CN112654601A - Diamine compound, and polyimide precursor and polyimide film using same - Google Patents
Diamine compound, and polyimide precursor and polyimide film using same Download PDFInfo
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- CN112654601A CN112654601A CN202080004937.XA CN202080004937A CN112654601A CN 112654601 A CN112654601 A CN 112654601A CN 202080004937 A CN202080004937 A CN 202080004937A CN 112654601 A CN112654601 A CN 112654601A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 106
- -1 Diamine compound Chemical class 0.000 title claims abstract description 60
- 239000004642 Polyimide Substances 0.000 title claims description 61
- 239000002243 precursor Substances 0.000 title claims description 52
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 185
- 125000004432 carbon atom Chemical group C* 0.000 claims description 119
- 239000000203 mixture Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 24
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000001188 haloalkyl group Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 5
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 5
- 125000001769 aryl amino group Chemical group 0.000 claims description 5
- 125000005104 aryl silyl group Chemical group 0.000 claims description 5
- 125000005110 aryl thio group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005366 cycloalkylthio group Chemical group 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 3
- 239000004305 biphenyl Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- UNBZBXXCBHHBPW-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[2-(trifluoromethyl)phenyl]sulfanylbenzene Chemical class FC(F)(F)C1=CC=CC=C1SC1=CC=CC=C1C(F)(F)F UNBZBXXCBHHBPW-UHFFFAOYSA-N 0.000 claims description 2
- FCKJXWMULCUWKK-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[2-(trifluoromethyl)phenyl]sulfonylbenzene Chemical class FC(F)(F)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1C(F)(F)F FCKJXWMULCUWKK-UHFFFAOYSA-N 0.000 claims description 2
- BDAJBOIAMYRWFR-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)sulfanylbenzene Chemical class CC1=CC=CC=C1SC1=CC=CC=C1C BDAJBOIAMYRWFR-UHFFFAOYSA-N 0.000 claims description 2
- KZCDMIJHGSSDFO-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)sulfonylbenzene Chemical class CC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1C KZCDMIJHGSSDFO-UHFFFAOYSA-N 0.000 claims description 2
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 3
- 125000005462 imide group Chemical group 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 157
- 239000011541 reaction mixture Substances 0.000 description 114
- 239000007787 solid Substances 0.000 description 113
- 238000002360 preparation method Methods 0.000 description 81
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 72
- 238000006243 chemical reaction Methods 0.000 description 71
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 68
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 44
- 238000010438 heat treatment Methods 0.000 description 43
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 29
- 238000010992 reflux Methods 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 23
- 235000019260 propionic acid Nutrition 0.000 description 22
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 22
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 125000002950 monocyclic group Chemical group 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- WREOTYWODABZMH-DTZQCDIJSA-N [[(2r,3s,4r,5r)-3,4-dihydroxy-5-[2-oxo-4-(2-phenylethoxyamino)pyrimidin-1-yl]oxolan-2-yl]methoxy-hydroxyphosphoryl] phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O[C@H]1N(C=C\1)C(=O)NC/1=N\OCCC1=CC=CC=C1 WREOTYWODABZMH-DTZQCDIJSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229940125758 compound 15 Drugs 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 3
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 3
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229940126657 Compound 17 Drugs 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 229940126543 compound 14 Drugs 0.000 description 3
- 229940126142 compound 16 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940125810 compound 20 Drugs 0.000 description 3
- 229940126086 compound 21 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
- 125000004438 haloalkoxy group Chemical group 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
- C07D209/49—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
Disclosed is a novel diamine compound in which an imide ring is directly bonded to a (hetero) aryl ring in a molecule, and a polyimide film prepared by polymerizing the novel diamine compound exhibits improved thermal characteristics and storage stability.
Description
Technical Field
The present application claims the benefit of priority from korean patent application No. 10-2019-.
The present invention relates to a novel diamine compound, and a polyimide precursor and a polyimide film using the same.
Background
In recent years, weight reduction and miniaturization of products have been emphasized in the field of displays. The glass substrates currently used are heavy and brittle and are difficult to apply to a continuous process. Therefore, research is actively being conducted on applying a plastic substrate, which has advantages of lightness, flexibility and applicability to a continuous process and can replace a glass substrate, to a mobile phone, a notebook computer and a PDA (personal digital assistant).
In particular, polyimide has advantages in that it is easy to synthesize, can be formed into a thin film, and does not require a crosslinking group for curing. Recently, polyimide is widely used as a material for integration in semiconductors such as Liquid Crystal Displays (LCDs), Plasma Display Panels (PDPs), and the like, due to weight reduction and precision of electronic products. Many studies have been made on applying polyimide to a flexible plastic display panel having light weight and flexible characteristics.
A polyimide film produced by forming a polyimide film is generally prepared by: the method includes polymerizing an aromatic dianhydride with an aromatic diamine or an aromatic diisocyanate solution to prepare a solution of a polyamic acid derivative, coating the solution on a silicon wafer or glass, and curing by heat treatment.
Flexible devices involving high temperature processes require heat resistance at high temperatures. In particular, Organic Light Emitting Diode (OLED) devices fabricated using a Low Temperature Polysilicon (LTPS) process may have a process temperature of approximately 500 ℃. However, at this temperature, thermal decomposition by hydrolysis tends to occur even with polyimide having excellent heat resistance. Therefore, in order to manufacture a flexible device, excellent chemical resistance and storage stability must be ensured so that thermal decomposition caused by hydrolysis during a high-temperature process does not occur.
Disclosure of Invention
Technical problem
One problem to be solved by the present invention is to provide a novel diamine compound for producing a polyimide having improved heat resistance, storage stability and the like.
Another problem to be solved by the present invention is to provide a polyimide precursor prepared by using the novel diamine compound.
Still another problem to be solved by the present invention is to provide a polyimide film prepared by using the polyimide precursor and a flexible device including the polyimide film.
Technical scheme
In order to solve the problems of the present invention, the present invention provides a diamine compound represented by the following formula 1:
[ formula 1]
In the formula 1, the first and second groups,
l is selected from
The linking group of (a) is,
Ar1and Ar2Each independently is selected from
The divalent organic group of (a) is,
R1to R11Each independently is hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a, Substituted or unsubstituted aralkyl having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, -COOH group, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, amide group, substituted or unsubstituted cycloalkoxy having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkylthio having 1 to 30 carbon atoms, ester group, -CD3An azido group, a nitro group, or a substituted or unsubstituted (3-to 30-membered) heteroaryl group containing at least one heteroatom selected from B, N, O, S, P (═ O), Si, and P,
y is selected from
l, m, n, o, p, q, r, s, t, u and v are each an integer of 0 to 4, and when l, m, n, o, p, q, r, s, t, u and v are 2 to 4When an integer of (1) is (b), R1To R11Each of which may be the same or different.
Advantageous effects
The diamine compound of the present invention is a novel compound containing a moiety having an imide ring directly bonded to a (hetero) aryl ring in a molecule, and a polyimide precursor containing the same as a polymerization component can provide a polyimide film having improved thermal and mechanical characteristics after curing.
Detailed Description
Since various modifications and changes can be made in the present invention, specific embodiments of the present invention will be described in detail in the following detailed description. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described, but to include all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the following description of the present invention, a detailed description of known functions will be omitted if it is determined that the detailed description of known functions may obscure the gist of the present invention.
