H)，δ3.59～3.50(m，4H)，δ1.15(t，6H)。
(3) synthesis of P-170
500 ml three-neck flask, nitrogen protection, 200 ml dry toluene, 7.27 g (0.01mol) P-170-1Compound, 5.39 g (0.022mol) of P-170-2, 0.0575 g (0.0001mol) of Pd (dba)2(palladium bis (dibenzylideneacetone)), 0.4 g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 2.3 g (0.024mol) of sodium tert-butoxide, heated to reflux for 8 hours, cooled, separated by water, the organic layer concentrated to dryness, separated by silica gel column chromatography, petroleum ether: ethyl acetate ═ 9: 1 (volume ratio) to obtain 6.7 g of the compound P-170, the yield is 63.5%.
Performing mass spectrum detection on the compound shown as P-170, and determining that the molecular m/z is as follows: 1054.
the nuclear magnetic detection is carried out on the compound shown as P-170, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3):δ7.73(m，4H)，δ7.55～7.38(m，14H)，δ7.33(m，8H)，δ7.29(m，4H)，δ7.18(m，4H)，δ7.10(s，8H)，δ4.65(s，4H)，δ3.62～3.49(m，12H)，δ3.40(s，6H)，δ1.15(t，6H)。
synthesis example 16 Synthesis of P-176
(1) Synthesis of N4, N4' -bis (2-methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine
Adding 19.5 g (0.1mol) of N- (2- (2-methoxyethoxy) ethyl) aniline, 300 ml of toluene and 25 g (0.1mol) of copper sulfate pentahydrate into a 500 ml three-neck flask, stirring and heating to 80 ℃, reacting for 48 hours, cooling, adding water for separating liquid, washing an organic layer to be neutral, separating by silica gel column chromatography, adding petroleum ether: ethyl acetate ═ 8: 2 to obtain 5.8g of N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine with the yield of 29.9 percent.
The obtained product N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine is subjected to mass spectrum detection, and the molecular m/z is determined as follows: 388.
the obtained product N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine was subjected to nuclear magnetic resonance analysis, and the data were analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.50(m，4H)，δ6.52(m，4H)，δ3.80(s，2H)，δ3.66(m，4H)，δ3.57～3.50(m，8H)，δ3.48～3.43(m，4H)，δ3.41(s，6H)。
(2) synthesis of P-176
A 500 ml three-neck flask, protected by nitrogen, 150 ml of dry toluene, 3.9 g (0.01mol) of N4, N4 '-bis (2-methoxyethoxy) ethyl) - [1,1' -biphenyl]-4,4' -diamine, 9.7 g (0.022mol) of P-176-1, 0.0575 g (0.0001mol) of Pd (dba)2(palladium bis (dibenzylideneacetone)), 0.4 g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 2.3 g (0.024mol) of sodium tert-butoxide, heated to reflux for 12 hours, cooled, separated by water, concentrated to dryness in the organic layer, separated by silica gel column chromatography, petroleum ether: ethyl acetate ═ 9: 1 (volume ratio) to obtain 6.8 g of the compound P-176 with the yield of 61.4%.
Performing mass spectrum detection on the compound shown as P-176, and determining that the m/z of the molecule is as follows: 1106.
the nuclear magnetic detection is carried out on the compound shown as P-176, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ7.88(m，2H)，δ7.85(d，2H)，δ7.56～7.46(m，8H)，δ7.37～7.28(m，6H)，δ7.25～7.17(m，8H)，δ7.12(s，8H)，δ7.07(m，4H)，δ6.98(m，2H)，δ3.65(m，4H)，δ3.55～3.49(m，8H)，δ3.48～3.41(m，4H)，δ3.39(s，6H)，δ1.69(s，12H)。
synthesis example 17 Synthesis of P-180
(1) Synthesis of P-180-1
5.53 g (0.01mol) of 2,2', 7-tribromo-9, 9' -spirobifluorene, 4.5 g (0.1mol) of ethylamine, 30 ml of toluene, 60 ml of N, N-dimethylformamide, 0.1 g of cuprous iodide and 5.52 g (0.04mol) of potassium carbonate are added into a 250 ml autoclave, the mixture is subjected to nitrogen replacement, then the mixture is heated in a sealed manner to 100 ℃ for reaction for 8 hours, cooled, added with water for liquid separation, an organic layer is washed to be neutral and concentrated to be dry, and subjected to silica gel column chromatography separation, petroleum ether: ethyl acetate ═ 9: 1, 3.1 g of a product shown by P-180-1 is obtained by elution, and the yield is 69.6 percent.
