CN101563395A - Polyimide, diamine compound and method for producing the same - Google Patents
Polyimide, diamine compound and method for producing the same Download PDFInfo
- Publication number
- CN101563395A CN101563395A CNA2007800464894A CN200780046489A CN101563395A CN 101563395 A CN101563395 A CN 101563395A CN A2007800464894 A CNA2007800464894 A CN A2007800464894A CN 200780046489 A CN200780046489 A CN 200780046489A CN 101563395 A CN101563395 A CN 101563395A
- Authority
- CN
- China
- Prior art keywords
- biphenyl
- general formula
- ester
- reaction
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 diamine compound Chemical class 0.000 title claims abstract description 177
- 229920001721 polyimide Polymers 0.000 title claims abstract description 128
- 239000004642 Polyimide Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 44
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 24
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 150
- 150000002148 esters Chemical class 0.000 claims description 130
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 63
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 44
- 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 41
- 239000003513 alkali Substances 0.000 claims description 38
- 239000004305 biphenyl Substances 0.000 claims description 32
- 235000010290 biphenyl Nutrition 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 18
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 14
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- HVSDTPCELAXJRF-UHFFFAOYSA-N phenyl 4-(4-phenoxycarbonylphenyl)benzoate Chemical compound C=1C=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HVSDTPCELAXJRF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 7
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical group SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 2
- RYKPVSKKEUSVAM-UHFFFAOYSA-N bis(2-nitrophenyl) 3-phenylbenzene-1,2-dicarboxylate Chemical compound [O-][N+](=O)C1=CC=CC=C1OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(=O)OC1=CC=CC=C1[N+]([O-])=O RYKPVSKKEUSVAM-UHFFFAOYSA-N 0.000 claims 2
- IANDZFLKFYOHTK-UHFFFAOYSA-N (2-chlorophenyl) 4-[4-(2-chlorophenoxy)carbonylphenyl]benzoate Chemical compound ClC1=CC=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C(=CC=CC=2)Cl)C=C1 IANDZFLKFYOHTK-UHFFFAOYSA-N 0.000 claims 1
- UIZIZIPEEWDBCL-UHFFFAOYSA-N (4-aminophenyl) 4-[4-(4-aminophenoxy)carbonylphenyl]benzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC(N)=CC=2)C=C1 UIZIZIPEEWDBCL-UHFFFAOYSA-N 0.000 claims 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 100
- 239000000243 solution Substances 0.000 description 81
- 239000000203 mixture Substances 0.000 description 63
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 56
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 50
- 239000007787 solid Substances 0.000 description 49
- 238000002360 preparation method Methods 0.000 description 46
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- 229920005575 poly(amic acid) Polymers 0.000 description 37
- 239000002904 solvent Substances 0.000 description 35
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 34
- 239000000047 product Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000002243 precursor Substances 0.000 description 29
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 25
- 238000001035 drying Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 230000032050 esterification Effects 0.000 description 20
- 238000005886 esterification reaction Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 15
- 239000012530 fluid Substances 0.000 description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 150000001408 amides Chemical class 0.000 description 14
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 13
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 13
- 238000013019 agitation Methods 0.000 description 13
- 150000002170 ethers Chemical class 0.000 description 13
- 239000005357 flat glass Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical group [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000007766 curtain coating Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 12
- 230000008961 swelling Effects 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical class ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 10
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 10
- 239000012312 sodium hydride Substances 0.000 description 10
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- 206010013786 Dry skin Diseases 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 235000013877 carbamide Nutrition 0.000 description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 9
- 238000004445 quantitative analysis Methods 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 9
- 150000003672 ureas Chemical class 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 125000001246 bromo group Chemical group Br* 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 229940059260 amidate Drugs 0.000 description 7
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 6
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 6
- 150000008046 alkali metal hydrides Chemical class 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000007429 general method Methods 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 5
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 5
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical class OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QMMRPSGUDDHQOK-UHFFFAOYSA-N C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(O)=O)C=C1 Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(O)=O)C=C1 QMMRPSGUDDHQOK-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 229910000103 lithium hydride Inorganic materials 0.000 description 4
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 4
- 125000006501 nitrophenyl group Chemical group 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 3
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910000105 potassium hydride Inorganic materials 0.000 description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001409 amidines Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- RZBACTHRRHJDGC-UHFFFAOYSA-N phenyl 4-[4-(4-aminophenoxy)carbonylphenyl]benzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC=CC=2)C=C1 RZBACTHRRHJDGC-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- IIQLVLWFQUUZII-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxyphenyl)benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1C1=CC=C(N)C(C(O)=O)=C1 IIQLVLWFQUUZII-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- GTKIGDZXPDCIKR-UHFFFAOYSA-N 2-phenylbenzamide Chemical class NC(=O)C1=CC=CC=C1C1=CC=CC=C1 GTKIGDZXPDCIKR-UHFFFAOYSA-N 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- VILWHDNLOJCHNJ-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfanylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1SC1=CC=C(C(O)=O)C(C(O)=O)=C1 VILWHDNLOJCHNJ-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- VVDCZOHBKQQLMH-UHFFFAOYSA-N 4-(4-amino-3,5-diethylphenyl)-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(C=2C=C(CC)C(N)=C(CC)C=2)=C1 VVDCZOHBKQQLMH-UHFFFAOYSA-N 0.000 description 1
- VLZIZQRHZJOXDM-UHFFFAOYSA-N 4-(4-amino-3-ethylphenyl)-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(C=2C=C(CC)C(N)=CC=2)=C1 VLZIZQRHZJOXDM-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- AQVOMFPTJXMAQE-UHFFFAOYSA-N 4-propylphthalic acid Chemical compound CCCC1=CC=C(C(O)=O)C(C(O)=O)=C1 AQVOMFPTJXMAQE-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
公开了一种通过使四羧酸组分与二胺组分反应所获得的聚酰亚胺，所述二胺组分含由以上通式(1)表示的二胺化合物(在式中，A表示可以被含4个以下的碳原子的烷基取代的亚联苯基)。
Disclosed is a polyimide obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the above general formula (1) (in the formula, A represents a biphenylene group which may be substituted with an alkyl group having 4 or less carbon atoms).
Description
Technical field
The present invention relates to new polyimide.More specifically, the present invention relates to from the polyimide resin of tetracarboxylic acid component with the diamine components acquisition that contains new diamine compound.In addition, the present invention relates to be particularly suitable for preparing the new diamine compound of polyimide.
Background technology
Because the thermal characteristics and the electrical property of polyimide film excellence, so polyimide film has been widely used in electronics such as flexible printed circuit board, TAB (belt is welded automatically) usefulness band etc.Especially, known from respectively as 3,3 ', 4 of tetracarboxylic acid component and diamine components, 4 '-biphenyl tetracarboxylic dianhydride and Ursol D obtain Young's modulus height and the low polyimide of coefficient of linear expansion.
In the use of flexible printed circuit board, TAB etc., the dimensional stability of the polyimide that requirement will be used.For example, when the difference between the thermal expansivity of the thermal expansivity of film and copper becomes big, take place to curl and precision machining decline, therefore be difficult to the accurate installation of electron gain element.In addition, because wiring diagram forms by etching lamination Copper Foil, so the problem that the precision machining of the wiring diagram that expansion that existence causes owing to absorbing water and the dry contraction that causes cause and installation accuracy are lowered.Consider from these problems, except thermal expansivity, also require the suction polyimide film that per-cent is low and the wet swelling coefficient is low.
As the polyimide that shows low water absorbable and low hygro-expansivity, Japanese publication announces that H11-199668 (patent documentation 1) discloses based on comprising by H
2N-Ph-OCO-X-COO-Ph-NH
2The diamine components of the diamine compound of (at this, X is a phenylene) expression and the polyimide structures of tetracarboxylic acid component.Yet according to the inspection that the inventor did, when X represented phenylene, suction per-cent and wet swelling coefficient remained not enough.In addition, because in the use of flexible printed circuit board, apply vibration or crooked repeatedly, so except breaking tenacity, also need elongation at break.Yet, demonstrate elongation at break based on the polyimide of above-mentioned diamine compound and greatly reduced.In addition, in patent documentation 1, exemplify other group, but this patent documentation does not show that from X wherein be the effect of the polyimide that diamine components obtained of the group except that phenylene as X.
Patent documentation 1: Japanese publication is announced H11-199668
Summary of the invention
The problem to be solved in the present invention
An object of the present invention is to provide the suction polyimide material that per-cent is low and the wet swelling coefficient is low.Especially, an object of the present invention is to provide and significantly do not reducing under the situation of elongation at break, the polyimide material that suction per-cent and wet swelling coefficient reduce.
In addition, the purpose of another aspect of the present invention provides new diamine compound, and this diamine compound is used as the raw material that is used to prepare the polyimide with these character.
The means of dealing with problems
The present invention relates to following project.
1. one kind by making tetracarboxylic acid component and diamine components react resulting polyimide, and described diamine components contains the diamine compound by following general formula (1) expression:
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most.
2. according to above-mentioned project 1 described polyimide, wherein said tetracarboxylic acid component comprises 3, and 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, and described 3,3 ', 4, the amount of 4 '-biphenyl tetracarboxylic dianhydride is that 10 moles of all tetracarboxylic acid components are more than the %.
3. according to above-mentioned project 1 or 2 described polyimide, wherein the described diamine compound by above-mentioned general formula (1) expression comprises the compound of being represented by following formula (1a):
4. polyimide film, described polyimide film comprises according to each the described polyimide in the above-mentioned project 1 to 3.
5. diamine compound by general formula (1) expression:
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most.
6. by the biphenyl-4 of following formula (1a) expression, 4 '-dicarboxylic acid two (4-aminophenyl) ester:
7. method that is used for preparation according to the described diamine compound by general formula (1) expression of above-mentioned project 5 said method comprising the steps of:
Make biphenyl two carbonyl halide derivatives by general formula (2) expression:
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most; And X represents halogen atom,
React in the presence of alkali with nitrophenols, prepare biphenyl-dicarboxylic acid two (nitrophenyl) ester thus by general formula (3) expression:
And
Biphenyl-dicarboxylic acid two (nitrophenyl) ester of the above-mentioned general formula of reason (3) expression also.
8. method that is used for preparation according to the described diamine compound by general formula (1) expression of above-mentioned project 5 said method comprising the steps of:
Make biphenylyl carbonyl derivative by general formula (21) expression:
Wherein, A has the implication identical with above-mentioned definition; And LG be can with the leavings group of amino-benzene oxygen exchange,
React in the presence of alkali with amino-phenol.
9. according to the above-mentioned project 8 described methods that are used to prepare diamine compound, wherein above-mentioned general formula (21) is biphenyl-dicarboxylic acid two (aryl) ester cpds by following general formula (22) expression:
Wherein, A has the implication identical with above-mentioned definition; Y represents halogen atom, nitro, trifluoromethyl, cyano group or ethanoyl; And n represents 0 to 3 integer.
10. according to the above-mentioned project 9 described methods that are used to prepare diamine compound, wherein by the biphenyl-4 of above-mentioned general formula (22) expression, 4 '-dicarboxylic acid two (aryl) ester cpds obtains by making following compound reaction:
Biphenyl two carbonyl halide derivatives by general formula (2) expression:
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most; And X represents halogen atom,
Hydroxy aryl compound by general formula (23) expression:
Wherein, Y has the implication identical with above-mentioned definition with n,
And alkali.
11. according to the above-mentioned project 9 described methods that are used to prepare diamine compound, wherein said being reflected under the situation the about hydroxy aryl compound that is produced not being removed from reaction soln carried out.
12. according to the above-mentioned project 9 described methods that are used to prepare diamine compound, wherein said being reflected under the situation that the hydroxy aryl compound that will be produced removes from reaction soln carried out.
13. according to the above-mentioned project 9 described methods that are used to prepare diamine compound, the position of substitution in the aryl moiety of biphenyl-dicarboxylic acid two (aryl) ester cpds of wherein above-mentioned general formula (22) is at least one the position of substitution that is selected from 2,4 and 6.
14. according to the above-mentioned project 9 described methods that are used to prepare diamine compound, wherein Y is the chlorine atom.
15. biphenyl-dicarboxylic acid two (aryl) ester cpds by following general formula (22) expression:
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most; Y represents halogen atom, nitro, trifluoromethyl, cyano group or ethanoyl; And n represents 0 to 3 integer;
Condition is not comprise biphenyl-4,4 '-dicarboxylic acid diphenyl ester, biphenyl-4,4 '-dicarboxylic acid two (2-chloro-phenyl-) ester and biphenyl-4,4 '-dicarboxylic acid two (2-nitrophenyl) ester.
16. according to above-mentioned project 15 described biphenyl-dicarboxylic acid two (aryl) ester cpds, wherein A represents 4,4 '-biphenylene.
17. according to the above-mentioned project 8 described methods that are used to prepare diamine compound, wherein above-mentioned general formula (21) is the biphenyl carbamide compound by general formula (32) expression:
Wherein, A has the implication identical with above-mentioned definition.
18. according to the above-mentioned project 17 described methods that are used to prepare diamine compound, wherein the biphenyl carbamide compound by above-mentioned general formula (32) expression obtains by making following compound reaction: the biphenyl two carbonyl halide derivatives of representing by general formula (2):
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most; And X represents halogen atom,
2-thiazoline-2-mercaptan and
Alkali.