Aromatic polyimides are widely used in high-tech industries such as microelectronics, aerospace, insulating materials and refractory materials due to their excellent bulk properties (e.g., thermo-oxidative stability and high mechanical strength). However, aromatic polyimides having high absorbance in the ultraviolet-visible light region show strong coloring from light yellow to dark brown. This limits its widespread use in the field of optoelectronics where transparency and colorless properties are essential requirements. The reason for the coloration in aromatic polyimides is the formation of intramolecular charge transfer complexes (CT-complexes) between alternating electron donors (dianhydrides) and electron acceptors (diamines) in the polymer backbone and between internal molecules.
In order to solve this problem, attempts have been made to introduce specific functional groups, bulky side groups, fluorinated functional groups, etc. into the polymer main chain or to introduce-S-, -O-, -CH2The method of (a) or (b) to develop an optically transparent polyimide film having a high glass transition temperature (Tg).
The inventors of the present invention have made extensive studies based on the prior art to solve the problems of the prior art, and found that a novel diamine compound having a specific structure provides excellent thermal and mechanical properties, and completed the present invention.
Accordingly, the present invention provides a diamine compound of the following formula 1:
[ formula 1]
In the formula 1, the first and second groups,
l is selected from
The linking group of (a) is,
Ar1and Ar2Each independently is selected from
R1to R11Each independently hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio groupSubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, -COOH group, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, amide group, substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkylthio group having 1 to 30 carbon atoms, ester group, -CD3An azido group, a nitro group, or a substituted or unsubstituted (3-to 30-membered) heteroaryl group containing at least one heteroatom selected from B, N, O, S, P (═ O), Si, and P,
y is selected from
l, m, n, o, p, q, R, s, t, u and v are each an integer of 0 to 4, and when l, m, n, o, p, q, R, s, t, u and v are integers of 2 to 4, R is an integer of 2 to 41To R11Each of which may be the same or different.
The term "substituted" in the description of "substituted or unsubstituted" as described herein means that the hydrogen atom in any functional group is replaced by another atom or another functional group, i.e., another substituent.
In formula 1, the substituents of substituted alkyl, substituted haloalkyl, substituted alkylsilyl, substituted arylsilyl, substituted alkylamino, substituted arylamino, substituted alkoxy, substituted alkylthio, substituted arylthio, substituted aryl, substituted aralkyl, substituted aryloxy, substituted cycloalkyl, substituted cycloalkoxy, substituted cycloalkylthio, and substituted heteroaryl are each independently at least one selected from the group consisting of: deuterium, a halogen atom, a cyano group, an amino group, a carboxyl group, a nitro group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an arylcarbonyl group having 6 to 30 carbon atoms, a carboxyl group having 2 to 30 carbon atoms, a carboxyl group, an alkoxy group having 1, An alkylboronyl group having 1 to 30 carbon atoms, an arylboronyl group having 6 to 30 carbon atoms.
As used herein, "alkyl group having 1 to 30 carbon atoms" means a straight-chain or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.
As used herein, "alkenyl group having 2 to 30 carbon atoms" means a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples of alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, and the like.
As used herein, "alkynyl group having 2 to 30 carbon atoms" means a straight-chain or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, and the like.
As used herein, "alkoxy group having 1 to 30 carbon atoms" means a straight-chain or branched alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy, and the like.
As used herein, "cycloalkyl group having 3 to 30 carbon atoms" means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 7 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
As used herein, "aryl (ene) group having 6 to 30 carbon atoms (en)" means a monocyclic or fused ring group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, preferably having 6 to 20 ring skeleton carbon atoms, and more preferably 6 to 15 ring skeleton carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthryl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, perylene,
Mesityl, phenanthrenyl, fluoranthenyl, and the like.
As used herein, "(3-to 30-membered) (arylene) (en) refers to an aryl group having 3 to 30 ring backbone atoms and comprising one or more heteroatoms selected from B, N, O, S, P (═ O), Si, and P. The aryl group preferably has 3 to 20 ring skeleton carbon atoms, and more preferably has 3 to 15 ring skeleton carbon atoms, and preferably contains 1 to 4 hetero atoms. The aryl group may be a monocyclic group or a condensed ring to which one or more benzene rings are condensed, and may be partially saturated. Furthermore, heteroaryl herein includes forms wherein one or more heteroaryl or aryl groups are attached to the heteroaryl group by a single bond. Examples of heteroaryl groups include monocyclic heteroaryl groups, such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl
Azolyl group,
Azolyl group,
Oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; and fused heteroaryl groups, e.g. benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl
Azolyl, benzo
Azolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, thiophene
Oxazinyl, phenanthridinyl and benzodioxolyl.
As used herein, "halogen" includes F atoms, Cl atoms, Br atoms, and I atoms.
According to one embodiment, in the compound of formula 1, L is selected from
A linking group of Ar1And Ar2Each independently is
R1To R8Each independently being a halogen atom, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R9Is a halogen atom, or an unsubstituted or substituted (C1-C6) alkyl group, Y is selected from
And l, m, n, o, p, q, r, s and t are each an integer of 0 to 2.
According to one embodiment, in the compound of formula 1, L is phenyl unsubstituted or substituted with one or more substituents selected from trifluoromethyl, methyl, chloro (Cl) and methoxy; biphenyl unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chloro; unsubstituted or trifluoromethyl-substituted terphenyl; bis (trifluoromethylphenyl) sulfone, bis (methylphenyl) sulfone, { (trifluoromethylphenyl) sulfonyl } phenyl, diphenylsulfide, bis (methylphenyl) sulfide, bis (trifluoromethylphenyl) sulfide or diphenylether, Ar1And Ar2Each independently is phenyl which is unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chlorine, l is an integer from 0 to 2, and m, n, o, p, q, r, s and t are each an integer of 0 or 1.
According to one embodiment, the diamine compound of formula 1 may be selected from compounds of the following structural formula, but is not limited thereto:
according to one embodiment, the diamine compound of formula 1 may be selected from the following compounds of structural formulae 1 to 21, but is not limited thereto:
as described above, the diamine compound of the present invention has such a structure in the molecule: having a phenylene linking group (L) to an imide ring and bonded directly to an aryl ring (Ar)1And Ar2) An imide ring of (a). When the diamine compound is used as a polymerization component, it may impart improved thermal and mechanical properties after curing.
The method for preparing the diamine compound of formula 1 according to the present invention is not particularly limited, and may be prepared by synthetic methods known to those skilled in the art, for example, according to the following reaction scheme 1.
[ reaction scheme 1]
In reaction scheme 1, Ar1、Ar2And L is the same as defined in formula 1.
Step (1) of reaction scheme 1 may be performed by reacting the reaction compound in a solvent such as acetic acid or propionic acid under reflux for 10 hours to 14 hours (e.g., 12 hours).
In step (2) of reaction scheme 1, the reduction reaction may be performed by injecting hydrogen gas in the presence of a Pd/C catalyst, wherein the solvent may be Tetrahydrofuran (THF), N-methylpyrrolidone, or the like.
After step (2), recrystallization may be performed by adding an alcohol such as ethanol or isopropanol to obtain a solid.