Performing mass spectrum detection on the obtained product shown in the formula P-180-1, and determining that the molecular m/z is as follows: 445.
the obtained product shown in P-180-1 is subjected to nuclear magnetic detection, and the data analysis is as follows:
1HNMR(500MHz，CDCl3)：δ7.87(m，1H)，δ7.82～7.77(m，3H)，δ7.47(m，1H)，δ7.28～7.21(m，2H)，δ6.90(d，2H)，δ6.87(d，1H)，δ6.72～6.64(m，3H)，δ3.56(s，3H)，δ3.45(m，6H)，δ1.28(t，9H)。
(2) synthesis of P-180
A 500 ml three-neck flask, protected by nitrogen, 200 ml of dry toluene, 4.46 g (0.01mol) of the compound represented by P-180-1, 12.96 g (0.04mol) of 4-bromo-N, N-diphenylaniline represented by P-180-2, 0.115 g (0.0002mol) of Pd (dba)2(bis (dibenzylideneacetone palladium)), 0.8 g (0.0004mol) of a toluene solution containing 10% tri-tert-butylphosphine, 3.46 g (0.036mol) of sodium tert-butoxide, reflux-heating for 8 hours, cooling, adding water for separating liquid, washing the organic layer with water to neutrality, separating by silica gel column chromatography, petroleum ether: ethyl acetate: dichloromethane ═ 9: 0.5: elution at 0.5 (vol.%) gave 9.2 g of the compound P-180 in 78.3% yield.
Performing mass spectrum detection on the compound shown as P-180, and determining that the m/z of the molecule is as follows: 1174.
the nuclear magnetic detection is carried out on the compound shown as P-180, and the data are analyzed as follows:
1HNMR(500MHz，CDCl3)：δ8.13(d，1H)，δ7.95～7.82(m，5H)，δ7.67(m，1H)，δ7.29～7.20(m，14H)，δ7.15(s，12H)，δ7.09(m，12H)，δ7.02(m，6H)，δ6.66(d，2H)，δ6.21(m，2H)，δ3.43(m，3H)，δ3.34(m，3H)，δ1.15(t，9H)。
the following examples and comparative examples provide organic electroluminescent devices using materials having the following specific structures:
examples 1-1 to 1-18, comparative examples 1-1 and 1-2
The above numbered examples used the compound of the present invention as a hole transport material in an organic electroluminescent device, and comparative examples 1-1 and 1-2 used NPB and HT-2, respectively, as a hole transport material in an organic electroluminescent device, as detailed in table 1.
The organic electroluminescent device has the following structure: ITO/HIL02(100 nm)/hole transport material (40nm)/EM1(30nm)/TPBI (30nm)/LiF (0.5nm)/Al (150 nm).
The preparation process of the organic electroluminescent device is as follows:
carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent conductive layer (serving as an anode) in a cleaning agent, then washing the glass substrate in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol, baking the glass substrate in a clean environment until the water is completely removed, cleaning the glass substrate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cation beams to improve the surface property and improve the binding capacity with a hole injection layer;
placing the glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode to form HIL02 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 100 nm;
vacuum evaporating the compound or the contrast material of the invention on the hole injection layer to be used as a hole transmission layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporating EM1 on the hole transport layer to serve as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 30 nm;
vacuum evaporating TPBI on the organic light-emitting layer to be used as an electron transport layer of the organic electroluminescent device; the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
LiF with the thickness of 0.5nm and Al with the thickness of 150nm are evaporated on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.
Performance testing
The luminance, driving voltage, and current efficiency of the organic electroluminescent devices prepared in the above examples and comparative examples were tested using the Hangzhou remote-produced OLED-1000 multichannel accelerated aging life and photochromic performance analysis system, and the test results are shown in Table 1.