19. biphenyl carbamide compound by general formula (32) expression:
Wherein, A represents to be contained the biphenylene of the alkyl replacement of 4 carbon atoms at the most.
20. according to above-mentioned project 19 described biphenyl carbamide compounds, wherein A represents 4,4 '-biphenylene.
The invention effect
Polyimide excellent heat resistance of the present invention, have low suction per-cent and low linear wet swelling coefficient, and have excellent size stability.Especially, because contain the compound of above-mentioned formula (1) in the raw material diamine components,, easily obtained the low and low polyimide of linear wet swelling coefficient of suction per-cent so significantly do not reducing under the situation of elongation at break.Therefore, polyimide of the present invention can be used for TAB film, electronic component plate, running board etc. suitably.
In addition, according to the present invention, can provide new diamine compound and preparation method thereof as the raw material of the polyimide that is used for the processability excellence.
Implement best mode of the present invention
The present invention relates to the polyimide that diamine components by making the diamine compound that contains formula (1) and tetracarboxylic acid component reaction are obtained.
In formula (1), A can have one or more substituent biphenylenes, and preferably by 4 of formula (A1) expression, 4 '-biphenylene:
At this, n and m are illustrated respectively in the number of substituent R on each ring, and represent 0,1,2,3 or 4 respectively independently, and when n and m are 0, and it is unsubstituted 4 that the compound of formula (A1) is represented, 4 '-biphenylene.R represents to contain the alkyl of 4 carbon atoms at the most, and preferable methyl, ethyl, propyl group etc.If R occurs in formula (A1) more than once, then each R has the implication identical with above-mentioned definition independently of each other.A is preferably by formula (A2), (A3), (A4) or (A5) biphenylene of expression, and most preferably by the group of formula (A2) expression,
Wherein, R has the implication identical with above-mentioned definition.
End-the NH of formula (1) compound
2Base combines in ortho position, a position or contraposition with respect to-O-base with phenylene.Preferably, the end-NH of formula (1) compound
2Base combines in the contraposition with respect to-O-group with phenylene.
The diamine components that is used to prepare polyimide of the present invention comprises the diamine compound of formula (1), thereby the suction per-cent of polyimide is reduced.Depend on embodiment, at described diamine compound is under the situation of 100 moles of %, and the ratio that the diamine compound of formula (1) can be involved is that 5 moles of % are above, 10 moles % is above, preferred 30 moles of % are above, more preferably 50 moles of % are above, also preferred 60 moles of % are above and further preferred 70 moles more than the %.In particular aspects, this content can be 100 moles of %.
In addition, as what in following APBP unit, exemplified with description, depend on embodiment, at component units is under the situation of 100 weight %, and the ratio of the weight % that the component units of being made up of the diamine components of acid dianhydride component and formula (1) can be involved is that 5 weight % are above, 15 weight % are above, preferred 40 weight % are above, more preferably 50 weight % are above, 60 weight % are above, also more than the preferred 70 weight % and more than the 80 weight %.In particular aspects, it can be 100 weight %.
Except the diamine compound of formula (1), diamine components can contain one or more the diamine compound that is different from formula (1) diamine compound.The example of diamine compound comprises: Ursol D, mphenylenediamine, 4,4 '-diamino diphenyl propane, 4, the 4-diaminodiphenylmethane, p-diaminodiphenyl, 3,3 '-dichlorobenzidine, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl oxide (oxydianiline), 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino, two styroyl phosphine oxides, 1,4-diaminobenzene (Ursol D), 1,4-diaminobenzene (Ursol D), two { 4-(4-amino-benzene oxygen) phenyl } sulfone, two { 4-(3-amino-benzene oxygen) phenyl } sulfone, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 1,3-two (3-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,4-two (4-amino-benzene oxygen) benzene, 1,4-two (3-amino-benzene oxygen) benzene, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone and their analogue.
In addition, the example that is different from the diamine compound of formula (1) diamine compound comprises: 3,3 ', 5,5 '-tetramethyl--4,4 '-benzidine, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenyl oxide, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyl--4,4 '-benzidine, 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenyl oxide, 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane, 4,4-methylene radical-two (2, the 6-diisopropyl aniline), 3,3 '-dicarboxyl-4,4 '-diamino-5,5 '-dimethyl diphenyl methane, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-diethyl-4,4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenyl oxide, 3,3 '-diethyl-4,4 '-diaminodiphenyl oxide, 3,3 '-dihydroxyl-4,4 '-diaminodiphenyl oxide, 3,3 '-dicarboxyl-4,4 '-diaminodiphenyl oxide, 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenyl oxide, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 '-diethyl-4,4 '-diaminodiphenylmethane, 3,3 '-dihydroxyl-4,4 '-diaminodiphenylmethane, 3,3 '-dicarboxyl-4,4 '-diaminodiphenylmethane, 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane etc.
In these diamine compounds, as the preferred diamine compound that uses with the diamine compound of formula (1) of quilt, the example comprises: Ursol D, 4, the 4-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl oxide, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 1,3-two (3-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,4-two (4-amino-benzene oxygen) benzene, 1,4-two (3-amino-benzene oxygen) benzene, 3,3 '-diaminobenzophenone and 4,4 '-diaminobenzophenone.What more preferably use is Ursol D and 4,4 '-diaminodiphenyl oxide.
As the tetracarboxylic acid component, can use known tetracarboxylic anhydride.Tetracarboxylic dianhydride's example comprises the aromatic tetracarboxylic acid dianhydride, such as 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2-two (3,4-dicarboxyl phenyl) propane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, two (3,4-dicarboxyl phenyl) thioether dianhydride, to phenylene two (trimellitic acid monoesters acid anhydride), ethylene (trimellitic acid monoesters acid anhydride), dihydroxyphenyl propane two (trimellitic acid monoesters acid anhydride), 2,2-two (3,4-dicarboxyl phenyl)-1,1,1,3,3, the 3-hexafluoropropane dianhydride, 2,2-two (2,3-dicarboxyl phenyl)-1,1,1,3,3, the 3-hexafluoropropane dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2, { 4-[4-(1 for 2-two, the 2-dicarboxyl) phenoxy group] phenyl } the propane dianhydride, 2,2-two 4-[3-(1, the 2-dicarboxyl) phenoxy group] and phenyl } the propane dianhydride, two { 4-[4-(1, the 2-dicarboxyl) phenoxy group] phenyl } the ketone dianhydride, two { 4-[3-(1, the 2-dicarboxyl) phenoxy group] phenyl } the ketone dianhydride, 4,4 '-two [4-(1, the 2-dicarboxyl) phenoxy group] biphenyl dianhydride, 4,4 '-two [3-(1, the 2-dicarboxyl) phenoxy group] biphenyl dianhydride, two 4-[4-(1, the 2-dicarboxyl) phenoxy group] and phenyl } the ketone dianhydride, two 4-[3-(1, the 2-dicarboxyl) phenoxy group] and phenyl } the ketone dianhydride, two { 4-[4-(1, the 2-dicarboxyl) phenoxy group] phenyl } the sulfone dianhydride, two { 4-[3-(1, the 2-dicarboxyl) phenoxy group] phenyl } the sulfone dianhydride, two 4-[4-(1, the 2-dicarboxyl) phenoxy group] and phenyl } the thioether dianhydride, two 4-[3-(1, the 2-dicarboxyl) phenoxy group] phenyl } the thioether dianhydride etc.
Preferred tetracarboxylic acid component contains 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and/or 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride is 100 moles of % in the tetracarboxylic acid component, described 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and/or 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride can be involved amount be that 10 moles of % are above, preferred 30 moles of % above, more preferably above, above and preferred especially 80 moles of % above (can contain) of preferred 70 moles of % again of 50 moles of % with the amount of 100 moles of %.In addition, the tetracarboxylic acid component can contain other above-mentioned aromatic tetracarboxylic acid dianhydride in the scope of not damaging feature of the present invention.
As the tetracarboxylic acid component, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride is used as main ingredient, obtains the polyimide of breaking tenacity and elongation at break excellence thus.
As mentioned above, polyimide of the present invention obtains by making diamine components and tetracarboxylic acid component reaction.As the preparation method, can adopt known method.For example, polyimide can be by a kind of like this method preparation, and this method comprises: by making tetracarboxylic acid component and diamine components prepared in reaction polyimide precursor in organic solvent, make precursor carry out chemical imidization or hot-imide afterwards; Maybe can be by such method preparation, this method comprises the direct imidization by making tetracarboxylic acid component and diamine components react or directly react in organic solvent.
As the preparation method of polyimide and polyimide precursor, can use all known methods.Usually can prepare polyimide precursor by following steps: in organic solvent, (any is preferably 100 moles of % in the component with equimolar amount basically or with any excessive amount in tetracarboxylic dianhydride or the diamine components to make tetracarboxylic dianhydride and diamines, and another kind of component is preferably 100 to 110 moles of %, more preferably 100 to 107 moles of % and preferred again 100 to 105 moles of %) reaction, and under the condition of controlled temperature, stir these materials and finish until the polyreaction (almost) of tetracarboxylic dianhydride and diamines.Usually can obtain concentration is the polyimide precursor solution of 1 to 35 weight %, preferred 5 to 30 weight % and further preferred 7 to 25 weight %.In this concentration range, can obtain suitable molecular weight and suitable soltion viscosity.
Because in the diamine compound of formula (1), the A in the formula is a biphenylene, so the solvability of this diamine components is extremely low, and is that the compound that routinizes of phenylene is compared with A wherein, and described diamine compound almost can't synthesize.Yet, as following with shown in the embodiment that describes, unexpectedly, when the diamine compound of formula (1) and tetracarboxylic acid component reaction, easily obtain to have the polyimide precursor solution of suitable viscosity and good preservation stability, therefore can easily prepare film.
As the polymerization process of polyimide precursor, can use known method.
Be used in diamine components that polyimide precursor is provided and tetracarboxylic dianhydride in 0 to 100 ℃, preferred 5 to 50 ℃ temperature polymerization in organic solvent, with preparation polyimide precursor solution (as long as maintenance homogeneous solution state, can also be with its part imidization), and if desired, a plurality of polyimide precursor solution are mixed, and resulting mixing solutions is coated with to become to film or form film, then with film drying, imidization and heat drying (curing), thereby can prepare polyimide.The maximum heating temperature that is used for heat drying preferably in 350 to 600 ℃ scope, more preferably in 400 to 550 ℃ scope, and particularly preferably in 400 to 500 ℃ the scope.
As the method for preparing polyimide precursor, can use known method.The example comprises:
Method 1), that is, carboxylic acid dianhydride component and diamine components are reacted separately in organic solvent with equimolar amount, maybe can depend on condition, under the situation of excessive acid or diamines, react; With
Method 2), that is, make the carboxylic acid dianhydride component and react in organic solvent with equimolar amount basically separately, with preparation polyimide precursor solution A by the diamine components of general formula (1) expression; The diamine components that makes the carboxylic acid dianhydride component simultaneously and be different from diamines shown in the general formula (1) is reacted in organic solvent with equimolar amount basically respectively, with preparation polyimide precursor solution B; And, polyimide precursor solution A and B can be mixed, and if desired, further polymerization.In the method, depend on condition, in them one can contain excessive acid and another can contain excessive diamines.
When need be with the amine end-capped of polyimide precursor, can add dicarboxylic acid dianhydride, for example Tetra hydro Phthalic anhydride and substitution compound thereof (for example 3-methylphthalic acid acid anhydride or 4-methylphthalic acid acid anhydride), hexahydrophthalic anhydride and substitution compound, succinyl oxide and substitution compound thereof etc.For example, can add the small amounts of ortho phthalate anhydride.
In addition, the purpose for promoting imidization can add imidization reagent in polyimide precursor solution.For example, based on polyimide precursor, can use imidazoles, 1-Methylimidazole, glyoxal ethyline, 1,2 dimethylimidazole, 2-phenylimidazole, benzoglyoxaline, isoquinoline 99.9, substituted pyridines etc. with the ratio of 0.05 to 10 quality % and particularly 0.1 to 2 quality %.By using these compounds, can under low relatively temperature, finish imidization.
In polyimide of the present invention, carboxylic acid dianhydride component and specific diamine components can have block structure or random structure.
In order to prepare film by polyimide of the present invention, for the purpose of the gelation that suppresses film, can be in the polymerization process of polyamic acid, based on solids component (polymkeric substance) concentration, add the phosphorus stabilizer agent in 0.01 to 1% scope, for example triphenyl phosphite, triphenylphosphate etc.
The example that is used to prepare the organic solvent of polyimide precursor comprises: N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N,N-dimethylacetamide, N, N-diethyl acetamide, methyl-sulphoxide, hexamethylphosphoramide, N-methyl caprolactam etc.These organic solvents can be used alone or in combination use of two or more.
Polyimide of the present invention can prepare the film with following feature:
1) suction per-cent is below 1.3%, and the coefficient of wet swelling simultaneously is preferably below the 10ppm;
2) suction per-cent is below 1.0% and preferred below 0.9%, and the wet swelling coefficient is below the 7ppm; Or
3) suction per-cent is below 0.7%, and the coefficient of wet swelling simultaneously is preferably below the 5ppm.
In addition, polyimide of the present invention can prepare except having above-mentioned feature, also has elongation at break and be more than 12%, preferred more than the 14% and more preferably film more than 15%.
Polyimide of the present invention can or be used for film (using pin tenter with uncured film thermal treatment and stretching fully) as the coating agent.