Further, the present invention provides a polyimide precursor (polyamic acid) prepared by polymerizing polymerization components including at least one diamine compound and at least one acid dianhydride, wherein the diamine compound includes the diamine compound of formula 1. Imidization of the polyimide precursor may be performed to obtain the desired polyimide.
As the acid anhydride used for the polymerization reaction, for example, tetracarboxylic dianhydride can be used. For example, the tetracarboxylic dianhydride includes a tetracarboxylic dianhydride containing an aliphatic, alicyclic or aromatic tetravalent organic group, or a combination thereof (in which the aliphatic, alicyclic or aromatic tetravalent organic groups are linked to each other via a crosslinking structure) in the molecule. Preferably, the tetracarboxylic dianhydride comprises an acid dianhydride containing a structure having a monocyclic or polycyclic aromatic group, a monocyclic or polycyclic alicyclic group, or two or more of them connected by a single bond or a functional group. Alternatively, it may include tetracarboxylic dianhydride containing a tetravalent organic group having an aliphatic ring or an aromatic ring in which each ring is a single ring structure, each ring is fused to form a heterocyclic structure, or each ring is connected by a single bond.
For example, the tetracarboxylic dianhydride may comprise a tetravalent organic group selected from the following formulas 2a to 2 e.
[ formula 2a ]
[ formula 2b ]
[ formula 2c ]
[ formula 2d ]
[ formula 2e ]
In formulae 2a to 2e, R11To R17May be each independently selected from a halogen atom (selected from F, Cl, Br and I), a hydroxyl group, a thiol group (-SH), a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, a1 may be an integer of 0 to 2, a2 may be an integer of 0 to 4, a3 may be an integer of 0 to 8, a4, a5, a6, a7, a8 and a9 may each independently be an integer of 0 to 3, and a11And A12May be each independently selected from a single bond, -O-, -CR 'R "(wherein R' and R" are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, etc.), and a haloalkyl group having 1 to 10 carbon atoms (e.g., trifluoromethyl, etc.)), -C (═ O) -, -C (═ O) O-, -C (═ O) NH-, -S-, -SO-, -and —)2-、-O[CH2CH2O]y- (y is an integer of 1 to 44), -NH (C ═ O) NH-, -NH (C ═ O) O-, monocyclic or polycyclic cycloalkylene having 6 to 18 carbon atoms (e.g., cyclohexylene and the like), monocyclic or polycyclic arylene having 6 to 18 carbon atoms (e.g., phenylene, naphthylene, fluorenylene and the like), and the group thereofAnd (6) mixing.
Further, the tetracarboxylic dianhydride may comprise a tetravalent organic group selected from the following formulas 3a to 3 n:
at least one hydrogen atom in the tetravalent organic group of formulae 3a to 3n may be substituted by a substituent selected from: halogen atoms (selected from F, Cl, Br and I), hydroxyl groups, thiol groups, nitro groups, cyano groups, alkyl groups having 1 to 10 carbon atoms, haloalkoxy groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms. For example, the halogen atom may be fluorine, and the haloalkyl group may be a fluoroalkyl group having 1 to 10 carbon atoms containing a fluorine atom, selected from a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, and the like. The alkyl group may be selected from methyl, ethyl, propyl, isopropyl, t-butyl, pentyl and hexyl, and the aryl group is selected from phenyl and naphthyl. More preferably, it may be a fluorine atom or a substituent group containing a fluorine atom such as a fluoroalkyl group.
According to one embodiment, in the polymerization of the polyimide precursor, one or more additional diamines may be used in addition to the diamine compound of formula 1. For example, diamine compounds comprising: a monocyclic or polycyclic aromatic divalent organic group having 6 to 24 carbon atoms, a monocyclic or polycyclic alicyclic divalent organic group having 6 to 18 carbon atoms, or a structural divalent organic group in which two or more of them are linked by a single bond or a functional group. Alternatively, it may include a diamine compound containing a divalent organic group having an aliphatic ring or an aromatic ring in which each ring is a single ring structure, each ring is fused to form a heterocyclic structure, or each ring is connected by a single bond.
For example, the additional diamine compound may comprise a divalent organic group selected from the following formulas 4a to 4 e:
[ formula 4a ]
[ formula 4b ]
[ formula 4c ]
[ formula 4d ]
[ formula 4e ]
In formulae 4a to 4e, R21To R27May each be independently selected from the group consisting of halogen atoms (selected from F, Cl, Br and I), hydroxyl groups, thiol groups, nitro groups, cyano groups, alkyl groups having 1 to 10 carbon atoms, haloalkoxy groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms, A21And A22May be each independently selected from a single bond, -O-, -CR 'R "(wherein R' and R" are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, etc.), and a haloalkyl group having 1 to 10 carbon atoms (e.g., trifluoromethyl, etc.)), -C (═ O) -, -C (═ O) O-, -C (═ O) NH-, -S-, -SO-, -and —)2-、-O[CH2CH2O]y- (y is an integer of 1 to 44), -NH (C ═ O) NH-, -NH (C ═ O) O-, monocyclic or polycyclic cycloalkylene groups having 6 to 18 carbon atoms (e.g., cyclohexylene and the like), monocyclic or polycyclic arylene groups having 6 to 18 carbon atoms (e.g., phenylene, naphthylene, fluorenylene and the like), and combinations thereof,b1 is an integer from 0 to 4, b2 is an integer from 0 to 6, b3 is an integer from 0 to 3, b4 and b5 are each independently an integer from 0 to 4, b7 and b8 are each independently an integer from 0 to 4, and b6 and b9 are each independently an integer from 0 to 3.
For example, the additional diamine compound may comprise a divalent organic group selected from the following formulas 5a to 5 p:
alternatively, the additional diamine compound may contain a divalent organic group in which an aromatic ring or an aliphatic structure forms a rigid chain structure, for example, a divalent organic group having an aliphatic ring or an aromatic ring in which each ring is a single ring structure, each ring is connected by a single bond, or each ring is fused to form a heterocyclic structure.
According to one embodiment of the present invention, the reaction molar ratio of the total tetracarboxylic dianhydride to the diamine may be 1:1.1 to 1.1: 1. In order to improve reactivity and processability, it is preferable that the total tetracarboxylic dianhydride is reacted in excess with respect to the diamine compound, or that the diamine compound is reacted in excess with respect to the total tetracarboxylic dianhydride.
According to one embodiment of the present invention, the tetracarboxylic dianhydride and the diamine compound may be reacted in a molar ratio of 1:0.98 to 0.98:1, preferably 1:0.99 to 0.99: 1.
The polymerization reaction can be carried out by a conventional polymerization method (e.g., solution polymerization) of the polyimide or its precursor.
Organic solvents that may be used in the polymerization reaction may include: ketones such as gamma-butyrolactone, 1, 3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; alcohol ethers (cellosolves) such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethyl acetateGlycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, Dimethylpropionamide (DMPA), Diethylpropionamide (DEPA), dimethylacetamide (DMAc), N-diethylacetamide, Dimethylformamide (DMF), Diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-dimethylmethoxyacetamide, dimethyl sulfoxide, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, tetrahydrofuran, m-dibutylurea, N-dimethylpyrrolidone, N-dimethylacetamide, N-dimethylsulphoxide, pyridine, dimethylsulphone, hexamethylphosphoramide, tetramethylurea, N-
Alkane, para-di
Alkane, 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy)]Ethers, Equamide M100 (3-methoxy-N, N-dimethylpropionamide, Idemitsu Kosan co., Ltd.), Equamide B100 (3-butoxy-N, N-dimethylpropionamide, Idemitsu Kosan co., Ltd.), etc., and these solvents may be used alone or as a mixture of two or more.
