CN102060994B - Precursor composition of polyimide and method for preparing polyimide - Google Patents
Precursor composition of polyimide and method for preparing polyimide Download PDFInfo
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- CN102060994B CN102060994B CN 201010552670 CN201010552670A CN102060994B CN 102060994 B CN102060994 B CN 102060994B CN 201010552670 CN201010552670 CN 201010552670 CN 201010552670 A CN201010552670 A CN 201010552670A CN 102060994 B CN102060994 B CN 102060994B
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- polyimide
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 69
- 239000004642 Polyimide Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 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 45
- 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 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- -1 anilide diphenyl phosphine oxide Chemical class 0.000 claims description 25
- 125000003368 amide group Chemical group 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 238000004519 manufacturing process Methods 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
- 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
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 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 21
- 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
- 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
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-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
- 239000002253 acid Substances 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
- 0 CC(CC1C)*=C=C1OCCC=[C@]=CC(C)=CC Chemical compound CC(CC1C)*=C=C1OCCC=[C@]=CC(C)=CC 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 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
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- 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
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-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
- 238000006482 condensation reaction Methods 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
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 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
- 239000000758 substrate Substances 0.000 description 3
- 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 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 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
- DALXKVYCELRTIS-UHFFFAOYSA-N 2,3-dihydro-1h-indene-4,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C2CCCC2=C1C(O)=O DALXKVYCELRTIS-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
- 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 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
- 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
- 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 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 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 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-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
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000001228 spectrum 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-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
- ZJHZCFSWXVUBHT-UHFFFAOYSA-N 2,3-dihydro-1h-indene-5,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC2=C1CCC2 ZJHZCFSWXVUBHT-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
- 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
- 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
- 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
- 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
- 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 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
- YXBIAYXZUDJVEB-UHFFFAOYSA-N Cc(c(C)c1)ccc1-c1ccc(C)c(C)c1 Chemical compound Cc(c(C)c1)ccc1-c1ccc(C)c(C)c1 YXBIAYXZUDJVEB-UHFFFAOYSA-N 0.000 description 1
- FJPWCEGGZNHWPI-UHFFFAOYSA-N Cc(cc1C(F)(F)F)ccc1-c1c(C(F)(F)F)cc(C)cc1 Chemical compound Cc(cc1C(F)(F)F)ccc1-c1c(C(F)(F)F)cc(C)cc1 FJPWCEGGZNHWPI-UHFFFAOYSA-N 0.000 description 1
- PZCRCGZQRHMEDY-UHFFFAOYSA-N Cc(cc1C)ccc1-c1ccc(C)cc1C Chemical compound Cc(cc1C)ccc1-c1ccc(C)cc1C PZCRCGZQRHMEDY-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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-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
- 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
- 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
- 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
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 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
- 238000011076 safety test Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
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 one 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 said compsn 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 semi-conductor requiring on characteristic is increasingly high, 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 receive widely and to note, 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 through the integrated circuit package safety 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 substrate, sensing component, separatory membrane and the structured material, playing the part of the role of key material.
Generally be with synthetic polyimide with the polymerization condensation reaction mode of two-stage.Wherein, diamine monomer is dissolved in the polar aprotic solvent like N-N-methyl 2-pyrrolidone N-(NMP), dimethyl-ethanamide (DMAC), dimethyl amide (DMF) or DMSO 99.8MIN. (DMSO) in the fs usually, again mole of diacid anhydride monomer such as adding., 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 through 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) like the polyamide acidic molecular weight of fs gained, after vinegar imidization (imidization), can't obtain the polyimide film of tool good physical properties.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 leveling characteristics is bad arranged when being easy to be coated with.One example it, being rotated when coating, be easy to generate convexity and webbing etc. and be 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 leveling characteristics 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, the polyimide film of the good rerum natura of tool can be provided just.
The China people close state's patented claim altogether; Application number: 200610162485.X discloses the precursor composition and the application thereof of a polyimide, and wherein vinegar amino acid oligomer end has diamines; The dicarboxylic anhydride verivate 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, at room temperature can't produce reaction with the vinegar amino acid oligopolymer that end have a diamines, and because of vinegar amino acid oligomer molecules amount low; So handling good, and then polyimide of acquisition tool excellent heat character, mechanical properties and tensile property.But said compsn 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 in several hours and just can obtain 100% vinegar imidization; Time-consuming and the easy generation safety-problems of this processing procedure, and when product had the side chain of low bond energy, the pyritous environment tended to before cyclisation, just destroy side chain.
In view of this, the research and development achievement that the present invention promptly does to foregoing problems is through 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 verivate 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 through 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 through 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.One example it (but not as limit), the straight or branched alkyl of 1 to 14 carbon atom of said tool can be methyl, ethyl, n-propyl, sec.-propyl, 1-methyl-propyl, 2-methyl-propyl, normal-butyl, isobutyl-, new butyl, 1-methylbutyl, 2-methylbutyl, amyl group, hexyl, heptyl and octyl group etc.; Substituent R can be a phenolic group independently separately also, for example does
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 naphthenic base 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 do 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 do 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, said quadrivalent organic radical G of group and G
1Be independently to do separately
In one embodiment, said 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) does not have particular restriction, and generally speaking, said divalent organic group P is an aromatic group, preferably independently does 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, said divalent organic group P independently does separately
In a practical implementation method, said 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 definition; And respectively do for oneself 1 to 3 integer of w and z, preferred, said divalent organic group P does
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 does separately
Optional, the present composition can further comprise a polar aprotic solvent.Preferably, said polar aprotic solvent is to be selected from following group: N-N-methyl 2-pyrrolidone N-(NMP), dimethyl-ethanamide (DMAC), dimethyl amide (DMF), DMSO 99.8MIN. (DMSO) and combination thereof.
The present composition is optional comprises the known additive that can be used for preparing polyimide of prior art, one example it (but not as limit): leveling agent, skimmer, 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: UVNUL MS-40, 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.
The method preparation that precursor composition of the present invention can this technical field be known.One example it (but not as limit), 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 like 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 said metering is dissolved in formation one solution in the polar aprotic solvent earlier; Add an amount of dicarboxylic anhydride again, react and make said formula (8) vinegar amino acid oligopolymer.One example it (but not as limit) can be dissolved in the polar aprotic solvent that is selected from following group with diamines earlier: N-N-methyl 2-pyrrolidone N-(NMP), dimethyl-ethanamide (DMAC), dimethyl amide (DMF), DMSO 99.8MIN. (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, and the example comprises (but being 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)-2,3,5 of 4-, 6-benzene tertacarbonic acid dianhydride (P6FDA), 1-(3 ', 4 '-the dicarboxyl phenyl)-1,3; 3-trimethylammonium indane-5,6-dicarboxylic acid dianhydride, 1-(3 ', 4 '-the dicarboxyl phenyl)-1,3,3-trimethylammonium indane-6,7-dicarboxylic acid dianhydride, 1-(3 ', 4 '-the dicarboxyl phenyl)-3-methyl indan-5; 6-dicarboxylic acid dianhydride, 1-(3 ', 4 '-the dicarboxyl phenyl)-3-methyl indan-6,7-dicarboxylic acid dianhydride, 2,3,9,10-perylene tetracarboxylic dianhydride, 1,4; 5,8-naphthalene tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1; 4,5,8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-2,4; 5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-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, be 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 practical 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 definition) diamines, the aromatic diamine known of technical field for this reason.One example it (but not as limit), can adopt the diamines that is selected from following group: 4,4 '-oxydianiline (ODA), Ursol D (pPDA), a dimethyl-to benzidine (DMDB), two (trifluoromethyl) 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-stretch phenylenediamine (tetrafluorophenylene diamine), tetrafluoro--stretch phenylenediamine, 1, two (4-amido the phenoxy)-2-tributyl benzene (BATB), 2 of 4-; 2 '-dimethyl--4,4 '-two (4-amido phenoxy) biphenyl (DBAPB), 2, two [4-(the 4-amido phenoxy) phenyl] HFC-236fas (BAPPH), 2,2 of 2-'-two [4-(4-amido phenoxy) 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 UVNUL MS-40,1; 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 UVNUL MS-40,3,3 '-dimethoxy-4 '; 4 '-two amido UVNUL MS-40,3,3 '-two chloro-4,4 '-two amido UVNUL MS-40,4; 4 '-benzidine ,-phenylenediamine, 4,4 '-methylene dianiline (MDA) (MDA), 4,4 '-sulfenyl pentanoic, 4; 4 '-sulphur anilide pentanoic, 4,4 '-isopropylidene pentanoic, 3,3 '-dimethoxy benzidine, 3; 3 '-dicarboxylate biphenyl amine, 2,4-tolyl diamines, 2,5-tolyl diamines, 2; 6-tolyl diamines ,-xylyl diamines, 2,4-two amidos-5-toluene(mono)chloride, 2,4-two amidos-6-toluene(mono)chloride and the 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 a practical implementation 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, if the nucleophilic reagent that is easy to do is 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 (like 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 under any the present invention technical field and have common knowledge the knowledgeable and show 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), compsn 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 property 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 does not have particular restriction, and all groups that is easy to remove can supply the present invention to use.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 through the protective material reaction that makes tool following formula (a 8) compound and tool following formula (9):
Wherein D be such as preamble definition, i is 0 or 1 integer.
The protective material of formula (9), with N, N '-carbonyl dimidazoles compound is an example; Formula (8) reaction with two ends tool amido can protect amido, and 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 spectrum of gained is 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 is 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 through making a tool following formula (5) and the compound reaction of tool hydroxyl get:
G wherein
1And R be such as preamble definition.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.One example it (but not as limit) can be dissolved in the polar aprotic solvent that is selected from following group with dicarboxylic anhydride earlier: N-N-methyl 2-pyrrolidone N-(NMP), dimethyl-ethanamide (DMAC), dimethyl amide (DMF), DMSO 99.8MIN. (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, divalent 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 said tool comprises (but being 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,
Like
or have the oxy-compound of photosensitive group, it is unsaturated group that said 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 naphthenic base 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 methylacrylic acid (HEMA), 2-hydroxypropyl vinylformic acid, 2-hydroxypropyl methylacrylic acid and combination thereof.Better, said formula (6) compound is to adopt 2-hydroxyethyl vinylformic acid (HEA), 2-hydroxyethyl methylacrylic acid (HEMA) and combination thereof.
Generally speaking, polyimide precursor composition of the present invention, its Chinese style (2) compound is if having photosensitive group, and said compsn 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 compsn of photosensitive group of not having is compared, owing to do not need to be coated with in addition photoresist layer, so can reduce preparation process; On the other hand, the circuit after also can not causing developing because of the extra removal photoresist layer of need is out of shape, and therefore can improve the yield of product.Generally speaking, compsn of the present invention can select suitable compound to come the component (a) and the component (b) of synthetic composition to user demand.
The employed formula of above-mentioned preparation formula (5) dicarboxylic anhydride generally adopts the aromatic diacid acid anhydride, its described formula of optional preamble freely (4) dicarboxylic anhydride.In a practical implementation method, said 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, in solvent, heats 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 compsn, 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 subsequent use.
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 such as preamble definition, and the mole ratio of the component in the said compsn (a) and component (b) is 0.8: 1 to 1.2: 1, is preferably 0.9: 1 to 1.1: 1.
The present invention provides a kind of method of manufacture 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 before cyclisation, just destroy side chain, 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.
One example it, polyimide of the present invention can make through polymerization method shown in the following reaction process:
(a) the vinegar amino acid oligopolymer (for example
) that makes a tool following formula (1) and dewatering agent (for example diacetyl oxide) and catalyzer (like 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 compound 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, be prone to when coating, have shortcomings such as leveling characteristics is bad.In addition, had the high-molecular weight polyamide acidic when the vinegar imidization, be prone to shortening, produced great internal stress, caused institute's substrates coated film buckling deformation because of intermolecular interaction and molecular chain bond distance.
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 is high, carrying out softly when roasting, and solvent and moisture are not volatile, are prone to 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 verivate 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, slowly added the PMDA of 21.59 grams (0.099 mole) again, and the constant temperature reaction is stirred and got final product in 12 hours.
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into methylacrylic 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is 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., the ODA of 20.024 grams (0.1 mole) is added in the solution, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) more thereafter, 50 ℃ of constant temperatures down reaction stirred six hours.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) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into methylacrylic 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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.
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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) is dissolved among the NMP of 200 grams, is 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 property (polydispersity)
Can be known that by table 1 data the inventive method can provide tool the polyimide dispersed than low-grade polymer, that is the molecular weight ranges narrow distribution of obtained polyimide, height molecular weight differences be apart from less, 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 with 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 said omnipotent puller system; Under 23 ℃ of temperature, carry out, speed setting is 10mm/min, respectively to making tensile test by embodiment 1 and 11 compsns and comparative example 1 compsn gained polyimide film; To measure different tensile strength, the result is as shown in table 2:
Table 2
Can know that by table 2 result 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, common variation that those skilled in the art carries out in technical scheme scope of the present invention and replacement all should be included in protection scope of the present invention.
Claims (15)
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 independently is
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 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. compsn 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. compsn 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. compsn as claimed in claim 1 is characterized in that said 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-.
5. compsn as claimed in claim 4 is characterized in that said quadrivalent organic radical group is selected from following group:
6. compsn as claimed in claim 1 is characterized in that said 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.
7. compsn as claimed in claim 6 is characterized in that said divalent organic group is to be selected from following group:
And
8. compsn as claimed in claim 1 is characterized in that D is selected from following group:
9. compsn as claimed in claim 1 is characterized in that m is 5 to 50 integer.
10. compsn 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, DMSO 99.8MIN. and combination thereof.
11. compsn as claimed in claim 1; It is characterized in that further comprising the light trigger that is selected from following group: UVNUL MS-40, 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.
12. compsn 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.
13. a polyimide is characterized in that utilizing like each precursor composition in the claim 1 to 12 making through polyreaction.
14. the method for manufacture of a polyimide is characterized in that comprising with each precursor composition in chemical vinegar imidization method polymerization such as the claim 1 to 12.
15. the method for manufacture of polyimide as claimed in claim 14 is characterized in that said chemical vinegar imidization method is under the temperature of reaction that is not higher than 150 ° of C, to carry out.
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| CN101190969A (en) * | 2006-11-17 | 2008-06-04 | 长兴化学工业股份有限公司 | Precursor composition for polyimide and application thereof |
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| CN101190969A (en) * | 2006-11-17 | 2008-06-04 | 长兴化学工业股份有限公司 | Precursor composition for polyimide and application thereof |
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| JP特开平11-100443A 1999.04.13 |
| JP特开平5-93066A 1993.04.16 |
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