When polyimide of the present invention was used for film, the thickness of film was about 3 to 200 μ m, and maybe when it was applied as the coating agent, its thickness was about 0.1 to 2 μ m.
In addition, polyimide of the present invention can also be used for the modified polyimide as the top layer on the sandwich layer that the heat resistant poly imide is constituted.In this case, the polyimide precursor solution curtain coating that is used to provide the polyimide sandwich layer that is made of the heat resistant poly imide is to carrier, and is dry then to form self-supported membrane.On the one side, coating or spray and of the present inventionly be used to provide the polyimide precursor solution of polyimide so that dried thickness is about 0.1 to 2 μ m, and carry out drying, if desired, on opposite side, coating or spray this polyimide precursor solution so that dried thickness is about 0.1 to 2 μ m and is carried out drying.Heat resulting material to remove solvent and imidization, if desired, carry out heat drying (curing), thereby can prepare the lamination polyimide film that at least a side has been carried out modification at 350 to 600 ℃ maximum heating temperatures.This lamination polyimide film has the thickness of preferred about 5 to 150 μ m and preferred especially about 10 to 125 μ m.
The example of the polyimide in the heat resistant poly imide layer of lamination polyimide film can comprise:
I) polyimide that obtains by following steps: will be by 3 of 7.5 to 100 moles of %, 3 ', 4, aromatic tetracarboxylic acid dianhydride's component that the pyromellitic dianhydride of 4 '-biphenyl tetracarboxylic dianhydride and 0 to 92.5 mole of % is formed and by 4 of the Ursol D of 15 to 100 moles of % and 0 to 85 mole of %, diamine components polymerization and imidization that 4 '-diaminodiphenyl oxide is formed, and if desired, carry out heat drying (curing) at 350 to 600 ℃ maximum heating temperature;
The ii) polyimide that obtains by following steps: with the acid constituents and 4 of pyromellitic dianhydride, the diamine components polymerization and the imidization of 4 '-diaminodiphenyl oxide and Ursol D, wherein said 4,4 '-diaminodiphenyl oxide and Ursol D ratio (mol ratio) are 90/10 to 10/90, and if desired, carry out heat drying (curing) at 350 to 600 ℃ maximum heating temperature; And
The iii) polyimide that obtains by following steps: will have 3 of 7.5 to 100 moles of %, 3 ', 4, the aromatic tetracarboxylic acid dianhydride of the pyromellitic dianhydride of 4 '-biphenyl tetracarboxylic dianhydride and 0 to 92.5 mole of % and contain ortho-tolidine or-the diamine components polymerization and the imidization of tolidine, and if desired, carry out heat drying (curing) at 350 to 600 ℃ maximum heating temperature.
By compacting or pressurized, heated (laminating method) at least one side of polyimide of the present invention and base material directly or via tackiness agent are carried out lamination, they being formed layered product, thereby can prepare the layered product that at least one side of polyimide of the present invention, has base material.
Use film forming method and electrochemical plating at least one side of polyimide of the present invention, to form the metal tunic, thereby can prepare layered product.
In addition, can chemically or by heat drying finish imidization then, thereby also can obtain layered product with the polyimide precursor solution curtain coating that is used to polyimide of the present invention is provided to base material such as tinsel etc.
Polyimide of the present invention can form laminated film.Afterwards, directly or via compressed with adhesive or pressurized, heated (laminating method) polyimide layer of the present invention and base material with they laminations, thereby can prepare the layered product that on the one side, has base material at least.
Can use film forming method and electrochemical plating on that side of the polyimide layer of the present invention of lamination polyimide film, to form the metal tunic, can prepare layered product thus.
In laminating method, on the one or both sides of polyimide film of the present invention, form the thermotolerance binder layer, and tinsel is placed (piling up) thereon, hot pressing then can obtain layered product thus.
The thermotolerance tackiness agent is not particularly limited, as long as it is the thermotolerance tackiness agent that uses, and can exemplify polyimide adhesive, epoxide modified polyimide adhesive, phenolic resin modified epoxy resin binder, epoxide modified acrylic adhesive, epoxide modified polyamide binder etc. in electronic applications.This thermotolerance binder layer itself can form by any method that can use in electronic applications.For example, binder solution can be applied on above-mentioned polyimide film or the formed product, and dry.As selection, the binder for film formation that can use independent formation is with they laminations.
As base material, can exemplify single metal or alloy such as copper, aluminium, gold and silver, nickel or stainless tinsel, metal plating (can use many known technologies suitably) etc. such as metal deposition basic unit-metal plating, chemical metal plating etc.Its preferred embodiment comprises rolled copper foil, electrolytic copper foil, copper coating etc.Thickness to tinsel is not particularly limited, and preferred 0.1 μ m to 10mm, more preferably 1 to 50 μ m and preferred especially 5 to 18 μ m.
Can also this layered product further be adhered on other base material by using the thermotolerance tackiness agent, for example, pottery, glass baseplate, silicon wafer, or the product of similar or different metal formation, polyimide film etc.
According to suitable embodiment of the present invention, because the suction per-cent of polyimide film is little, so, on adhesive interface, also can take place hardly to bubble or peel off even at the layered product of high temperature as 280 ℃ this films of processing use such as deposite metal bath.
Polyimide film of the present invention or have at least the layered product of one deck polyimide of the present invention can be used as suitably TAB with film, electronic component with plate and running board.It can be used as for example printed circuit board (PCB), electric power circuit plate, flexible heater and resistor plate suitably.In addition, it is used in the low material of coefficient of linear expansion such as LSI and goes up the insulating film that forms, protective membrane etc. with base material etc.
The diamine compound that various details is new.
Diamine compound of the present invention is the compound by following formula (1) expression:
In formula (1), A can have substituent biphenylene and preferably by 4 of formula (A1) expression, 4 '-biphenylene:
Wherein, n and m are illustrated respectively in the number of substituent R on each ring, and represent 0,1,2,3 or 4 respectively independently, and when n and m are 0, and it is unsubstituted 4 that the compound of formula (A1) is represented, 4 '-biphenylene.R represents to contain the alkyl of 4 carbon atoms at the most, and is preferably methyl, ethyl, propyl group etc.If R occurs in formula (A1) more than once, then each R has the implication identical with above-mentioned definition independently of each other.A is preferably by formula (A2), (A3), (A4) or (A5) biphenylene of expression, and most preferably is the group by formula (A2) expression,
Wherein, R has the implication identical with above-mentioned definition.
End-the NH of formula (1) compound
2Base combines in ortho position, a position or contraposition with respect to-O-group with phenylene.Preferably, the end-NH of formula (1) compound
2Base combines in the contraposition with respect to-O-group with phenylene.
The diamine compound of formula of the present invention (1) expression is preferably the biphenyl-4 by following formula (1a) expression, 4 '-dicarboxylic acid two (4-aminophenyl) ester.
This compound can be used as the raw material of aforesaid polyimide.In addition, this compound can also be as the raw material of polymeric amide etc.This compound is new, and it exists and the preparation method is unknown fully.
In preparation method I and preparation method II, the preparation method of formula (1) compound will be described based on the difference of reaction process respectively.
First preparation method (preparation method I)
Compound that can synthesis type as follows (1).That is, the diamine compound of formula (1) can be by making the biphenyl two carbonyl halide derivatives shown in the general formula (2):
(wherein, A has the implication identical with top description; And X represents halogen atom.)
React in the presence of alkali with nitrophenols, to prepare biphenyl-dicarboxylic acid two (nitrophenyl) ester by general formula (3) expression:
, and go back biphenyl-dicarboxylic acid two (nitrophenyl) ester of reason general formula (3) expression subsequently.
With reference to biphenyl-4, synthesizing of 4 '-dicarboxylic acid two (4-aminophenyl) ester describes in further detail reaction of the present invention.Yet, also can synthesize the compound that group A wherein represents other group in an identical manner.As shown in reactions steps formula (1), reaction of the present invention comprises two reactions steps, i.e. (A) esterification and (B) reduction reaction.
Reactions steps formula (1)
(wherein, X has the implication identical with above-mentioned definition.)
This two reactions will be described successively.
(A) esterification
Esterification is meant by making the reaction of biphenyl two carbonyl halides and 4-nitrophenols to obtain biphenyl-4, the reaction of 4 '-dicarboxylic acid two (4-nitrophenyl) ester.Biphenyl two carbonyl halides that are used are represented by above-mentioned general formula (2), and are preferably biphenyl-4,4 '-two carbonyl halides.The example of the halogen atom of being represented by X comprises fluorine atom, chlorine atom, bromine atoms and iodine atom.What preferably use is chlorine atom and bromine atoms.
As the alkali that uses in esterification, what can exemplify has an alkalimetal hydride, as sodium hydride, potassium hydride KH, lithium hydride etc.; Alkali metal hydroxide or alkaline earth metal hydroxides are as sodium hydroxide, potassium hydroxide, calcium hydroxide etc.; Alkaline carbonate or alkaline earth metal carbonate are as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, lime carbonate etc.; Alkali metal hydrocarbonate or alkali metal bicarbonates are as sodium bicarbonate, saleratus, Calcium hydrogen carbonate etc.; Amine is as triethylamine, Diisopropylamine, n-Butyl Amine 99, N-methyl piperidine, N-methylmorpholine etc.; And pyridines, as pyridine, lutidine etc.Preferred what use is alkalimetal hydride, alkaline carbonate, amine and pyridines, and what more preferably use is sodium hydride, yellow soda ash, triethylamine and pyridine.These alkali can be used alone or in combination use of two or more.
Based on 1 mole biphenyl, two carbonyl halides, the amount of employed alkali is preferably 1 to 10 mole and more preferably 1.5 to 5.0 moles.
Based on 1 mole biphenyl, two carbonyl halides, the amount of employed 4-nitrophenols is preferably 1 to 10 mole and more preferably 1.5 to 5.0 moles in esterification.
Esterification is preferably carried out in the presence of organic solvent.As the solvent that is used, it is not particularly limited, as long as it can not hinder reaction, what can exemplify has an ethers, as diethyl ether, diisopropyl ether, diox, glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF) etc.; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.; Ureas, as N, N '-dimethyl-2-imidazolone etc.; Nitrile is as acetonitrile, propionitrile, benzonitrile etc.; Ketone is as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; Aromatic hydrocarbons is as benzene,toluene,xylene, cumene etc.; And halogenation aliphatic hydrocrbon such as methylene dichloride, ethylene dichloride etc.Preferred what use is ethers, amides, nitrile and ketone, and what more preferably use is ethers and amides.These solvents can be used alone or in combination use of two or more.
According to the degree of uniformity of reaction soln or the state of stirring, suitably adjust the amount of the above-mentioned solvent that will use, and based on 1g biphenyl two carbonyl halides, the amount of described solvent is preferably 1 to 100ml and more preferably 10 to 80ml.
Esterification is by for example wherein biphenyl two carbonyl halides, 4-nitrophenols and alkali being mixed, and the method that can stir these materials is carried out.Temperature of reaction in reaction process is preferably 0 to 200 ℃ and more preferably 10 to 100 ℃, and reaction pressure is not particularly limited.
After reaction is finished, by general method for example as extraction, filter, concentrate, recrystallization, column chromatography etc. are resulting biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester separates and purifying.As selection, can be under the condition of it not being separated with purifying, with prepared biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester is used for following reduction reaction.
(B) reduction reaction
Reduction reaction is meant that by reduction biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester is to obtain biphenyl-4, the reaction of 4 '-dicarboxylic acid two (4-aminophenyl) ester.This reduction reaction is not particularly limited, as long as it is to comprise nitro is converted into amino method, and preferable methods is included in the existence time of metal catalyst and the reaction of hydrogen.Atoms metal can comprise as used herein, for example nickel, palladium, platinum, rhodium, ruthenium, cobalt, copper etc.Atoms metal can use or use with the state of metal oxide according to original state.In addition, can also use with the form that loads on carrier such as carbon, barium sulfate, silica gel, aluminum oxide, the diatomite etc., and nickel, cobalt, copper etc. can also be used as Raney catalyst according to the atoms metal of original state or metal oxide.
Based on biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester, the above-mentioned catalyzer that is used is preferably 0.01 to 10 quality % and more preferably 0.05 to 5 quality % according to the amount of atoms metal meter.At this, these metal catalysts can be used alone or in combination use of two or more, and they can be the product done or wet product.
Based on 1 mole biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester, the amount of the hydrogen that uses in this reaction is preferably 1 to 20 mole and more preferably 4 to 10 moles.At this, can use the gas of reactionlessness such as nitrogen, argon etc. diluted in hydrogen.
Reduction reaction is preferably carried out in the presence of solvent.To as the solvent that will use, it is not particularly limited, as long as it can not hinder reaction, what can exemplify has water; Alcohols is as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol etc.; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.; Ureas, as N, N '-dimethyl-2-imidazolone etc.; And ethers, as diethyl ether, diisopropyl ether, tetrahydrofuran (THF) etc.Preferred what use is alcohols and amides, and that more preferably use is N, dinethylformamide, N,N-dimethylacetamide and N-N-methyl-2-2-pyrrolidone N-.These solvents can be used alone or in combination use of two or more.
Depend on the degree of uniformity of reaction soln or the state of stirring, suitably adjust the amount of the above-mentioned solvent that will use, and based on 1g biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester, the amount of described solvent is preferably 1 to 100ml and more preferably 5 to 50ml.