According to one embodiment, the organic solvent may have a boiling point of 300 ℃ or less and a positive partition coefficient Log P at 25 ℃, more specifically, the partition coefficient Log P may be 0.01 to 3, or 0.01 to 2, or 0.01 to 1. The distribution coefficients may be calculated using an ACD/LogP module from the ACD/Percepta platform of ACD/Labs. The ACD/LogP module uses an algorithm based on a QSPR (Quantitative Structure-Property Relationship) method using a 2D molecular Structure.
A solvent having a positive partition coefficient Log P refers to a hydrophobic solvent. According to the studies of the present inventors, it was found that when a polyimide precursor composition is prepared using a specific solvent having a positive partition coefficient Log P, an edge back phenomenon is improved. Further, in the present invention, by using the solvent having the positive distribution coefficient Log P as described above, it is possible to control the edge receding phenomenon of the solution without using an additive for controlling the surface tension of the material and the smoothness of the coating film, such as a leveling agent. Since no additional additive is used, quality problems and process problems such as the presence of low molecular substances in the final product can be eliminated, and a polyimide film having uniform characteristics can be more efficiently formed.
For example, in the process of coating the polyimide precursor composition on a glass substrate, an edge-receding phenomenon may occur due to shrinkage of the coating layer during curing or under conditions in which the coating solution is allowed to stand in a wet condition. The edge-receding phenomenon of the coating solution may cause variation in the film thickness. As a result, the film may be cut or have a broken edge at the time of cutting due to the lack of flexibility of the film, thereby causing problems of poor process operability and a reduction in yield.
In addition, when fine foreign substances having polarity are introduced into the polyimide precursor composition applied on the substrate, for the polyimide precursor composition including the polar solvent having the negative partition coefficient Log P, sporadic coating cracks or thickness variations may occur based on the position of the foreign substances due to the polarity of the foreign substances. In the case of using a hydrophobic solvent having a positive partition coefficient Log P, even when fine foreign substances having polarity are introduced, the occurrence of thickness variation due to cracking of the coating layer can be reduced or suppressed.
Specifically, in the polyimide precursor composition including a solvent having a positive Log P, the edge recession rate defined by the following equation 1 may be 0% to 0.1% or less.
[ equation 1]
Edge retraction ratio (%) [ (a-B)/a ] × 100
In formula 1:
a: the polyimide precursor composition was completely coated on an area of a substrate (100mm x 100mm),
b: area after edge recession phenomenon from the edge of the substrate on which the polyimide precursor composition or polyimide film is coated.
The edge pull-back phenomenon of the polyimide precursor composition and the polyimide film may occur within 30 minutes after the polyimide precursor composition solution is applied, and particularly, the film may be rolled up from the edge to make the thickness of the edge thicker.
After the polyimide precursor composition is coated on a substrate and then allowed to stand at a temperature of 20 to 30 ℃ and in a humidity condition of 40% or more (more specifically, in a humidity condition of 40 to 80%, i.e., in each of 40%, 50%, 60%, 70%, and 80%) for 10 minutes or more (e.g., 40 minutes or more), the edge recession rate of the coated composition solution may be 0.1% or less, preferably 0.05%, more preferably almost 0%.
The edge set back as described above is maintained even after curing by heat treatment, and specifically, the edge set back may be 0.05% or less, more preferably almost 0%.
By solving such edge-receding phenomenon, the polyimide precursor composition according to the present invention can obtain a polyimide film having more uniform characteristics, thereby further improving the yield of the manufacturing process.
Furthermore, the solvent used in the polymerization reaction may have a density, measured by the standard ASTM D1475, of 1g/cm3Or smaller. If the density is more than 1g/cm3The relative viscosity may increase and the process efficiency may decrease.
The polymerization reaction may be carried out in a flow of inert gas or nitrogen, and may be carried out under anhydrous conditions.
The reaction temperature during the polymerization reaction may be-20 ℃ to 80 ℃, preferably 0 ℃ to 80 ℃. If the reaction temperature is too high, reactivity may become high, molecular weight may become large, and viscosity of the precursor composition may increase, which may be disadvantageous in terms of processes.
The polyimide precursor composition including the polyamic acid may be in the form of a solution dissolved in an organic solvent. For example, when the polyimide precursor is synthesized in an organic solvent, the solution may be a reaction solution as obtained, or may be obtained by diluting the reaction solution with another solvent. When the polyimide precursor is obtained as a solid powder, it may be dissolved in an organic solvent to prepare a solution.
According to one embodiment, the content of the composition may be adjusted by adding an organic solvent so that the total polyimide precursor content is 8 to 25 wt%, preferably 10 to 25 wt%, more preferably 10 to 20 wt%. The polyimide precursor composition may be adjusted to have a viscosity of 3,000cP or more and 10,000cP or less, preferably 4,000cP or more and 9,000cP or less, more preferably 4,000cP or more and 8,000cP or less. When the viscosity of the polyimide precursor composition exceeds 10,000cP, the efficiency of defoaming during processing of the polyimide film is reduced. This not only results in a decrease in process efficiency, but also results in deterioration of surface roughness of the produced film due to bubble generation. This may result in degraded electrical, optical and mechanical properties.
Then, a polyimide precursor resulting from the polymerization reaction may be imidized by chemical imidization or thermal imidization to prepare a transparent polyimide film.
According to one embodiment, a polyimide film may be manufactured by a method including:
applying a polyimide precursor composition to a substrate; and
the applied polyimide precursor composition is heated and cured.
As the substrate, a glass substrate, a metal substrate, a plastic substrate, or the like can be used without any particular limitation. Among them, a glass substrate, which is excellent in thermal stability and chemical stability during imidization and curing processes of a polyimide precursor, and can be easily separated even without any treatment with an additional release agent, while not damaging a polyimide film formed after curing, may be preferable.
The application process may be carried out according to conventional application methods. Specifically, a spin coating method, a bar coating method, a roll coating method, an air knife method, a gravure printing method, a reverse roll method, a kiss roll method, a doctor blade method, a spray coating method, a dipping method, a brush coating method, or the like can be used. Among them, it is more preferable to carry out by a casting method which allows a continuous process and enables the imidization rate of polyimide to be increased.
Further, the polyimide precursor composition may be applied on the substrate in a thickness range such that the finally produced polyimide film has a thickness suitable for the display substrate. For example, it may be applied in an amount such that the thickness is 10 μm to 30 μm.
After the polyimide precursor composition is applied, a drying process for removing the solvent remaining in the polyimide precursor composition may also be optionally performed before the curing process.
The drying process may be carried out according to a conventional method. Specifically, the drying process may be performed at a temperature of 140 ℃ or less or 80 ℃ to 140 ℃. If the drying temperature is lower than 80 deg.C, the drying process becomes longer. If the drying temperature exceeds 140 ℃, imidization rapidly proceeds, making it difficult to form a polyimide film having a uniform thickness.