TABLE 1
| Hole transport material | Required luminance cd/m2 | Drive voltage V | Current efficiency cd/A | |
| Comparative examples 1 to 1 | NPB | 1000 | 6.15 | 1.63 |
| Comparative examples 1 to 2 | HT-2 | 1000 | 5.22 | 1.73 |
| Examples 1 to 1 | P-18 | 1000 | 4.69 | 1.68 |
| Examples 1 to 2 | P-11 | 1000 | 4.94 | 1.83 |
| Examples 1 to 3 | P-14 | 1000 | 5.08 | 1.71 |
| Examples 1 to 4 | P-32 | 1000 | 4.26 | 1.88 |
| Examples 1 to 5 | P-38 | 1000 | 5.13 | 1.84 |
| Examples 1 to 6 | P-47 | 1000 | 4.5 | 1.71 |
| Examples 1 to 7 | P-98 | 1000 | 4.71 | 1.79 |
| Examples 1 to 8 | P-107 | 1000 | 5.13 | 1.77 |
| Examples 1 to 9 | P-113 | 1000 | 4.66 | 1.73 |
| Examples 1 to 10 | P-122 | 1000 | 5.17 | 1.66 |
| Examples 1 to 11 | P-131 | 1000 | 4.74 | 1.88 |
| Examples 1 to 12 | P-140 | 1000 | 4.51 | 1.73 |
| Examples 1 to 13 | P-145 | 1000 | 4.71 | 1.89 |
| Examples 1 to 14 | P-149 | 1000 | 4.50 | 1.78 |
| Examples 1 to 15 | P-158 | 1000 | 4.32 | 2.05 |
| Examples 1 to 16 | P-161 | 1000 | 4.49 | 1.82 |
| Examples 1 to 17 | P-162 | 1000 | 4.45 | 1.76 |
| Examples 1 to 18 | P-170 | 1000 | 4.36 | 1.89 |
As can be seen from the above table, compared with conventional NPB and HT-2, the compound provided by the invention as a hole transport material of an organic electroluminescent device can improve the comprehensive performance of the device in terms of luminous efficiency and driving voltage.
Examples 2-1 to 2-17, comparative example 2-1
The compound of the invention is used as a hole injection material in an organic electroluminescent device in the numbered examples, and HIL02 is used as a hole injection material in an organic electroluminescent device in the comparative examples 2-1, which are detailed in Table 2.
The organic electroluminescent device has the following structure: ITO/hole injection material (100nm)/NPB (40nm)/EM1(30nm)/TPBI (30nm)/LiF (0.5nm)/Al (150 nm).
The preparation process of the organic electroluminescent device is as follows:
carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent conductive layer (serving as an anode) in a cleaning agent, then washing the glass substrate in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol, baking the glass substrate in a clean environment until the water is completely removed, cleaning the glass substrate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cation beams to improve the surface property and improve the binding capacity with a hole injection layer;
placing the glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, evaporating a contrast material HIL02 or the compound of the invention as a hole injection layer on the anode at the evaporation rate of 0.1nm/s and the evaporation film thickness of 100 nm;
carrying out vacuum evaporation on NPB (N-propyl bromide) on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporating EM1 on the hole transport layer to serve as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 30 nm;
vacuum evaporating TPBI on the organic light-emitting layer to be used as an electron transport layer of the organic electroluminescent device; the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
LiF with the thickness of 0.5nm and Al with the thickness of 150nm are evaporated on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.
Performance testing
The luminance, driving voltage, and current efficiency of the organic electroluminescent devices prepared in the above examples and comparative examples were tested using the Hangzhou remote-produced OLED-1000 multichannel accelerated aging life and photochromic performance analysis system, and the test results are shown in Table 2.
