CN102060994A - Precursor composition of polyimide and method for preparing polyimide - Google Patents
Precursor composition of polyimide and method for preparing polyimide Download PDFInfo
- Publication number
- CN102060994A CN102060994A CN2010105526706A CN201010552670A CN102060994A CN 102060994 A CN102060994 A CN 102060994A CN 2010105526706 A CN2010105526706 A CN 2010105526706A CN 201010552670 A CN201010552670 A CN 201010552670A CN 102060994 A CN102060994 A CN 102060994A
- Authority
- CN
- China
- Prior art keywords
- group
- composition
- polyimide
- mole
- grams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 69
- 239000004642 Polyimide Substances 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002243 precursor Substances 0.000 title claims abstract description 31
- 239000000052 vinegar Substances 0.000 claims description 62
- 235000021419 vinegar Nutrition 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 44
- -1 methylpropenyl Chemical group 0.000 claims description 34
- 150000001413 amino acids Chemical class 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000003368 amide group Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000003880 polar aprotic solvent Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- GFXHFYHUJAATBP-UHFFFAOYSA-N CO[Si](OC)(OC)CCCC(N)=O Chemical compound CO[Si](OC)(OC)CCCC(N)=O GFXHFYHUJAATBP-UHFFFAOYSA-N 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- LDKULBOPHABTAT-UHFFFAOYSA-N NC(=O)C=1C=C(C=CC1)[Si](OC)(OC)OC Chemical compound NC(=O)C=1C=C(C=CC1)[Si](OC)(OC)OC LDKULBOPHABTAT-UHFFFAOYSA-N 0.000 claims description 2
- SYGUXQAYOVEDPL-UHFFFAOYSA-N NC(=O)C=1C=C(C=CC1)[Si](OCC)(OCC)OCC Chemical compound NC(=O)C=1C=C(C=CC1)[Si](OCC)(OCC)OCC SYGUXQAYOVEDPL-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 49
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-methyl-pyrrolidinone Natural products CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 22
- 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 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000004952 Polyamide Substances 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 9
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- GLLJEXIFFRQOQX-UHFFFAOYSA-N n-[2-(benzenesulfonamido)-4,5-dimethylphenyl]benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC=1C=C(C)C(C)=CC=1NS(=O)(=O)C1=CC=CC=C1 GLLJEXIFFRQOQX-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006210 cyclodehydration reaction Methods 0.000 description 4
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- FVFYRXJKYAVFSB-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diamine Chemical compound NC1=C(F)C(F)=C(N)C(F)=C1F FVFYRXJKYAVFSB-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MPUIUFJXCAFVGK-UHFFFAOYSA-N 5-[(3-amino-4-methylphenyl)methyl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC=C1CC1=CC=C(C)C(N)=C1 MPUIUFJXCAFVGK-UHFFFAOYSA-N 0.000 description 2
- DWHJJLTXBKSHJG-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid Chemical compound OC(=O)C(C)=CCCO DWHJJLTXBKSHJG-UHFFFAOYSA-N 0.000 description 2
- CUBSYRCTISCQAF-UHFFFAOYSA-N 5-hydroxypent-2-enoic acid Chemical compound OCCC=CC(O)=O CUBSYRCTISCQAF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 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
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- DCTFCVYVHBHICU-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetrafluorobenzene-1,2-diamine Chemical compound FN(F)C1=CC=CC=C1N(F)F DCTFCVYVHBHICU-UHFFFAOYSA-N 0.000 description 1
- RCYNJDVUURMJOZ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC=C1CC1=CC=C(N)C(O)=C1 RCYNJDVUURMJOZ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 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
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- LKHVCEWNPKEPBT-UHFFFAOYSA-N 4-[(4-amino-3-methoxyphenyl)methyl]-2-methoxyaniline Chemical compound C1=C(N)C(OC)=CC(CC=2C=C(OC)C(N)=CC=2)=C1 LKHVCEWNPKEPBT-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 description 1
- ULLLJOGNYWAUJL-UHFFFAOYSA-N 5-hydroxy-2-methylhex-2-enoic acid Chemical compound CC(O)CC=C(C)C(O)=O ULLLJOGNYWAUJL-UHFFFAOYSA-N 0.000 description 1
- XQOCAGXQSXUMHJ-UHFFFAOYSA-N 5-hydroxyhex-2-enoic acid Chemical compound CC(O)CC=CC(O)=O XQOCAGXQSXUMHJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DWTNXDLEYMEHND-NSHAEOJLSA-N C=N/N=N/[NH+]([O-])OCC(CO)(CO[NH+]([N+]1(CC1)[N-]N)[O-])CO[NH+]([N+]([NH-])=C)[O-] Chemical compound C=N/N=N/[NH+]([O-])OCC(CO)(CO[NH+]([N+]1(CC1)[N-]N)[O-])CO[NH+]([N+]([NH-])=C)[O-] DWTNXDLEYMEHND-NSHAEOJLSA-N 0.000 description 1
- 0 CCC(CC)(NC(*(C(C1CC1)O)(C(N(C)PC(CC)(CC)NC(N1C=CNC1)=O)=O)C(N=O)=O)=*)P*C([n]1cncc1)=O Chemical compound CCC(CC)(NC(*(C(C1CC1)O)(C(N(C)PC(CC)(CC)NC(N1C=CNC1)=O)=O)C(N=O)=O)=*)P*C([n]1cncc1)=O 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N Cc(cc1)ccc1O Chemical compound Cc(cc1)ccc1O IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CJQVURJLLPOIIJ-UHFFFAOYSA-N FN(C1=C(C=CC=C1)N(F)F)F.C1(=C(C=CC=C1)N)N Chemical compound FN(C1=C(C=CC=C1)N(F)F)F.C1(=C(C=CC=C1)N)N CJQVURJLLPOIIJ-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CHISTDPSKQQHCD-UHFFFAOYSA-N NC(=O)C1=CC=C(C=C1)P(CC)=O Chemical compound NC(=O)C1=CC=C(C=C1)P(CC)=O CHISTDPSKQQHCD-UHFFFAOYSA-N 0.000 description 1
- WQSQCMCLIATTKL-UHFFFAOYSA-N NC(=O)C1=CC=C(C=C1)[SiH](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound NC(=O)C1=CC=C(C=C1)[SiH](C1=CC=CC=C1)C1=CC=CC=C1 WQSQCMCLIATTKL-UHFFFAOYSA-N 0.000 description 1
- RVOLIYOJRZKPHS-UHFFFAOYSA-N NC(=O)C1=CC=C(C=C1)[SiH](CC)CC Chemical compound NC(=O)C1=CC=C(C=C1)[SiH](CC)CC RVOLIYOJRZKPHS-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- LBDSXVIYZYSRII-IGMARMGPSA-N alpha-particle Chemical compound [4He+2] LBDSXVIYZYSRII-IGMARMGPSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- AGSPXMVUFBBBMO-UHFFFAOYSA-N beta-aminopropionitrile Chemical compound NCCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FFYPMLJYZAEMQB-UHFFFAOYSA-N diethyl pyrocarbonate Chemical compound CCOC(=O)OC(=O)OCC FFYPMLJYZAEMQB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XPEFOHCUPVNIAG-UHFFFAOYSA-N perylene-2,3,9,10-tetracarboxylic acid Chemical compound C1=CC2=C(C(O)=O)C(C(=O)O)=CC(C=3C4=C5C=CC(=C4C(C(O)=O)=CC=3)C(O)=O)=C2C5=C1 XPEFOHCUPVNIAG-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a precursor composition of polyimide and a method for preparing polyimide. The precursor composition of the polyimide comprises an acid amide oligomer which is shown as a formula (1) and a dicarboxylic anhydride derivative which is shown as a formula (2) and of which the tail end is provided with an ester group, namely (-C(O)OR) and a carboxyl group, namely (-C(O)OH), wherein R, G, G1, P, D and m are defined in the specifications. The invention also provides polyimide synthesized from the precursor composition.
Description
The application is that application number is dividing an application of 200910001935.0 Chinese patent application;
The applying date of original application is: on January 14th, 2009;
The application number of original application is: 200910001935.0;
The denomination of invention of original application is: the precursor composition of polyimide and prepare the method for polyimide.
The precursor composition of polyimide and prepare the method for polyimide
Technical field
The invention relates to a kind of polyimide precursor composition of (polyimide is called for short PI), the present invention also relates to the application of described composition in the preparation of polyimide.
Background technology
Polyimide is the first-selection of high performance polymer material owing to having excellent heat-resistant quality and favorable mechanical, electric and chemical property always.In addition, because the requirement of semi-conductor on characteristic be more and more higher, and traditional inorganic materials has its limit and shortcoming of using, and the characteristic of polyimide just can remedy the insufficient place of traditional material in some aspects.Therefore, after the aromatic series polyimide technological development of E.I.Du Pont Company, promptly be subjected to noting widely, and develop and many multiduty polyimides that have.
On semi-conductor industry, polyimide is widely used in aspects such as passive film, stress buffer film, alpha-particle shielding film, dry-etching shield cap, micro electronmechanical and interlayer dielectric, and develops other new purposes just successively.Wherein, with as the protection integrated circuit package film be applied as large, because of the polyimide material can be by the integrated circuit package reliability test.The application of polyimide only is not used for integrated circuit industry, and is all quite important on remaining electronic packaging, enameled wire, printed circuit board (PCB), sensing component, separatory membrane and the structured material, playing the part of the role of key material.
Generally be with synthetic polyimide in the polymerization condensation reaction mode of two-stage.Wherein, diamine monomer is dissolved in polar aprotic solvent in the fs usually, again mole of diacid anhydride monomer such as adding as N-N-methyl 2-pyrrolidone N-(NMP), dimethyl ethanamide (DMAC), dimethyl amide (DMF) or dimethyl sulfoxide (DMSO) (DMSO)., under low temperature or normal temperature carry out condensation reaction, form polyimide precursor (precursor) thereafter, that is, and polyamide acidic (poly (amic acid); Abbreviate PAA as).
Then, carry out subordinate phase,, carry out the reaction of condensation cyclodehydration, change polyamide acidic into polyimide by the vinegar imidization (thermal imidization) of type of heating or the vinegar imidization (chemical imidization) of chemical mode.
The reaction process of preparation polyimide can be summarized as follows at present:
In above-mentioned preparation method, do not reach certain standard (that is, molecular weight is too small) as the polyamide acidic molecular weight of fs gained, after vinegar imidization (imidization), can't obtain the polyimide film of the good rerum natura of tool.If the molecular weight of fs gained polyamide acidic is too high, then its viscosity just can be too big, so that the operability variation, shortcomings such as levelling property is bad arranged when being easy to be coated with.Say it for example, when being rotated coating, being easy to generate convexity and webbing etc. and being difficult for the levelling phenomenon.In addition, too high polyamide acidic molecular weight will be when the vinegar imidization of carrying out subordinate phase, and the shortening because of intermolecular interaction and molecular chain bond distance produces very big internal stress, causes institute's substrates coated flexural deformation.Therefore, for exempting foregoing problems, extensively inquired into the heating gradient curve and the internal stress relation of the imidization of subordinate phase vinegar on the document already, and worked out the mode of various reduction internal stress.Yet aforementioned levelling property and internal stress problem are traced it to its cause, all from fs gained polyamide acidic molecular weight too high due to.In other words, if can properly control the polyamide acidic molecular weight, just can provide the polyimide film of the good rerum natura of tool.
The China people close state's patent application altogether, application number: 200610162485.X, disclose the precursor composition and the application thereof of a polyimide, wherein vinegar amino acid oligomer end has diamines, the dicarboxylic anhydride derivative then has the ester group (end group of C (O) OR and carboxyl (C (O) OH) simultaneously, can be in the steady state (meta-stable status) that is situated between with vinegar amino acid oligopolymer, the vinegar amino acid oligopolymer generation reaction that at room temperature can't have diamines with end, and because of vinegar amino acid oligomer molecules amount low, so handling good, and then obtain tool excellent heat character, the polyimide of mechanical properties and tensile property.But described composition but only can be confined to the vinegar imidization of type of heating.Generally speaking, with the imidization of heating method vinegar, need under 250 ℃～350 ℃ high temperature, to carry out long thermalization of a few hours and just can obtain 100% vinegar imidization, this processing procedure is time-consuming and easily produce safety problem, and when product had the side chain of low bond energy, the pyritous environment tended to just side chain be destroyed before cyclisation.
In view of this, the research and development achievement that the present invention promptly does at foregoing problems is by special synthesis mode, via the precursor composition of specific polyimide, cyclodehydration at low temperatures, and take into account under the situation of operability, provide have desire the polyimide film of rerum natura, meet the demand of industry.
Summary of the invention
First purpose of the present invention is to provide a kind of precursor composition of polyimide, and it comprises the dicarboxylic anhydride derivative that vinegar amino acid oligopolymer and end have ester group (C (O) OR) and carboxyl (C (O) OH).
Second purpose of the present invention is to provide a kind of polyimide, and it is that precursor composition by the above-mentioned polyimide of polymerization obtains polyimide.
The 3rd purpose of the present invention is to provide a kind of method for preparing polyimide, and it is the precursor composition by the above-mentioned polyimide of chemical vinegar imidization method polymerization.
The precursor composition of polyimide of the present invention is to comprise:
(a) the vinegar amino acid oligopolymer of a tool following formula (1)
And
(b) compound of a tool following formula (2)
Wherein, R is a unsaturated group for straight or branched alkyl, phenolic group or the ethene of 1 to 14 carbon atom of tool independently separately;
G and G
1Can be the identical or different and independent separately quadrivalent organic radical group that is;
P is a divalent organic group;
D is separately independently for nitrogenous heterocyclic group or for containing OR
*Group, R wherein
*Straight or branched alkyl for 1 to 20 carbon atom of tool; And
M is 1 to 100 integer, is preferably 5 to 50 integer.
It is 0.8: 1 to 1.2: 1 that above-mentioned component (a) is counted ratio with the not ear of component (b), is preferably 0.9: 1 to 1.1: 1.
According to specific examples of the present invention, the substituent R of the straight or branched alkyl of 1 to 14 carbon atom of tool of above-mentioned formula (2) compound is to be selected from:
Wherein n is 0 to 10 integer.Say it (but not as limit) for example, the straight or branched alkyl of 1 to 14 carbon atom of described tool can be methyl, ethyl, n-propyl, sec.-propyl, 1-methyl-propyl, 2-methyl-propyl, normal-butyl, isobutyl-, new butyl, 1-methyl butyl, 2-methyl butyl, amyl group, hexyl, heptyl and octyl group etc.; Substituent R can be a phenolic group independently separately also, for example is
R wherein
1Be the C that stretches phenyl, straight or branched
1-C
8Stretch the C of alkyl, straight or branched
2-C
8Stretch thiazolinyl, C
3-C
8Stretch the C of cycloalkyl or straight or branched
1-C
8Hydroxyl is stretched alkyl; And R
2Be hydrogen or C
1-C
4Alkyl.
Preferably, the substituent R in the above-mentioned formula (2) is independently to be separately
——CH
3、——CH
2CH
3、——CH
2CH
2CH
3、?
According to the present invention, G and G
1Can be identical or different quadrivalent organic radical group, preferably independently be separately
Wherein Y independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; And B is-CH
2-,-O-,-S-,-CO-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-.Better, described quadrivalent organic radical G of group and G
1Be independently to be separately
In one embodiment, described quadrivalent organic radical G of group and G
1Be
The contained divalent organic group P of vinegar amino acid oligopolymer of formula of the present invention (1) there is no particular restriction, and generally speaking, described divalent organic group P is an aromatic group, preferably independently is separately
Wherein, X independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl, and A be-O-,-S-,-CO-,-CH
2-,-OC (O)-or-CONH-.Better, described divalent organic group P independently is separately
In a specific implementation method, described divalent organic group P is
Above-mentioned divalent organic group P also can be the non-aromatic group, for example:
Wherein, X such as preamble define; And respectively do for oneself 1 to 3 integer of w and z, preferred, described divalent organic group P is
The contained group D of the vinegar amino acid oligopolymer of formula of the present invention (1) is separately independently for nitrogenous heterocyclic group or for containing OR
*Group, R wherein
*Straight or branched alkyl for 1 to 20 carbon atom of tool preferably independently is separately
Optionally, the present composition can further comprise a polar aprotic solvent.Preferably, described polar aprotic solvent is to be selected from following group: N-N-methyl 2-pyrrolidone N-(NMP), dimethyl ethanamide (DMAC), dimethyl amide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and combination thereof.
The present composition optionally comprises the known additive that can be used for preparing polyimide of prior art, says it (but not as limit) for example: leveling agent, defoamer, coupler, dewatering agent, catalyzer and light trigger etc.
Be applicable to that light trigger of the present invention can be (but not as limit) and is selected from following group: benzophenone, bitter almond oil camphor, 2-hydroxy-2-methyl-1-Propiophenone, 2,2-dimethoxy-1,2-phenylbenzene second-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2,4,6-Three methyl Benzene first anilide diphenyl phosphine oxide and combination thereof.
Can be used for coupler of the present invention is to be selected from following group: 3-aminocarbonyl propyl Trimethoxy silane (APrTMOS), 3-three amido propyl-triethoxysilicanes (APrTEOS), 3-aminocarbonyl phenyl Trimethoxy silane (APTMOS), 3-aminocarbonyl phenyl triethoxyl silane (APTEOS) and combination thereof.
Precursor composition of the present invention can the known method preparation of this technical field.Say it (but not as limit) for example, the formula in the precursor composition of the present invention (1) vinegar amino acid oligopolymer can prepare in the following manner:
At first, make and have formula H
2N-P-NH
2Diamines mix with dicarboxylic anhydride and react with following formula (4), obtain the vinegar amino acid oligopolymer (8) that an end has two amidos:
Wherein G and P are defined as preamble.Preferably, according to institute think the molecular weight size (being the m value) of vinegar amino acid oligopolymer, calculate required diamines consumption, the diamines of described metering is dissolved in formation one solution in the polar aprotic solvent earlier, add an amount of dicarboxylic anhydride again, react and make described formula (8) vinegar amino acid oligopolymer.Say it (but not as limit) for example, can earlier diamines be dissolved in the polar aprotic solvent that is selected from following group: N-N-methyl 2-pyrrolidone N-(NMP), dimethyl ethanamide (DMAC), dimethyl amide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and combination thereof.The reaction of diamines and dicarboxylic anhydride, in 0 to 100 ℃ usually, be preferably under 0 to 50 ℃ the temperature and carry out, last 5 to 12 hours usually.
In the step of above-mentioned preparation formula (8) vinegar amino acid oligopolymer, the dicarboxylic anhydride of formula (4) is preferably the aromatic diacid acid anhydride, the example is including (but not limited to) pyromellitic dianhydride (PMDA), 4,4-two phthalandione dianhydrides (BPDA), 4,4 '-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P3FDA), 1, two (trifluoromethyl)-2 of 4-, 3,5,6-benzene tertacarbonic acid dianhydride (P6FDA), 1-(3 ', 4 '-the dicarboxyl phenyl)-1,3,3-trimethylammonium indane-5, the 6-dicarboxylic acid dianhydride, 1-(3 ', 4 '-the dicarboxyl phenyl)-1,3,3-trimethylammonium indane-6, the 7-dicarboxylic acid dianhydride, 1-(3 ', 4 '-the dicarboxyl phenyl)-3-methyl indan-5, the 6-dicarboxylic acid dianhydride, 1-(3 ', 4 '-the dicarboxyl phenyl)-3-methyl indan-6, the 7-dicarboxylic acid dianhydride, 2,3,9,10-perylene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-2,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 4,4 '-isopropylidene two phthalandione dianhydrides, 3,3 '-isopropylidene two phthalandione dianhydrides, 4,4 '-oxygen base two phthalandione dianhydrides, 4,4 '-sulphur anilide two phthalandione dianhydrides, 3,3 '-oxygen base two phthalandione dianhydrides, 4,4 '-methylene radical two phthalandione dianhydrides, 4,4 '-sulfenyl two phthalandione dianhydrides, 4,4 '-ethylene phthalandione dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and pyridine-2,3,5,6-tetracarboxylic dianhydride and combination thereof.
Preferably, it is to adopt the aromatic diacid acid anhydride that is selected from following group: pyromellitic dianhydride (PMDA), 4,4-two phthalandione dianhydrides (BPDA), 4,4 '-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P3FDA) and 1, two (trifluoromethyl)-2,3 of 4-, 5,6-benzene tertacarbonic acid dianhydride (P6FDA) and combination thereof.In a specific implementation method, be to adopt pyromellitic dianhydride (PMDA).
Employed formula H in the method shown in the above-mentioned preparation formula
2N-P-NH
2(wherein P such as preamble define) diamines, the known aromatic diamine of technical field for this reason.Say it (but not as limit) for example, can adopt the diamines that is selected from following group: 4,4 '-oxydianiline (ODA), Ursol D (pPDA), between dimethyl to benzidine (DMDB), between two (trifluoromethyls) to benzidine (TFMB), 3,3 '-dimethyl-4,4 '-benzidine (oTLD), 4,4 '-octafluoro p-diaminodiphenyl (OFB), tetrafluoro-p-phenylenediamine (TFPD), 2,2 '-5,5 '-tetrachloro benzidine (TCB), 3,3 '-dichlorobenzidine (DCB), 2,2 '-two (3-aminocarbonyl phenyl) HFC-236fa, 2,2 '-two (4-aminocarbonyl phenyl) HFC-236fa, 4,4 '-oxygen base-two [3-(trifluoromethyl) aniline, 3,5-two amido phenylfluoroforms (3,5-diaminobenzotrifluoride), tetrafluoro-1,4-stretches phenylenediamine (tetrafluorophenylene diamine), tetrafluoro--phenylenediamine stretched, 1, two (4-amido the phenoxy group)-2-tributyl benzene (BATB) of 4-, 2,2 '-dimethyl-4,4 '-two (4-amido phenoxy group) biphenyl (DBAPB), 2, two [4-(the 4-amido phenoxy group) phenyl] HFC-236fa (BAPPH) of 2-, 2,2 '-two [4-(4-amido phenoxy group) phenyl] norborneol alkane (BAPN), 5-amido-1-(4 '-aminocarbonyl phenyl)-1,3,3-trimethylammonium indane, 6-amido-1-(4 '-aminocarbonyl phenyl)-1,3,3-trimethylammonium indane, 4,4 '-methylene-bis (neighbour-chloroaniline), 3,3 '-dichloro diphenylamine, 3,3 '-sulphur anilide pentanoic, 4,4 '-two amido benzophenone, 1,5-two amido naphthalenes, two (4-aminocarbonyl phenyl) diethylsilane, two (4-aminocarbonyl phenyl) diphenyl silane, two (4-aminocarbonyl phenyl) ethyl phosphine oxide, N-(two (4-aminocarbonyl phenyl))-N-methylamine, N-(two (4-aminocarbonyl phenyl))-N-phenyl amine, 4,4 '-methylene-bis (2-aminotoluene), 4,4 '-methylene-bis(2methoxyaniline), 5,5 '-methylene-bis (2-amino-phenol), 4,4 '-methylene-bis (2-aminotoluene), 4,4 '-oxygen base two (2-anisidine), 4,4 '-oxygen base two (2-chloroaniline), 2,2 '-two (4-amino-phenols), 5,5 '-oxygen base two (2-amino-phenol), 4,4 '-sulfenyl two (2-aminotoluene), 4,4 '-sulfenyl two (2-anisidine), 4,4 '-sulfenyl two (2-chloroaniline), 4,4 '-sulphur anilide two (2-aminotoluene), 4,4 '-sulphur anilide two (2-phenetidine), 4,4 '-sulphur anilide two (2-chloroaniline), 5,5 '-sulphur anilide two (2-amino-phenol), 3,3 '-dimethyl-4,4 '-two amido benzophenone, 3,3 '-dimethoxy-4 ', 4 '-two amido benzophenone, 3,3 '-two chloro-4,4 '-two amido benzophenone, 4,4 '-benzidine, between-phenylenediamine, 4,4 '-methylene dianiline (MDA) (MDA), 4,4 '-the sulfenyl pentanoic, 4,4 '-sulphur anilide pentanoic, 4,4 '-the isopropylidene pentanoic, 3,3 '-dimethoxy benzidine, 3,3 '-dicarboxylate biphenyl amine, 2,4-tolyl diamines, 2,5-tolyl diamines, 2,6-tolyl diamines, between-the xylyl diamines, 2,4-two amidos-5-toluene(mono)chloride, 2,4-two amidos-6-toluene(mono)chloride, and combination.Preferably, be to adopt 4,4 '-oxydianiline (ODA), Ursol D (pPDA), a dimethyl to benzidine (DMDB), two (trifluoromethyl) to benzidine (TFMB), 3,3 '-dimethyl-4,4 '-benzidine (oTLD) or 4,4 '-methylene dianiline (MDA) (MDA) or its combination.In concrete enforcement in the aspect, be adopt 4,4 '-oxydianiline (ODA).
Because the vinegar amino acid oligopolymer end group of formula (8) is an amido, contain lone electron pair on the nitrogen-atoms of amido, nucleophilic reagent is easy to do, if directly with the imidization of chemical method vinegar, the vinegar amino acid oligopolymer of formula (8) can react with the carbon atom that has the part positive charge, reactions such as vinegarization take place in therefore meeting and dewatering agent (as diacetyl oxide) reaction, cause vinegar amino acid oligopolymer can't continue to aggregate into the high-molecular weight polyimide.For solving this technical problem, this case contriver discovers and can use a blocking group that the amido of the vinegar amino acid oligopolymer of formula (8) is carried out temporary protection, promptly utilizes protective material, for example nitrogen heterocyclic ring compounds or contain OR
*Group (wherein, R
*Straight or branched alkyl group for 1 to 20 carbon atom of tool) compound is with the amido reaction generation blocking group of vinegar amino acid oligopolymer, with amido and the dewatering agent reaction of avoiding vinegar amino acid oligopolymer.Be applicable to protective material of the present invention; can be any the technical field of the invention has and knows that usually the knowledgeable shows and Yi Zhizhe; it is such as but not limited to N; N '-carbonyl dimidazoles (N; N '-Carbonyldiimidazole; CDI), burnt ethylene carbonate (Diethyl pyrocarbonate, DEPC) or two carbonic acid, two tri-n-butyls (Di-tert-butyl dicarbonate, Boc
2O), composition of the present invention is applicable to chemical vinegar imidization method.Compared to the vinegar imidization of type of heating, chemical vinegar imidization method processing procedure fast and film good, again owing to use and contain the less vinegar amino acid oligopolymer of viscosity and work as precursor, so when being coated with, high-leveling and operability are arranged.
Above-mentioned amido blocking group there is no particular restriction, and all groups that is easy to remove can use for the present invention.According to a specific embodiment, the present invention utilizes nitrogenous heterocyclic group or contains OR
*Group amido is protected, wherein, R
*Be the straight or branched alkyl group of 1 to 20 carbon atom of tool, the better protection group is to be selected from following group:
Contained formula (1) compound is prepared as follows shown in the formula in the present composition, can get by the protective material reaction that makes tool following formula (a 8) compound and tool following formula (9):
Wherein D defines as preamble, and i is 0 or 1 integer.
The protective material of formula (9); with N; N '-carbonyl dimidazoles compound is an example, and formula (8) reaction with two ends tool amido can protect amido; reaction process is as follows; in addition, with a use N, after N '-carbonyl dimidazoles compound protects two ends to have the vinegar amino acid oligopolymer of amido; carry out NMR again and analyze, the hydrogen of gained is composed as shown in Figure 1:
If as protective material, its reaction process is as follows with two carbonic acid, two tri-n-butyls, in addition, use two carbonic acid, two tri-n-butyls to protect two ends to have the vinegar amino acid oligopolymer of amido with one after, carry out NMR again and analyze, the hydrogen spectrum of gained as shown in Figure 2:
Contained formula (2) compound is prepared as follows shown in the formula in the present composition, and the dicarboxylic anhydride that can be by making a tool following formula (5) and the compound reaction of tool hydroxyl get:
G wherein
1And R defines as preamble.Preferably, be earlier dicarboxylic anhydride to be dissolved in the aprotic solvent, add the compound of tool hydroxyl again, be formed at formula (2) compound that dual-side has ester group (C (O) OR) and carboxyl (C (O) OH) with reaction.Say it (but not as limit) for example, can earlier dicarboxylic anhydride be dissolved in the polar aprotic solvent that is selected from following group: N-N-methyl 2-pyrrolidone N-(NMP), dimethyl ethanamide (DMAC), dimethyl amide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and combination thereof.In this reaction, dicarboxylic anhydride is 1: 1.8 to 1: 2.5 with the mole dosage ratio of the compound of tool hydroxyl, is preferably in 1: 1.9 to 1: 2.1 the scope.Reaction generally is to carry out under in 50 to 90 ℃ the temperature, and preferably in 50 to 60 ℃ are carried out; Reaction lasts 1 to 3 hours usually.
Can be used for the compound of tool hydroxyl of the present invention, comprise alcohols, for example monohydroxy-alcohol, dibasic alcohol or polyvalent alcohol are preferably monohydroxy-alcohol.Can be used for the straight or branched alkyl alcohol that monohydroxy-alcohol of the present invention can be 1 to 14 carbon atom of tool, for example:
Wherein, n is 1 to 10 integer.The straight or branched alkyl alcohol of 1 to 14 carbon atom of described tool is including (but not limited to) methyl alcohol, ethanol, n-propyl alcohol, Virahol, 1-methylpropanol, propyl carbinol, isopropylcarbinol, new butanols, 1-methyl butanol, 2-methyl butanol, amylalcohol, hexanol, enanthol and octanol.
The compound that can be used for the tool hydroxyl in the inventive method also can be dihydroxy-benzene,
As
Or having the oxy-compound of photosensitive group, it is unsaturated group that described photosensitive group can be ethene.The oxy-compound that has a photosensitive group is such as but not limited to vinyl alcohol, vinylcarbinol, methylallyl alcohol, n-butene alcohol, isobutene alcohol, vinyl benzene alcohol, propenylbenzene alcohol, propenyloxy group methyl alcohol, propenyloxy group ethanol, the propenyloxy group propyl alcohol, the propenyloxy group butanols, the propenyloxy group amylalcohol, the propenyloxy group hexanol, metacryloxy methyl alcohol, metacryloxy ethanol, the metacryloxy propyl alcohol, the metacryloxy butanols, the metacryloxy amylalcohol, the metacryloxy hexanol, have the compound of following formula (6) and have the compound of following formula (10):
Wherein, R
1Be the C that stretches phenyl, straight or branched
1-C
8Stretch the C of alkyl, straight or branched
2-C
8Stretch thiazolinyl, C
3-C
8Stretch the C of cycloalkyl or straight or branched
1-C
8Hydroxyl is stretched alkyl, and R
2Be hydrogen or C
1-C
4Alkyl.Preferably, above-mentioned formula (6) compound is to be selected from following group: 2-hydroxyethyl vinylformic acid (HEA), 2-hydroxyethyl methacrylic acid (HEMA), 2-hydroxypropyl vinylformic acid, 2-hydroxypropyl methacrylic acid and combination thereof.Better, described formula (6) compound is to adopt 2-hydroxyethyl vinylformic acid (HEA), 2-hydroxyethyl methacrylic acid (HEMA) and combination thereof.
Generally speaking, polyimide precursor composition of the present invention, its Chinese style (2) compound is if having photosensitive group, described composition is fit to be applied to micro-photographing process, its former because, because of self has photosensitive group, so can have the effect of photoresistance and insulation layer concurrently, the composition of photosensitive group of not having is compared, since do not need to be coated with in addition photoresist layer, preparation process can be reduced, on the other hand, can not be out of shape yet, therefore can improve the yield of product because of the circuit that need are additionally removed after photoresist layer causes developing.Generally speaking, composition of the present invention can select suitable compound to come the component (a) and the component (b) of synthetic composition at user demand.
The employed formula of above-mentioned preparation formula (5) dicarboxylic anhydride generally adopts the aromatic diacid acid anhydride, and it is optional from formula (4) dicarboxylic anhydride as previously described.In a specific implementation method, described formula (5) dicarboxylic anhydride is a pyromellitic dianhydride.
This case contriver finds that existing preparation technology forms the method for the precursor composition of polyimide, needs the bigger polyamide acidic of first synthetic molecular weight, heats in solvent and degrades, and utilizes viscosity to control the molecular weight of gained.This kind method often makes that water ratio is too high in the composition, so need to store (as: subzero 20 ℃) at low temperatures, to slow down proceeding of degraded, avoids molecular weight too small.And the present invention need not utilize the mode of degraded can effectively control the molecular weight of gained, and is more stable yet, can at room temperature preserve standby.
But the present invention also provides a kind of polyimide of low temperature cyclisation, and it is to utilize the precursor composition of the polyimide that contains following composition to be polymerized:
(a) the vinegar amino acid polymers of a tool following formula (1)
And
(b) compound of a tool following formula (2)
Wherein, R, G, G1, P, D and m all define as preamble, and the mole ratio of the component in the described composition (a) and component (b) is 0.8: 1 to 1.2: 1, are preferably 0.9: 1 to 1.1: 1.
The present invention provides a kind of manufacture method of polyimide in addition, and it comprises the precursor composition that utilizes above-mentioned polyimide, is polymerized with chemical vinegar imidization method (chemical imidization).
Above-mentioned chemical vinegar imidization method, its reaction mechanism is (dewatering agent is example with the diacetyl oxide):
Above-mentioned chemical vinegar imidization method is meant formula (1) vinegar amino acid oligopolymer under the effect of dewatering agent, produces leaving group (leaving group) CH
3COO-, remove leaving group after, the process of vinegar imidization takes place.Be applicable to the dewatering agent kind among the present invention, particular restriction for example not can be acid anhydrides, is preferably diacetyl oxide.In addition, be accelerated reaction, can add catalyzer, for example triethylamine or pyridine.The advantage of chemistry vinegar imidization method can be reacted for (about below 200 ℃) at low temperatures.General high temperature vinegar imidization, when product had the side chain of low bond energy, the pyritous environment tended to just side chain be destroyed before cyclisation, or cause during cyclisation chain and chain between excessive crosslinked and the indissoluble that becomes is not easy to operate.According to the present invention, can under the low temperature that is not higher than under 150 ℃, carry out the vinegar imidization, above shortcoming can be overcome, and the energy can be saved.
Say it for example, polyimide of the present invention can make by polymerization process shown in the following reaction process:
(a) the vinegar amino acid oligopolymer that makes a tool following formula (1) (for example
) and dewatering agent (for example diacetyl oxide) and catalyzer (as pyridine), with chemical vinegar imidization method, carry out the reaction of condensation cyclodehydration, form formula (11) compound:
(b), form the vinegar imines oligopolymer of formula (12) with formula (11) compound hydrolysis:
(c) compound of adding type (2) in step (b) gained formula (12) vinegar imines oligopolymer forms the dicarboxylic anhydride of formula (5):
And
(d) dicarboxylic anhydride of formula (5) and formula (12) vinegar imines oligopolymer carry out condensation reaction, carry out intramolecular cyelization then, carry out intermolecular polymerization and cyclic action again, form polyimide
In the synthetic method of existing polyimide, all need the polyamide acidic of first synthetic macromolecule amount to be used as precursor, but because molecular weight is too high, and viscosity is too big, so that the operability variation, shortcomings such as levelling property is bad are arranged when coating easily.In addition, had the high-molecular weight polyamide acidic when the vinegar imidization, easily, produced great internal stress, caused institute's substrates coated film buckling deformation because of intermolecular interaction and molecular chain bond distance's shortening.
On the other hand, the polyimide of prior art is synthetic, the solid content when its polyreaction forms polyamide acidic, only approximately between 10% to 30%, therefore volumetric shrinkage is bigger than (shrinkable) after cyclisation, needs repeatedly coating can reach the thickness of product requirement, increases the preparation difficulty.Moreover the precursor of the polyimide of prior art is in the end during cyclodehydration, because of its viscosity height, carrying out softly when roasting, and solvent and moisture are not volatile, easily produce bubble when therefore in the end being roasted into film firmly.
Constituent of the present invention is low because of vinegar amino acid oligomer molecules amount, and therefore handling good, coating can reach smooth effect.And polyimide of the present invention is the dicarboxylic anhydride derivative polymerization that utilizes vinegar amino acid oligopolymer and formula (2); because the vinegar amino acid oligomer end of formula (1) has the blocking group that is easy to remove; therefore at room temperature can't produce reaction with dewatering agent; therefore can under low condition, use chemical vinegar imidization method; aggregate into bigger molecule, form polyimide with excellent heat character, mechanical properties and tensile property.
Compared with prior art, work as precursor, but not therefore the bigger polyamide acidic polymer of viscosity when coating, can present than high-leveling and operability because use contains vinegar amino acid oligopolymer (viscosity is less).In addition, because the molecule of the contained component of the present composition is less, therefore when carrying out the vinegar imidization, can avoid producing because of the high internal stress due to interaction between polymer and molecular chain bond distance's the shortening, and contained vinegar amino acid oligopolymer is earlier through intramolecular cyelization, carry out intermolecular polymerization and cyclic action again, therefore can effectively reduce the remaining internal stress of polyimide, have the not advantage of warpage.
Polyimide of the present invention, because its precursor composition has the high solids content between 25% to 50% (high solids content) approximately, so can reduce the consumption of solvent, shorten the soft roasting time and reduce soft roasting temperature, and it is fast and be reduced to and reach the required advantages such as coating number of times of product requirement thickness to have drying and forming-film speed.
General high molecular polymerization all can add some monomers or short chain oligomer, makes molecule and intermolecular energy form interlinkage (crosslinking).According to a preferred specific embodiment, when the contained formula of precursor composition of the present invention (2) but when compound has the sensitization polymer-based group because molecule is little, thus can the oneself when solidifying crosslinked, form stable and the stronger reticulated structure of toughness.Therefore, compared with prior art, the present invention need not to use extra unsaturated monomer or oligomer.
Description of drawings
Fig. 1: after utilizing CDI to protect two ends to have the vinegar amino acid oligopolymer of amido, the NMR hydrogen spectrogram of gained;
Fig. 2: utilize Boc
2After O protects two ends to have the vinegar amino acid oligopolymer of amido, the NMR hydrogen spectrogram of gained;
Embodiment
The pyromellitic acid dianhydride (pyromellitic dianhydride, hereinafter referred is PMDA) of 2.181 grams (0.01 mole) is dissolved in the N-N-methyl 2-pyrrolidone N-(N-methyl-2-pyrrolidinone of 200 grams; Be designated hereinafter simply as NMP) in, heating gained mixture to 50 ℃, reaction was stirred two hours again.Splash into the vinylformic acid 2-hydroxy methacrylate (2-Hydroxyethyl acrylate, hereinafter referred is HEA) of 2.322 grams (0.02 mole), react down for 50 ℃ at constant temperature and stirred two hours.Thereafter, with 20.024 the gram (0.1 mole) 4,4 '-oxydianiline (4,4 '-oxy-dianiline, hereinafter referred is ODA) add in the solution, after treating to dissolve fully, the PMDA that adds 18.0216 grams (0.09 mole) again reacts stirring six hours down for 50 ℃ at constant temperature.And then the N of adding 3.243g (0.02 mole), N '-carbonyl dimidazoles (N, N '-Carbonyldiimidazole; CDI), react stirring one hour down for 50 ℃ at constant temperature.
Comparative example 1
The ODA of 20.024 grams (0.1 mole) is dissolved among the NMP of 200 grams, ice bath to 0 ℃ and reaction were stirred one hour, thereafter the anhydride phthalic acid (phthalic anhydride) that adds 0.29 gram (0.002 mole), question response stirred after one hour, the PMDA that slowly adds 21.59 grams (0.099 mole) again, the constant temperature reaction is stirred and was got final product in 12 hours.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into methacrylic acid 2-hydroxyethyl ester (the 2-hydroxyethyl methacrylate of 2.60 grams (0.02 mole); Hereinafter referred is HEMA), constant temperature reacts down for 50 ℃ and stirred two hours.ODA with 20.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirs six hours then.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.Ursol D (para-phenylenediamine, hereinafter referred is pPDA) with 10.814 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.PPDA with 10.814 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reacts stirring two hours down.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.Again with 21.23 the gram (0.1 mole) between dimethyl to benzidine (dimethyl-dibenzilidene, hereinafter referred is DMDB) add in the solution, after treating to dissolve fully, add the PMDA of 18.0216 grams (0.09 mole) again, constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.DMDB with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.Again with 21.23 the gram (0.1 mole) 3,3 '-dimethyl-4,4 '-benzidine (o-Tolidine; Hereinafter referred is oTLD) add in the solution, after treating to dissolve fully, add the PMDA of 18.0216 grams (0.09 mole) again, constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.602 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.OTLD with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.Again with 32.024 the gram (0.1 mole) between two (trifluoromethyls) to benzidine (meta-bis (trifluoromethyl)-benzilidine, hereinafter referred is TFMB) add in the solution, after treating to dissolve fully, the PMDA that adds 18.0216 grams (0.09 mole) again, constant temperature react down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.TFMB with 32.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.The CDI that adds 3.243g (0.02 mole) again reacts stirring one hour down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, and heating gained mixture to 50 ℃ and reaction were stirred two hours.Splash into the HEA of 2.322 grams (0.02 mole), react down for 50 ℃ at constant temperature and stirred two hours., 20.024 ODAs that restrain (0.1 mole) added in solution, after treating to dissolve fully, add the PMDA of 18.0216 grams (0.09 mole) again, react down for 50 ℃ at constant temperature and stirred six hours thereafter.And then two carbonic acid, two tri-n-butyl (the Di-tert-butyl dicarbonate of adding 4.365g (0.02 mole); Hereinafter referred is Boc
2O), react stirring five hours down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into methacrylic acid 2-hydroxyethyl ester (the 2-hydroxyethyl methacrylate of 2.60 grams (0.02 mole); Hereinafter referred is HEMA), constant temperature reacts down for 50 ℃ and stirred two hours.ODA with 20.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.Again with the pPDA of 10.814 grams (0.1 mole)) add in the solution, after treating to dissolve fully, add the PMDA of 18.0216 grams (0.09 mole) again, 50 ℃ of constant temperatures reaction down stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.PPDA with 10.814 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
Embodiment 15
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reacts stirring two hours down.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.DMDB with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
Embodiment 16
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.DMDB with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
Embodiment 17
The PMDA of 2.181 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.OTLD with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
Embodiment 18
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.602 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.OTLD with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
Embodiment 19
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.TFMB with 32.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
Embodiment 20
The PMDA of 2.181 grams (0.01 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), constant temperature reacts down for 50 ℃ and stirred two hours.TFMB with 32.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, and constant temperature reacts down for 50 ℃ and stirred six hours.And then the Boc of adding 4.365g (0.02 mole)
2O reacts stirring five hours down for 50 ℃ at constant temperature.
The polyimide physical property measurement
At first utilize the molecular weight of the HT-GPC apparatus measures of Waters Model:2010 by the foregoing description and the prepared polyimide of comparative example, the gained data is as shown in table 1 below:
Table 1
(1) peak molecular weight
(2) polymer dispersed (polydispersity)
By table 1 data as can be known, the inventive method can provide the polyimide of tool than the low-grade polymer dispersiveness, that is the molecular weight ranges narrow distribution of obtained polyimide, height molecular weight differences be apart from less, and its quality is better.
Get embodiment 1,11 and comparative example 1 resulting composition, after giving solidification treatment and obtaining the polyimide film, macromolecular material is made film in the mode of rotary coating.Further toast again, and heating curve is divided into three sections with baking oven.Be respectively 150 ℃/60min, 250 ℃/60min and 350 ℃/120min, after its heat-up rate was 2 ℃/min, cooling was risen again and is promptly carried out physical property measurement.
Then, utilize omnipotent puller system (the hot bending determinator Model 9102 that HTC produces) to carry out the test of polyimide film mechanical properties.Gained polyimide film is cut into the size of 12cm * 10cm * 0.25mm, mount on described omnipotent puller system, under 23 ℃ of temperature, carry out, speed setting is 10mm/min, respectively to making tensile test by embodiment 1 and 11 compositions and comparative example 1 composition gained polyimide film, to measure different tensile strength, the result is as shown in table 2:
Table 2
By table 2 result as can be known, polyimide film provided by the present invention can represent comparatively excellent tensile strength and elongation.
Above-described embodiment, the present invention embodiment a kind of more preferably just, the common variation that those skilled in the art carries out in the technical solution of the present invention scope and replacing all should be included in protection scope of the present invention.
Claims (16)
1. the precursor composition of a polyimide, it comprises
(a) the vinegar amino acid oligopolymer of a tool following formula (1):
(b) compound of a tool following formula (2)
Wherein
R is a unsaturated group for straight or branched alkyl, phenolic group or the ethene of 1 to 14 carbon atom of tool independently separately;
Described ethene is that unsaturated group is to be selected from following group: vinyl, propenyl, methylpropenyl, the n-butene base, isobutenyl, ethenylphenyl, the propenyl phenyl, the propenyloxy group methyl, the propenyloxy group ethyl, the propenyloxy group propyl group, the propenyloxy group butyl, the propenyloxy group amyl group, the propenyloxy group hexyl, the metacryloxy methyl, the metacryloxy ethyl, the metacryloxy propyl group, the metacryloxy butyl, the metacryloxy amyl group, the group of metacryloxy hexyl and tool following formula (7):
G and G
1Can be the identical or different and independent separately quadrivalent organic radical group that is;
P is a divalent organic group;
D independently is nitrogenous heterocyclic group separately or is OR
*Group, wherein R
*Straight or branched alkyl for 1 to 20 carbon atom of tool; And
M is 1 to 100 integer.
2. composition as claimed in claim 1 is characterized in that the component (a) and the mole ratio of component (b) are 0.8: 1 to 1.2: 1.
3. composition as claimed in claim 1 is characterized in that the component (a) and the mole ratio of component (b) are 0.9: 1 to 1.1: 1.
4. composition as claimed in claim 1 is characterized in that R independently is separately
——CH
3、——CH
2CH
3、——CH
2CH
2CH
3、
5. composition as claimed in claim 1 is characterized in that described quadrivalent organic radical group is selected from following group:
Wherein Y independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; And B is-CH
2-,-O-,-S-,-CO-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-.
6. composition as claimed in claim 5 is characterized in that described quadrivalent organic radical group is selected from following group:
7. composition as claimed in claim 1 is characterized in that described divalent organic group is to be selected from following group:
Wherein X independently is hydrogen, halogen, C separately
1-C-
4Alkyl or C
1-C
4Perfluoroalkyl; A is-O-,-S-,-CO-,-CH
2-,-OC (O)-or-CONH-; And respectively do for oneself 1 to 3 integer of w and z.
8. composition as claimed in claim 7 is characterized in that described divalent organic group is to be selected from following group:
And
9. composition as claimed in claim 1 is characterized in that D is selected from following group:
10. composition as claimed in claim 1 is characterized in that m is 5 to 50 integer.
11. composition as claimed in claim 1 is characterized in that further comprising the polar aprotic solvent that is selected from following group: N-N-methyl 2-pyrrolidone N-, dimethyl ethanamide, dimethyl amide, dimethyl sulfoxide (DMSO) and combination thereof.
12. composition as claimed in claim 1, it is characterized in that further comprising the light trigger that is selected from following group: benzophenone, bitter almond oil camphor, 2-hydroxy-2-methyl-1-Propiophenone, 2,2-dimethoxy-1,2-phenylbenzene second-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2,4,6-Three methyl Benzene first anilide diphenyl phosphine oxide and combination thereof.
13. composition as claimed in claim 1 is characterized in that further comprising the coupler that is selected from following group: 3-aminocarbonyl propyl Trimethoxy silane, 3-three amido propyl-triethoxysilicanes, 3-aminocarbonyl phenyl Trimethoxy silane, and 3-aminocarbonyl phenyl triethoxyl silane and combination thereof.
14. a polyimide is characterized in that utilizing as each precursor composition in the claim 1 to 14 through polyreaction and the person of making.
15. the manufacture method of a polyimide is characterized in that comprising with each precursor composition in chemical vinegar imidization method polymerization such as the claim 1 to 14.
16. the manufacture method of polyimide as claimed in claim 15 is characterized in that described chemical vinegar imidization method is to carry out not being higher than under 150 ℃ the temperature of reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010552670 CN102060994B (en) | 2009-01-14 | 2009-01-14 | Precursor composition of polyimide and method for preparing polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010552670 CN102060994B (en) | 2009-01-14 | 2009-01-14 | Precursor composition of polyimide and method for preparing polyimide |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100019350A Division CN101492540B (en) | 2009-01-14 | 2009-01-14 | Forerunner composition of polyimide and method for preparing polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102060994A true CN102060994A (en) | 2011-05-18 |
| CN102060994B CN102060994B (en) | 2012-12-05 |
Family
ID=43996511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010552670 Expired - Fee Related CN102060994B (en) | 2009-01-14 | 2009-01-14 | Precursor composition of polyimide and method for preparing polyimide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102060994B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273614A (en) * | 2015-10-12 | 2016-01-27 | 广东省宜华木业股份有限公司 | UV super-hydrophobic polyimide paint prepared by room temperature reaction and used for wood material surface |
| CN108192098A (en) * | 2016-11-30 | 2018-06-22 | 长兴材料工业股份有限公司 | Polyimide precursor composition and use thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165079B (en) * | 2006-10-20 | 2011-05-25 | 长兴化学工业股份有限公司 | Polyamide acid ester oligomer, precursor composition of polyimide resin containing the same and application thereof |
| CN101190969B (en) * | 2006-11-17 | 2010-05-19 | 长兴化学工业股份有限公司 | Precursor composition for polyimide and application thereof |
-
2009
- 2009-01-14 CN CN 201010552670 patent/CN102060994B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273614A (en) * | 2015-10-12 | 2016-01-27 | 广东省宜华木业股份有限公司 | UV super-hydrophobic polyimide paint prepared by room temperature reaction and used for wood material surface |
| CN108192098A (en) * | 2016-11-30 | 2018-06-22 | 长兴材料工业股份有限公司 | Polyimide precursor composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102060994B (en) | 2012-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101190969B (en) | Precursor composition for polyimide and application thereof | |
| JP5935158B2 (en) | Precursor composition for polyimide and use thereof | |
| JP4498382B2 (en) | Amine ester oligomer, precursor composition for polyimide resin containing the same, and use | |
| TWI488887B (en) | Polyimides, coating composition formed therefrom and use thereof | |
| KR101442841B1 (en) | Precursor for polyimide and use thereof | |
| TWI621642B (en) | Precursor for polyimide and use thereof | |
| TWI707890B (en) | Polyimine compound and molded article containing the polyimine | |
| CN101492540B (en) | Forerunner composition of polyimide and method for preparing polyimide | |
| CN107189067A (en) | Polyimide precursor and application thereof | |
| WO2014038538A1 (en) | Polyimide, and heat resistant material | |
| CN101117384B (en) | Precursor of polyimide and uses thereof | |
| CN101165079B (en) | Polyamide acid ester oligomer, precursor composition of polyimide resin containing the same and application thereof | |
| CN102060994B (en) | Precursor composition of polyimide and method for preparing polyimide | |
| CN105295374A (en) | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article | |
| CN101698704B (en) | Polyimide precursor composition and application thereof | |
| CN102219901B (en) | Amic acid ester oligomer, precursor composition of polyimide resin containing amic acid ester oligomer, and application thereof | |
| TWI341851B (en) | Precursor composition for polyimide and use thereof | |
| CN114014810B (en) | Imidization rate accelerator, resin composition, preparation method and application thereof | |
| JP6844850B2 (en) | Polyimide compound, polyamic acid and molded article containing the polyimide compound | |
| JP6765093B2 (en) | Polyimide | |
| JP6812002B2 (en) | Polyimide compound, polyamic acid and molded article containing the polyimide compound | |
| KR101777450B1 (en) | Composition for formimg polyimide film and polyimide film prepared by using same | |
| Wang et al. | Low-temperature Curable and high Tg Polyimide with a pyrazine-contained unsaturated diamine | |
| JP2007099841A (en) | Novel polyimide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: ETERNAL MATERIALS CO., LTD. Free format text: FORMER NAME: CHANGXING CHEMICAL INDUSTRIAL CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: China's Taiwan City, Kaohsiung three people's District, 578 road construction Patentee after: ETERNAL MATERIALS CO.,LTD. Address before: China's Taiwan City, Kaohsiung three people's District, 578 road construction Patentee before: ETERNAL CHEMICAL CO.,LTD. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121205 |