The polyimide precursor composition is then applied to a substrate and heat treated in an IR oven, in a hot air oven, or on a hot plate. The heat treatment temperature may be 300 ℃ to 500 ℃, preferably 320 ℃ to 480 ℃. The heat treatment may be performed in a multi-step heating process within the above temperature range. The heat treatment process may be performed for 20 minutes to 70 minutes, and preferably for 20 minutes to 60 minutes.
The residual stress immediately after curing of the polyimide film prepared as described above may be 40MPa or less, and the residual stress change after leaving the polyimide film to stand at 25 ℃ and 50% humidity for 3 hours may be 5MPa or less.
The polyimide film may have a yellowness of 15 or less, and preferably 13 or less. Further, the haze of the polyimide film may be 2% or less, and preferably 1% or less
Further, the polyimide film may have a transmittance at 450nm of 75% or more, a transmittance at 550nm of 85% or more, and a transmittance at 630nm of 90% or more.
The polyimide film may have high heat resistance, for example, a thermal decomposition temperature (Td — 1%) in which mass loss is 1% may be 500 ℃ or more.
The modulus of the polyimide film prepared as described above may be 0.1GPa to 4 GPa. When the modulus (elastic modulus) is less than 0.1GPa, the film has low rigidity and is easily broken by external impact. When the modulus exceeds 4GPa, the cover film (cover film) has excellent rigidity, but sufficient flexibility may not be ensured.
Further, the polyimide film may have an elongation of 20% or more, preferably 50% or more, and a tensile strength of 130MPa or more, preferably 140MPa or more.
In addition, the polyimide film according to the present invention may have excellent thermal stability against temperature change. For example, after n +1 times (n is an integer of at least 0) of heating and cooling processes in a temperature range of 100 ℃ to 350 ℃, the coefficient of thermal expansion thereof may be-10 ppm/DEG C to 100 ppm/DEG C, preferably-7 ppm/DEG C to 90 ppm/DEG C, more preferably 80 ppm/DEG C or less.
Further, retardation (R) in the thickness direction of the polyimide film according to the present inventionth) May be-150 nm to +150nm, preferably-130 nm to +130nm, to exhibit optical isotropy to improve visual acuity.
According to one embodiment, the adhesion force of the polyimide film to the carrier substrate may be 5gf/in or more, and preferably 10gf/in or more.
In addition, the present invention provides a flexible device including the polyimide film as a substrate.
In one embodiment, the flexible device may be manufactured by a method comprising:
applying a polyimide precursor composition on a carrier substrate, and then heating it to form a polyimide film, and then forming a device on the polyimide film; and
the polyimide film with the devices formed thereon is peeled off from the carrier substrate.
The flexible device may be, for example, a thin film transistor, a Liquid Crystal Display (LCD), electronic paper, an organic EL display, a Plasma Display Panel (PDP), or an IC card.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily perform the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
< Synthesis example 1> preparation of Compound 1
Preparation of Compounds 1-3
Compound 1-1(108.0g, 0.65mol) and compound 1-2(73.0g, 0.32mol) were dissolved in THF (500mL) under a nitrogen atmosphere, and potassium carbonate (135.2g, 0.97mol) was dissolved in water (250mL), followed by heating to 100 ℃. Tetratriphenylphosphine palladium (11.29g) was added to the reaction mixture under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and then ethyl acetate (250mL) was added to separate an organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus (BUCHI Rotavapor R-300) to obtain compound 1-3(60.3g, yield 69%).
Preparation of Compounds 1-5
Compounds 1-3(20.0g, 74.3mmol) and compounds 1-4(4.0g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compounds 1 to 5(21.5g, yield 95%).
Preparation of Compound 1
Compounds 1-5(21.5g, 35.3mmol) were dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 1(19.0g, yield 98%).
For C34H22N4O4Calculated HR LC/MS/MS M/z (M +): 550.1641, respectively; measured value: 550.1639
< Synthesis example 2> preparation of Compound 2
Preparation of Compound 2-2
Compound 1-3(20.0g, 74.3mmol) and compound 2-1(9.07g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 2-2(24.9g, yield 90%).
Preparation of Compound 2
Compound 2-2(24.9g, 33.3mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 2(21.7g, yield 95%).
For C36H20F6N4O4Calculated HR LC/MS/MS M/z (M +): 687.1422, respectively; measured value: 687.1420
< Synthesis example 3> preparation of Compound 3
Preparation of Compound 3-2
Compound 1-3(20.0g, 74.3mmol) and compound 3-1(5.05g, 37.1mmol) were added to propionic acid (500mL) under reflux and stirred for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 3-2(21.8g, yield 92%).
Preparation of Compound 3
Compound 3-2(21.8g, 34.2mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 3(19.5g, yield 99%).
For C36H26N4O4Calculated HR LC/MS/MS M/z (M +): 578.1954, respectively; measured value: 578.1949
< Synthesis example 4> preparation of Compound 4
Preparation of Compound 4-2
Compound 1-3(20.0g, 74.3mmol) and compound 4-1(6.57g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 4-2(22.1g, yield 88%).
Preparation of Compound 4
Compound 4-2(22.1g, 32.6mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 4(16.1g, yield 80%).
For C34H20Cl2N4O4Calculated HR LC/MS/MS M/z (M +): 618.0862, respectively; measured value: 618.0859
< Synthesis example 5> preparation of Compound 5
Preparation of Compound 5-2
Compound 1-3(20.0g, 74.3mmol) and compound 5-1(6.57g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 5-2(22.9g, yield 91%).
Preparation of Compound 5
Compound 5-2(22.9g, 32.6mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 5(20.0g, yield 96%).
For C34H20Cl2N4O4Calculated HR LC/MS/MS M/z (M +): 618.0862, respectively; measured value: 618.0860
< Synthesis example 6> preparation of Compound 6
Preparation of Compound 6-2
Compound 1-3(20.0g, 74.3mmol) and compound 6-1(6.24g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 6-2(23.6g, yield 95%).
Preparation of Compound 6
Compound 6-2(23.6g, 35.3mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 6(20.8g, yield 97%).
For C36H26N4O6Calculated HR LC/MS/MS M/z (M +): 610.1852, respectively; measured value: 610.1851
< Synthesis example 7> preparation of Compound 7
Preparation of Compound 7-2
Compound 1-3(20.0g, 74.3mmol) and compound 7-1(7.88g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 7-2(23.6g, yield 89%).
Preparation of Compound 7
Compound 7-2(23.6g, 33.0mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 7(19.9g, yield 92%).
For C42H30N4O4Calculated HR LC/MS/MS M/z (M +): 654.2267, respectively; measured value: 654.2264
< Synthesis example 8> preparation of Compound 8
Preparation of Compound 8-2
Compound 1-3(20.0g, 74.3mmol) and compound 8-1(11.8g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 8-2(29.3g, yield 96%).
Preparation of Compound 8
Compound 8-2(29.3g, 35.6mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250mL) to obtain compound 8(24.2g, yield 89%).
For C42H24F6N4O4Calculated HR LC/MS/MS M/z (M +): 762.1702, respectively; measured value: 762.1700
< Synthesis example 9> preparation of Compound 9
Preparation of Compound 9-2
Compound 1-3(20.0g, 74.3mmol) and compound 9-1(11.8g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (250mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 9-2(29.3g, yield 96%).