TABLE 2
| Hole injection material | Required luminance cd/m2 | Drive voltage V | Current efficiency cd/A | |
| Comparative example 2-1 | HIL02 | 1000 | 6.13 | 1.64 |
| Example 2-1 | P-3 | 1000 | 5.49 | 1.71 |
| Examples 2 to 3 | P-29 | 1000 | 4.65 | 1.8 |
| Examples 2 to 4 | P-59 | 1000 | 4.96 | 1.7 |
| Examples 2 to 5 | P-76 | 1000 | 4.85 | 1.66 |
| Examples 2 to 6 | P-78 | 1000 | 5.21 | 1.76 |
| Examples 2 to 7 | P-85 | 1000 | 5.13 | 1.78 |
| Examples 2 to 8 | P-91 | 1000 | 4.58 | 1.82 |
| Examples 2 to 9 | P-107 | 1000 | 5.09 | 1.76 |
| Examples 2 to 10 | P-115 | 1000 | 4.83 | 1.83 |
| Examples 2 to 11 | P-121 | 1000 | 4.89 | 1.66 |
| Examples 2 to 12 | P-129 | 1000 | 5.14 | 1.89 |
| Examples 2 to 13 | P-148 | 1000 | 4.84 | 1.65 |
| Examples 2 to 14 | P-152 | 1000 | 4.72 | 1.72 |
| Examples 2 to 15 | P-158 | 1000 | 6.06 | 1.72 |
| Examples 2 to 16 | P-176 | 1000 | 5.76 | 1.88 |
| Examples 2 to 17 | P-180 | 1000 | 5.41 | 1.97 |
As can be seen from the above table, compared to the conventional HIL02, the compound provided by the present invention as a hole injection material of an organic electroluminescent device can improve the light emitting efficiency and reduce the driving voltage.
Examples 3-1 to 3-6, comparative examples 3-1 and 3-2
The above numbered examples used the compound of the present invention as a hole transport material in an organic electroluminescent device, comparative examples 3-1 and 3-2 used NPB and HT-2, respectively, as a hole transport material in an organic electroluminescent device, and the hole transport layers in the above examples and comparative examples were prepared by a solution method.
The organic electroluminescent device has the following structure: ITO/HIL02(100 nm)/hole transport material/EM 1(30nm)/TPBI (30nm)/LiF (0.5nm)/Al (150 nm).
The preparation process of the organic electroluminescent device is as follows:
carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent conductive layer (serving as an anode) in a cleaning agent, then washing the glass substrate in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol, baking the glass substrate in a clean environment until the water is completely removed, cleaning the glass substrate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cation beams to improve the surface property and improve the binding capacity with a hole injection layer;
placing the glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode to form HIL02 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 100 nm;
the glass substrate on which the hole injection layer had been deposited was transferred to a glove box filled with nitrogen, 0.02% (by weight) of a chlorobenzene solution of the compound of the present invention or the comparative compound was spin-coated on the hole injection layer at a spin-coating speed of 1000 rpm for 60 seconds, and then the glass substrate was heated at 80 ℃ for 2 hours, the solvent was removed in vacuo, and the film thickness of the hole transport layer on the spin-coating layer was measured by a step profiler (model amibiios XP-2surface profiler) and is shown in table 3.
Transferring the glass substrate which is spin-coated with the hole transport layer into a vacuum chamber, and performing vacuum evaporation on the hole transport layer to obtain an EM1 (effective organic light emitting layer) serving as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;
vacuum evaporating TPBI on the organic light-emitting layer to be used as an electron transport layer of the organic electroluminescent device; the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
LiF with the thickness of 0.5nm and Al with the thickness of 150nm are evaporated on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.
Performance testing
The luminance, driving voltage, and current efficiency of the organic electroluminescent devices prepared in the above examples and comparative examples were tested using the Hangzhou remote-produced OLED-1000 multichannel accelerated aging life and photochromic performance analysis system, and the test results are shown in Table 3.
TABLE 3
As can be seen from the above table, when the hole transport layer is prepared by a solution method, compared to the conventional NPB and HT-2, the compound provided by the present invention as a hole transport material of an organic electroluminescent device can improve the light emitting efficiency and reduce the driving voltage.
Examples 4-1 to 4-8, comparative example 4-1
The above-numbered examples used the compound of the present invention as a hole injection material in an organic electroluminescent device, comparative examples 4-1 used HIL02 as a hole injection material in an organic electroluminescent device, and the hole injection layers were prepared using a solution method in the above-mentioned examples and comparative examples.
The organic electroluminescent device has the following structure: ITO/hole injection material/NPB (40nm)/EM1(30nm)/TPBI (30nm)/LiF (0.5nm)/Al (150 nm).