Reduction reaction by for example wherein in the presence of metal catalyst with biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester and solvent, and these materials are carried out with the method for H-H reaction when stirring.Temperature of reaction in the reaction process is preferably 0 to 200 ℃ and more preferably 10 to 100 ℃, and reaction pressure is preferably 0.1 to 20MPa and more preferably 0.1 to 5MPa.This reaction can be undertaken or carry out in the reaction vessel of sealing by allowing to flow.If hydrogen is allowed to flow, then according to the size of the capacity of reaction mixture or reaction vessel and suitably regulate the flow of hydrogen.
After reaction is finished, by general method for example as extraction, filter, concentrate, recrystallization, column chromatography etc. are resulting biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester separates and purifying.
Second preparation method (preparation method II)
Second preparation method of the diamine compound of formula (1) expression is shown.In this preparation method, above-mentioned general formula (1):
Be by making the biphenylyl carbonyl derivative of general formula (21) expression:
(wherein, A is with top described identical; And LG is the matrix of leaving away.)
React in the presence of alkali with amino-phenol and obtain.
Amino-phenol is preferably the 4-amino-phenol.In addition, in formula (21), leavings group LG can be can with the amino-benzene oxygen in the amino-phenol:
The group of exchange.LG is preferably the group that can contain substituent phenoxy group and be represented by following formula (31):
To describe these situations in detail below.
Preparation method II-1
(LG can contain substituent phenoxy group)
In the compound of formula (21), when LG is in the time of can randomly containing substituent phenoxy group, general formula (21) is represented by general formula (22):
Preparation method II-1 is meant such method: the diamine compound of its formula of (1) expression is to obtain by making to be reacted in the presence of alkali by biphenyl-dicarboxylic acid two (aryl) ester of general formula (22) expression and amino-phenol.
In formula (22), A has the implication identical with above-mentioned definition, is preferably above-mentioned formula (A2) to (A5), and most preferably is the not replacement 4 of formula (A2), 4 '-biphenylene.Y preferably represents halogen atom, nitro, trifluoromethyl, cyano group or ethanoyl, and more preferably represents halogen atom or nitro.N preferably represents 0 to 3 integer.
The compound of formula (22) expression is to remove biphenyl-4,4 '-dicarboxylic acid diphenyl ester, biphenyl-4, the new compound beyond 4 '-dicarboxylic acid two (2-chloro-phenyl-) ester and the biphenyl-4,4 '-dicarboxylic acid two (2-nitrophenyl) ester.
Biphenyl-dicarboxylic acid two (aryl) ester cpds of formula (22) obtains by making following compound reaction:
The biphenyl two carbonyl halide derivatives of above-mentioned general formula (2) expression:
(wherein, A is with top described identical; And X represents halogen atom.)
The hydroxy aryl compound of general formula (23) expression:
(wherein, Y and n represent and the identical implication of definition in formula (22)) and
Alkali.
Below, with reference to biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic describes in further detail this reaction.Yet, also can synthesize the compound that group A wherein represents other group in an identical manner.
As the reactions steps formula, (2) shown in, comprise two reactions from the synthetic entire reaction of raw material, promptly, (A) by making biphenyl-4,4 '-two carbonyl halides and hydroxy aryl compound react and acquisition biphenyl-4,4 '-dicarboxylic acid two, the reaction of (aryl) ester cpds, (below be called esterification), with, (B) by making biphenyl-4,4 '-dicarboxylic acid two, (aryl) ester cpds and 4-amino-phenol react and acquisition biphenyl-4,4 '-dicarboxylic acid two, the reaction of (4-aminophenyl) ester, (below be called transesterification reaction)
Reactions steps formula (2)
Wherein, X, Y and n have implication same as described above in the formula.
Below, this two reactions will be described successively.
(A) esterification
In esterification, biphenyl-4,4 '-dicarboxylic acid two (aryl) ester cpds are by the compound that diphenyl dicarboxylic acid carboxylic acid halides, hydroxy aryl compound and the alkali reaction shown in the above-mentioned general formula (2) obtained (referring to the reference example C-1 to C-3 that describes below).In general formula (2), X is a halogen atom, for example fluorine atom, chlorine atom, bromine atoms or iodine atom, and preferred chlorine atom or bromine atoms.
The hydroxy aryl compound that is used in this reaction is represented by above-mentioned general formula (23).In general formula (23), Y is preferably for example fluorine atom, chlorine atom, bromine atoms, iodine atom or nitro, and more preferably chlorine atom, bromine atoms or nitro.N represents substituent number, and is specially 0 to 3 and preferred 0 to 2.
Particularly, above-mentioned hydroxy aryl compound is phenol or the phenols that replaced by 1 to 3 halogen atom or nitro.The position of substitution with substituted phenol of 1 to 3 group Y is suitably at least one the position of substitution that is selected from 2,4 and 6.
Based on 1 mole biphenyl-4,4 '-two phosphinylidyne dihalo-s, the amount of above-mentioned hydroxy aryl compound is preferably 2.0 to 20 moles and more preferably 2.0 to 10 moles.
As the alkali that uses in esterification, what can exemplify has an alkalimetal hydride, as sodium hydride, potassium hydride KH, lithium hydride etc.; Alkali metal hydroxide or alkaline earth metal hydroxides are as sodium hydroxide, potassium hydroxide, calcium hydroxide etc.; Alkaline carbonate or alkaline earth metal carbonate are as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, lime carbonate etc.; Alkali metal hydrocarbonate or alkali metal bicarbonates are as sodium bicarbonate, saleratus, Calcium hydrogen carbonate etc.; Amine is as triethylamine, Diisopropylamine, n-Butyl Amine 99, N-methyl piperidine, N-methylmorpholine etc.; And pyridines, as pyridine, lutidine etc.Preferred what use is alkalimetal hydride, alkaline carbonate, amine and pyridines, and what more preferably use is sodium hydride, yellow soda ash, triethylamine and pyridine.These alkali can be used alone or in combination use of two or more.
Based on 1 mole biphenyl-4,4 '-two carbonyl halides, the amount of the above-mentioned alkali that use is preferably 1 to 20 mole and more preferably 2 to 10 moles.
Esterification is preferably carried out in the presence of organic solvent.To being not particularly limited as the solvent that will use, as long as it can not hinder reaction, what can exemplify has an ethers, as diethyl ether, diisopropyl ether, diox, glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF) etc.; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.; Ureas, as N, N '-dimethyl-2-imidazolone etc.; Nitrile such as acetonitrile, propionitrile, benzonitrile etc.; Ketone is as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; Aromatic hydrocarbons is as benzene,toluene,xylene, cumene etc.; And the halogenation aliphatic hydrocrbon, as methylene dichloride, ethylene dichloride etc.Preferred what use is ethers, amides, nitrile and ketone, and what more preferably use is ethers and amides.These solvents can be used alone or in combination use of two or more.
According to the degree of uniformity of reaction soln or the state of stirring, suitably adjust the amount of the above-mentioned solvent that will use, and based on 1g biphenyl-4,4 '-two carbonyl halides, the amount of described solvent is preferably 1 to 100ml and more preferably 2 to 50ml.
Esterification is to be undertaken by such method: wherein for example with biphenyl-4,4 '-two carbonyl halides, hydroxy aryl compound and solvent mix in the presence of alkali, and can stir these materials.Temperature of reaction in reaction process is preferably-20 to 250 ℃, and more preferably 0 to 150 ℃ and be preferably 15 to 120 ℃ especially, and reaction pressure is not particularly limited.
After reaction is finished, by general method for example as extraction, filter, concentrate, recrystallization, column chromatography etc. are resulting biphenyl-4,4 '-dicarboxylic acid two (aryl) ester cpds separates and purifying.As selection, can be under the condition of it not being separated especially with purifying, with prepared biphenyl-4,4 '-dicarboxylic acid two (aryl) ester cpds is used for following transesterification reaction.
(B) transesterification reaction
Transesterification reaction is by making by above-mentioned general formula (22), more specifically by the biphenyl-4 of formula (22a) expression 4 '-dicarboxylic acid two (aryl) ester cpds:
In the presence of alkali, react and carry out with amino-phenol (preferred 4-amino-phenol), thereby obtain by above-mentioned general formula (1), more specifically by the represented compound of formula (1a).
Based on 1 mole biphenyl-4,4 '-dicarboxylic acid two (aryl) ester cpds, the amount of the amino-phenol that use in this transesterification reaction is preferably 2.0 to 20 moles and more preferably 2.0 to 10 moles.
As the alkali that will use in transesterification reaction, what can exemplify has triethylamine, 1, a 4-diazabicyclo [2,2,2] octane, pyridine, 1-methyl isophthalic acid, 3,4,6,7,8-six hydrogen-2H-Mi Dingbing [1,2-a] pyrimidine, N '-cyclohexyl-N, N, N, N-tetramethyl guanidine or contain organic amine as the guanidine skeleton of part-structure; Contain organic amine as the amidine skeleton of part-structure, as 1,8-diazabicylo [5,4,0]-7-undecylene, 1,5-diazabicylo [4,3,0]-5-nonene etc.; Inorganic carbonate is as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate etc.; The inorganic carbonate hydrogen salt is as sodium bicarbonate, saleratus etc.; Alkalimetal hydride such as sodium hydride, potassium hydride KH, lithium hydride etc.; Alkali metal hydroxide is as potassium hydroxide, sodium hydroxide etc.; And alkali metal alcoholates, as lithium methoxide, sodium methylate, sodium tert-butoxide, sodium ethylate, potassium tert.-butoxide etc. (these can use with the form of the alcoholic solution of correspondence).What preferably use is alkalimetal hydride, alkali metal alcoholates and organic amine, and what more preferably use is sodium hydride, sodium tert-butoxide, potassium tert.-butoxide, and contain organic amine as the amidine skeleton of part-structure, as 1,8-diazabicylo [5,4,0]-7-undecylene, 1,5-diazabicylo [4,3,0]-5-nonene etc.These alkali can be used alone or in combination use of two or more.
Based on 1 mole biphenyl-4,4 '-dicarboxylic acid two (aryl) ester, the amount of the alkali that use is preferably 0.005 to 2.5 mole, more preferably 0.01 to 1.99 mole and be preferably 0.1 to 1.0 mole especially.
Transesterification reaction is preferably carried out in the presence of solvent.To being not particularly limited as the solvent that will use, as long as it does not hinder reaction, what can exemplify has an ethers, as diethyl ether, diisopropyl ether, diox, glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF) etc.; Ketone is as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; Aromatic hydrocarbons is as benzene,toluene,xylene, cumene etc.; The halogenated aromatic hydro carbons, as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene etc.; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.; Ureas, as N, N '-dimethyl-2-imidazolone etc.; Nitrile is as acetonitrile, propionitrile, benzonitrile etc.; The nitroaromatic hydro carbons is as oil of mirbane etc.; And the sulfoxide class, as methyl-sulphoxide etc.What preferably use is ethers, halogenated aromatic hydro carbons, ureas, nitrated aromatic hydrocarbons and sulfoxide class.These solvents can be used alone or in combination use of two or more.
According to the degree of uniformity of reaction soln or the state of stirring, suitably adjust the amount of the above-mentioned solvent that will use, and based on 1g biphenyl-4,4 '-dicarboxylic acid two (aryl) ester cpds, this amount is preferably 1 to 100ml and more preferably 2 to 50ml.
Transesterification reaction is to be undertaken by such method: wherein for example with biphenyl-4,4 '-dicarboxylic acid two (aryl) ester cpds and solvent mix in the presence of alkali, and stir these materials.Temperature of reaction in the reaction process is preferably 50 to 250 ℃ and more preferably 80 to 200 ℃, and reaction pressure is not particularly limited.
Yet in above-mentioned formula (22), when n is 0, when promptly two ends were unsubstituted phenyl, preferred what use was the method that for example comprises the steps: in transesterification reaction, when stirring, remove the phenol that is produced from reaction soln.Be preferably 50 to 250 ℃ and more preferably 80 to 200 ℃ in this moment reaction temperature, reaction pressure be not particularly limited, and be preferably 0.6 to 70kPa and more preferably 1 to 40kPa.A preferred aspect in this case comprises for example such method: wherein with biphenyl-4,4 '-dicarboxylic acid diphenyl ester, 4-amino-phenol and solvent mix in the presence of alkali, and under the reaction pressure of 50 to 250 ℃ temperature of reaction and 0.6 to 70kPa, when making these material reactions, from reaction soln, remove the phenol that is produced.
After reaction is finished, by general method for example as extraction, filter, concentrate, recrystallization, crystallization, column chromatography etc. are resulting biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester separates and purifying.
Preparation method II-2
(LG is the group by formula (31) expression)
In the compound of formula (21), when LG was group by formula (31) expression, general formula (21) was expressed as general formula (32):
Preparation method II-2 is meant such method: be to obtain by making to be reacted in the presence of alkali by the biphenyl carbamide compound of general formula (32) expression and amino-phenol by the diamine compound of general formula (1) expression wherein.
In formula (32), A has the implication identical with above-mentioned definition, and preferred above-mentioned formula (A2) is to (A5), and the most preferably not replacement 4 of formula (A2), 4 '-biphenylene.