Preparation of Compound 9
Compound 9-2(29.3g, 35.6mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250mL) to obtain compound 9(22.0g, yield 89%).
For C40H24Cl2N4O4Calculated HR LC/MS/MS M/z (M +): 694.1175, respectively; measured value: 694.1172
< Synthesis example 10> preparation of Compound 10
Preparation of Compound 10-2
Compound 1-3(20.0g, 74.3mmol) and compound 10-1(14.7g, 37.1mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 10-2(32.7g, yield 98%).
Preparation of Compound 10
Compound 10-2(32.7g, 36.4mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 10(27.4g, yield 90%).
For C48H28F6N4O4Calculated HR LC/MS/MS M/z (M +): 838.2015, respectively; measured value: 838.2011
< Synthesis example 11> preparation of Compound 11
Preparation of Compound 11-3
Compound 11-1(20g, 85.4mmol) and compound 1-2(9.7g, 42.7mmol) were dissolved in THF (500mL) under a nitrogen atmosphere, and potassium carbonate (11.8g, 85.4mmol) was dissolved in water (250mL), followed by heating to 100 ℃. Tetratriphenylphosphine palladium (1.48g) was added to the reaction mixture under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and then ethyl acetate (250mL) was added to separate an organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 11-3(11.5g, yield 80%).
Preparation of Compound 11-5
Compound 11-3(11.5g, 34.1mmol) and compound 11-4(4.1g, 17.1mmol) were added to propionic acid (500mL) under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 11-5(14.4g, yield 96%).
Preparation of Compound 11
Compound 11-5(14.4g, 16.3mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150mL) to obtain compound 11(12.7g, yield 95%).
For C38H18F12N4O4Calculated HR LC/MS/MS M/z (M +): 822.1136, respectively; measured value: 822.1131
< Synthesis example 12> preparation of Compound 12
Preparation of Compound 12-3
Compound 12-1(30g, 166.6mmol) and compound 1-2(25.2g, 111.1mmol) were dissolved in THF (500mL) under a nitrogen atmosphere, and potassium carbonate (23.0g, 166.6mmol) was dissolved in water (250mL), followed by heating to 100 ℃. Tetratriphenylphosphine palladium (3.84g) was added to the reaction mixture under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and then ethyl acetate (250mL) was added to separate an organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 12-3(24.1g, yield 77%).
Preparation of Compounds 12-5
Compound 12-3(24.1g, 58.4mmol) and compound 12-4(13.6g, 42.7mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 12-5(32.6g, yield 90%).
Preparation of Compound 12
Compound 12-5(32.6g, 38.4mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250mL) to obtain compound 12(24.3g, yield 80%).
For C44H28F6N4O4Calculated HR LC/MS/MS M/z (M +): 790.2015, respectively; measured value: 790.2012
< Synthesis example 13> preparation of Compound 13
Preparation of Compound 13-3
Compound 13-1(30g, 128.2mmol) and compound 1-2(19.4g, 85.4mmol) were dissolved in THF (500mL) under a nitrogen atmosphere, and potassium carbonate (17.7g, 128.2mmol) was dissolved in water (250mL), followed by heating to 100 ℃. Tetratriphenylphosphine palladium (2.96g) was added to the reaction mixture under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and then ethyl acetate (250mL) was added to separate an organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 13-3(22.1g, yield 77%).
Preparation of Compound 13-5
Compound 13-3(22.1g, 65.8mmol) and compound 13-4(10.5g, 32.9mmol) were added to propionic acid (500mL) under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 13-5(28.9g, yield 92%).
Preparation of Compound 13
Compound 13-5(28.9g, 30.2mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250mL) to obtain compound 13(25.8g, yield 95%).
For C44H22F12N4O4Calculated HR LC/MS/MS M/z (M +): 898.1449, respectively; measured value: 898.1444
< Synthesis example 14> preparation of Compound 14
Preparation of Compound 14-3
Compound 14-1(30g, 149.2mmol) and compound 1-2(22.5g, 99.5mmol) were dissolved in THF (500mL) under a nitrogen atmosphere, and potassium carbonate (20.6g, 149.2mmol) was dissolved in water (250mL) and then heated to 100 ℃. Tetratriphenylphosphine palladium (3.43g) was added to the reaction mixture under reflux and stirred for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then ethyl acetate (250mL) was added to separate an organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 14-3(26.4g, yield 88%).
Preparation of Compound 14-5
Compound 14-3(26.4g, 87.2mmol) and compound 14-4(11.0g, 43.6mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 14-5(33.4g, yield 93%).
Preparation of Compound 14
Compound 14-5(33.4g, 40.5mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 14(26.9g, yield 87%).
For C40H22Cl4N4O4Calculated HR LC/MS/MS M/z (M +): 764.0366, respectively; measured value: 764.0363
< Synthesis example 15> preparation of Compound 15
Preparation of Compound 15-3
Compound 15-2(50.0g, 0.22mmol) was dissolved in N-methylpyrrolidinone (NMP) (500mL) and compound 15-1(26.6g, 0.11mol) was added in several portions, then heated to 140 ℃ and stirred for 6 hours. After the reaction was complete, water (1000mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 15-3(19.6g, yield 43%).
Preparation of Compound 15-4
After dispersing compound 15-3(19.6g, 47.7mmol) in glacial acetic acid (300mL), potassium permanganate (18.8g, 119mmol) was added and stirred at 0 ℃ for 1 hour, then warmed to room temperature and stirred for 6 hours. After the reaction was complete, water (600mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 15-4(19.4g, yield 92%).
Preparation of Compounds 15-5
Compound 15-4(19.4g, 43.7mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150mL) to obtain compound 15-5(14.9g, yield 89%).
Preparation of Compound 15-6
Compounds 15-5(14.9g, 38.9mmol) and compounds 1-3(20.9g, 77.9mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 15-6(33.3g, yield 97%).
Preparation of Compound 15
Compound 15-6(33.3g, 37.6mmol) was dissolved in THF (400mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 15(28.2g, yield 91%).
C42H24F6SN4O6Calculated HR LC/MS/MS M/z (M +): 826.1321, respectively; measured value: 826.1319
< Synthesis example 16> preparation of Compound 16
Preparation of Compound 16-3
Compound 16-2(42.7g, 0.25mmol) was dissolved in NMP (500mL) and compound 16-1(30.0g, 0.12mol) was added in several portions, then heated to 140 ℃ and stirred for 6 hours. After completion of the reaction, water (1000mL) was added to the reaction mixture and filtered to obtain a solid, and the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 16-3(20.5g, yield 54%).
Preparation of Compound 16-4
After dispersing compound 16-3(20.5g, 67.5mmol) in glacial acetic acid (300mL), potassium permanganate (26.6g, 168.7mmol) was added and stirred at 0 ℃ for 1 hour, then warmed to room temperature and stirred for 6 hours. After the reaction was complete, water (600mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200mL) to obtain compound 16-4(19.7g, yield 87%).
Preparation of Compound 16-5
Compound 16-4(19.7g, 58.6mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150mL) to obtain compound 16-5(14.7g, yield 91%).
Preparation of Compound 16-6
Compounds 16-5(14.7g, 53.3mmol) and compounds 1-3(28.7g, 106.7mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 16-6(39.4g, yield 95%).