The preparation process of the organic electroluminescent device is as follows:
carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent conductive layer (serving as an anode) in a cleaning agent, then washing the glass substrate in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol, baking the glass substrate in a clean environment until the water is completely removed, cleaning the glass substrate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cation beams to improve the surface property and improve the binding capacity with a hole injection layer;
the glass substrate was transferred to a glove box filled with nitrogen, 0.05% (by weight) of a chlorobenzene solution of the compound of the present invention or the comparative compound was spin-coated on the hole injection layer at a spin-coating speed of 1000 rpm for 60 seconds, and then the glass substrate was heated at 80 ℃ for 2 hours, the solvent was removed in vacuo, and the film thickness of the hole injection layer on the spin-coating was measured by a step profiler (model amibiios XP-2surface profiler) and is shown in table 4.
Placing the above glass substrate spin-coated with the hole injection layer in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the NPB on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporating EM1 on the hole transport layer to serve as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 30 nm;
vacuum evaporating TPBI on the organic light-emitting layer to be used as an electron transport layer of the organic electroluminescent device; the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
LiF with the thickness of 0.5nm and Al with the thickness of 150nm are evaporated on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.
Performance testing
The luminance, driving voltage, and current efficiency of the organic electroluminescent devices prepared in the above examples and comparative examples were tested using the Hangzhou remote-produced OLED-1000 multichannel accelerated aging life and photochromic performance analysis system, and the test results are shown in Table 4.
TABLE 4
As can be seen from the above table, when the hole injection layer is prepared by a solution method, compared to the conventional HIL02, the compound provided by the present invention as a hole injection material of an organic electroluminescent device can improve the light emitting efficiency and reduce the driving voltage.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A compound having a structure according to formula I;
in the formula I, Ar is1Selected from substituted or unsubstitutedSubstituted C6-C60 arylene, wherein the substituent of the C6-C60 arylene is selected from C1-C30 aliphatic alkyl or C1-C30 aliphatic alkoxy;
in the formula I, Ar is2、Ar3And Ar4Each independently selected from the group shown in formula II or substituted or unsubstituted C6-C60 aryl, wherein the substituent of the C6-C60 aryl is selected from C1-C30 aliphatic alkyl or C1-C30 aliphatic alkoxy;
in formula II, the wavy line represents the linkage of the group;
in the formula II, W is selected from C6-C60 arylene;
in the formula II, Ar is5And Ar6Each independently selected from C6-C60 aryl;
in the formula I, X, Y and Z are respectively and independently selected from any one of substituted or unsubstituted C1-C30 aliphatic alkyl, substituted or unsubstituted C3-C30 cycloalkyl and substituted or unsubstituted C1-C30 aliphatic alkoxy, and the substituent of the C1-C30 aliphatic alkyl, the C3-C30 cycloalkyl or the C1-C30 aliphatic alkoxy is selected from C6-C60 aryl;
in the formula I, n is 0 or 1;
any hydrogen atom in formula I is replaced or not replaced by deuterium.
2. The compound of claim 1, wherein the compound has a structure according to formula III;
in the formula III, the X, Y, Ar1、Ar2And Ar3Each independently having the same limitations as in formula I.
3. According to the rightThe compound of claim 1 or 2, wherein Ar is1Any one selected from phenyl, naphthyl, anthryl, phenanthryl, 9-dialkyl substituted fluorenyl, spirofluorenyl, carbazolyl, dibenzothienyl, dibenzofuranyl, indolocarbazolyl, indenocarbazolyl, biphenyl, binaphthyl, bianthryl, binafluorenyl, terphenyl, triphenylene, fluoranthenyl, benzophenanthryl or hydrogenated benzanthryl;
preferably, Ar is2、Ar3And Ar4Each independently selected from the group shown in the formula II, or at least two groups formed by connecting any one or more of phenyl, naphthyl, anthryl, phenanthryl, 9-diphenyl substituted fluorenyl, 9-dialkyl substituted fluorenyl, biphenyl, binaphthyl, bianthryl, terphenyl, triphenylene, fluoranthenyl, benzophenanthryl or hydrogenated benzoanthryl;
preferably, when n is 1, Ar is2、Ar3And Ar4At least one group selected from the group represented by formula II; when n is 0, Ar is2And Ar3At least one group selected from the group represented by formula II;
preferably, in formula III, Ar is2And Ar3At least one group selected from the group represented by formula II;
preferably, W is selected from any one of phenylene, biphenylene, naphthylene, 9-diphenyl substituted fluorenylene or 9, 9-dialkyl substituted fluorenylene, spirobifluorenylene and terphenylene;
preferably, Ar is5And Ar6Each independently selected from any one of phenyl, naphthyl, anthryl, phenanthryl, 9-diphenyl substituted fluorenyl, 9-dialkyl substituted fluorenyl, biphenyl, binaphthyl, bianthryl, binaphthyl, terphenyl, triphenylene, fluoranthyl, benzophenanthryl or hydrogenated benzanthryl.