The biphenyl carbamide compound of formula (32) is new compound, and by the following compounds reaction is obtained:
Biphenyl two carbonyl halide derivatives by above-mentioned general formula (2) expression:
, 2-thiazoline-2-mercaptan formula (33):
And
Alkali.
Below, with reference to biphenyl-4, this reaction is described in synthesizing of 4 '-dicarboxylic acid two (4-aminophenyl) ester in detail.Yet, also can synthesize the compound that group A wherein represents other group in an identical manner.
As shown in reactions steps formula (3), the entire reaction synthetic from raw material comprises two reactions, promptly, (A) by making biphenyl two carbonyl halides and 2-thiazoline-2-thiol reactant obtain the reaction (below be called amidate action) of biphenyl carbamide compound and (B) by making the reaction of biphenyl carbamide compound and 4-amino-phenol obtain biphenyl-4, the reaction of 4 '-dicarboxylic acid two (4-aminophenyl) ester (below be called esterification).
Reactions steps formula (3)
(wherein, X has the implication identical with above-mentioned definition.)
Below, this two reactions will be described successively.
(A) amidate action
Biphenyl two carbonyl halides that will use in this amidate action are represented by above-mentioned general formula (1).In general formula (1), X has the implication identical with above-mentioned definition, and as halogen atom, can exemplify fluorine atom, chlorine atom, bromine atoms and iodine atom, and preferred use is chlorine atom and bromine atoms.
Based on 1 mole biphenyl, two carbonyl halides, the amount of the 2-that uses in amidate action thiazoline-2-mercaptan is preferably 1.6 to 20 moles and more preferably 2.0 to 10 moles.
As the alkali that in amidate action, uses, for example, can mention organic bases, as triethylamine, pyridine, 1,8-diazabicylo [5,4,0]-7-undecylene, 1,5-diazabicylo [4,3,0]-5-nonene, 1,4-diazabicylo [2,2,2] octane etc.; And mineral alkali, as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, sodium bicarbonate, saleratus etc.What preferably use is organic bases.These alkali can be used alone or in combination use of two or more.
Based on 1 mole biphenyl, two carbonyl halides, the amount of the above-mentioned alkali that use is preferably 1 to 20 mole and more preferably 2 to 10 moles.
Amidate action carries out having solvent or do not exist under the condition of solvent.To being not particularly limited as the solvent that will use, as long as it does not hinder reaction, what can exemplify is that aromatic hydrocarbons is as benzene,toluene,xylene, cumene etc.; Halogenated aliphatic hydrocarbons, as methylene dichloride, 1,2-ethylene dichloride, 1,1-ethylene dichloride etc.; The halogenated aromatic hydro carbons, as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene etc.; Ethers is as diethyl ether, diisopropyl ether, diox, glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF) etc.; Ketone is as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.; Ureas, as N, N '-dimethyl-2-imidazolone etc.; Nitrile, as acetonitrile, propionitrile, benzonitrile etc., oil of mirbane, methyl-sulphoxide etc.What preferably use is ethers, amides, ureas, methyl-sulphoxide etc.These solvents can be used alone or in combination use of two or more.
According to the degree of uniformity of reaction soln or the state of stirring, suitably adjust the amount of the above-mentioned solvent that will use, and based on 1g biphenyl two carbonyl halides, this amount is preferably 1 to 100ml and more preferably 2 to 50ml.
This amidate action is to be undertaken by such method: wherein for example with biphenyl two carbonyl halides, 2-thiazoline-2-mercaptan, alkali and solvent, and can stir these materials.Temperature of reaction in the reaction process is preferably 0 to 150 ℃ and more preferably 10 to 100 ℃, and reaction pressure is not particularly limited.
After reaction is finished, by general method for example as extraction, filter, concentrate, recrystallization, column chromatography etc. separate resulting biphenyl carbamide compound and purifying.As selection, can under the condition of it not being separated with purifying, prepared biphenyl carbamide compound be used for following esterification.
(B) esterification
Based on 1 mole biphenyl carbamide compound, the amino-phenol that uses in this esterification (preferred 4-amino-phenol) is preferably 1.0 to 20 moles and more preferably 2.0 to 10 moles.
As the alkali that uses in esterification, what can exemplify is organic bases, as 1, and 8-diazabicylo [5,4,0]-7-undecylene, 1,5-diazabicylo [4,3,0]-5-nonene, 1,4-diazabicylo [2,2,2] octane etc.; Mineral alkali is as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, sodium hydride, lithium hydride etc.; And metal alkoxide, as sodium methylate, sodium ethylate, potassium tert.-butoxide, sodium tert-butoxide etc.Preferred what use is organic bases, metal alkoxide and sodium hydride, and what more preferably use is 1,8-diazabicylo [5,4,0]-7-undecylene, potassium tert.-butoxide, sodium tert-butoxide and sodium hydride.These alkali can be used alone or in combination use of two or more.
Based on 1 mole biphenyl carbamide compound, the amount of the above-mentioned alkali that use is preferably 0.01 to 10 mole and more preferably 0.1 to 5 mole.
This esterification is carried out having solvent or do not exist under the condition of solvent.To being not particularly limited as the solvent that will use, as long as it does not hinder reaction, what can exemplify has an aromatic hydrocarbons, as benzene,toluene,xylene, cumene etc.; Halogenated aliphatic hydrocarbons, as methylene dichloride, 1,2-ethylene dichloride, 1,1-ethylene dichloride etc.; The halogenated aromatic hydro carbons, as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene etc.; Ethers is as diethyl ether, diisopropyl ether, diox, glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF) etc.; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.; Ureas, as N, N '-dimethyl-2-imidazolone etc.; Nitrile, as acetonitrile, propionitrile, benzonitrile etc., oil of mirbane, methyl-sulphoxide etc.What preferably use is ethers, amides, ureas and methyl-sulphoxide.These solvents can be used alone or in combination use of two or more.
According to the degree of uniformity of reaction soln or the state of stirring, suitably adjust the amount of the above-mentioned solvent that will use, and based on 1g biphenyl carbamide compound, this amount is preferably 1 to 100ml and more preferably 2 to 50ml.
This esterification is to be undertaken by such method: wherein for example with biphenyl carbamide compound, 4-amino-phenol, alkali and solvent, and can stir these materials.Temperature of reaction in the reaction process is preferably-50 to 100 ℃ and more preferably-20 to 60 ℃, and reaction pressure is not particularly limited.
After reaction is finished, by general method for example as extraction, filter, concentrate, recrystallization, column chromatography etc. are resulting biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester separates and purifying.
Embodiment
With reference to following examples and comparative example the present invention is described more specifically.
By the synthetic embodiment of the diamine compound of preparation method I
Embodiment A-1
(A) biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester synthetic
To internal capacity is 2, and 000ml and disposing in the flask of whipping appts, thermometer and dropping funnel adds 4 of 41.87g (0.15mol), the 4-nitrophenols and 1 of 4-biphenyl two carbonyl chlorides, 45.91g (0.33mol), 050ml tetrahydrofuran (THF).At 25 ℃, last 2 hours, the solution that is dissolved in 37.95g (0.38mol) triethylamine in the 75ml tetrahydrofuran (THF) is joined in the blended solution, make resulting mixture 45 ℃ of reactions 3 hours then.After reaction is finished, reaction soln is cooled to 25 ℃, filter then.Thereby filter residue and drying is obtained the 112g yellow powder.With the powder and 1 that is obtained, it is 2 that 750mlN, dinethylformamide join internal capacity, 000ml and dispose whipping appts and the flask of thermometer in, and mixture stirred 20 minutes at 95 ℃.After stirring is finished, mixing solutions is cooled to 25 ℃, filter then.Use 1 successively, 200ml water and 600ml tetrahydrofuran (THF) washing filter residue.With filter residue and drying, thus the biphenyl-4 of acquisition 57.4g (0.12mol) colourless powder form, 4 '-dicarboxylic acid two (4-nitrophenyl) ester (separation yield: 80%, based on 4,4 '-biphenyl dicarbapentaborane muriate).
Biphenyl-4, the physical properties of 4 '-dicarboxylic acid two (4-nitrophenyl) ester is as follows.
1H-NMR(DMSO-d
6，δ(ppm))；7.68(4H，d，J＝9.3Hz)，8.08(4H，d，J＝8.6Hz)，8.31(4H，d，J＝8.6Hz)，8.39(4H，d，J＝9.3Hz)
Embodiment A-2
(B) biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester (below be abbreviated as APBP) synthetic
Be 500ml and dispose in the flask of whipping appts, thermometer and reflux exchanger to internal capacity, add 30.0g (61.9mmol) with embodiment A-1 in the biphenyl-4 prepared of identical mode, 4 '-dicarboxylic acid two (4-nitrophenyl) ester, 330ml N, 5 quality % palladium/carbon of dinethylformamide and 6.29g (counting 150mg) (by the AD catalyzer that Kawaken fine chemicals limited-liability company produces, 52.33 quality % wet product) with the palladium atom.Flask disposes the balloon (balloon) that is filled with hydrogen, and reaction was under agitation carried out 7 hours in 80 ℃.After reaction is finished, reaction soln is cooled to 60 ℃, filter then.In filtrate, add 300ml water, and mixture was stirred 0.5 hour at 25 ℃.The crystal that is settled out is filtered, and use 50ml N successively, dinethylformamide, 100ml water and 100ml methanol wash filter residue, dry then, thereby the purity that obtains 24.3g (57.3mmol) colour of skin powder type is the biphenyl-4 of 97.0% (by the area percentage of high performance liquid chromatography), 4 '-dicarboxylic acid two (4-aminophenyl) ester (reaction yield; 93%, based on biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester).
With the biphenyl-4 that 18.9g obtained, 4 '-dicarboxylic acid two (4-aminophenyl) ester and 90ml methyl-sulphoxide mix and recrystallization, thereby the purity that obtains the light grey powder type of 12.6g (29.7mmol) is the biphenyl-4 of 99.4% (by the area percentage of high performance liquid chromatography), 4 '-dicarboxylic acid two (4-aminophenyl) ester.
At this, biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester is a kind of new compound that shows following physical properties.
Fusing point; 248 to 251 ℃
1H-NMR(DMSO-d
6，δ(ppm))；5.10(4H，brs，NH2)，6.40-6.66(4H，m)，6.90-6.98(4H，m)，7.80-8.08(4H，m)，8.01-8.25(4H，m)
Embodiment A-3
(B) biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Be 500ml and dispose in the flask of whipping appts, thermometer and reflux exchanger to internal capacity, add 30.0g (61.9mmol) with embodiment A-1 in the biphenyl-4 prepared of identical mode, 4 '-dicarboxylic acid two (4-nitrophenyl) ester, 330ml N, dinethylformamide and 6.29g (count 52mg with the palladium atom, count 78mg with pt atom) 2 quality % palladium-3 quality % platinum/carbon (by the UKH-10 that N.E.CHEMCAT company produces, 49.8 quality % wet product).Flask disposes the balloon that is filled with hydrogen, and reaction was under agitation carried out 5 hours at 80 ℃.After reaction is finished, reaction soln is cooled to 60 ℃, filter then.In filtrate, add 300ml water, and mixture was stirred 0.5 hour at 25 ℃.The crystal that is settled out is filtered, and use 50ml N successively, dinethylformamide, 100ml water and 100ml methanol wash filter residue, dry then, thereby the purity that obtains 24.8g (58.4mmol) colour of skin powder type is the biphenyl-4 of 96.7% (by the area percentage of high performance liquid chromatography), 4 '-dicarboxylic acid two (4-aminophenyl) ester (reaction yield; 94%, based on biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester).
Compare reference example A-1
For the physical properties of polyimide relatively, with synthetic terephthalic acid two (4-aminophenyl) ester of the identical mode described in the patent documentation 1 as diamine compound.
The evaluation of the synthetic and film of polyimide
Below, will explain the embodiment of polyimide of the present invention.Herein, the observed value that shows in embodiment and comparative example is measured in following method.
1) soltion viscosity
The TV-20 viscometer (cone-plate type) that the soltion viscosity of polyamic acid is to use Toki Sangyo limited-liability company to produce uses 3 ° * R14 of cone rotor, at 25 ℃, measures in 0.5 to 10rpm scope.
2) tension test
Film is struck out IEC450 standard dumb-bell shape with the preparation testing plate.By using the TENSILON that produces by ORIENTEC company limited, at the chuck of 30mm measurement initial elasticity modulus, breaking tenacity and elongation at break under the condition of the rate of extension of (space of chuck) and 2mm/min at interval.
3) the viscoelastic measurement of solid
The strip that film is cut into 2cm * 2mm is with the preparation testing plate, and use is measured solid visco-elasticity by the RSAIII that TA Instruments produces with stretch mode.With testing plate in nitrogen stream when room temperature is heated to ultimate temperature with the speed of 3 ℃/grade (step), measure at 10Hz.Determine 400 ℃ Young's modulus from the E ' curve that is obtained.From E " maximum of curve determines second-order transition temperature (Tg).
4) suction per-cent
With the film of 15cm * 15cm 150 ℃ of vacuum-dryings 2 hours and measure dry weight W
0Afterwards, film is immersed in 23 ℃ the water and it was left standstill 24 hours.To wipe attached to the lip-deep water of film with filter paper, measure the weight W after absorbing
1And determine suction per-cent by formula (1).
Water-intake rate (%)=(W
1-W
0)/W
0* 100 ... formula (1)
5) wet swelling coefficient (CHE)
By using cutting unit that the shallow line of lattice shape at about 1cm interval is set in the zone of the 5cm * 5cm of film, and at 150 ℃ with resulting material vacuum-drying 2 hours.The MM-40 measuring microscope that uses Nikon production is with the interval L between the lattice point of this desciccator diaphragm of unit record of 1 μ m
0Afterwards, film is immersed in 23 ℃ the water and it was left standstill 24 hours.To wipe the interval L between the lattice point after record absorbs in an identical manner attached to the lip-deep water of film with filter paper
1, and according to formula (2) calculating wet swelling coefficient.Average from 15 values.
Wet swelling coefficient (ppm/RH%)=(L
1-L
0)/L
0/ 100 * 10
6Formula (2)
6) thermal expansivity (CTE)
Film is cut into the long bar shaped of 10mm with the preparation testing plate, and the TMA-50 that uses Shimadzu company to produce, under the 5g load, this film is heated to 400 ℃ with the speed of 5 ℃/min.Determine 50 ℃ to 200 ℃ mean thermal expansion coefficients from the TMA curve that is obtained.
7) thermogravimetric analysis
The TGA-50 that uses Shimadzu company to produce, the speed with 10 ℃/min in nitrogen atmosphere heats this film.Determine 5% weight loss temperature (Td from the thermogravimetric loss curve that obtains
5).
8) APBP unit weight %
For example, when acid dianhydride and diamines are made up of two kinds of components respectively, determine the unitary weight % of APBP from formula (3).
APBP unit weight %=(M
1A
1B
1+ M
3A
2B
1)/(M
1A
1B
1+ M
2A
1B
2+ M
3A
2B
1+ M
4A
2B
2) * 100
Formula (3)
At this, in monomer feed, the molar fraction that first component of acid dianhydride is occupied in total acid dianhydride component is expressed as A
1, and the molar fraction of second component of acid dianhydride is expressed as A
2In addition, the molar fraction that APBP is occupied in total diamine components is expressed as B
1, and the molar fraction of second component of diamines is expressed as B
2In the final composition of polyimide, the molecular weight form of the structural unit (constituent unit) that will be made of first component and the APBP of acid dianhydride is shown M
1, the molecular weight form of the structural unit that will be made of second component of first component of acid dianhydride and diamines is shown M
2, the molecular weight form of the structural unit that will be made of second component and the APBP of acid dianhydride is shown M
3, and the molecular weight form of the structural unit that will be made of second component of second component of acid dianhydride and diamines is shown M
4For example, when second component of first and second components of acid dianhydride and diamines is respectively s-BPDA, PMDA and PPD, M
1, M
2, M
3And M
4Be respectively 682.63,366.33,606.54 and 290.23.
Even each component be can't help two kinds of one-tenth and is grouped into, also can determine the unitary weight % of APBP by the item number that increases or reduce in the formula based on identical idea.At this, the APBP unit is meant in the final composition of polyimide, the structural unit of being made up of acid dianhydride and APBP.For example, the structural unit that is made of s-BPDA and APBP is represented by formula (4).
At this, also determine the unitary weight fraction of APB with same idea.
Diamine compound:
Use is synthetic biphenyl-4 in embodiment A-2,4 '-dicarboxylic acid two (4-aminophenyl) ester (below be abbreviated as APBP).
Use in reference example A-1 relatively synthetic to benzene dicarboxylic acid two (4-aminophenyl) ester (below be abbreviated as APB).
To use following abbreviation.
S-BPDA:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
PPD: Ursol D
PMDA: pyromellitic dianhydride
ODPA: two (3,4-dicarboxyl benzene) ether dianhydride
DMAc:N, the N-N,N-DIMETHYLACETAMIDE
Embodiment B-1
The preparation of s-BPDA/APBP film
The APBP of 5.000g is dissolved in the N,N-dimethylacetamide of 38.6g, under agitation gradually to wherein adding 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA) to mole such as APBP, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.The viscosity of solution is 150Pas.The polyamic acid solution curtain coating is made that on sheet glass final film thickness is about 30 μ m, and 120 ℃ of dryings 20 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 1, and the character of polyimide film is presented in the table 2.
Embodiment B-2
The preparation of s-BPDA/APBP/PPD (3/2/1) hot-imide film
The APBP of 6.000g and the PPD of 0.764g are dissolved among the DMAc of 59.22g, under agitation gradually to wherein add s-BPDA to mole such as diamine components, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.The viscosity of solution is 180Pas.The polyamic acid solution curtain coating is made that on sheet glass final film thickness is about 20 μ m, and 120 ℃ of dryings 30 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 1, and the character of polyimide film is presented in the table 2.
Embodiment B-3
The preparation of the chemical imidization film of s-BPDA/APBP/PPD (3/2/1)
At-10 ℃, add the DMAc solution of 1 equivalent diacetyl oxide and the DMAc solution of 0.5 equivalent isoquinoline 99.9 in the polyamic acid solution that in Embodiment B-2, obtains, the equivalent of the two is all based on the carboxylic acid meter of polyamic acid, and with the mixture degasification.The amount of DMAc is for making that polyamic acid is 9 weight %.The 9 weight % polyamic acid solution curtain coatings that obtained on sheet glass, are made that final film thickness is about 20 μ m, and 120 ℃ of dryings 5 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 1, and the character of polyimide film is presented in the table 2.
Comparative example B-1
The preparation of s-BPDA/APB
The APB of 5.000g is dissolved among the DMAc of 42.06g, under agitation gradually to wherein add s-BPDA to mole such as APB, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.This solution has high viscosity.With DMAc with solution dilution to 9 weight % to obtain the solution of 7Pas.Solution casting is made that on sheet glass final film thickness is about 30 μ m, and 120 ℃ of dryings 30 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 1, and the character of polyimide film is presented in the table 2.
[table 1]
1) the s-BPDA mole % in one or more acid dianhydrides
2) APBP in one or more diamines or APB mole %
[table 2]
Embodiment B-4
The preparation of s-BPDA/APBP/PPD (2/1/1) film
The APBP of 5.000g and the PPD of 1.273g are dissolved among the DMAc of 60.16g, under agitation gradually to wherein add s-BPDA to mole such as diamine components, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.The viscosity of solution is 150Pas.The polyamic acid solution curtain coating is made that on sheet glass final film thickness is about 30 μ m, and 120 ℃ of dryings 20 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 3, and the character of polyimide film is presented in the table 4.
Embodiment B-5
The preparation of s-BPDA/APBP/PPD (10/3/7) film
The APBP of 3.000g and the PPD of 1.783g are dissolved among the DMAc of 53.34g, under agitation gradually to wherein add s-BPDA to mole such as diamine components, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.The viscosity of solution is 150Pas.The polyamic acid solution curtain coating is made that on sheet glass final film thickness is about 30 μ m, and 120 ℃ of dryings 20 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 3, and the character of polyimide film is presented in the table 4.
Embodiment B-6
The preparation of s-BPDA/APBP/PPD (10/1/9) film
The APBP of 2.000g and the PPD of 4.586g are dissolved among the DMAc of 93.16g, under agitation gradually to wherein add s-BPDA to mole such as diamine components, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.The viscosity of solution is 150Pas.The polyamic acid solution curtain coating is made that on sheet glass final film thickness is about 30 μ m, and 120 ℃ of dryings 20 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 3, and the character of polyimide film is presented in the table 4.
Comparative example B-2
The preparation of s-BPDA/PPD film
The PPD of 5.000g is dissolved among the DMAc of 84.8g, under agitation gradually to wherein add s-BPDA to mole such as PPD, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.The viscosity of solution is 150Pas.The polyamic acid solution curtain coating is made that on sheet glass final film thickness is about 30 μ m, and 120 ℃ of dryings 20 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 3, and the character of polyimide film is presented in the table 4.
[table 3]
1) the s-BPDA mole % in one or more acid dianhydrides
2) the APBP mole % in one or more diamines
[table 4]
Reference example B-1
The preparation of PMDA/APBP film
The APBP of 6.000g is dissolved among the DMAc of 37.20g, under agitation gradually to wherein add pyromellitic dianhydride (PMDA) to mole such as APBP, and to make mixture reaction be the polyamic acid solution of 18 weight % to obtain the monomer feed amount.Solution has high viscosity.With the moment of DMAc after with solution dilution to 14 weight %, the viscosity of solution is 18Pas.When allowing solution left standstill one, thereby it becomes gel state and can't prepare film.
Embodiment B-7
The preparation of PMDA/s-BPDA/APBP (2/1/3) film
The APBP of 5.000g is dissolved among the DMAc of 37.20g, under agitation gradually to wherein add PMDA and s-BPDA to mole such as APBP, and to make mixture reaction be the polyamic acid solution of 14 weight % to obtain the monomer feed amount.The mol ratio of PMDA and s-BPDA is 2: 1.The viscosity of solution is 190Pas.With the polyamic acid solution curtain coating on sheet glass so that final film thickness is about 30 μ m, and 120 ℃ of dryings 20 minutes.Resulting film is peeled off, be fixed on the pin tenter, heated separately 5 minutes at 180 ℃ and 210 ℃ respectively, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film.The composition and the viscosity of polyamic acid solution are presented in the table 5, and the character of polyimide film is presented in the table 6.
Embodiment B-8
The preparation of ODPA/APBP film
The APBP of 5.000g is dissolved among the DMAc of 39.42g, under agitation gradually to wherein add ODPA to mole such as APBP, and to make mixture reaction be the polyamic acid solution of 14 weight % to obtain the monomer feed amount.The viscosity of solution is 80Pas.With the polyamic acid solution curtain coating on sheet glass so that final film thickness is about 30 μ m, and 120 ℃ of heating 20 minutes and 180 ℃ of heating 5 minutes.Resulting film is peeled off from sheet glass, be fixed on the pin tenter,, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film 210 ℃ of heating 5 minutes.The composition and the viscosity of polyamic acid solution are presented in the table 5, and the character of polyimide film is presented in the table 6.
Embodiment B-9
The preparation of ODPA/s-BPDA/APBP (2/1/3) film
The APBP of 5.000g is dissolved among the DMAc of 38.84g, under agitation gradually to wherein add ODPA and s-BPDA to mole such as APBP, and to make mixture reaction be the polyamic acid solution of 14 weight % to obtain the monomer feed amount.The mol ratio of ODPA and s-BPDA is 2: 1.The viscosity of solution is 190Pas.With the polyamic acid solution curtain coating on sheet glass so that final film thickness is about 30 μ m, and 120 ℃ of heating 20 minutes and 180 ℃ of heating 5 minutes.Resulting film is peeled off from sheet glass, be fixed on the pin tenter,, heated 9 minutes from 270 ℃ to 450 ℃ then, thereby obtain polyimide film 210 ℃ of heating 5 minutes.The composition and the viscosity of polyamic acid solution are presented in the table 5, and the character of polyimide film is presented in the table 6.
[table 5]
1) the s-BPDA mole % in one or more acid dianhydrides
2) the APBP mole % in one or more diamines
[table 6]
Synthetic embodiment according to the diamine compound of preparation method II-1
Below, with the synthetic embodiment that describes in detail according to the diamine compound of preparation method II-1.The analysis condition that passes through high performance liquid chromatograph that uses in each embodiment and reference example is as follows.
Instrument type: Shimadzu high performance liquid chromatograph, LC-10A
Post: YMC-PackPro, C
18, s-5 μ m, 4.6I.D*150mm
Eluent: water/acetonitrile=1.2/1.8 (volume ratio)
PH:7.0 (under the situation of triethylamine, add acetate (0.1ml/l) to pH be 7.0)
Flow: 1.0ml/min
Column oven temperature: 40C
Detect wavelength: 254nm
Reference example C-1
Biphenyl-4,4 '-dicarboxylic acid diphenyl ester synthetic
At internal capacity is 1,000ml and dispose whipping appts and the flask of thermometer in, mix triethylamine, 680ml tetrahydrofuran (THF) and 29.7g (0.316mol) phenol of 41.5g (0.410mol).When fluid temperature being remained on below 25 ℃, in this mixing solutions, slowly add 40.0g (0.143mol) 4,4 '-biphenyl, two carbonyl chlorides stir resulting mixture 15 hours at 25 ℃ then.After reaction is finished, reaction soln is filtered.In resulting solid, add 1,300ml water.Mixture is stirred filtration then in 1 hour at 25 ℃.Wash resulting solid with 800ml water and 60ml tetrahydrofuran (THF) successively, thus the dry then biphenyl-4 that obtains 51.4g white solid form, 4 '-dicarboxylic acid diphenyl ester (separation yield: 91%, based on 4,4 '-biphenyl, two carbonyl chlorides).
The biphenyl that is obtained-4, the physical properties of 4 '-dicarboxylic acid diphenyl ester is as follows.
1H-NMR(300MHz，THF-d
8，δ(ppm))；7.15-7.30(6H，m)，7.33-7.50(4H，m)，7.88-8.01(4H，m)，8.22-8.35(4H，m)
Reference example C-2
Biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester synthetic
With with embodiment A-1 in the synthetic biphenyl-4 of identical mode, 4 '-dicarboxylic acid two (4-nitrophenyl) ester.
Reference example C-3
Biphenyl-4,4 '-dicarboxylic acid two (2-chloro-phenyl-) ester
Internal capacity be 500ml and dispose whipping appts and the flask of thermometer in, mix 20.7g (205mmol) triethylamine, 340ml tetrahydrofuran (THF) and 20.3g (158mmol) 2-chlorophenol.When fluid temperature being remained on below 30 ℃, in this mixing solutions, add 20.0g (71.7mmol) 4,4 '-biphenyl, two carbonyl chlorides stir resulting mixture 15 hours at 25 ℃ then.After reaction is finished, reaction soln is filtered and adding 670ml water in resulting solid.Mixture was stirred 1 hour at 25 ℃, filter then.Wash resulting solid with 800ml water and 60ml tetrahydrofuran (THF) successively, dry then, thus the biphenyl-4 of acquisition 25.8g white solid form, 4 '-dicarboxylic acid two (2-chloro-phenyl-) ester (separation yield: 78%, based on 4,4 '-biphenyl, two carbonyl chlorides).
Resulting biphenyl-4, the physical properties of 4 '-dicarboxylic acid two (2-chloro-phenyl-) ester is as follows.
1H-NMR(300MHz，THF-d
8，δ(ppm))；7.25-7.32(2H，m)，7.37-7.39(4H，m)，7.52-7.55(2H，m)，7.94-7.88(4H，m)，8.31-8.35(4H，m)
Embodiment C-1
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Internal capacity be 25ml and dispose whipping appts and the flask of thermometer in, under argon gas stream, mix 1.58g (4.00mmol) synthetic biphenyl-4 in reference example C-1,4 '-dicarboxylic acid diphenyl ester, 1.31g (12.0mmol) 4-amino-phenol, 40ml N, dinethylformamide and 0.304g (2.00mmol) 1,8-diazabicylo [5,4,0]-the 7-undecylene, and mixing solutions stirred 3 hours at 93 ℃ fluid temperature.After reaction is finished, reaction soln is cooled to below 25 ℃, to wherein adding 40ml water, then mixture is filtered.Use 10ml water and the resulting solid of 10ml methanol wash successively, thus the dry then 1.62g light brown solid that obtains.
By high-efficient liquid phase chromatogram technique analysis light brown solid, the result is, biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4, the ratio of 4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-phenyl ester (precursor of required product) is 87: 13 (area percentage).In addition, by this solid of high performance liquid chromatography quantitative analysis, the result is, biphenyl-4, and the amount of 4 '-dicarboxylic acid two (4-aminophenyl) ester is 1.41g (yield: 83%, based on biphenyl-4,4 '-dicarboxylic acid diphenyl ester).
Biphenyl-4, the physical properties of 4 '-dicarboxylic acid two (4-aminophenyl) ester is as follows.
1H-NMR(300MHz，DMSO-d
6，δ(ppm))；5.10(4H，brs，NH2)，6.40-6.66(4H，m)，6.90-6.98(4H，m)，7.80-8.08(4H，m)，8.01-8.25(4H，m)
Biphenyl-4, the physical properties of 4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-phenyl ester is as follows.
1H-NMR(300MHz，DMSO-d
6，δ(ppm))；5.10(2H，brs，NH2)，6.60-6.65(2H，m)，6.88-6.70(2H，m)，7.28-7.41(3H，m)，7.42-7.58(2H，m)，7.95-8.10(4H，m)，8.15-8.33(4H，m)
Embodiment C-2
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Except the quantitative change of the 4-amino-phenol that will in Embodiment C-1, use as the 2.18g (20.0mmol), with Embodiment C-1 in identical mode carry out all operations, thereby obtain 1.62g light brown solid.By high-efficient liquid phase chromatogram technique analysis light brown solid, the result is, having prepared ratio is the biphenyl-4 of 95: 5 (area percentage), 4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4,4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-phenyl ester (precursor of required product).In addition, by this solid of high performance liquid chromatography quantitative analysis, the result is, contains the biphenyl-4 of 1.52g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 90%, based on biphenyl-4,4 '-dicarboxylic acid diphenyl ester).
Embodiment C-1-2
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Be 25ml and dispose in the flask of whipping appts, thermometer and dropping funnel at internal capacity, mix 1.58g (4.00mmol) synthetic biphenyl-4 in reference example C-1,1 of the 4-amino-phenol of 4 '-dicarboxylic acid diphenyl ester, 1.31g (12.0mmol), 10ml, 1 of 2-dichlorobenzene and 0.122g (0.801mmol), 8-diazabicylo [5,4,0]-7-undecylene, and, resulting mixture was stirred 1 hour fluid temperature being remained under 100 ℃ the condition.Subsequently, in this mixing solutions, add 1 of 3ml, 2-dichlorobenzene.Under the reaction pressure of 95 to 99 ℃ temperature of reaction and 9.3kPa, carry out the operation of under vacuum, slowly removing solvent 5 times altogether repeatedly.After reaction is finished, reaction soln is cooled to 25 ℃, filter then, and dry resulting solid, thereby obtain the 2.14g brown ceramic powder.
Analyze resulting powder by high performance liquid chromatography (absolute calibration curve method), the result is, contains the biphenyl-4 of 1.26g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester, promptly required product (yield: 74%, based on biphenyl-4,4 '-dicarboxylic acid diphenyl ester).In addition, in powder, contain the biphenyl-4 of 0.38g amount, 4 '-dicarboxylic acid 4-(4-aminophenyl) ester-4 '-phenyl ester (precursor of required product) (yield: 23%, based on biphenyl-4,4 '-dicarboxylic acid diphenyl ester).
The physical properties of resulting powder is as follows.
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester;
1H-NMR(300MHz，DMSO-d
6，δ(ppm))；5.10(4H，brs)，6.40-6.66(4H，m)，6.90-6.98(4H，m)，7.80-8.08(4H，m)，8.01-8.25(4H，m)
Biphenyl-4,4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-phenyl ester;
1H-NMR(300MHz，DMSO-d
6，δ(ppm))；5.10(2H，brs)，6.60-6.65(2H，m)，6.88-6.70(2H，m)，7.28-7.41(3H，m)，7.42-7.58(2H，m)，7.95-8.10(4H，m)，8.15-8.33(4H，m)
Embodiment C-3
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Internal capacity be 500ml and dispose whipping appts and the flask of thermometer in, in room temperature, under argon gas stream, 10.5g (109mmol) sodium tert-butoxide is mixed with the 250ml tetrahydrofuran (THF), slowly to wherein adding 12.4g (114mmol) 4-amino-phenol, then resulting mixture was stirred 30 minutes subsequently.In resulting mixing solutions, slowly add 24.0g (49.5mmol) synthetic biphenyl-4 in reference example C-2 in room temperature, 4 '-dicarboxylic acid two (4-nitrophenyl) ester, and with mixture stirring 2 hours.After reaction is finished, reaction soln is filtered, and use 30ml tetrahydrofuran (THF) and the resulting solid of 50ml methanol wash successively, dry then, thus obtain the 17.8g light yellow solid.By high performance liquid chromatography quantitative analysis light yellow solid, the result is, biphenyl-4, and the amount of 4 '-dicarboxylic acid two (4-aminophenyl) ester is 16.6g (yield: 79%, based on biphenyl-4,4 '-dicarboxylic acid two (4-nitrophenyl) ester).
Embodiment C-4
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Internal capacity be 25ml and dispose whipping appts and the flask of thermometer in, under argon gas stream, mix 1.75g (3.78mmol) synthetic biphenyl-4 in reference example C-3,4 '-dicarboxylic acid two (2-chloro-phenyl-) ester, the 4-amino-phenol of 2.06g (18.9mmol), the N of 14.2ml, 1 of dinethylformamide and 0.115g (0.755mmol), 8-diazabicylo [5,4,0]-7-undecylene.And the fluid temperature of this mixing solutions at 90 ℃ stirred 6.5 hours.After reaction is finished, reaction soln is cooled to below 25 ℃, filter then.Use the N of 2ml successively, the resulting solid of the methanol wash of dinethylformamide and 2ml, dry then, thus obtain the 1.07g light yellow solid.
By this light yellow solid of high-efficient liquid phase chromatogram technique analysis, the result is, having prepared ratio is the biphenyl-4 of 99.6: 0.4 (area percentage), 4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4,4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-(2-chloro-phenyl-) ester (precursor of required product).In addition, by this solid of high performance liquid chromatography quantitative analysis, the result is, contains the biphenyl-4 of 1.06g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 66%, based on biphenyl-4,4 '-dicarboxylic acid two (2-chloro-phenyl-) ester).
Simultaneously, by high-efficient liquid phase chromatogram technique analysis resulting filtrate after filtering above-mentioned reaction soln, the result is, biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4, the ratio of 4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-(2-chloro-phenyl-) ester (precursor of required product) is 97.6: 2.4 (area percentage).In addition, by this filtrate of high performance liquid chromatography quantitative analysis, the result is, contains the biphenyl-4 of 0.4g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 24%, based on biphenyl-4,4 '-dicarboxylic acid two (2-chloro-phenyl-) ester).
Embodiment C-5
Biphenyl-4,4 '-dicarboxylic acid two (4-chloro-phenyl-) ester synthetic
Be 500ml and dispose in the flask of whipping appts, thermometer and dropping funnel at internal capacity, mix 20.7g (205mmol) triethylamine, 340ml tetrahydrofuran (THF) and 20.3g (158mmol) 4-chlorophenol, and when fluid temperature being remained on below 10 ℃ lentamente to wherein adding 20.0g (71.7mmol) 4,4 '-biphenyl, two carbonyl halides, and make resulting mixture 25 ℃ of reactions 19 hours.After reaction is finished, reaction soln is filtered, filter residue is mixed with 333ml water, and stirred 1 hour at 25 ℃.Mixture is filtered once more, and wash resulting solid with 800ml water and 60ml tetrahydrofuran (THF) successively, dry then, thereby obtain the biphenyl-4 of 27.5g white powder form, 4 '-dicarboxylic acid two (4-chloro-phenyl-) ester (separation yield: 81%, based on 4,4 '-biphenyl, two carbonyl chlorides).
Resulting biphenyl-4,4 '-dicarboxylic acid two (4-chloro-phenyl-) ester is a kind of new compound, it shows following physical properties.
1H-NMR(300MHz，DMSO-d
6，δ(ppm))；7.31-7.47(4H，m)，7.49-7.63(4H，m)，7.98-8.10(4H，m)，8.30-8.33(4H，m)
Embodiment C-6
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Internal capacity be 25ml and dispose whipping appts and the flask of thermometer in, under argon gas stream, mix 1.85g (4.00mmol) synthetic biphenyl-4 in Embodiment C-5,4 '-dicarboxylic acid two (4-chloro-phenyl-) ester, 1.31g (12.0mmol) 4-amino-phenol, 15ml N, dinethylformamide and 0.122g (0.800mmol) 1,8-diazabicylo [5,4,0]-the 7-undecylene.With this mixing solutions in the heating of 92 ℃ fluid temperature and stirred 6.5 hours.After reaction is finished, reaction soln is cooled to 25 ℃ and to wherein adding 15ml water, and mixture is filtered.Use 15ml water and the resulting solid of 10ml methanol wash successively, dry then, thus obtain the 1.42g brown solid.
By this brown solid of high-efficient liquid phase chromatogram technique analysis, the result is, having prepared ratio is the biphenyl-4 of 94: 6 (area percentage), 4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4,4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-(4-chloro-phenyl-) ester (intermediate of required product).In addition, by this brown solid of high performance liquid chromatography quantitative analysis, the result is, contains the biphenyl-4 of 1.30g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 76%, based on biphenyl-4,4 '-dicarboxylic acid two (4-chloro-phenyl-) ester).
Embodiment C-7
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Except the alkali that will in Embodiment C-6, use from 1,8-diazabicylo [5,4,0]-the 7-undecylene becomes salt of wormwood, beyond its usage quantity becomes 1.11g (8.00mmol) and will become in the reaction times 4 hours, with with Embodiment C-6 in identical mode carry out all operations, thereby obtain 1.43g light brown solid.By the resulting solid of high-efficient liquid phase chromatogram technique analysis, the result is, having prepared ratio is the biphenyl-4 of 96: 4 (area percentage), 4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4,4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-(4-chloro-phenyl-) ester (intermediate of required product).In addition, by this solid of high performance liquid chromatography quantitative analysis, the result is, contains the biphenyl-4 of 1.33g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 78%, based on biphenyl-4,4 '-dicarboxylic acid two (4-chloro-phenyl-) ester).
Embodiment C-8
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Be 25ml and dispose in the flask of whipping appts, thermometer and dropping funnel at internal capacity, the synthetic biphenyl-4 in Embodiment C-5 that under argon gas stream, mixes 1.85g (4.00mmol), 4 '-dicarboxylic acid two (4-chloro-phenyl-) ester, 1.31g (12.0mmol) 4-amino-phenol, 15ml methyl-sulphoxide and 0.122g (0.800mmol) 1,8-diazabicylo [5,4,0]-the 7-undecylene, and resulting mixture stirred 2.5 hours at 92 ℃ fluid temperature.After reaction is finished, resulting reaction soln is cooled to 25 ℃, then to wherein adding 15ml water, and mixture is filtered.Use 15ml water and the resulting solid of 10ml methanol wash successively, dry then, thus obtain the 1.67g light yellow solid.
By this light yellow solid of high-efficient liquid phase chromatogram technique analysis, the result is, having prepared ratio is the biphenyl-4 of 94: 6 (area percentage), 4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4,4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-(4-chloro-phenyl-) ester (precursor of required product).In addition, by this solid of high performance liquid chromatography quantitative analysis, the result is, contains the biphenyl-4 of 1.51g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 89%, based on biphenyl-4,4 '-dicarboxylic acid two (4-chloro-phenyl-) ester).
Embodiment C-9
Biphenyl-4,4 '-dicarboxylic acid two (2,4 dichloro benzene base) ester synthetic
To internal capacity be 500ml and dispose whipping appts and the flask of thermometer in, add 10.4g (103mmol) triethylamine, 170ml tetrahydrofuran (THF) and 12.9g (78.8mmol) 2,4 dichloro phenol.When fluid temperature being remained on below 30 ℃, in this mixing solutions, add 10.0g (35.8mmol) 4,4 '-biphenyl, two carbonyl chlorides stir resulting mixture 4.5 hours at 25 ℃ then.After reaction is finished, reaction soln is filtered.Filter residue is suspended in the 333ml water and stirred 1 hour at 25 ℃.This mixture is filtered once more, and wash resulting solid with 400ml water and 40ml tetrahydrofuran (THF) successively, dry then, thus the biphenyl-4 of acquisition 17.8g (33.4mmol) white solid form, 4 '-dicarboxylic acid two (2,4 dichloro benzene base) ester (separation yield; 93%, based on 4,4 '-biphenyl, two carbonyl chlorides).
Resulting biphenyl-4,4 '-dicarboxylic acid two (2,4 dichloro benzene base) ester is a kind of new compound, it shows following physical properties.
1H-NMR(300MHz，THF-d
8，δ(ppm))；7.38-7.50(4H，m)，7.60-7.71(2H，m)，7.93-8.01(4H，m)，8.25-8.39(4H，m)
Embodiment C-10
Biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Internal capacity be 25ml and dispose whipping appts and the flask of thermometer in, the synthetic biphenyl-4 in Embodiment C-9 that under argon gas stream, mixes 2.13g (4.00mmol), 4 '-dicarboxylic acid two (2, the 4-dichlorophenyl) ester, 1.31g (12.0mmol) 4-amino-phenol, 15ml N, dinethylformamide and 0.122g (0.800mmol) 1,8-diazabicylo [5,4,0]-7-undecylene.Stirred 16 hours with this mixture heating up and at 92 ℃ fluid temperature.After reaction is finished, reaction soln is cooled to 25 ℃ and to wherein adding 15ml water.This reaction soln is filtered, and use 15ml water and the resulting solid of 10ml methanol wash successively, dry then, thus obtain 1.60g light brown solid.
By this light brown solid of high-efficient liquid phase chromatogram technique analysis, the result is, biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester (required product) and biphenyl-4, the ratio of 4 '-dicarboxylic acid 4-(4-aminophenyl) ester 4 '-(2,4 dichloro benzene base) ester (precursor of required product) is 99: 1 (area percentage).In addition, by this solid of high performance liquid chromatography quantitative analysis, the result is, biphenyl-4, and the amount of 4 '-dicarboxylic acid two (4-aminophenyl) ester is 1.06g (yield: 62%, based on biphenyl-4,4 '-dicarboxylic acid two (2,4 dichloro benzene base) ester).
Synthetic embodiment according to the diamine compound of preparation method II-2
To be shown specifically synthetic embodiment below according to the diamine compound of preparation method II-2.
Embodiment D-1
(A) biphenyl carbamide compound (3,3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1,3-thiazoles alkane-2-thioketones) is synthetic
Be 200ml and dispose in the flask of whipping appts, thermometer and dropping funnel to internal capacity, add 7.26g (0.072mmol) triethylamine, 99ml tetrahydrofuran (THF) and 6.58g (0.055mmol) 2-thiazolidine-2-mercaptan.Then, when fluid temperature is remained on 10 ℃ to wherein adding 7.00g (0.025mol) 4 lentamente, 4 '-biphenyl, two carbonyl chlorides, and make resulting mixture room temperature reaction 17 hours.After reaction is finished, reaction soln is filtered, then filter residue is suspended in the 300ml water and and stirred 1 hour at 25 ℃.Resulting solution is filtered, then successively with 200ml water and 50ml tetrahydrofuran (THF) washing filter residue, then with resulting solid drying, thereby obtain 3 of 10.18g yellow powder form, 3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1,3-thiazoles alkane-2-thioketones (separation yield: 92%, based on 4,4 '-biphenyl, two carbonyl chlorides).
3,3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1,3-thiazoles alkane-the 2-thioketones is a kind of new compound, and it shows following physical properties.
1H-NMR(THF-d
6，δ(ppm))；3.58-3.92(2H，m)，4.45-4.59(2H，m)，7.76-7.93(8H，m)
Embodiment D-2
(B) biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Be 25ml and dispose in the flask of whipping appts, thermometer and dropping funnel to internal capacity, add 60% sodium hydride of 0.35g (8.8mmol), under argon atmospher, when fluid temperature is remained on 5 ℃, add the 14ml tetrahydrofuran (THF) then.Subsequently, fluid temperature being remained in 5 ℃, then resulting mixture was stirred 20 minutes at 25 ℃ to wherein dropwise adding 0.87g (8.0mmol) the 4-amino-phenol that is dissolved in the 34ml tetrahydrofuran (THF) lentamente.Afterwards, fluid temperature is being remained in 5 ℃, in mixing solutions, dropwise add 1.78g (4.0mmol) synthetic biphenyl carbamide compound (3 in embodiment D-1 lentamente, 3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1, and make resulting mixture the 3-thiazolidine-2-thio-ketone), identical thermotonus 2 hours.After reaction is finished, reaction soln filtered and be divided into filter residue and filtrate.Wash resulting filter residue and drying with the 10ml tetrahydrofuran (THF), thereby obtain 1.30g colour of skin solid.By this solid of high-efficient liquid phase chromatogram technique analysis, the result is, contains the biphenyl-4 of 1.20g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 71%, based on 3,3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1,3-thiazoles alkane-2-thioketones).
On the other hand, under reduced pressure resulting filtrate is concentrated.In this enriched material of 2.18g, add 10ml methyl alcohol, then this mixture was at room temperature stirred 30 minutes, and then filter.Dry resulting filter residue.Thereby obtain 0.40g colour of skin solid.By this solid of high-efficient liquid phase chromatogram technique analysis, the result is, contains the biphenyl-4 of 0.34g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 20%, based on 3,3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1,3-thiazoles alkane-2-thioketones).
At this, biphenyl-4, the physical properties of 4 '-dicarboxylic acid two (4-aminophenyl) ester is as follows.
1H-NMR(DMSO-d
6，δ(ppm))；5.10(4H，brs，NH2)，6.40-6.66(4H，m)，6.90-6.98(4H，m)，7.80-8.08(4H，m)，8.01-8.25(4H，m)
Embodiment D-3
(B) biphenyl-4,4 '-dicarboxylic acid two (4-aminophenyl) ester synthetic
Be 25ml and dispose in the flask of whipping appts, thermometer and dropping funnel to internal capacity, add 0.77g (8.0mmol) sodium tert-butoxide and 14ml tetrahydrofuran (THF).To wherein dropwise adding 0.87g (8.0mmol) 4-amino-phenol lentamente, then resulting mixture was stirred 20 minutes at 25 ℃ then.Afterwards, fluid temperature is being remained on the synthetic biphenyl carbamide compound (3 in embodiment D-1 that in mixing solutions, dropwise adds 1.78g (4.0mmol) in 5 ℃ lentamente, 3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1, and resulting mixture was reacted 2 hours under identical temperature the 3-thiazolidine-2-thio-ketone).After reaction is finished, in resulting reaction soln, add 20ml methyl alcohol, and make mixture, and then filter stirring at room 30 minutes.With resulting filter residue and drying, thereby obtain 1.60g colour of skin solid.By this solid of high-efficient liquid phase chromatogram technique analysis, the result is, contains the biphenyl-4 of 1.44g amount, 4 '-dicarboxylic acid two (4-aminophenyl) ester (yield: 85%, based on 3,3 '-(biphenyl-4,4 '-dicarbapentaborane)-two-1,3-thiazoles alkane-2-thioketones).
Industrial applicibility
Polyimides excellent heat resistance of the present invention has low suction percentage and low linear moisture expantion Coefficient, and excellent in dimensional stability. In addition, diamine compound and the intermediate thereof of formula (1) can be used as The raw material of preparation polyimides.
Claims (20)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006305196 | 2006-11-10 | ||
| JP305196/2006 | 2006-11-10 | ||
| JP093731/2007 | 2007-03-30 | ||
| JP093732/2007 | 2007-03-30 | ||
| JP090482/2007 | 2007-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101563395A true CN101563395A (en) | 2009-10-21 |
Family
ID=41221557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800464894A Pending CN101563395A (en) | 2006-11-10 | 2007-11-12 | Polyimide, diamine compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101563395A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463454A (en) * | 2016-01-14 | 2018-08-28 | 日产化学工业株式会社 | Diamines and its utilization |
| CN109427440A (en) * | 2017-08-28 | 2019-03-05 | 丰田自动车株式会社 | Insulated electric conductor |
| CN110218315A (en) * | 2018-03-01 | 2019-09-10 | 中天电子材料有限公司 | The preparation method and substrate of Kapton |
| CN110628025A (en) * | 2010-07-22 | 2019-12-31 | 宇部兴产株式会社 | Polyimide precursor, polyimide and materials used in its preparation |
| CN114616269A (en) * | 2019-11-07 | 2022-06-10 | 聚酰亚胺先端材料有限公司 | Polyimide film with low dielectric and preparation method thereof |
-
2007
- 2007-11-12 CN CNA2007800464894A patent/CN101563395A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628025A (en) * | 2010-07-22 | 2019-12-31 | 宇部兴产株式会社 | Polyimide precursor, polyimide and materials used in its preparation |
| CN110628025B (en) * | 2010-07-22 | 2022-07-12 | 宇部兴产株式会社 | Polyimide precursor, polyimide, and material for use in production thereof |
| CN108463454A (en) * | 2016-01-14 | 2018-08-28 | 日产化学工业株式会社 | Diamines and its utilization |
| CN108463454B (en) * | 2016-01-14 | 2021-03-12 | 日产化学工业株式会社 | Diamine and use thereof |
| CN109427440A (en) * | 2017-08-28 | 2019-03-05 | 丰田自动车株式会社 | Insulated electric conductor |
| CN110218315A (en) * | 2018-03-01 | 2019-09-10 | 中天电子材料有限公司 | The preparation method and substrate of Kapton |
| CN110218315B (en) * | 2018-03-01 | 2021-03-12 | 中天电子材料有限公司 | Preparation method of polyimide film and substrate |
| CN114616269A (en) * | 2019-11-07 | 2022-06-10 | 聚酰亚胺先端材料有限公司 | Polyimide film with low dielectric and preparation method thereof |
| CN114616269B (en) * | 2019-11-07 | 2024-02-13 | 聚酰亚胺先端材料有限公司 | Polyimide film with low dielectric property and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201512345A (en) | Polyimide precursor and polyimide | |
| KR101922417B1 (en) | Diamine compounds, and polyimide compounds and moldings using the same | |
| TWI801480B (en) | Polyimide precursor, polyimide, polyimide film, varnish and substrate | |
| EP2119739A2 (en) | Polyimide, polyamic acid and processes for the production thereof | |
| JP5027416B2 (en) | Aromatic polyamic acid and polyimide | |
| KR101582379B1 (en) | Diamine-based compound and polymer prepared by using the same | |
| US5399715A (en) | Polyamino oligomers and polymaleimide compounds | |
| CN101563395A (en) | Polyimide, diamine compound and method for producing the same | |
| JP5526547B2 (en) | Polyimide, diamine compound and production method thereof | |
| US20240383844A1 (en) | Meta-ester aromatic diamines, method for producing same, and polyimide having said meta-ester aromatic diamines as raw material | |
| JP2025032249A (en) | Resin raw material composition | |
| KR101553234B1 (en) | Polyimide-base poymer, polyamic acid, and flexible metal-clad laminate and printed circuit board using the polymer or the polyamic acid | |
| JP6790756B2 (en) | Polyimide, polyimide precursor, and polyimide film | |
| US5886131A (en) | Method for preparing 1,4-Bis(4-aminophenoxy)naphthalene and its polymers | |
| KR20210033925A (en) | Method for producing polyimide film with excellent transparency and flexibility | |
| JP2011173806A (en) | Phosphorus-containing diamine compound and flame-retardant polyimide | |
| CN111072585A (en) | Diamine containing phenoxazine and amide structures and polyimide thereof | |
| JPH02225522A (en) | Fluorinated polyimide and polyimide acid | |
| JP4907142B2 (en) | Aromatic polyamic acid, polyimide and laminate for wiring board | |
| KR100586107B1 (en) | Flexible metal thin film laminated film containing polyimide flexible insulating film | |
| JP2005314630A (en) | Aromatic polyamic acid and polyimide | |
| KR100607300B1 (en) | A manufacturing method for flexible metal clad laminate film | |
| JP3456256B2 (en) | Polyimide copolymer and method for producing the same | |
| JP7345158B2 (en) | Diamino or dinitrobenzene compound having five aromatic rings, method for producing the same, and polyimide | |
| JP5570793B2 (en) | Phosphorus-containing tetracarboxylic dianhydride and flame retardant polyimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091021 |