Preparation of Compound 16
Compound 16-6(39.4g, 50.7mmol) was dissolved in THF (500mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (350mL) to obtain compound 16(33.8g, yield 93%).
C42H30SN4O6Calculated HR LC/MS/MS M/z (M +): 718.1886, respectively; measured value: 718.1883
< Synthesis example 17> preparation of Compound 17
Preparation of Compound 17-3
Compound 17-1(30.0g, 0.13mol) and compound 17-2(31.0g, 0.2mol) were dissolved in Dimethylformamide (DMF) (600mL) and potassium carbonate was added, followed by heating to 150 ℃. After the reaction was complete, water (1000mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (350mL) to obtain compound 17-3(34.8g, yield 76%).
Preparation of Compound 17-4
After dispersing compound 17-3(34.8g, 101.3mmol) in glacial acetic acid (400mL), potassium permanganate (40.0g, 253.3mmol) was added and stirred at 0 ℃ for 1 hour, then warmed to room temperature and stirred for 6 hours. After the reaction was complete, water (800mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 17-4(32.3g, yield 85%).
Preparation of Compound 17-5
Compound 17-4(32.3g, 85.9mmol) was dissolved in THF (300mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol to obtain compound 17-5(25.8g, yield 95%).
Preparation of Compound 17-6
Compounds 17-5(25.8g, 81.6mmol) and compounds 1-3(43.9g, 163.3mmol) were added to propionic acid (500mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (500mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 17-6(58.7g, yield 88%).
Preparation of Compound 17
Compound 17-6(58.7g, 71.8mmol) was dissolved in THF (600mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (500mL) to obtain compound 17(50.1g, yield 92%).
C41H25F3SN4O6Calculated HR LC/MS/MS M/z (M +): 758.1447, respectively; measured value: 758.1443
< Synthesis example 18> preparation of Compound 18
Preparation of Compound 18-2
Compound 18-1(15.0g, 54.3mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (100mL) to obtain compound 18-2(11.0g, yield 94%).
Preparation of Compound 18-3
Compound 18-2(11.0g, 51.0mmol) and compound 1-3(27.4g, 102.1mmol) were added to propionic acid (400mL) under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (400mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 18-3(31.5g, yield 86%).
Preparation of Compound 18
Compound 18-3(31.5g, 43.9mmol) was dissolved in THF (300mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250mL) to obtain compound 18(26.5g, yield 93%).
C40H26SN4O4Calculated HR LC/MS/MS M/z (M +): 658.1675, respectively; measured value: 658.1670
< Synthesis example 19> preparation of Compound 19
Preparation of Compound 19-2
Compound 19-1(15.0g, 49.3mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (110mL) to obtain compound 19-2(11.7g, yield 98%).
Preparation of Compound 19-3
Compound 19-2(11.7g, 48.3mmol) and compound 1-3(26.0g, 96.7mmol) were added to propionic acid (400mL) under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (400mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 19-3(34.9g, yield 97%).
Preparation of Compound 19
Compound 19-3(34.9g, 46.9mmol) was dissolved in THF (400mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 19(27.3g, yield 85%).
C42H30SN4O4Calculated HR LC/MS/MS M/z (M +): 686.1988, respectively; measured value: 686.1986
< Synthesis example 20> preparation of Compound 20
Preparation of Compound 20-2
Compound 20-1(15.0g, 36.4mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150mL) to obtain compound 20-2(12.1g, yield 95%).
Preparation of Compound 20-3
Compound 20-2(12.1g, 34.5mmol) and compound 1-3(18.6g, 69.1mmol) were added to propionic acid (300mL) at reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (300mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 20-3(26.5g, yield 90%).
Preparation of Compound 20
Compound 20-3(26.5g, 31.1mmol) was dissolved in THF (300mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250mL) to obtain compound 20(22.4g, yield 91%).
C42H24F6SN4O4Calculated HR LC/MS/MS M/z (M +): 794.1422, respectively; measured value: 794.1419
< Synthesis example 21> preparation of Compound 21
Preparation of Compound 21-2
Compound 21-1(15.0g, 57.6mmol) was dissolved in THF (200mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (100mL) to obtain compound 21-2(10.6g, yield 92%).
Preparation of Compound 21-3
Compound 21-2(10.6g, 53.0mmol) and compound 1-3(28.5g, 106.1mmol) were added to propionic acid (400mL) under reflux and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and ethanol (400mL) was added to disperse the resulting solid. After the reaction mixture was filtered, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 21-3(36.1g, yield 97%).
Preparation of Compound 21
Compound 21-3(36.1g, 51.4mmol) was dissolved in THF (300mL) and Pd/C catalyst was added, followed by heating to 60 ℃. The reaction mixture was stirred for 4 hours while hydrogen was continuously injected. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300mL) to obtain compound 21(29.4g, yield 89%).
C40H26N4O5Calculated HR LC/MS/MS M/z (M +): 642.1903, respectively; measured value: 642.1901
< example 1>
An organic solvent DEAc (N, N-diethylacetamide) (100mL) was charged into a reactor in a nitrogen stream, and then 24.2g (0.031mol) of the diamine compound 8 prepared in synthesis example 8 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which the compound 8 was added, 9.12g (0.031mol) of BPDA (biphenyl-tetracarboxylic dianhydride) as an acid anhydride was added at the same temperature, and stirred for 24 hours to obtain a polyimide precursor composition.
< example 2>
An organic solvent DEAc (150mL) was charged into the reactor in a nitrogen stream, and then 33.8g (0.041mol) of the diamine compound 15 prepared in Synthesis example 15 was added to dissolve it while keeping the reactor temperature at 25 ℃. To the solution to which compound 15 was added, 12.1g (0.041mol) of BPDA as an acid anhydride was added at the same temperature, and stirred for 24 hours to obtain a polyimide precursor composition.
< example 3>
An organic solvent DEAc (150mL) was charged into the reactor in a nitrogen stream, and then 30.5g (0.040mol) of the same diamine compound 8 as used in example 1 was added to dissolve it while keeping the reactor temperature at 25 ℃. To the solution to which compound 8 was added, 17.7g (0.040mol) of 6-FDA (4,4' - (hexafluoroisopropylidene) diphthalic anhydride) as an acid anhydride was added at the same temperature, and stirred for 24 hours to obtain a polyimide precursor composition.
< example 4>
An organic solvent DEAc (200mL) was charged into the reactor in a nitrogen stream, and then 37.2g (0.045mol) of the same diamine compound 15 as used in example 2 was added to dissolve it while keeping the reactor temperature at 25 ℃. To the solution to which the compound 15 was added, 20.0g (0.045mol) of 6-FDA as an acid anhydride was added at the same temperature, and stirred for 24 hours to obtain a polyimide precursor composition.
< comparative example 1>
An organic solvent DEAc (150mL) was charged into the reactor in a nitrogen stream, and then 27.8g (0.087mol) of TFMB (2,2' -bis (trifluoromethyl) benzidine) as a diamine compound was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which TFMB was added, 25.6g (0.087mol) of BPDA as an acid anhydride was added at the same temperature, and stirred for 24 hours to obtain a polyimide precursor composition.