4. A compound according to any one of claims 1 to 3 wherein X, Y and Z are each independently selected from a group of formula IV or C3-C30 cycloalkyl;
in the formula IV, L1Selected from C1-C10 aliphatic alkyl, L2Selected from C1-C6 aliphatic alkyl;
in the formula IV, m is an integer of 0-6;
in formula IV, the wavy line represents the linkage of the group.
5. The compound of claim 1, wherein the compound has any one of the structures shown below as P-1 through P-182:
6. an intermediate for the preparation of a compound according to any one of claims 1 to 5, wherein the intermediate has the following structure:
in the formula V, the X, Y, Z and Ar1All having the same limitations as in formula I.
7. Use of a compound according to any one of claims 1 to 5 in an organic electroluminescent device;
preferably, the compound is used as a hole transport layer material or a hole injection layer material of an organic electroluminescent device.
8. An organic electroluminescent device comprising an anode layer and a cathode layer, and an organic layer interposed between the anode layer and the cathode layer, the organic layer containing the compound according to any one of claims 1 to 5;
preferably, the organic layer comprises a hole injection layer containing the compound according to any one of claims 1 to 5;
preferably, the organic layer comprises a hole transport layer containing the compound according to any one of claims 1 to 5.
9. A display panel comprising the organic electroluminescent device according to claim 8.
10. A display device comprising the organic electroluminescent device according to claim 8 or the display panel according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010241193.5A CN113461550B (en) | 2020-03-31 | 2020-03-31 | Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010241193.5A CN113461550B (en) | 2020-03-31 | 2020-03-31 | Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113461550A true CN113461550A (en) | 2021-10-01 |
| CN113461550B CN113461550B (en) | 2024-04-12 |
Family
ID=77865980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010241193.5A Active CN113461550B (en) | 2020-03-31 | 2020-03-31 | Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461550B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102541056B1 (en) * | 2022-09-15 | 2023-06-07 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2843468A (en) * | 1954-07-22 | 1958-07-15 | Eastman Kodak Co | Stabilized hydrocarbon compositions and antioxidant therefor |
| JPS62208054A (en) * | 1986-03-08 | 1987-09-12 | Canon Inc | Electrophotographic sensitive body |
| US5508136A (en) * | 1993-02-10 | 1996-04-16 | Yasuhiko Shirota | Trisarylaminobenzene derivatives, compounds for organic EL element, and organic EL element |
| JPH11111458A (en) * | 1997-09-29 | 1999-04-23 | Toyo Ink Mfg Co Ltd | Organic electroluminescent device material and organic electroluminescent device using the same |
| JP2003031372A (en) * | 2002-06-10 | 2003-01-31 | Ricoh Co Ltd | Electroluminescent element |
| US20030118866A1 (en) * | 2001-10-30 | 2003-06-26 | Lg Electronics Inc. | Organic electroluminescent device |
| KR20110107679A (en) * | 2010-03-25 | 2011-10-04 | 에스에프씨 주식회사 | Pyrene compound and organic light emitting device comprising the same |
-
2020
- 2020-03-31 CN CN202010241193.5A patent/CN113461550B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2843468A (en) * | 1954-07-22 | 1958-07-15 | Eastman Kodak Co | Stabilized hydrocarbon compositions and antioxidant therefor |
| JPS62208054A (en) * | 1986-03-08 | 1987-09-12 | Canon Inc | Electrophotographic sensitive body |
| US5508136A (en) * | 1993-02-10 | 1996-04-16 | Yasuhiko Shirota | Trisarylaminobenzene derivatives, compounds for organic EL element, and organic EL element |
| JPH11111458A (en) * | 1997-09-29 | 1999-04-23 | Toyo Ink Mfg Co Ltd | Organic electroluminescent device material and organic electroluminescent device using the same |
| US20030118866A1 (en) * | 2001-10-30 | 2003-06-26 | Lg Electronics Inc. | Organic electroluminescent device |
| JP2003031372A (en) * | 2002-06-10 | 2003-01-31 | Ricoh Co Ltd | Electroluminescent element |
| KR20110107679A (en) * | 2010-03-25 | 2011-10-04 | 에스에프씨 주식회사 | Pyrene compound and organic light emitting device comprising the same |
