CN112654601B - Diamine compound, polyimide precursor using same, and polyimide film - Google Patents
Diamine compound, polyimide precursor using same, and polyimide film Download PDFInfo
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- CN112654601B CN112654601B CN202080004937.XA CN202080004937A CN112654601B CN 112654601 B CN112654601 B CN 112654601B CN 202080004937 A CN202080004937 A CN 202080004937A CN 112654601 B CN112654601 B CN 112654601B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 108
- -1 Diamine compound Chemical class 0.000 title claims abstract description 59
- 239000004642 Polyimide Substances 0.000 title claims description 63
- 239000002243 precursor Substances 0.000 title claims description 53
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 181
- 125000004432 carbon atom Chemical group C* 0.000 claims description 104
- 238000006243 chemical reaction Methods 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 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 20
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical group 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 3
- UNBZBXXCBHHBPW-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[2-(trifluoromethyl)phenyl]sulfanylbenzene Chemical compound 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 compound 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 compound 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 compound CC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1C KZCDMIJHGSSDFO-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound 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
- HFHIRIFLPGQKFI-UHFFFAOYSA-N 1-(benzenesulfonyl)-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 HFHIRIFLPGQKFI-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 125000006836 terphenylene group Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 25
- 125000005842 heteroatom Chemical group 0.000 abstract description 6
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 58
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 44
- 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
- 238000010992 reflux Methods 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 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
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000005259 measurement Methods 0.000 description 21
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 125000000962 organic group Chemical group 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 125000002950 monocyclic group Chemical group 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 125000001072 heteroaryl group Chemical group 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 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
- 125000001188 haloalkyl group Chemical group 0.000 description 9
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 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
- 125000003545 alkoxy group Chemical group 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
- 238000005192 partition Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000005103 alkyl silyl group Chemical group 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000001769 aryl amino group Chemical group 0.000 description 4
- 125000005104 aryl silyl group Chemical group 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 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 description 4
- 230000008859 change Effects 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000000126 substance Substances 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
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000003943 azolyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 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
- 229910052805 deuterium Inorganic materials 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
- 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
- 239000000463 material Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
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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
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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. 10-2019-0009547, filed on 25 th 1 month in 2019, and korean patent application No. 10-2020-0005487, filed on 15 th 1 month in 2020, the entire disclosures of which are incorporated herein by reference.
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 in use are heavy and brittle and difficult to apply to continuous processes. Accordingly, research is actively being conducted into application of a plastic substrate, which has advantages of portability, flexibility, and applicability to a continuous process, and which can replace a glass substrate, to mobile phones, notebook computers, and PDAs (personal digital assistant, personal digital assistants).
In particular, polyimide has advantages in that it is easy to synthesize, can be formed into a film, and does not require a crosslinking agent for curing. Recently, polyimide is widely used as an integration material 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 the application of polyimide to a flexible plastic display panel having light weight and flexible characteristics.
Polyimide films produced by film-forming polyimide are generally prepared by: an aromatic dianhydride is polymerized with an aromatic diamine or an aromatic diisocyanate solution to prepare a solution of a polyamic acid derivative, which is coated on a silicon wafer or glass, and cured by a heat treatment.
Flexible devices involving high temperature processes require heat resistance at high temperatures. In particular, organic Light Emitting Diode (OLED) devices fabricated using Low Temperature Polysilicon (LTPS) processes may have process temperatures approaching 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 polyimide having improved heat resistance, storage stability, etc.
Another problem to be solved by the present invention is to provide a polyimide precursor prepared by using the novel diamine compound.
Yet 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 proposal
In order to solve the problems of the present invention, the present invention provides a diamine compound represented by the following formula 1:
[ 1]
In the formula (1) of the present invention,
l is selected from Is used as a base for the reaction of the amino acid with the hydroxyl group,
Ar 1 and Ar is a group 2 Each independently is selected from Is a group of a divalent organic group of (a),
R 1 to R 11 Each independently is hydrogen, deuterium, a halogen atom, cyano, hydroxy, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted haloalkyl having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms, substituted or unsubstituted alkylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylamino having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted arylthio having 6 to 30 carbon atoms, substituted or unsubstituted arylthio Aryl having 6 to 30 carbon atoms, 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, -CD 3 An 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 1 To R 11 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 properties after curing.
Detailed Description
Since various modifications and changes may be made in the present invention, specific embodiments of the invention will be described in detail in the following detailed description. It should be understood, however, that the invention is not intended to be limited 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, if it is determined that detailed description of known functions may obscure the gist of the present invention, detailed description of known functions will be omitted.
Aromatic polyimides are widely used in high tech industries such as microelectronics, aerospace, insulation and fire-resistant materials due to their excellent overall properties (e.g., thermal oxidative stability and high mechanical strength). However, aromatic polyimides having high absorbance in the ultraviolet-visible region exhibit intense coloration ranging from pale yellow to dark brown. This limits its wide application in the photovoltaic field where transparency and colorless properties are essential requirements. The reason for 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 the problem, attempts have been made to introduce specific functional groups, bulky side groups, fluorinated functional groups, etc. into the polymer backbone or to introduce-S-, -O-, -CH 2 And the like to develop optically transparent polyimide films with high glass transition temperatures (Tg).
The present inventors have made extensive studies based on the prior art to solve the problems of the prior art, and have found that a novel diamine compound having a specific structure provides excellent thermal and mechanical characteristics, and completed the present invention.
Accordingly, the present invention provides a diamine compound of the following formula 1:
[ 1]
In the formula (1) of the present invention,
l is selected from Is used as a base for the reaction of the amino acid with the hydroxyl group,
Ar 1 and Ar is a group 2 Each independently is selected from
Is a group of a divalent organic group of (a),
R 1 to R 11 Each independently is hydrogen, deuterium, a halogen atom, cyano, hydroxy, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted haloalkyl having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms, substituted or unsubstituted alkylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylamino having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted aralkyl having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, -3-substituted cycloalkyl having 3-to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3-to 30 carbon atoms, CD, substituted or unsubstituted cycloalkyl having 1 to 30 carbon atoms 3 An 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 fromAnd
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 1 To R 11 May be the same or different.
The term "substituted" in the description of "substituted or unsubstituted" as described herein means that a 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 the 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, halogen atom, cyano group, amino group, carboxyl group, nitro group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylthio group having 1 to 30 carbon atoms, arylthio group having 6 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, cycloalkenyl group having 3 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, alkylsilyl group having 1 to 30 carbon atoms, arylsilyl group having 6 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, alkylcarbonyl group having 1 to 30 carbon atoms, alkoxycarbonyl group having 1 to 30 carbon atoms, arylcarbonyl group having 6 to 30 carbon atoms, arylboronyl group (arylboronyl) having 1 to 30 carbon atoms, arylboronyl group having 6 to 30 carbon atoms.
As used herein, "alkyl having 1 to 30 carbon atoms" means a straight or branched alkyl 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 having 2 to 30 carbon atoms" means a straight or branched alkenyl 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 vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl and the like.
As used herein, "alkynyl having 2 to 30 carbon atoms" means a straight or branched alkynyl 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 having 1 to 30 carbon atoms" means a straight or branched alkoxy 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 having 3 to 30 carbon atoms" means a mono-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 (en)) having 6 to 30 carbon atoms" means a monocyclic or fused ring group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, preferably having 6 to 20 ring backbone carbon atoms, and more preferably 6 to 15 ring backbone carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl,A group, a fused tetraphenyl group (napthacryl group), a fluoranthenyl group, and the like.
As used herein, "(3-30 membered) (arylene) heteroaryl (heteroaryl (en))" means having 3 to 30 ring backbone atoms and comprising one or more selected from B, N, O, S, P (=o), si, and PAryl groups of multiple heteroatoms. Heteroaryl groups preferably have 3 to 20 ring backbone carbon atoms, and more preferably have 3 to 15 ring backbone carbon atoms, and preferably contain 1 to 4 heteroatoms. An aryl group may be a monocyclic group or a fused ring fused to one or more benzene rings, and may be partially saturated. Furthermore, heteroaryl groups herein include forms in which one or more heteroaryl groups or aryl groups are linked to a heteroaryl group by a single bond. Examples of heteroaryl groups include monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, and isozyl Azolyl, (-) -and (II) radicals>Azolyl, (-) -and (II) radicals>Diazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; and fused ring heteroaryl groups, such as benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisothiol>Azolyl, benzo->Oxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl (cynolinyl), quinazolinyl, quinoxalinyl, carbazolyl, phenoxazin>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 Ar of (2) 1 And Ar is a group 2 Each independently is->R 1 To R 8 Each independently is 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, R 9 Is a halogen atom, or an unsubstituted or halogen atom-substituted (C1-C6) alkyl group, Y is selected from +.>And l, m, n, o, p, q, r, s and t are each integers of 0 to 2.
According to one embodiment, in the compound of formula 1, L is phenyl which is unsubstituted or substituted with one or more substituents selected from trifluoromethyl, methyl, chloro (Cl) and methoxy; biphenyl group which is unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chloro; a terphenyl group unsubstituted or substituted with trifluoromethyl; bis (trifluoromethylphenyl) sulfone, bis (methylphenyl) sulfone, { (trifluoromethylphenyl) sulfonyl } phenyl, diphenyl sulfide, bis (methylphenyl) sulfide, bis (trifluoromethylphenyl) sulfide or diphenyl ether, ar 1 And Ar is a group 2 Each independently is phenyl unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chloro, l is an integer from 0 to 2, m, n, o, p, q, r, s and t are each integers of 0 or 1.
According to one embodiment, the diamine compound of formula 1 may be selected from the group consisting of compounds of the following structural formulas, but is not limited thereto:
/>
/>
according to one embodiment, the diamine compound of formula 1 may be selected from the compounds of the following structural formulas 1 to 21, but is not limited thereto:
/>
。
as described above, the diamine compound of the present invention is molecularly bonded toHas the following structure: having a phenylene linking group (L) attached to the imide ring and being directly bonded to the aryl ring (Ar) 1 And Ar is a group 2 ) Is an imide ring of (a). When the diamine compound is used as a polymerization component, it can 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, ar 1 、Ar 2 And 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 in the presence of a Pd/C catalyst, wherein the solvent may be Tetrahydrofuran (THF), N-methylpyrrolidone, etc.
After step (2), recrystallization may be performed by adding an alcohol such as ethanol or isopropanol to obtain a solid.
Furthermore, the present invention provides a polyimide precursor (polyamic acid) prepared by polymerizing a polymerization component comprising at least one diamine compound and at least one acid dianhydride, wherein the diamine compound comprises a diamine compound of formula 1. Imidization of the polyimide precursor may be performed to obtain a desired polyimide. The acid dianhydride may include BPDA (biphenyl-tetracarboxylic dianhydride), 6-FDA (4, 4' - (hexafluoroisopropylidene) diphthalic anhydride), or a mixture thereof.
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 crosslinked structure, in a molecule. Preferably, the tetracarboxylic dianhydride includes an acid dianhydride having a structure having a monocyclic or polycyclic aromatic group, a monocyclic or polycyclic alicyclic group, or two or more of them linked by a single bond or a functional group. Alternatively, it may include a tetracarboxylic dianhydride containing a tetravalent organic group having an aliphatic or aromatic ring in which each ring is a monocyclic structure, each ring is condensed to form a heterocyclic structure, or each ring is connected by a single bond.
For example, the tetracarboxylic dianhydride may contain a tetravalent organic group selected from the following formulas 2a to 2 e.
[ 2a ]
[ 2b ]
[ 2c ]
[ 2d ]
[ 2e ]
In the formulae 2a to 2e, R 11 To R 17 Can be each independently selected from halogen atoms (selected from F, cl, br and I), hydroxyl groups, thiol groups (-SH), nitro groups, cyano groups, having 1 to 10 carbonsAlkyl of atoms, haloalkoxy of 1 to 10 carbon atoms, haloalkyl of 1 to 10 carbon atoms and aryl of 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, a 11 And A 12 May each be 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 2 -、-O[CH 2 CH 2 O] y - (y is an integer of 1 to 44), -NH (c=o) NH-, -NH (c=o) O-, a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms (e.g., cyclohexylene, etc.), a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., phenylene, naphthylene, fluorenylene, etc.), and combinations thereof.
In addition, the tetracarboxylic dianhydride may contain a tetravalent organic group selected from the following formulas 3a to 3 n:
at least one hydrogen atom in the tetravalent organic group of formulas 3a to 3n may be substituted with a substituent 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. 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 fluoromethyl, perfluoroethyl, trifluoromethyl, 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 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, a diamine compound 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 connected 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 condensed 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:
[ 4a ]
[ 4b ]
/>
[ 4c ]
[ 4d ]
[ 4e ]
In the formulae 4a to 4e, R 21 To R 27 Can be used forEach independently selected from the group consisting of halogen atoms (selected from F, cl, br and I), hydroxy 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, A 21 And A 22 May each be 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 2 -、-O[CH 2 CH 2 O] 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, etc.), monocyclic or polycyclic arylene having 6 to 18 carbon atoms (e.g. phenylene, naphthylene, fluorenylene, etc.), and combinations thereof, b1 is an integer of 0 to 4, b2 is an integer of 0 to 6, b3 is an integer of 0 to 3, b4 and b5 are each independently an integer of 0 to 4, b7 and b8 are each independently an integer of 0 to 4, and b6 and b9 are each independently an integer of 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 comprise a divalent organic group in which an aromatic ring or 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 condensed to form a heterocyclic structure.
According to one embodiment of the invention, the reaction molar ratio of the total tetracarboxylic dianhydride to the diamine may be from 1:1.1 to 1.1:1. In order to improve the reactivity and the 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 may be carried out by a conventional polymerization method (e.g., solution polymerization) of polyimide or a precursor thereof.
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, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, dimethyl propionamide (DMPA), diethyl propionamide (DEPA), dimethylacetamide (DMAc), N-diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, tetrahydrofuran, m-dimethylpyrrolidone Alkane, p-diAlkane, 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 in combinationAs 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 ACD/LogP modules from the ACD/Labs ACD/Percepa platform. The ACD/LogP module uses an algorithm based on the QSPR (Quantitative Structure-Property Relationship ) method using a 2D molecular structure.
The solvent having a positive partition coefficient Log P means a hydrophobic solvent. According to the studies of the present inventors, it was found that the edge back phenomenon is improved when a polyimide precursor composition is prepared using a specific solvent having a positive partition coefficient Log P. Further, in the present invention, by using a solvent having a positive partition coefficient Log P as described above, the edge-back phenomenon of the solution can be controlled without using an additive such as a leveling agent for controlling the surface tension of the material and the smoothness of the coating film. Since no additional additives are 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 formed more effectively.
For example, in the process of coating a polyimide precursor composition on a glass substrate, an edge-back phenomenon may occur due to shrinkage of the coating layer during curing or under the condition of allowing the coating solution to stand in a wet condition. The edge-shrink phenomenon of the coating solution may cause a change in film thickness. As a result, the film may be cut or have broken edges at the time of cutting due to the lack of flexibility resistance of the film, thereby causing problems of poor process operability and reduced yield.
Further, when a fine foreign matter having polarity is introduced into a polyimide precursor composition applied on a substrate, with respect to the polyimide precursor composition including a polar solvent having a negative partition coefficient Log P, sporadic coating cracks or thickness variation may occur based on the position of the foreign matter due to the polarity of the foreign matter. In the case of using a hydrophobic solvent having a positive partition coefficient Log P, even when a fine foreign matter having polarity is introduced, occurrence of thickness variation due to cracking of the coating layer can be reduced or suppressed.
Specifically, in the polyimide precursor composition including the solvent having positive Log P, the edge pull-back ratio defined by the following equation 1 may be 0% to 0.1% or less.
[ equation 1]
Edge reduction (%) = [ (a-B)/a ] ×100
In formula 1:
a: the polyimide precursor composition was entirely coated on the area of the substrate (100 mm. Times.100 mm),
b: area after edge-shrink phenomenon occurs from the edge of the substrate on which the polyimide precursor composition or polyimide film is coated.
Edge retraction of the polyimide precursor composition and the polyimide film may occur within 30 minutes after the polyimide precursor composition solution is applied, and in particular, the film may be rolled up from the edge so that the thickness of the edge is 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 humidity conditions of 40%, 50%, 60%, 70% and 80%) for 10 minutes or more (e.g., 40 minutes or more), the edge post-shrinkage of the coated composition solution may be 0.1% or less, preferably 0.05%, more preferably almost 0%.
The edge shrinkage as described above is maintained even after curing by heat treatment, and in particular, the edge shrinkage may be 0.05% or less, more preferably almost 0%.
By solving such edge-shrink phenomenon, the polyimide precursor composition according to the present invention can obtain a polyimide film having more uniform characteristics, thereby further improving the productivity of the manufacturing process.
In addition, the solvent used in the polymerization reaction may have a density of 1g as measured by standard ASTM D1475/cm 3 Or smaller. If the density is greater than 1g/cm 3 The relative viscosity may increase and the process efficiency may decrease.
The polymerization reaction may be carried out under an inert gas or nitrogen flow, 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, the reactivity may become high, the molecular weight may become large, and the viscosity of the precursor composition may increase, which may be disadvantageous in terms of process.
The polyimide precursor composition comprising 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 such 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 can 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 results not only in a decrease in process efficiency but also in degradation of the surface roughness of the produced film due to bubble generation. This may lead to deteriorated electrical, optical and mechanical properties.
Then, the polyimide precursor produced by the polymerization reaction may be imidized by chemical imidization or thermal imidization to prepare a transparent polyimide film. The present invention provides polyimide films formed from polyimide precursors.
According to one embodiment, a polyimide film may be manufactured by a method comprising:
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 which can be easily separated without any treatment with an additional release agent while not damaging a polyimide film formed after curing can be preferable.
The application process may be performed according to a conventional application method. Specifically, spin coating, bar coating, roll coating, air knife, gravure, reverse roll, contact roll, doctor blade, spray coating, dipping, brush coating, and the like can be used. Among them, it is more preferable to conduct by a casting method which allows a continuous process and enables the imidization rate of polyimide to be improved.
In addition, the polyimide precursor composition may be applied to the substrate in a thickness range such that the finally produced polyimide film has a thickness suitable for displaying the 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 performed 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 ℃, the drying process becomes longer. If the drying temperature exceeds 140 ℃, imidization proceeds rapidly, 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 at 25 ℃ and 50% humidity for 3 hours may be 5MPa or less.
The yellowness of the polyimide film may be 15 or less, and is preferably 13 or less. Further, the haze of the polyimide film may be 2% or less, and is 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 a mass loss is 1% may be 500 ℃ or higher.
The polyimide film prepared as described above may have a modulus of 0.1GPa to 4GPa. When the modulus (elastic modulus) is less than 0.1GPa, the film has low rigidity and is easily fragile against external impact. When the modulus exceeds 4GPa, the coverlay film has excellent rigidity, but may not secure sufficient flexibility.
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 variation. For example, after n+1 times of heating and cooling processes (n is an integer of at least 0) in a temperature range of 100 ℃ to 350 ℃, the coefficient of thermal expansion thereof may be-10 ppm/. Degree.C.to 100 ppm/. Degree.C., preferably-7 ppm/. Degree.C.to 90 ppm/. Degree.C., more preferably 80 ppm/. Degree.C.or less.
Further, the retardation (R th ) Can be from-150 nm to +150nm, preferably from-130 nm to+130nm, thereby exhibiting 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.
Further, the present invention provides a flexible device comprising the polyimide film as a substrate.
In one embodiment, the flexible device may be manufactured by a method comprising:
applying a polyimide precursor composition onto a carrier substrate, then heating it to form a polyimide film, and then forming a device on the polyimide film; and
the polyimide film with the device formed thereon is peeled 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 (108.0 g,0.65 mol) and compound 1-2 (73.0 g,0.32 mol) were dissolved in THF (500 mL) and potassium carbonate (135.2 g,0.97 mol) was dissolved in water (250 mL) under nitrogen, then heated to 100deg.C. To the reaction mixture was added tetrakis triphenylphosphine palladium (11.29 g) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then ethyl acetate (250 mL) was added to separate an organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation (BUCHI Rotavapor R-300) to obtain compounds 1-3 (60.3 g, yield 69%).
Preparation of Compounds 1-5
Compounds 1-3 (20.0 g,74.3 mmol) and 1-4 (4.0 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 1-5 (21.5 g, yield 95%).
Preparation of Compound 1
Compound 1-5 (21.5 g,35.3 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 1 (19.0 g, yield 98%).
For C 34 H 22 N 4 O 4 HR LC/MS M/z calculated for (m+): 550.1641; actual measurement value: 550.1639
< synthetic example 2> preparation of Compound 2
Preparation of Compound 2-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 2-1 (9.07 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (24.9 g, yield 90%).
Preparation of Compound 2
Compound 2-2 (24.9 g,33.3 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 2 (21.7 g, yield 95%).
For C 36 H 20 F 6 N 4 O 4 HR LC/MS M/z calculated for (m+): 687.1422; actual measurement value: 687.1420
< synthesis example 3> preparation of Compound 3
Preparation of Compound 3-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 3-1 (5.05 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (21.8 g, yield 92%).
Preparation of Compound 3
Compound 3-2 (21.8 g,34.2 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 3 (19.5 g, yield 99%).
For C 36 H 26 N 4 O 4 HR LC/MS M/z calculated for (m+): 578.1954; actual measurement value: 578.1949
< Synthesis example 4> preparation of Compound 4
Preparation of Compound 4-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 4-1 (6.57 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (22.1 g, yield 88%).
Preparation of Compound 4
Compound 4-2 (22.1 g,32.6 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 4 (16.1 g, yield 80%).
For C 34 H 20 Cl 2 N 4 O 4 HR LC/MS M/z calculated for (m+): 618.0862; actual measurement value: 618.0859
< synthetic example 5> preparation of Compound 5
Preparation of Compound 5-2
Compounds 1-3 (20.0 g,74.3 mmol) and 5-1 (6.57 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (22.9 g, yield 91%).
Preparation of Compound 5
Compound 5-2 (22.9 g,32.6 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 5 (20.0 g, yield 96%).
For C 34 H 20 Cl 2 N 4 O 4 HR LC/MS M/z calculated for (m+): 618.0862; actual measurement value: 618.0860
< Synthesis example 6> preparation of Compound 6
Preparation of Compound 6-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 6-1 (6.24 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (23.6 g, yield 95%).
Preparation of Compound 6
Compound 6-2 (23.6 g,35.3 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 6 (20.8 g, yield 97%).
For C 36 H 26 N 4 O 6 HR LC/MS M/z calculated for (m+): 610.1852; actual measurement value: 610.1851
< Synthesis example 7> preparation of Compound 7
Preparation of Compound 7-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 7-1 (7.88 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (23.6 g, yield 89%).
Preparation of Compound 7
Compound 7-2 (23.6 g,33.0 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 7 (19.9 g, yield 92%).
For C 42 H 30 N 4 O 4 HR LC/MS M/z calculated for (m+): 654.2267; actual measurement value: 654.2264
< Synthesis example 8> preparation of Compound 8
Preparation of Compound 8-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 8-1 (11.8 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (29.3 g, yield 96%).
Preparation of Compound 8
Compound 8-2 (29.3 g,35.6 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250 mL) to obtain compound 8 (24.2 g, yield 89%).
For C 42 H 24 F 6 N 4 O 4 HR LC/MS M/z calculated for (m+): 762.1702; actual measurement value: 762.1700
< synthetic example 9> preparation of Compound 9
Preparation of Compound 9-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 9-1 (11.8 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (250 mL) 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 (29.3 g, yield 96%).
Preparation of Compound 9
Compound 9-2 (29.3 g,35.6 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250 mL) to obtain compound 9 (22.0 g, yield 89%).
For C 40 H 24 Cl 2 N 4 O 4 HR LC/MS M/z calculated for (m+): 694.1175; actual measurement value: 694.1172
< Synthesis example 10> preparation of Compound 10
Preparation of Compound 10-2
Compound 1-3 (20.0 g,74.3 mmol) and compound 10-1 (14.7 g,37.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (32.7 g, yield 98%).
Preparation of Compound 10
Compound 10-2 (32.7 g,36.4 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 10 (27.4 g, yield 90%).
For C 48 H 28 F 6 N 4 O 4 HR LC/MS M/z calculated for (m+): 838.2015; actual measurement value: 838.2011
< Synthesis example 11> preparation of Compound 11
Preparation of Compound 11-3
Compound 11-1 (20 g,85.4 mmol) and compound 1-2 (9.7 g,42.7 mmol) were dissolved in THF (500 mL) and potassium carbonate (11.8 g,85.4 mmol) was dissolved in water (250 mL) under nitrogen, then heated to 100deg.C. To the reaction mixture was added tetrakis triphenylphosphine palladium (1.48 g) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then ethyl acetate (250 mL) 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 (11.5 g, yield 80%).
Preparation of Compound 11-5
Compound 11-3 (11.5 g,34.1 mmol) and compound 11-4 (4.1 g,17.1 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (14.4 g, yield 96%).
Preparation of Compound 11
Compound 11-5 (14.4 g,16.3 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150 mL) to obtain compound 11 (12.7 g, yield 95%).
For C 38 H 18 F 12 N 4 O 4 HR LC/MS M/z calculated for (m+): 822.1136; actual measurement value: 822.1131
< Synthesis example 12> preparation of Compound 12
Preparation of Compound 12-3
Compound 12-1 (30 g,166.6 mmol) and compound 1-2 (25.2 g,111.1 mmol) were dissolved in THF (500 mL) and potassium carbonate (23.0 g,166.6 mmol) was dissolved in water (250 mL) under nitrogen, then heated to 100deg.C. To the reaction mixture was added tetrakis triphenylphosphine palladium (3.84 g) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then ethyl acetate (250 mL) 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 (24.1 g, yield 77%).
Preparation of Compound 12-5
Compound 12-3 (24.1 g,58.4 mmol) and compound 12-4 (13.6 g,42.7 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (32.6 g, yield 90%).
Preparation of Compound 12
Compound 12-5 (32.6 g,38.4 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250 mL) to obtain compound 12 (24.3 g, yield 80%).
For C 44 H 28 F 6 N 4 O 4 HR LC/MS M/z calculated for (m+): 790.2015; actual measurement value: 790.2012
< Synthesis example 13> preparation of Compound 13
Preparation of Compound 13-3
Compound 13-1 (30 g,128.2 mmol) and compound 1-2 (19.4 g,85.4 mmol) were dissolved in THF (500 mL) and potassium carbonate (17.7 g,128.2 mmol) was dissolved in water (250 mL) under nitrogen, then heated to 100deg.C. To the reaction mixture was added tetrakis triphenylphosphine palladium (2.96 g) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then ethyl acetate (250 mL) 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 (22.1 g, yield 77%).
Preparation of Compound 13-5
Compound 13-3 (22.1 g,65.8 mmol) and compound 13-4 (10.5 g,32.9 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (28.9 g, yield 92%).
Preparation of Compound 13
Compound 13-5 (28.9 g,30.2 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250 mL) to obtain compound 13 (25.8 g, yield 95%).
For C 44 H 22 F 12 N 4 O 4 HR LC/MS M/z calculated for (m+): 898.1449; actual measurement value: 898.1444
Synthesis example 14 preparation of Compound 14
Preparation of Compound 14-3
Compound 14-1 (30 g,149.2 mmol) and compound 1-2 (22.5 g,99.5 mmol) were dissolved in THF (500 mL) and potassium carbonate (20.6 g,149.2 mmol) was dissolved in water (250 mL) under nitrogen, then heated to 100deg.C. To the reaction mixture was added tetrakis triphenylphosphine palladium (3.43 g) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then ethyl acetate (250 mL) 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 (26.4 g, yield 88%).
Preparation of Compound 14-5
Compound 14-3 (26.4 g,87.2 mmol) and compound 14-4 (11.0 g,43.6 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (33.4 g, yield 93%).
Preparation of Compound 14
Compound 14-5 (33.4 g,40.5 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 14 (26.9 g, yield 87%).
For C 40 H 22 Cl 4 N 4 O 4 HR LC/MS M/z calculated for (m+): 764.0366; actual measurement value: 764.0363
< Synthesis example 15> preparation of Compound 15
Preparation of Compound 15-3
Compound 15-2 (50.0 g,0.22 mmol) was dissolved in N-methylpyrrolidone (NMP) (500 mL) and compound 15-1 (26.6 g,0.11 mol) was added in several portions, then heated to 140℃and stirred for 6 hours. After the reaction was completed, water (1000 mL) 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 (19.6 g, yield 43%).
Preparation of Compound 15-4
After compound 15-3 (19.6 g,47.7 mmol) was dispersed in glacial acetic acid (300 mL), potassium permanganate (18.8 g,119 mmol) was added at 0deg.C and stirred for 1 hour, then warmed to room temperature and stirred for 6 hours. After the reaction was completed, water (600 mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 15-4 (19.4 g, yield 92%).
Preparation of Compound 15-5
Compound 15-4 (19.4 g,43.7 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150 mL) to obtain compound 15-5 (14.9 g, yield 89%).
Preparation of Compound 15-6
Compounds 15-5 (14.9 g,38.9 mmol) and 1-3 (20.9 g,77.9 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (33.3 g, yield 97%).
Preparation of Compound 15
Compound 15-6 (33.3 g,37.6 mmol) was dissolved in THF (400 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 15 (28.2 g, yield 91%).
C 42 H 24 F 6 SN 4 O 6 HR LC/MS M/z calculated for (m+): 826.1321; actual measurement value: 826.1319
< Synthesis example 16> preparation of Compound 16
Preparation of Compound 16-3
Compound 16-2 (42.7 g,0.25 mmol) was dissolved in NMP (500 mL) and compound 16-1 (30.0 g,0.12 mol) was added in several portions, then heated to 140℃and stirred for 6 hours. After completion of the reaction, water (1000 mL) 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 (20.5 g, yield 54%).
Preparation of Compound 16-4
After compound 16-3 (20.5 g,67.5 mmol) was dispersed in glacial acetic acid (300 mL), potassium permanganate (26.6 g,168.7 mmol) was added at 0deg.C and stirred for 1 hour, then warmed to room temperature and stirred for 6 hours. After the reaction was completed, water (600 mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (200 mL) to obtain compound 16-4 (19.7 g, yield 87%).
Preparation of Compound 16-5
Compound 16-4 (19.7 g,58.6 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150 mL) to obtain compound 16-5 (14.7 g, yield 91%).
Preparation of Compound 16-6
Compound 16-5 (14.7 g,53.3 mmol) and compound 1-3 (28.7 g,106.7 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (39.4 g, yield 95%).
Preparation of Compound 16
Compound 16-6 (39.4 g,50.7 mmol) was dissolved in THF (500 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (350 mL) to obtain compound 16 (33.8 g, yield 93%).
C 42 H 30 SN 4 O 6 HR LC/MS M/z calculated for (m+): 718.1886; actual measurement value: 718.1883
< Synthesis example 17> preparation of Compound 17
Preparation of Compound 17-3
Compound 17-1 (30.0 g,0.13 mol) and compound 17-2 (31.0 g,0.2 mol) were dissolved in Dimethylformamide (DMF) (600 mL) and potassium carbonate was added, followed by heating to 150 ℃. After the reaction was completed, water (1000 mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (350 mL) to obtain compound 17-3 (34.8 g, yield 76%).
Preparation of Compound 17-4
After compound 17-3 (34.8 g,101.3 mmol) was dispersed in glacial acetic acid (400 mL), potassium permanganate (40.0 g,253.3 mmol) was added at 0deg.C and stirred for 1 hour, then warmed to room temperature and stirred for 6 hours. After the reaction was completed, water (800 mL) was added to the reaction mixture and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 17-4 (32.3 g, yield 85%).
Preparation of Compound 17-5
Compound 17-4 (32.3 g,85.9 mmol) was dissolved in THF (300 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, 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 (25.8 g, yield 95%).
Preparation of Compound 17-6
Compound 17-5 (25.8 g,81.6 mmol) and compound 1-3 (43.9 g,163.3 mmol) were added to propionic acid (500 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (500 mL) 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 (58.7 g, yield 88%).
Preparation of Compound 17
Compound 17-6 (58.7 g,71.8 mmol) was dissolved in THF (600 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (500 mL) to obtain compound 17 (50.1 g, yield 92%).
C 41 H 25 F 3 SN 4 O 6 HR LC/MS M/z calculated for (m+): 758.1447; actual measurement value: 758.1443
< Synthesis example 18> preparation of Compound 18
Preparation of Compound 18-2
Compound 18-1 (15.0 g,54.3 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (100 mL) to obtain compound 18-2 (11.0 g, yield 94%).
Preparation of Compound 18-3
Compound 18-2 (11.0 g,51.0 mmol) and compound 1-3 (27.4 g,102.1 mmol) were added to propionic acid (400 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (400 mL) 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 (31.5 g, yield 86%).
Preparation of Compound 18
Compound 18-3 (31.5 g,43.9 mmol) was dissolved in THF (300 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250 mL) to obtain compound 18 (26.5 g, yield 93%).
C 40 H 26 SN 4 O 4 HR LC/MS/MS M/z meter of (M +)Calculating: 658.1675; actual measurement value: 658.1670
< Synthesis example 19> preparation of Compound 19
Preparation of Compound 19-2
Compound 19-1 (15.0 g,49.3 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (110 mL) to obtain compound 19-2 (11.7 g, yield 98%).
Preparation of Compound 19-3
Compound 19-2 (11.7 g,48.3 mmol) and compound 1-3 (26.0 g,96.7 mmol) were added to propionic acid (400 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (400 mL) 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 (34.9 g, yield 97%).
Preparation of Compound 19
Compound 19-3 (34.9 g,46.9 mmol) was dissolved in THF (400 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 19 (27.3 g, yield 85%).
C 42 H 30 SN 4 O 4 HR LC/MS M/z calculated for (m+): 686.1988; actual measurement value: 686.1986
< Synthesis example 20> preparation of Compound 20
Preparation of Compound 20-2
Compound 20-1 (15.0 g,36.4 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (150 mL) to obtain compound 20-2 (12.1 g, yield 95%).
Preparation of Compound 20-3
Compound 20-2 (12.1 g,34.5 mmol) and compound 1-3 (18.6 g,69.1 mmol) were added to propionic acid (300 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (300 mL) 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 (26.5 g, yield 90%).
Preparation of Compound 20
Compound 20-3 (26.5 g,31.1 mmol) was dissolved in THF (300 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (250 mL) to obtain compound 20 (22.4 g, yield 91%).
C 42 H 24 F 6 SN 4 O 4 HR LC/MS M/z calculated for (m+): 794.1422; actual measurement value: 794.1419
Synthesis example 21 preparation of Compound 21
Preparation of Compound 21-2
Compound 21-1 (15.0 g,57.6 mmol) was dissolved in THF (200 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (100 mL) to obtain compound 21-2 (10.6 g, yield 92%).
Preparation of Compound 21-3
Compound 21-2 (10.6 g,53.0 mmol) and compound 1-3 (28.5 g,106.1 mmol) were added to propionic acid (400 mL) under reflux and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (400 mL) 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 (36.1 g, yield 97%).
Preparation of Compound 21
Compound 21-3 (36.1 g,51.4 mmol) was dissolved in THF (300 mL) and Pd/C catalyst was added and then heated to 60 ℃. The reaction mixture was stirred for 4 hours while continuously injecting hydrogen. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered to obtain a solid. The obtained solid was recrystallized from ethanol (300 mL) to obtain compound 21 (29.4 g, yield 89%).
C 40 H 26 N 4 O 5 HR LC/MS M/z calculated for (m+): 642.1903; actual measurement value: 642.1901
Example 1 ]
An organic solvent, DEAc (N, N-diethylacetamide) (100 mL), was charged into the reactor in a nitrogen stream, and then 24.2g (0.031 mol) 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 compound 8 was added, 9.12g (0.031 mol) 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 ]
The organic solvent DEAc (150 mL) was charged into the reactor in a nitrogen stream, and then 33.8g (0.041 mol) of the diamine compound 15 prepared in Synthesis example 15 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 15 was added, 12.1g (0.041 mol) 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 ]
The organic solvent DEAc (150 mL) was charged into the reactor in a nitrogen stream, and then 30.5g (0.040 mol) of the same diamine compound 8 as used in example 1 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 8 was added, 17.7g (0.040 mol) 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 ]
The organic solvent DEAc (200 mL) was charged into the reactor in a nitrogen stream, and then 37.2g (0.045 mol) of the same diamine compound 15 as used in example 2 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 15 was added, 20.0g (0.045 mol) 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 >
The organic solvent DEAc (150 mL) was charged into the reactor in a nitrogen stream, and then 27.8g (0.087 mol) 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 (0.087 mol) 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 >
Organic solvent DEAc (100 mL) was charged into the reactor in a nitrogen stream, and then 22.4g (0.070 mol) 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 (0.070 mol) 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 aryl rings) was used instead 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 aryl rings) was used instead 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 4 was spin-coated on a glass substrate. The glass substrates coated with the respective polyimide precursor solutions were placed in an oven, heated at a rate of 5 deg.c/min, and cured at 80 deg.c for 30 minutes and at 430 deg.c for 30 minutes to prepare respective polyimide films.
< evaluation of polyimide film Properties >
1. Coefficient of thermal expansion (Thermal expansion coefficient, CTE)
Each polyimide film 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 film actually measured is equal to 16mm. The tensile force of the film sample was set to 0.02N. The first temperature increasing step is performed from 100 to 350 ℃ at a heating rate of 5 ℃ per minute, and the cooling step is performed from 350 to 100 ℃ at a cooling rate of 4 ℃ per minute. The change in thermal expansion was measured with TMA (Q400, TA Instruments).
2. Thermal decomposition temperature
The temperature (Td 1%) at which the weight loss of the polyimide film sample was 1% in a nitrogen atmosphere was measured using a thermogravimetric analyzer (TGA) (TGA 8000, perkinelmer).
The CTE and Td1% 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 compositions comprising the novel diamine compound according to the present invention have lower CTE values under the same acid anhydride conditions as those of the polyimide films of comparative examples 1 to 4 prepared by using the diamine compound having a structure different from that of the diamine compound of the present invention. 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 invention has been particularly shown and described with reference to a particular embodiment thereof, it will be apparent to one skilled in the art that the particular description is only 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:
[ 1]
In the above-mentioned formula (1),
l is selected from Is used as a base for the reaction of the amino acid with the hydroxyl group,
Ar 1 and Ar is a group 2 Each independently is
R 1 To R 8 Each independently is hydrogen, a halogen atom, an unsubstituted or halogen atom-substituted alkyl group having 1 to 30 carbon atoms, or an unsubstituted or halogen atom-substituted alkoxy group having 1 to 30 carbon atoms,
R 9 each independently is hydrogen, a halogen atom, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 30 carbon atoms,
y is selected from
l, m, n, o, p, q, R, s and t are each an integer of 0 to 4, and when l, m, n, o, p, q, R, s and t are integers of 2 to 4, R 1 To R 9 The same or different.
2. The diamine compound according to claim 1, whereinL in the formula 1 is selected fromIs used as a base for the reaction of the amino acid with the hydroxyl group,
Ar 1 and Ar is a group 2 Each independently is
R 1 To R 8 Each independently is 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,
R 9 is a halogen atom, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms,
y is selected fromAnd
l, m, n, o, p, q, r, s and t are each integers from 0 to 2.
3. The diamine compound of claim 1, wherein L in formula 1 is phenylene that is unsubstituted or substituted with one or more substituents selected from trifluoromethyl, methyl, chloro (Cl), and methoxy; biphenylene unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chloro (Cl); an unsubstituted or trifluoromethyl-substituted terphenylene group; divalent radicals of bis (trifluoromethylphenyl) sulfone, divalent radicals of bis (methylphenyl) sulfone, { (trifluoromethylphenyl) sulfonyl } benzene, divalent radicals of diphenyl sulfide, divalent radicals of bis (methylphenyl) sulfide, divalent radicals of bis (trifluoromethylphenyl) sulfide or divalent radicals of diphenyl ether,
Ar 1 And Ar is a group 2 Each independently is phenylene that is unsubstituted or substituted with one or more substituents selected from methyl, trifluoromethyl and chloro,
l is an integer of 0 to 2
m, n, o, p, q, r, s and t are each integers of 0 or 1.
4. The diamine compound of claim 1, wherein the diamine compound of formula 1 is selected from the group consisting of compounds of the following structural formulas 1 to 21:
。
5. a polyimide precursor prepared by polymerizing the diamine compound according to any one of claims 1 to 4 and at least one polymeric component of acid dianhydride.
6. The polyimide precursor of claim 5, wherein the acid dianhydride is biphenyl-tetracarboxylic dianhydride, 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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| CN105683155A (en) * | 2013-10-23 | 2016-06-15 | 日产化学工业株式会社 | Novel diamine, polyamic acid, and polyimide |
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