< comparative example 2>
An organic solvent DEAc (100mL) was charged into the reactor in a nitrogen stream, and then 22.4g (0.070mol) of TFMB as a diamine compound was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which TFMB was added, 31.1g (0.070mol) of 6-FDA as an acid anhydride was added at the same temperature, and stirred for 24 hours to obtain a polyimide precursor composition.
< comparative example 3>
A polyimide precursor composition was obtained according to the same procedure as in example 1, except that the following control compound C (in which two amide rings are not bonded with an aryl ring) was used in place of the diamine compound 8.
< comparative example 4>
A polyimide precursor composition was obtained according to the same procedure as in example 3, except that the following control compound C (in which two amide rings are not bonded with an aryl ring) was used in place of the diamine compound 8.
The solid content and viscosity of each of the polyimide precursor compositions obtained in examples 1 to 4 and comparative examples 1 to 4 are shown in table 1 below.
< Experimental example 1>
Each of the polyimide precursor compositions (solutions) prepared in examples 1 to 4 and comparative examples 1 to 2 was spin-coated on a glass substrate. The glass substrate coated with each polyimide precursor solution was put into an oven, heated at a rate of 5 ℃/min, and cured at 80 ℃ for 30 minutes and at 430 ℃ for 30 minutes to prepare each polyimide film.
< evaluation of polyimide film characteristics >
1. Coefficient of Thermal Expansion (CTE)
Each of the polyimide films obtained in experimental example 1 was cut into 5 × 20mm to prepare a sample, and then the sample was loaded using an accessory of TMA (thermo-mechanical analyzer) (Q400, TA Instruments). The length of the actual measured film is equal to 16 mm. The tensile force of the film sample was set to 0.02N. The first warming step is carried out at a heating rate of 5 ℃/min from 100 ℃ to 350 ℃ and the cooling step is carried out at a cooling rate of 4 ℃/min from 350 ℃ to 100 ℃. Changes in thermal expansion were measured using TMA (Q400, TA Instruments).
2. Temperature of thermal decomposition
The temperature at which the weight loss of the polyimide film sample was 1% in a nitrogen atmosphere (Td 1%) was measured using a thermogravimetric analyzer (TGA) (TGA 8000, PerkinElmer).
The CTE and Td 1% values of the polyimide films measured are shown in table 1 below.
[ Table 1]
As can be seen from table 1 above, the polyimide films (examples 1 to 4) prepared by using the polyimide precursor composition comprising the novel diamine compound according to the present invention have lower CTE values than those of comparative examples 1 to 4 prepared by using a diamine compound having a different structure from that of the diamine compound of the present invention under the condition of using the same acid anhydride. This shows that the polyimide film according to the present invention has very little shrinkage behavior or change due to heating, from which it can be seen that the polyimide film according to the present invention has excellent heat resistance.
While the present invention has been particularly shown and described with reference to particular embodiments thereof, it will be obvious to those skilled in the art that the detailed description is merely a preferred embodiment and that the scope of the invention is not limited thereto. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (8)
1. A diamine compound represented by the following formula 1:
[ formula 1]
In the case of the above-mentioned formula 1,
l is selected from
The linking group of (a) is,
Ar1and Ar2Each independently is selected from
The divalent organic group of (a) is,
R1to R11Each independently is hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a, Substituted or unsubstituted aralkyl having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, -COOH group, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, amide group, substituted or unsubstituted cycloalkoxy having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkylthio having 1 to 30 carbon atoms, ester group, -CD3An azido group, a nitro group, or a substituted or unsubstituted (3-to 30-membered) heteroaryl group containing at least one heteroatom selected from B, N, O, S, P (═ O), Si, and P,
y is selected from
l、m、n、o、p、q、r、s, t, u and v are each an integer of 0 to 4, and when l, m, n, o, p, q, R, s, t, u and v are integers of 2 to 4, R is1To R11Each of which may be the same or different.
2. The diamine compound according to claim 1, wherein L in the formula 1 is selected from
The linking group of (a) is,
Ar1and Ar2Each independently is
R1To R8Each independently of the others, a halogen atom, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms or an unsubstituted or halogen atom-substituted alkoxy group having 1 to 6 carbon atoms,
R9is a halogen atom, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms,
y is selected from
And
l, m, n, o, p, q, r, s and t are each an integer of 0 to 2.
3. The diamine compound according to claim 1, wherein L in the formula 1 is a phenyl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of trifluoromethyl, methyl, chlorine (Cl) and methoxy; biphenyl unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chlorine (Cl); unsubstituted or trifluoromethyl-substituted terphenyl; bis (trifluoromethylphenyl) sulfone, bis (methylphenyl) sulfone, { (trifluoromethylphenyl) sulfonyl } phenyl, diphenylsulfide, bis (methylphenyl) sulfide, bis (trifluoromethylphenyl) sulfide or diphenylether,
Ar1and Ar2Each independently a phenyl group unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chlorine (Cl),
l is an integer of 0 to 2, and
m, n, o, p, q, r, s and t are each an integer of 0 or 1.
4. Diamine compound according to claim 1, wherein the diamine compound of formula 1 is selected from the compounds of the following formulae 1 to 21:
5. a polyimide precursor prepared by polymerizing polymerization components comprising the diamine compound of formula 1 according to any one of claims 1 to 4 and at least one acid dianhydride.
6. The polyimide precursor according to claim 5, wherein the acid anhydride comprises BPDA (biphenyl-tetracarboxylic dianhydride), 6-FDA (4,4' - (hexafluoroisopropylidene) diphthalic anhydride), or a mixture thereof.
7. A polyimide film formed from the polyimide precursor according to claim 5.
8. A flexible device comprising the polyimide film according to claim 7 as a substrate.
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| WO2016013403A1 (en) * | 2014-07-24 | 2016-01-28 | デクセリアルズ株式会社 | Polyimide, polyamic acid, resin composition and substrate for flexible display |
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| WO2003027178A2 (en) * | 2001-09-27 | 2003-04-03 | Lg Chem Ltd. | Polyimide copolymer and methods for preparing the same |
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| US9828469B2 (en) * | 2013-09-27 | 2017-11-28 | Toray Industries, Inc. | Polyimide precursor, polyimide resin film produced from said polyimide precursor, display element, optical element, light-receiving element, touch panel and circuit board each equipped with said polyimide resin film, organic EL display, and methods respectively for producing organic EL element and color filter |
| KR102285777B1 (en) * | 2013-10-23 | 2021-08-03 | 닛산 가가쿠 가부시키가이샤 | Novel diamine, polyamic acid, and polyimide |
| EP3099730A4 (en) * | 2014-01-31 | 2017-08-09 | Fujifilm Electronic Materials USA, Inc. | Novel polyimide compositions |
| EP3266808B1 (en) * | 2015-03-05 | 2020-12-09 | LG Chem, Ltd. | Composition for polyimide film for flexible substrate of optoelectronic device |
| WO2016158674A1 (en) * | 2015-03-27 | 2016-10-06 | 東レ株式会社 | Diamine compound, and heat-resistant resin or heat-resistant resin precursor comprising same |
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| KR102319883B1 (en) | 2021-11-01 |
| CN112654601B (en) | 2024-01-23 |
| TW202028176A (en) | 2020-08-01 |
| TWI710551B (en) | 2020-11-21 |
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