Non-Patent Citations (3)
| Title |
|---|
| CHEMICAL ABSTRACT SERVICE: "RN: 2301869-40-7等" * |
| CHEMICAL ABSTRACT SERVICE: "RN: 959508-89-5等" * |
| SUDHAKAR MADDALA等: "Metal-Free Oxidative C −C Coupling of Arylamines Using a Quinone-Based Organic Oxidant", vol. 82, pages 8958 - 8972 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102541056B1 (en) * | 2022-09-15 | 2023-06-07 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113461550B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1966124B1 (en) | 4-aminofluorene compounds and organic light emitting devices | |
| CN109912431B (en) | Triarylamine organic compound containing naphthalene and application thereof | |
| CN113735759B (en) | Diamine derivative and organic electroluminescent device thereof | |
| WO2013039221A1 (en) | Aromatic amine derivative and organic electroluminescence element using same | |
| US9184395B2 (en) | Aromatic amine derivative and organic electroluminescent element using same | |
| WO2018113538A1 (en) | Organic compound with homobenzene as core and use thereof in organic electroluminescence device | |
| CN110964021A (en) | Compound with fluorene as core, preparation method and application thereof | |
| CN117800850A (en) | Compound and organic electroluminescent device, display device | |
| WO2013042775A1 (en) | Aromatic amine derivative and organic electroluminescence element using same | |
| CN104513662A (en) | Organic light-emitting material and application thereof | |
| CN111410952A (en) | Organic electroluminescent material containing boron and application thereof in organic electroluminescent device | |
| CN110526901A (en) | A kind of luminous organic material and its application for preparing organic electroluminescence device | |
| CN111675714B (en) | Organic electroluminescent compound with balanced carrier transmission performance and application thereof | |
| CN110845393A (en) | Compound with spirofluorene anthrone as core and application thereof in organic electroluminescent device | |
| CN109134456B (en) | Quinoline derivative, application thereof and organic electroluminescent device | |
| CN115073356A (en) | Fused ring organic luminescent compound, preparation method thereof and organic electroluminescent device | |
| CN110577523B (en) | Compound containing triarylamine structure and organic electroluminescent device prepared from compound | |
| CN111362947A (en) | Benzimidazole-containing organic compound and application thereof | |
| CN113461550B (en) | Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device | |
| CN115043801A (en) | Anthracene-based naphtho heteroaryl compound, intermediate, organic electroluminescent device and display device | |
| CN109796450B (en) | Compound with pyridoindole as core and application thereof in electroluminescent device | |
| CN111233675B (en) | Organic compound containing benzoanthracene and application thereof | |
| CN113461549B (en) | Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device | |
| CN114014764B (en) | Organic compound containing triphenylene group, electroluminescent device and display device | |
| JP2015013805A (en) | Aromatic amine derivative and organic electroluminescent element using 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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240130 Address after: 236000 No.1 Tianzhushan Road, Hefei modern industrial park, Yingzhou District, Fuyang City, Anhui Province Applicant after: FUYANG SINEVA MATERIAL TECHNOLOGY Co.,Ltd. Country or region after: China Address before: 100176 building 10, yard 18, Kechuang 10th Street, Beijing Economic and Technological Development Zone, Daxing District, Beijing Applicant before: BEIJING SINEVA TECHNOLOGY Co.,Ltd. Country or region before: China Applicant before: FUYANG SINEVA MATERIAL TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 236000 No.1 Tianzhushan Road, Hefei modern industrial park, Yingzhou District, Fuyang City, Anhui Province Patentee after: Fuyang Xinyihua New Material Technology Co.,Ltd. Country or region after: China Address before: 236000 No.1 Tianzhushan Road, Hefei modern industrial park, Yingzhou District, Fuyang City, Anhui Province Patentee before: FUYANG SINEVA MATERIAL TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |