JP2015074683A - Method for producing polyamide resin, polyamideimide resin or polyimide resin - Google Patents
Method for producing polyamide resin, polyamideimide resin or polyimide resin Download PDFInfo
- Publication number
- JP2015074683A JP2015074683A JP2013210429A JP2013210429A JP2015074683A JP 2015074683 A JP2015074683 A JP 2015074683A JP 2013210429 A JP2013210429 A JP 2013210429A JP 2013210429 A JP2013210429 A JP 2013210429A JP 2015074683 A JP2015074683 A JP 2015074683A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- acid
- iron
- carboxylic acid
- polyamideimide
- 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
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- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 37
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 35
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229920001721 polyimide Polymers 0.000 title claims abstract description 29
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000001412 amines Chemical class 0.000 claims abstract description 35
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000002966 varnish Substances 0.000 description 13
- -1 carboxylic acid halide Chemical class 0.000 description 12
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 150000003628 tricarboxylic acids Chemical class 0.000 description 10
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-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
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 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 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- 239000013034 phenoxy resin Substances 0.000 description 2
- 229920006287 phenoxy resin 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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- KYEACNNYFNZCST-UHFFFAOYSA-N 1-methylpyrrolidine-2,5-dione Chemical compound CN1C(=O)CCC1=O KYEACNNYFNZCST-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 1
- YYDRNPOEMZZTPM-UHFFFAOYSA-N 2,4,6-triaminotoluene Chemical compound CC1=C(N)C=C(N)C=C1N YYDRNPOEMZZTPM-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- DGBKTJIQJQNAIN-UHFFFAOYSA-N 2-butyl-3-methylbutanedioic acid Chemical compound CCCCC(C(O)=O)C(C)C(O)=O DGBKTJIQJQNAIN-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- QLVKECUOHNDWOI-UHFFFAOYSA-N 2-oxo-1,3,2$l^{5}-diazaphosphonan-2-amine Chemical compound NP1(=O)NCCCCCCN1 QLVKECUOHNDWOI-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
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- ZIKOFLSRJZCPKF-UHFFFAOYSA-N 3-(4-aminophenoxy)benzoic acid Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(C(O)=O)=C1 ZIKOFLSRJZCPKF-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- NJCOLSAFYMXOGO-UHFFFAOYSA-N 3-(trifluoromethyl)benzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(F)(F)F)=C1C(O)=O NJCOLSAFYMXOGO-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 description 1
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 1
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- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 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
- IRNVCLJBFOZEPK-UHFFFAOYSA-N pyridine-2,3,6-triamine Chemical compound NC1=CC=C(N)C(N)=N1 IRNVCLJBFOZEPK-UHFFFAOYSA-N 0.000 description 1
- MWVKGSABHBJPOX-UHFFFAOYSA-N pyridine-2,4,6-triamine Chemical compound NC1=CC(N)=NC(N)=C1 MWVKGSABHBJPOX-UHFFFAOYSA-N 0.000 description 1
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- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 description 1
- YKWDNEXDHDSTCU-UHFFFAOYSA-N pyrrolidine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1NC(C(O)=O)C(C(O)=O)C1C(O)=O YKWDNEXDHDSTCU-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- XYDGZBIMFVKRQW-UHFFFAOYSA-N thiophene-2,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)S1 XYDGZBIMFVKRQW-UHFFFAOYSA-N 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、多価カルボン酸と多価アミン、アミノカルボン酸又はこれらの組み合わせを原料とした、ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の製造方法に関する。 The present invention relates to a method for producing a polyamide resin, a polyamideimide resin or a polyimide resin using a polycarboxylic acid and a polyvalent amine, an aminocarboxylic acid or a combination thereof as raw materials.
ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の製造方法は、（ａ）多価カルボン酸誘導体と多価アミンの組み合わせ、多価カルボン酸と多価アミン誘導体の組み合わせ、又は多価カルボン酸誘導体と多価アミン誘導体の組み合わせを原料とする製造方法と、（ｂ）多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせを原料とする製造方法に大別できる。 The method for producing the polyamide resin, polyamideimide resin or polyimide resin is as follows: (a) a combination of a polyvalent carboxylic acid derivative and a polyvalent amine, a combination of a polyvalent carboxylic acid and a polyvalent amine derivative, or a polyvalent carboxylic acid derivative and a polyvalent amine. It can be roughly divided into a production method using a combination of amine derivatives as a raw material and (b) a production method using a polyvalent carboxylic acid and a polyvalent amine, an aminocarboxylic acid, or a combination thereof as a raw material.
上記（ａ）の例としては、多価カルボン酸誘導体であるカルボン酸エステルと多価アミンを高温下で長時間加熱してポリアミド樹脂を製造する方法（特許文献１）、多価カルボン酸誘導体であるカルボン酸エステルと多価アミンを触媒存在下で反応させポリアミド樹脂を製造する方法（特許文献２）、多価カルボン酸誘導体である酸無水物と多価アミンとの反応によって生じたポリアミド酸を熱的又は化学的に処理してポリイミド樹脂を製造する方法（特許文献３）、多価カルボン酸誘導体であるカルボン酸ハロゲン化物と多価アミンを触媒の存在下で反応させポリアミド樹脂を製造する方法（特許文献４）、多価カルボン酸と多価アミン誘導体又はアミノカルボン酸誘導体であるイソシアネートを反応させポリアミド樹脂を製造する方法（非特許文献１）、多価カルボン酸誘導体である無水トリメリット酸と多価アミン誘導体であるイソシアネートを反応させポリアミドイミド樹脂を製造する方法（特許文献５）、多価カルボン酸誘導体である酸無水物と多価アミン誘導体であるイソシアネートを反応させポリイミド樹脂を製造する方法（特許文献６）、多価カルボン酸誘導体のトリメリット酸クロライドと多価アミンを反応させポリアミドイミド樹脂を製造する方法（特許文献７）等が知られている。 Examples of the above (a) include a method of producing a polyamide resin by heating a carboxylic acid ester which is a polyvalent carboxylic acid derivative and a polyvalent amine for a long time at a high temperature (Patent Document 1). A method of producing a polyamide resin by reacting a certain carboxylic acid ester with a polyvalent amine in the presence of a catalyst (Patent Document 2), a polyamic acid generated by the reaction of a polycarboxylic acid derivative with an acid anhydride and a polyvalent amine A method of producing a polyimide resin by thermal or chemical treatment (Patent Document 3), A method of producing a polyamide resin by reacting a carboxylic acid halide that is a polyvalent carboxylic acid derivative with a polyvalent amine in the presence of a catalyst. (Patent Document 4), a method for producing a polyamide resin by reacting a polyvalent carboxylic acid with an isocyanate which is a polyvalent amine derivative or aminocarboxylic acid derivative ( Patent Document 1), a method of producing a polyamideimide resin by reacting a trimellitic anhydride, which is a polyvalent carboxylic acid derivative, and an isocyanate, which is a polyvalent amine derivative (Patent Document 5), an acid anhydride which is a polyvalent carboxylic acid derivative A method for producing a polyimide resin by reacting an isocyanate, which is a polyvalent amine derivative (Patent Document 6), and a method for producing a polyamidoimide resin by reacting a trimellitic acid chloride of a polyvalent carboxylic acid derivative and a polyvalent amine (Patent Document 6) 7) etc. are known.
上記（ｂ）の例としては、多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせから形成されるアンモニウム塩を高温下で長時間加熱してポリアミド樹脂を製造する方法（特許文献８）、ホウ酸触媒の存在下に反応させポリアミド樹脂を製造する方法（特許文献９、非特許文献２）、ＤＣＣ（ジシクロヘキシルカルボジイミド）等の縮合剤を用いて反応させポリアミド樹脂を製造する方法（特許文献１０）、脱水触媒の存在下に１６０℃で反応させポリアミド樹脂を製造する方法（特許文献１１）、アルカリ金属水酸化物、アルカリ金属炭酸塩及び／又はアルカリ金属炭酸水素塩から選ばれる１種又はそれ以上の触媒の存在下にスルホランを溶剤として用いて反応させポリアミド及び／又はポリアミド酸樹脂を製造する方法（特許文献１２）、脱水触媒並びにニトロベンゼン、ｏ−ニトロトルエン及びベンゾニトリルからなる群より選ばれる溶剤の存在下に加熱してポリアミドイミド樹脂を製造する方法（特許文献１３）、ホスホネート触媒の存在下に反応させポリアミド樹脂を製造する方法（特許文献１４）等が知られている。 As an example of the above (b), a method for producing a polyamide resin by heating an ammonium salt formed from a polyvalent carboxylic acid and a polyvalent amine, an aminocarboxylic acid, or a combination thereof for a long time at a high temperature (Patent Document) 8) A method for producing a polyamide resin by reacting in the presence of a boric acid catalyst (Patent Document 9, Non-Patent Document 2) and a reaction using a condensing agent such as DCC (dicyclohexylcarbodiimide) ( Patent Document 10), a method of producing a polyamide resin by reacting at 160 ° C. in the presence of a dehydration catalyst (Patent Document 11), an alkali metal hydroxide, an alkali metal carbonate and / or an alkali metal bicarbonate 1 A polyamide and / or polyamic acid resin is produced by reacting with sulfolane as a solvent in the presence of a seed or a catalyst. (Patent Document 12), a method for producing a polyamideimide resin by heating in the presence of a dehydration catalyst and a solvent selected from the group consisting of nitrobenzene, o-nitrotoluene and benzonitrile (Patent Document 13), in the presence of a phosphonate catalyst A method of producing a polyamide resin by reacting with (Patent Document 14) is known.
ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の製造方法において、上記（ａ）では、原料となる多価カルボン酸誘導体及び多価アミン誘導体の入手が必ずしも容易でなく、入手できる場合でも高価である場合がある。さらに、イソシアネート、酸無水物及びカルボン酸ハロゲン化物は空気中の水分と反応しやすいため、取り扱い及び保存に注意が必要である。また、カルボン酸ハロゲン化物を用いる製造方法では生成する副生成物の除去を必要とし、必ずしも経済的に有利な製造方法ではない。一方、上記（ｂ）では、高温下で反応できる設備又は高価な触媒を必要としたり、使用できる多価カルボン酸、多価アミン又は溶剤が限定される場合があり、必ずしも簡便で経済的に有利な製造方法ではなかった。 In the method for producing a polyamide resin, a polyamideimide resin or a polyimide resin, in the above (a), it is not always easy to obtain a polyvalent carboxylic acid derivative and a polyvalent amine derivative as raw materials, and even when available, they may be expensive. is there. Furthermore, since isocyanates, acid anhydrides and carboxylic acid halides easily react with moisture in the air, care must be taken in handling and storage. In addition, the production method using a carboxylic acid halide requires removal of by-products to be produced, and is not necessarily an economically advantageous production method. On the other hand, in the above (b), equipment that can react at a high temperature or an expensive catalyst may be required, and the polyvalent carboxylic acid, polyvalent amine, or solvent that can be used may be limited. It was not a simple manufacturing method.
本発明は、空気中で安定な多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせから、容易にポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂を製造する方法を提供することを目的とする。 An object of the present invention is to provide a method for easily producing a polyamide resin, a polyamideimide resin, or a polyimide resin from a polyvalent carboxylic acid stable in air and a polyvalent amine, an aminocarboxylic acid, or a combination thereof. To do.
本発明は、多価カルボン酸と多価アミン、アミノカルボン酸又はこれらの組み合わせを原料としたポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の製造において、鉄系触媒を用いることを特徴とする、ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の製造方法を提供する。 The present invention relates to a polyamide resin characterized by using an iron-based catalyst in the production of a polyamide resin, a polyamideimide resin or a polyimide resin using a polycarboxylic acid and a polyvalent amine, an aminocarboxylic acid or a combination thereof as raw materials. A method for producing a polyamide-imide resin or a polyimide resin is provided.
本発明によれば、入手が容易で安価な鉄系触媒を用いて、空気中で安定な多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせを原料として、ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂を効率よく製造できる。 According to the present invention, an easily available and inexpensive iron-based catalyst is used as a raw material for a polyvalent carboxylic acid, a polyvalent amine, an aminocarboxylic acid, or a combination thereof, which are stable in air, as a raw material. Resin or polyimide resin can be produced efficiently.
また、上記鉄系触媒が鉄又は酸化鉄である場合、鉄系触媒が溶剤に難溶であることから、鉄系触媒の除去がより容易である。 Moreover, when the said iron-type catalyst is iron or iron oxide, since an iron-type catalyst is hardly soluble in a solvent, removal of an iron-type catalyst is easier.
一方、ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂が溶剤に可溶であることは、反応の効率及び製造物の取り扱いがより容易となる点で好ましい。 On the other hand, it is preferable that the polyamide resin, the polyamideimide resin or the polyimide resin is soluble in a solvent from the viewpoint that the efficiency of the reaction and the handling of the product become easier.
さらに、多価カルボン酸又は多価アミンのうち少なくとも１種がポリオキシアルカンジイル基を含有することが、製造された樹脂が溶剤に可溶化しやすくなる点で好ましい。 Furthermore, it is preferable that at least one of the polyvalent carboxylic acid or the polyvalent amine contains a polyoxyalkanediyl group from the viewpoint that the produced resin is easily solubilized in a solvent.
本発明によれば、入手が容易で安価な鉄系触媒を用いて、空気中で安定な多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせを原料とし、ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の効率的な製造方法が提供される。 According to the present invention, a readily available and inexpensive iron-based catalyst is used as a raw material from a polyvalent carboxylic acid, a polyvalent amine, an aminocarboxylic acid, or a combination thereof, which are stable in the air, and a polyamide resin, a polyamideimide An efficient method for producing a resin or polyimide resin is provided.
本発明の、多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせを原料とし、鉄系触媒を用いて、ポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂を効率的に製造する方法の好適な実施形態について、以下に説明する。 Suitable for the method of efficiently producing a polyamide resin, a polyamideimide resin or a polyimide resin using an iron-based catalyst using a polyvalent carboxylic acid and a polyvalent amine, an aminocarboxylic acid, or a combination thereof as raw materials. Such an embodiment will be described below.
本発明は、多価カルボン酸と多価アミン、アミノカルボン酸、又はこれらの組み合わせを原料とし、鉄系触媒の存在下に重合反応を行うことで効率よく対応するポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂を得ることができるものである。 The present invention uses a polyvalent carboxylic acid and a polyvalent amine, an aminocarboxylic acid, or a combination thereof as raw materials, and performs a polymerization reaction in the presence of an iron-based catalyst to efficiently cope with a polyamide resin, a polyamideimide resin, or a polyimide A resin can be obtained.
上記鉄系触媒は、効率と経済性、入手の容易さの観点から、鉄又は鉄化合物であることが好ましい。本発明に係る反応機構の詳細は明らかとなっていないが、発明者らは鉄又は鉄化合物がカルボン酸のカルボニル基と相互作用をし、カルボニル基の炭素の求電子性を高めているためではないかと推測している。 The iron-based catalyst is preferably iron or an iron compound from the viewpoints of efficiency, economy, and availability. Although the details of the reaction mechanism according to the present invention have not been clarified, the inventors have not been able to interact with the carbonyl group of the carboxylic acid to increase the electrophilicity of carbon of the carbonyl group. I'm guessing.
鉄化合物としては、鉄の酸化物、水酸化物、炭酸化物、硫化物、硝酸化物、硫酸化物、フッ化物、塩化物、臭化物、ヨウ化物、カルボン酸塩、有機金属化合物を例示でき、具体的には酸化鉄（ＩＩ）、酸化鉄（ＩＩＩ）、水酸化鉄（ＩＩ）、酸化水酸化鉄（ＩＩＩ）、炭酸鉄（ＩＩ）、硫化鉄（ＩＩ）、硫化鉄（ＩＩＩ）、硝酸鉄（ＩＩ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸鉄（ＩＩＩ）、フッ化鉄（ＩＩ）、フッ化鉄（ＩＩＩ）、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、臭化鉄（ＩＩ）、臭化鉄（ＩＩＩ）、ヨウ化鉄（ＩＩ）、酢酸鉄（ＩＩ）、鉄（ＩＩＩ）アセチルアセトナート、フェロセン、ペンタカルボニル鉄（０）等を挙げることができる。またこれら鉄化合物の水和物も触媒として用いることができ、２種以上を併用することもできる。 Examples of iron compounds include iron oxides, hydroxides, carbonates, sulfides, nitrates, sulfates, fluorides, chlorides, bromides, iodides, carboxylates, and organometallic compounds. Include iron oxide (II), iron oxide (III), iron hydroxide (II), iron oxide hydroxide (III), iron carbonate (II), iron sulfide (II), iron sulfide (III), iron nitrate ( II), iron nitrate (III), iron sulfate (II), iron sulfate (III), iron fluoride (II), iron fluoride (III), iron chloride (II), iron chloride (III), iron bromide (II), iron (III) bromide, iron (II) iodide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, iron pentacarbonyl (0) and the like. Moreover, the hydrate of these iron compounds can also be used as a catalyst, and can also use 2 or more types together.
鉄系触媒の使用量は、カルボン酸の質量を基準として０.０００１〜０.５当量、好ましくは０.００１〜０.１当量用いることにより、収率良く目的物を得ることができる。また、鉄系触媒が溶剤に不溶又は難溶の場合は、触媒効率は触媒の表面積に依存する傾向があるため、粒状、塊状、線状等の形状の触媒を上記の使用量の範囲以上に用いることが好ましい。このようにバルクで用いる場合、生成した樹脂を含むワニスのろ過性が向上する点で有利である。 When the iron-based catalyst is used in an amount of 0.0001 to 0.5 equivalent, preferably 0.001 to 0.1 equivalent based on the mass of the carboxylic acid, the target product can be obtained in good yield. In addition, when the iron-based catalyst is insoluble or hardly soluble in the solvent, the catalyst efficiency tends to depend on the surface area of the catalyst. Therefore, the granular, massive, or linear shape of the catalyst exceeds the above usage amount range. It is preferable to use it. Thus, when using in bulk, it is advantageous at the point which the filterability of the varnish containing the produced | generated resin improves.
本発明において、重合反応は１８０℃以上で行うことが好ましく、１８０〜２２０℃で行うことが特に好ましい。１８０℃以上であると鉄系触媒の効果がより高くなる傾向にあり、２２０℃以下である場合は汎用溶剤を用いることができ、さらにフィルム形成の乾燥時に高温を必要としないためコスト的により有利となる。 In the present invention, the polymerization reaction is preferably performed at 180 ° C. or higher, and particularly preferably performed at 180 to 220 ° C. If the temperature is 180 ° C. or higher, the effect of the iron-based catalyst tends to be higher. If the temperature is 220 ° C. or lower, a general-purpose solvent can be used. It becomes.
本発明において、重合反応は溶剤中で行うことが好ましい。反応に使用できる溶剤としては、１８０℃以上の沸点を有し、生成するポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂を反応温度で溶解させるものであることがさらに好ましい。１８０℃以上の沸点を有する溶剤が、上記反応温度の理由から好ましく、１８０℃未満の沸点を有する溶剤を使用する場合は加圧密閉容器中で、上記反応温度で使用するのが好ましい。一方、生成する樹脂が反応溶剤に溶解する場合、重合速度が遅くならずに、分子量分布が小さくなる傾向にある。 In the present invention, the polymerization reaction is preferably performed in a solvent. The solvent that can be used for the reaction is more preferably a solvent that has a boiling point of 180 ° C. or higher and dissolves the polyamide resin, polyamideimide resin, or polyimide resin to be produced at the reaction temperature. A solvent having a boiling point of 180 ° C. or higher is preferable for the above reaction temperature. When a solvent having a boiling point of less than 180 ° C. is used, it is preferably used at the above reaction temperature in a pressurized sealed container. On the other hand, when the produced resin is dissolved in the reaction solvent, the polymerization rate does not become slow and the molecular weight distribution tends to be small.
具体的な溶剤としては、Ｎ−メチルピロリドン、Ｎ−エチルピロリドン、Ｎ−メチルスクシイミド、ジメチルフラン、キシレン、テトラリン、Ｎ，Ｎ−ジメチルアセトアミド、ヘキサメチレンホスホルアミド、ジメチルスルホキシド、γ−ブチロラクトン、エチレングリコール、エチレングリコールジアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、モノ酢酸ジエチレングリコールモノメチルエーテル、シクロヘキサノン等を挙げることができる。１８０℃以上の沸点と生成する樹脂の溶解性の観点から、特にＮ−メチルピロリドン、Ｎ−エチルピロリドン、γ−ブチロラクトンが好ましい。これらの溶剤は、単独で用いてもよく、２種以上を併用してもよい。 Specific solvents include N-methylpyrrolidone, N-ethylpyrrolidone, N-methylsuccinimide, dimethylfuran, xylene, tetralin, N, N-dimethylacetamide, hexamethylene phosphoramide, dimethyl sulfoxide, and γ-butyrolactone. And ethylene glycol, ethylene glycol diacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, monoacetic acid diethylene glycol monomethyl ether, and cyclohexanone. N-methylpyrrolidone, N-ethylpyrrolidone, and γ-butyrolactone are particularly preferred from the viewpoint of the boiling point of 180 ° C. or higher and the solubility of the resulting resin. These solvents may be used alone or in combination of two or more.
本発明において、円滑に重合反応を進行させるために、反応系中に含まれる水を除去することが好ましい。反応系中に水が含まれる場合、生成する樹脂の加水分解反応が起こり、重合度又は重合速度が低下する。反応系中に含まれる水を除去する方法として、水と共沸する溶剤を用いてディーンスターク管等により捕集する方法、又は反応容器内にガスを吹き込み反応系外に除去する方法が簡便で好ましい。また、減圧下で水を除去する方法も可能であるが、減圧下で上記反応温度を確保するために、沸点がより高い溶剤を使用する必要がある。 In the present invention, it is preferable to remove water contained in the reaction system in order to allow the polymerization reaction to proceed smoothly. When water is contained in the reaction system, a hydrolysis reaction of the produced resin occurs, and the degree of polymerization or the polymerization rate decreases. As a method of removing water contained in the reaction system, a method of collecting by a Dean-Stark tube using a solvent azeotropic with water, or a method of blowing gas into the reaction vessel and removing it outside the reaction system is simple. preferable. Moreover, although the method of removing water under reduced pressure is also possible, in order to ensure the said reaction temperature under reduced pressure, it is necessary to use a solvent with a higher boiling point.
本発明の一実施形態であるポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂の製造において使用できる多価カルボン酸及びアミノカルボン酸について、以下に説明する。 The polyvalent carboxylic acid and aminocarboxylic acid that can be used in the production of a polyamide resin, a polyamideimide resin, or a polyimide resin according to an embodiment of the present invention will be described below.
ポリアミド樹脂の製造には二つのカルボキシ基が隣接する炭素上に各々配置されたユニットがないジカルボン酸若しくはトリカルボン酸、又はアミノカルボン酸を、ポリアミドイミド樹脂の製造に対しては二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを一つ含むトリカルボン酸を、また、ポリイミド樹脂の製造に対しては二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを二組含むテトラカルボン酸を用いることが一般的である。 For the production of polyamide resin, dicarboxylic acid or tricarboxylic acid or aminocarboxylic acid without units each having two carboxy groups located on adjacent carbons are used. For the production of polyamideimide resin, two carboxy groups are adjacent. A tricarboxylic acid containing one unit arranged on each carbon, and for the production of polyimide resin, a tetracarboxylic acid containing two sets of units each arranged on two adjacent carbons on the carbon. It is common to use.
本発明の一実施形態であるポリアミド樹脂の製造方法においては、二つのカルボキシ基が隣接する炭素上に各々配置されたユニットがないジカルボン酸若しくはトリカルボン酸、又はアミノカルボン酸を用いることができる。 In the method for producing a polyamide resin according to an embodiment of the present invention, dicarboxylic acid or tricarboxylic acid or aminocarboxylic acid having no unit in which two carboxy groups are arranged on adjacent carbons can be used.
二つのカルボキシ基が隣接する炭素上に各々配置されたユニットがないジカルボン酸の具体例としては、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、１，９−ノナンジカルボン酸、ドデカン二酸、テトラデカン二酸、ペンタデカン二酸、オクタデカン二酸、テレフタル酸、イソフタル酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、５−ヒドロキシイソフタル酸、ジフェニルエーテル−４，４’−ジカルボン酸、２，６−ピリジンジカルボン酸、１，４−シクロヘキサンジカルボン酸等を挙げられるが、これらに特に制限されない。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of dicarboxylic acids having no units in which two carboxy groups are arranged on adjacent carbons include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 , 9-nonanedicarboxylic acid, dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalene Examples include dicarboxylic acid, 5-hydroxyisophthalic acid, diphenyl ether-4,4′-dicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like, but are not particularly limited thereto. These may be used alone or in combination of two or more.
二つのカルボキシ基が隣接する炭素上に各々配置されたユニットがないトリカルボン酸の具体例としては、ベンゼン−１，３，５−トリカルボン酸、シクロヘキサン−１，３，５−トリカルボン酸、ビフェニル−２，４’，５−トリカルボン酸、２，４，６−ピリジントリカルボン酸等を挙げられるが、これらに特に制限されない。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of tricarboxylic acids having no unit in which two carboxy groups are arranged on adjacent carbons include benzene-1,3,5-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, and biphenyl-2. , 4 ′, 5-tricarboxylic acid, 2,4,6-pyridinetricarboxylic acid and the like, but are not particularly limited thereto. These may be used alone or in combination of two or more.
アミノカルボン酸としては、分子中にアミノ基とカルボキシ基を有する化合物であれば特に制限はなく、アミノ酸、ω−アミノウンデカン酸、アミノドデカン酸、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、６−アミノナフタレン−２−カルボン酸、４−（ｐ−アミノフェノキシ）安息香酸、３−（ｐ−アミノフェノキシ）安息香酸、４−（ｍ−アミノフェノキシ）安息香酸、３−（ｍ−アミノフェノキシ）安息香酸等を例示できる。これらは単独で用いてもよく、２種以上を併用してもよい。 The aminocarboxylic acid is not particularly limited as long as it is a compound having an amino group and a carboxy group in the molecule, and an amino acid, ω-aminoundecanoic acid, aminododecanoic acid, p-aminobenzoic acid, m-aminobenzoic acid, 6 -Aminonaphthalene-2-carboxylic acid, 4- (p-aminophenoxy) benzoic acid, 3- (p-aminophenoxy) benzoic acid, 4- (m-aminophenoxy) benzoic acid, 3- (m-aminophenoxy) Examples thereof include benzoic acid. These may be used alone or in combination of two or more.
本発明の一実施形態であるポリアミドイミド樹脂の製造方法においては、二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを一つ含むトリカルボン酸を用いることができる。 In the method for producing a polyamide-imide resin according to an embodiment of the present invention, a tricarboxylic acid containing one unit in which two carboxy groups are arranged on adjacent carbons can be used.
二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを一つ含むトリカルボン酸の具体例としては、ベンゼン−１，２，４−トリカルボン酸、シクロヘキサン−１，２，４−トリカルボン酸、シクロヘキサン−１，２，３−トリカルボン酸、ブタン−１，２，４−トリカルボン酸、ナフタレン−１，２，４−トリカルボン酸、２，３，５−ピラジントリカルボン酸、２，３，５−チオフェントリカルボン酸等を挙げられるが、これらに特に制限されない。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of the tricarboxylic acid containing one unit in which two carboxy groups are arranged on adjacent carbons include benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane -1,2,3-tricarboxylic acid, butane-1,2,4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, 2,3,5-pyrazinetricarboxylic acid, 2,3,5-thiophenetricarboxylic acid Although an acid etc. are mentioned, it does not restrict | limit in particular to these. These may be used alone or in combination of two or more.
本発明の一実施形態であるポリイミド樹脂の製造方法においては、二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを二組含むテトラカルボン酸を用いることができる。 In the method for producing a polyimide resin according to an embodiment of the present invention, tetracarboxylic acid containing two sets of units each having two carboxy groups arranged on adjacent carbons can be used.
二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを二組含むテトラカルボン酸の具体例としては、ベンゼン−１，２，４，５−テトラカルボン酸、１，２，５，６−ナフタレンテトラカルボン酸、２，３，６，７−ナフタレンテトラカルボン酸、１，２，４，５−ナフタレンテトラカルボン酸、１，４，５，８−ナフタレンテトラカルボン酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸、３，３’，４，４’−ビフェニルテトラカルボン酸、２，３，５，６−ピリジンテトラカルボン酸、３，４，９，１０−ペリレンテトラカルボン酸、４，４’−スルホニルジフタル酸、１−トリフルオロメチル−２，３，５，６−ベンゼンテトラカルボン酸、２，２’，３，３’−ビフェニルテトラカルボン酸、２，２−ビス（３，４−ジカルボキシフェニル）プロパン、２，２−ビス（２，３−ジカルボキシフェニル）プロパン、１，１−ビス（２，３−ジカルボキシフェニル）エタン、１，１−ビス（３，４−ジカルボキシフェニル）エタン、ビス（２，３−ジカルボキシフェニル）メタン、ビス（３，４−ジカルボキシフェニル）メタン、ビス（３，４−ジカルボキシフェニル）スルホン、ビス（３，４−ジカルボキシフェニル）エーテル、ベンゼン−１，２，３，４−テトラカルボン酸、２，３，２’，３−ベンゾフェノンテトラカルボン酸、２，３，３’，４’−ベンゾフェノンテトラカルボン酸、フェナンスレン−１，８，９，１０−テトラカルボン酸、ピラジン−２，３，５，６−テトラカルボン酸、チオフェン−２，３，４，５−テトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸、３，３’，４，４’−ビフェニルテトラカルボン酸、２，２’，３，３’−ビフェニルテトラカルボン酸、ビス（３，４−ジカルボキシフェニル）ジメチルシラン、ビス（３，４−ジカルボキシフェニル）メチルフェニルシラン、ビス（３，４−ジカルボキシフェニル）ジフェニルシラン、１，４−ビス（３，４−ジカルボキシフェニルジメチルシリル）ベンゼン、１，３−ビス（３，４−ジカルボキシフェニル）−１，１，３，３−テトラメチルジシクロヘキサン、ｐ−フェニレンビス（トリメリテート）、エチレンテトラカルボン酸、１，２，３，４−ブタンテトラカルボン酸、デカヒドロナフタレン−１，４，５，８−テトラカルボン酸、４，８−ジメチル−１，２，３，５，６，７−ヘキサヒドロナフタレン−１，２，５，６−テトラカルボン酸、シクロペンタン−１，２，３，４−テトラカルボン酸、ピロリジン−２，３，４，５−テトラカルボン酸、１，２，３，４−シクロブタンテトラカルボン酸、ビシクロ［２．２．２］−オクト（７）−エン−２，３，５，６−テトラカルボン酸、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン、２，２−ビス（４−（３，４−ジカルボキシフェノキシ）フェニル）ヘキサフルオロプロパン、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルフィド、４，４’−（４，４’−イソプロピリデンジフェノキシ）−ビス（フタル酸）、テトラヒドロフラン−２，３，４，５−テトラカルボン酸、ビス（エキソビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸）スルホン、１，２，４，５−テトラカルボキシシクロヘキサン、ビシクロ［２．２．２］オクタン−２，３，５，６−テトラカルボン酸、５，５’−エンド−（ポリシロキサン−１，５−ジイル）−ビスビシクロ［２．２．１］ヘプタン−エキソ−２，３−ジカルボン酸等を挙げられるが、これらの例に特に制限されない。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of tetracarboxylic acid containing two sets of units each having two carboxy groups arranged on adjacent carbons include benzene-1,2,4,5-tetracarboxylic acid, 1,2,5,6- Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4 , 4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-biphenyl tetracarboxylic acid, 2,3,5,6-pyridinetetra Carboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4′-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2, ', 3,3'-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1-bis ( 2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane, Bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2 ′, 3-benzophenonetetracarboxylic Acid, 2,3,3 ′, 4′-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetra Rubonic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) methylphenylsilane, bis (3,4-dicarboxyphenyl) diphenyl Silane, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane, p- Phenylenebis (trimellitate), ethylenetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, decahydronaphthalene-1,4,5,8- Tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid, cyclopentane-1,2,3,4-tetra Carboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, bicyclo [2.2.2] -oct (7) -ene-2,3 5,6-tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane, 4 , 4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide, 4,4 ′-(4,4′-isopropylidenediphenoxy) -bis (phthalic acid), tetrahydrofuran-2,3,4, -Tetracarboxylic acid, bis (exobicyclo [2.2.1] heptane-2,3-dicarboxylic acid) sulfone, 1,2,4,5-tetracarboxycyclohexane, bicyclo [2.2.2] octane-2 , 3,5,6-tetracarboxylic acid, 5,5′-endo- (polysiloxane-1,5-diyl) -bisbicyclo [2.2.1] heptane-exo-2,3-dicarboxylic acid, and the like. Although not limited to these examples. These may be used alone or in combination of two or more.
ポリアミドイミド樹脂は、以下のように製造することもできる。ポリアミドイミド樹脂の原料となるトリカルボン酸と、ポリイミド樹脂の原料となるテトラカルボン酸を併用することで、イミド結合の割合が多いポリアミドイミド樹脂が製造できる。また、ポリアミドイミド樹脂の原料となるトリカルボン酸と、ポリアミド樹脂の原料となるジカルボン酸、トリカルボン酸又はアミノカルボン酸を併用することで、アミド基の割合が多いポリアミドイミド樹脂が製造できる。さらに、ポリアミドイミド樹脂は、ポリイミド樹脂の原料となるテトラカルボン酸と、ポリアミド樹脂の原料となるジカルボン酸、トリカルボン酸又はアミノカルボン酸とを、任意の比で併用することによっても製造できる。 Polyamideimide resin can also be manufactured as follows. By using together the tricarboxylic acid used as the raw material of a polyamideimide resin, and the tetracarboxylic acid used as the raw material of a polyimide resin, the polyamideimide resin with many imide bond ratios can be manufactured. Moreover, the polyamidoimide resin with many ratios of an amide group can be manufactured by using together tricarboxylic acid used as the raw material of polyamideimide resin, and dicarboxylic acid, tricarboxylic acid, or aminocarboxylic acid used as the raw material of polyamide resin. Furthermore, the polyamide-imide resin can also be produced by using a tetracarboxylic acid that is a raw material for the polyimide resin and a dicarboxylic acid, a tricarboxylic acid, or an aminocarboxylic acid that is a raw material for the polyamide resin in any ratio.
本発明において、多価アミンとしては、分子内に２つ以上のアミノ基を有する化合物であれば特に制限はなく、入手の容易さからジアミン、トリアミンが一般的に用いられる。 In the present invention, the polyvalent amine is not particularly limited as long as it is a compound having two or more amino groups in the molecule, and diamines and triamines are generally used because of their availability.
このようなジアミンの具体例としては、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、２，２’−ジメチルビフェニル−４，４’−ジアミン、２，２’−ビス（トリフルオロメチル）ビフェニル−４，４’−ジアミン、２，６，２’，６’−テトラメチル−４，４’−ジアミン、５，５’−ジメチル−２，２’−スルフォニル−ビフェニル−４，４’−ジアミン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、ｍ−キシリジンジアミン、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、トルイレンジアミン、エチレンジアミン、プロピレンジアミン、ジアミノブタン、ヘキサメチレンジアミン、トリメチルヘキサメチレンジアミン、ポリエチレンオキサイドジアミン、ポリプロピレンオキサイドジアミン、４，４’−ジアミノジシクロヘキシルメタン、イソホロンジアミン、１，４−ビスアミノプロピルピペラジン、［３，４−ビス（１−アミノヘプチル）−６−ヘキシル−５−（１−オクテニル）］シクロヘキセン、ビスアミノメチルノルボルネン、ポリジメチルシロキサンジアミン等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of such diamines include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4-amino). Phenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-amino) Phenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) Biphenyl-4,4'-diamine, 2,6,2 ', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl-biphenyl-4,4'- Diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, m-xylidinediamine, p-phenylenediamine, m-phenylenediamine, toluylenediamine, ethylenediamine, propylenediamine, diaminobutane, hexamethylenediamine, trimethyl Hexamethylenediamine, poly Tylene oxide diamine, polypropylene oxide diamine, 4,4′-diaminodicyclohexylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1 -Octenyl)] cyclohexene, bisaminomethylnorbornene, polydimethylsiloxanediamine and the like. These may be used alone or in combination of two or more.
このようなトリアミンの具体例としては、メラミン、４，４’，４”−トリアミノトリフェニルメタン、ポリプロピレンオキサイドトリアミン、ビス（３−アミノプロピル）アミン、１，４，７−ヘプタントリアミン、２，３，６−ピリジントリアミン、２，４，６−ピリジントリアミン、２，４，５−ピリミジントリアミン、２，４，６−トリアミノトルエン、１，２，３−ベンゼントリアミン、１，３，５−ベンゼントリアミン等を挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of such triamines include melamine, 4,4 ′, 4 ″ -triaminotriphenylmethane, polypropylene oxide triamine, bis (3-aminopropyl) amine, 1,4,7-heptanetriamine, 2, 3,6-pyridinetriamine, 2,4,6-pyridinetriamine, 2,4,5-pyrimidinetriamine, 2,4,6-triaminotoluene, 1,2,3-benzenetriamine, 1,3,5- Examples thereof include benzenetriamine, etc. These may be used alone or in combination of two or more.
本発明における、多価カルボン酸、多価アミン及びアミノカルボン酸の混合量は、多価カルボン酸が、２つのカルボキシ基が隣接する炭素上に各々配置されたユニットを含まない場合、多価カルボン酸とアミノカルボン酸におけるカルボキシ基の総量と、多価アミンとアミノカルボン酸のアミノ基の総量の比が、０．８〜１．２５の範囲にあることが好ましく、０．９〜１．１がより好ましい。上記比がこの範囲内であると、重合反応がより進行しやすい傾向にあり、充分な分子量の樹脂を得られる傾向にある。一方、多価カルボン酸が、二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを含む場合、二つのカルボキシ基が隣接する炭素上に各々配置されたユニットを一つのカルボキシ基とみなした多価カルボン酸とアミノカルボン酸におけるカルボキシ基の総量と、多価アミンとアミノカルボン酸のアミノ基の総量の比が、０．８〜１．２５の範囲にあることが好ましく、０．９〜１．１がより好ましい。 In the present invention, the mixed amount of the polyvalent carboxylic acid, the polyvalent amine and the aminocarboxylic acid is such that the polyvalent carboxylic acid does not contain a unit in which two carboxy groups are arranged on adjacent carbons. The ratio between the total amount of carboxy groups in the acid and aminocarboxylic acid and the total amount of amino groups in the polyvalent amine and aminocarboxylic acid is preferably in the range of 0.8 to 1.25, 0.9 to 1.1 Is more preferable. When the ratio is within this range, the polymerization reaction tends to proceed more easily, and a resin having a sufficient molecular weight tends to be obtained. On the other hand, when the polyvalent carboxylic acid includes units each having two carboxy groups arranged on adjacent carbons, the units each having two carboxy groups arranged on adjacent carbons are regarded as one carboxy group. The ratio of the total amount of carboxy groups in the polyvalent carboxylic acid and aminocarboxylic acid and the total amount of the amino groups in the polyvalent amine and aminocarboxylic acid is preferably in the range of 0.8 to 1.25, 0.9 to 1.1 is more preferable.
本発明において、重合反応終了後、生成した樹脂を含むワニスが均一である場合、そのままワニスとして用いることが可能であり、例えば、支持体上に塗布し、乾燥させることによってフィルムを形成することができる。また、生成した樹脂を含むワニスに、貧溶媒又は水を加えることによって樹脂を沈殿させ、樹脂のみを分離することもできる。この場合、得られた樹脂を溶剤に再溶解することにより再びワニスとすることも可能である。また、これら生成した樹脂を含むワニスは、所定のフィルターを用いて触媒残渣及び不純物を取り除くことができる。一方、生成した樹脂が溶解せず不均一の場合は、所定のフィルターを用いて樹脂を分離することができる。 In the present invention, after the polymerization reaction is completed, when the varnish containing the generated resin is uniform, it can be used as it is as a varnish. For example, a film can be formed by coating on a support and drying. it can. Moreover, the resin can be precipitated by adding a poor solvent or water to the varnish containing the produced resin, and only the resin can be separated. In this case, it is also possible to make a varnish again by re-dissolving the obtained resin in a solvent. Moreover, the varnish containing these produced | generated resin can remove a catalyst residue and an impurity using a predetermined filter. On the other hand, when the produced resin does not dissolve and is non-uniform, the resin can be separated using a predetermined filter.
本発明において、重合反応終了後、生成した樹脂を含むワニスが均一である、すなわち生成するポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂が溶剤に可溶であれば、重合反応が効率よく進行し、反応終了後の取り扱いが容易になるため好ましい。このような溶剤に可溶であるポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂は、上記多価カルボン酸、多価アミン及びアミノカルボン酸の組み合わせから選択され、特に制限はないが、多価カルボン酸及び多価アミンの少なくとも１種がポリオキシアルカンジイル基を含有した場合、生成したポリアミド樹脂、ポリアミドイミド樹脂又はポリイミド樹脂が溶解性に優れることから特に好ましい。 In the present invention, after completion of the polymerization reaction, if the varnish containing the generated resin is uniform, that is, if the generated polyamide resin, polyamideimide resin or polyimide resin is soluble in the solvent, the polymerization reaction proceeds efficiently, and the reaction This is preferable because the handling after the end becomes easy. The polyamide resin, polyamideimide resin or polyimide resin which is soluble in such a solvent is selected from the combination of the polyvalent carboxylic acid, polyvalent amine and aminocarboxylic acid, and there is no particular limitation. When at least one of the polyvalent amines contains a polyoxyalkanediyl group, the produced polyamide resin, polyamideimide resin or polyimide resin is particularly preferable because of excellent solubility.
ここで、ポリオキシアルカンジイル基としては、下記式（１）で表される基が挙げられる。なお、式中、ｎは２以上の整数を示し、２〜９０であることが好ましく、３〜７０であることがより好ましい。また、下記式（１）におけるＲ１はアルキレン基を示す。複数存在するＲ１は互いに同一でも異なっていてもよい。
このようなポリオキシアルカンジイル基を有する多価アミンは、ポリオキシアルキレンジアミンが挙げられ、例えば、ジェファーミンＤ−２３０（ＨＵＮＴＳＭＡＮ社製、商品名）、ジェファーミンＤ−４００（ＨＵＮＴＳＭＡＮ社製、商品名）、ジェファーミンＤ−２０００（ＨＵＮＴＳＭＡＮ社製、商品名）、ジェファーミンＤ−４０００（ＨＵＮＴＳＭＡＮ社製、商品名）等のポリオキシプロピレンジアミン、ジェファーミンＥＤ−６００（ＨＵＮＴＳＭＡＮ社製、商品名）、ジェファーミンＥＤ−９００（ＨＵＮＴＳＭＡＮ社製、商品名）等のポリプロピレンオキサイドとポリエチレンオキサイドの共重合体ジアミン、ジェファーミンＥＤＲ−１４８（ＨＵＮＴＳＭＡＮ社製、商品名）、ジェファーミンＥＤＲ−１７６（ＨＵＮＴＳＭＡＮ社製、商品名）等のポリオキシエチレンジアミン、ジェファーミンＴ−４０３（ＨＵＮＴＳＭＡＮ社製、商品名）、ジェファーミンＴ−３０００（ＨＵＮＴＳＭＡＮ社製、商品名）及びジェファーミンＴ−５０００（ＨＵＮＴＳＭＡＮ社製、商品名）等のトリアミンを好適に用いることができる。これらは単独で用いてもよく、２種以上を併用してもよい。 Examples of the polyvalent amine having such a polyoxyalkanediyl group include polyoxyalkylene diamine. For example, Jeffamine D-230 (manufactured by HUNTSMAN, trade name), Jeffamine D-400 (manufactured by HUNTSMAN, product) Name), Jeffermin D-2000 (trade name, manufactured by HUNTSMAN), polyoxypropylenediamine such as Jeffamine D-4000 (trade name, manufactured by HUNTSMAN), Jeffamine ED-600 (trade name, manufactured by HUNTSMAN) Copolymer diamine of polypropylene oxide and polyethylene oxide such as Jeffermin ED-900 (trade name, manufactured by HUNTSMAN), Jeffermine EDR-148 (trade name, manufactured by HUNTSMAN), Jeffamine EDR-176 (HUNTS) Polyoxyethylenediamine such as AN (trade name), Jeffamine T-403 (trade name, HUNTSMAN), Jeffamine T-3000 (trade name, HUNTSMAN) and Jeffamine T-5000 (trade name, HUNTSMAN) , Trade name) and the like can be suitably used. These may be used alone or in combination of two or more.
本発明における、生成した樹脂を含むワニスは、単一の樹脂成分に限定されず、生成した樹脂に加えて、アクリル系樹脂、スチレン系樹脂、エポキシ系樹脂、アミド系樹脂、アミドエポキシ系樹脂、アルキド系樹脂、フェノール系樹脂、フェノキシ系樹脂などを任意に組み合わせて用いて、樹脂組成物とすることも可能である。さらに硬化剤、硬化促進剤、可塑剤、密着付与剤、レベリング剤、剥離促進剤、消泡剤、酸化防止剤、イオン捕捉剤、難燃剤、顔染料、無機粒子、有機粒子、希釈剤等の添加剤成分を含んでいてもよい。具体的には、樹脂成分としては、例えばアクリルゴム、ブタジエンゴム、アクリロニトリルブタジエンゴム等のゴム化合物；フェノキシ樹脂；ポリビニルブチラール樹脂等を例示でき、硬化剤としては、フェノール基、エポキシ基又はアクリロイル基を含有する樹脂又はモノマーを用いることもできる。また、硬化促進剤としては、例えば、イミダゾール、酸無水物、過酸化物、光開始剤等を添加しても良い。 In the present invention, the varnish containing the generated resin is not limited to a single resin component, and in addition to the generated resin, an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, An alkyd resin, a phenol resin, a phenoxy resin, or the like can be used in any combination to form a resin composition. In addition, curing agents, curing accelerators, plasticizers, adhesion promoters, leveling agents, release accelerators, antifoaming agents, antioxidants, ion scavengers, flame retardants, facial dyes, inorganic particles, organic particles, diluents, etc. An additive component may be included. Specifically, examples of the resin component include rubber compounds such as acrylic rubber, butadiene rubber, and acrylonitrile butadiene rubber; phenoxy resins; polyvinyl butyral resins and the like, and examples of the curing agent include phenol groups, epoxy groups, and acryloyl groups. Resin or monomer to contain can also be used. Moreover, as a hardening accelerator, you may add an imidazole, an acid anhydride, a peroxide, a photoinitiator etc., for example.
以上、本発明の好適な実施形態について説明したが、本発明は前記実施形態に限定されるものではない。 The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
以下、実施例により本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.
（精製例）
鉄粉は、文献（Ｐｕｒｉｆｉｃａｔｉｏｎ ｏｆ Ｌａｂｏｒａｔｏｒｙ Ｃｈｅｍｉｃａｌｓ， Ｆｉｆｔｈ Ｅｄ．， Ｅｌｓｅｖｉｅｒ， ２００３， ｐ４３３）に従って、塩酸、イオン交換水、アセトンで順次洗浄後、減圧下で乾燥して用いた。
(Purification example)
The iron powder was used after being sequentially washed with hydrochloric acid, ion-exchanged water and acetone according to the literature (Purification of Laboratory Chemicals, Fifth Ed., Elsevier, 2003, p433).
（分子量測定例）
本発明の実施例によって製造された樹脂の分子量は、ＨＰＬＣ−Ｌ７０００シリーズ（日立製作所製）を用いて測定した。臭化リチウム及びリン酸をそれぞれ０．０３ｍｏｌ／Ｌ、０．０６ｍｏｌ／Ｌとなるように加えたＮ−メチルピロリドンの溶液に、測定対象となる樹脂を１質量％となるように溶解し、３０℃に加温されたカラム（ＫＤ−８０６Ｍ（昭和電工製））に注入し、溶出時間から、標準ポリスチレンを用いて作製した分子量／溶出時間曲線を用いて重量平均分子量（Ｍｗ）を算出した。
(Example of molecular weight measurement)
The molecular weight of the resin produced according to the example of the present invention was measured using HPLC-L7000 series (manufactured by Hitachi, Ltd.). In a solution of N-methylpyrrolidone to which lithium bromide and phosphoric acid were added to 0.03 mol / L and 0.06 mol / L, respectively, the resin to be measured was dissolved to 1% by mass, and 30 The polymer was poured into a column (KD-806M (manufactured by Showa Denko)) heated to ° C., and the weight average molecular weight (Mw) was calculated from the elution time using a molecular weight / elution time curve prepared using standard polystyrene.
（実施例１）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、ベンゼン−１，２，４−トリカルボン酸１２．５ｇ、４，４’−ジアミノジフェニルメタン１２．５ｇ、精製後空気中で１週間保存した鉄粉３５ｍｇ及びγ−ブチロラクトン４７ｇを加えた。毎分０．５Ｌの窒素の気流下、２００℃で８時間重合させ、ポリアミドイミド樹脂のワニスを得た。
(Example 1)
In a four-necked separable flask equipped with a stirrer, Dean-Stark tube, thermometer, and nitrogen introduction tube, 12.5 g of benzene-1,2,4-tricarboxylic acid, 12.5 g of 4,4′-diaminodiphenylmethane, purification Thereafter, 35 mg of iron powder and 47 g of γ-butyrolactone stored in the air for 1 week were added. Polymerization was performed at 200 ° C. for 8 hours under a flow of nitrogen of 0.5 L per minute to obtain a polyamideimide resin varnish.
（実施例２）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、ベンゼン−１，２，４−トリカルボン酸１０．５ｇ、ポリオキシプロピレンジアミン（ＪＥＦＦＡＭＩＮＥ（登録商標）Ｄ−２０００、ＨＵＮＴＳＭＡＮ社製）１２．６ｇ、１，４−ビスアミノプロピルピペラジン８．８ｇ、４，４’−ジアミノジシクロヘキシルメタン２．７ｇ、精製した鉄粉４０ｍｇ及びγ−ブチロラクトン７３ｇを加えた。毎分０．５Ｌの窒素の気流下、２００℃で２時間反応させたところ、１，２，４−ベンゼントリカルボン酸と１，４−ビスアミノプロピルピペラジンの重合物と考えられる不溶物を生じた。反応溶液にγ−ブチロラクトン１．５ｇと水１．５ｇの混合溶液を加え、さらに２００℃で１時間反応させたところ不溶物が溶解した。再び反応溶液にγ−ブチロラクトン１．５ｇと水１．５ｇの混合溶液を加え、２００℃で７時間重合させ、ポリアミドイミド樹脂のワニスを得た。
(Example 2)
Into a four-necked separable flask equipped with a stirrer, a Dean-Stark tube, a thermometer, and a nitrogen introduction tube, 10.5 g of benzene-1,2,4-tricarboxylic acid, polyoxypropylenediamine (JEFFAMINE® D- 2000, manufactured by HUNTSMAN) 12.6 g, 1,4-bisaminopropylpiperazine 8.8 g, 4,4′-diaminodicyclohexylmethane 2.7 g, purified iron powder 40 mg and γ-butyrolactone 73 g were added. When the reaction was carried out at 200 ° C. for 2 hours under a flow of nitrogen of 0.5 L / min, an insoluble material thought to be a polymer of 1,2,4-benzenetricarboxylic acid and 1,4-bisaminopropylpiperazine was produced. . A mixed solution of 1.5 g of γ-butyrolactone and 1.5 g of water was added to the reaction solution, and the mixture was further reacted at 200 ° C. for 1 hour to dissolve insoluble matters. Again, a mixed solution of 1.5 g of γ-butyrolactone and 1.5 g of water was added to the reaction solution and polymerized at 200 ° C. for 7 hours to obtain a polyamideimide resin varnish.
（実施例３）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、ベンゼン−１，２，４−トリカルボン酸１０．５ｇ、１，４−ビスアミノプロピルピペラジン１２．６ｇ、精製した鉄粉３５ｍｇ及びγ−ブチロラクトン６７ｇを加えた。毎分０．５Ｌの窒素の気流下、２００℃で１時間反応させたところ、１，２，４−ベンゼントリカルボン酸と１，４−ビスアミノプロピルピペラジンからなるポリアミドイミド樹脂と考えられる不溶物を生じた。さらに、２００℃で７時間重合させたが、ポリアミドイミド樹脂と考えられる不溶物は溶解しなかった。
(Example 3)
In a four-necked separable flask equipped with a stirrer, Dean-Stark tube, thermometer and nitrogen introduction tube, 10.5 g of benzene-1,2,4-tricarboxylic acid, 12.6 g of 1,4-bisaminopropylpiperazine, 35 mg of purified iron powder and 67 g of γ-butyrolactone were added. When reacted at 200 ° C. for 1 hour under a flow of nitrogen of 0.5 L / min, an insoluble material considered to be a polyamideimide resin composed of 1,2,4-benzenetricarboxylic acid and 1,4-bisaminopropylpiperazine was obtained. occured. Furthermore, although it superposed | polymerized at 200 degreeC for 7 hours, the insoluble matter considered to be a polyamide-imide resin did not melt | dissolve.
（実施例４）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、イソフタル酸９．２ｇ、テレフタル酸１．３ｇ、ポリプロピレンオキサイドジアミン（ＪＥＦＦＡＭＩＮＥ（登録商標）Ｄ−２０００、ＨＵＮＴＳＭＡＮ社製）１２．６ｇ、１，４−ビスアミノプロピルピペラジン８．８ｇ、４，４’−ジアミノジシクロヘキシルメタン２．７ｇ、精製した鉄粉３５ｍｇ及びγ−ブチロラクトン６４ｇを加えた。毎分０．７５Ｌの窒素の気流下、２００℃で７．５時間重合させ、ポリアミド樹脂のワニスを得た。
Example 4
In a four-necked separable flask equipped with a stirrer, Dean-Stark tube, thermometer and nitrogen inlet tube, 9.2 g of isophthalic acid, 1.3 g of terephthalic acid, polypropylene oxide diamine (JEFFAMINE (registered trademark) D-2000, HUNTSMAN 12.6 g, 8.8 g of 1,4-bisaminopropylpiperazine, 2.7 g of 4,4′-diaminodicyclohexylmethane, 35 mg of purified iron powder and 64 g of γ-butyrolactone were added. Polymerization was performed at 200 ° C. for 7.5 hours under a nitrogen stream of 0.75 L / min to obtain a polyamide resin varnish.
（実施例５）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、テレフタル酸１０．５ｇ、ポリオキシプロピレンジアミン（ＪＥＦＦＡＭＩＮＥ（登録商標）Ｄ−２０００、ＨＵＮＴＳＭＡＮ社製）１２．６ｇ、１，４−ビスアミノプロピルピペラジン８．８ｇ、４，４’−ジアミノジシクロヘキシルメタン２．７ｇ、精製した塩化鉄（ＩＩ）７０ｍｇ及びγ−ブチロラクトン６４ｇを加えた。毎分０．７５Ｌの窒素の気流下、２００℃で６．５時間重合させ、ポリアミド樹脂のワニスを得た。
(Example 5)
In a four-necked separable flask equipped with a stirrer, Dean-Stark tube, thermometer and nitrogen introduction tube, 10.5 g of terephthalic acid, polyoxypropylenediamine (JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN) 12. 6 g, 8.8 g of 1,4-bisaminopropylpiperazine, 2.7 g of 4,4′-diaminodicyclohexylmethane, 70 mg of purified iron (II) chloride and 64 g of γ-butyrolactone were added. Polymerization was carried out at 200 ° C. for 6.5 hours under a nitrogen stream of 0.75 L / min to obtain a polyamide resin varnish.
（実施例６）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、イソフタル酸９．２ｇ、テレフタル酸１．３ｇ、ポリオキシプロピレンジアミン（ＪＥＦＦＡＭＩＮＥ（登録商標）Ｄ−２０００、ＨＵＮＴＳＭＡＮ社製）１２．６ｇ、１，４−ビスアミノプロピルピペラジン８．８ｇ、４，４’−ジアミノジシクロヘキシルメタン２．７ｇ、精製した酸化鉄（ＩＩＩ）（α体９９．９％）５０ｍｇ及びγ−ブチロラクトン６４ｇを加えた。毎分０．７５Ｌの窒素の気流下、２００℃で６時間重合させ、ポリアミド樹脂のワニスを得た。
(Example 6)
In a four-necked separable flask equipped with a stirrer, a Dean-Stark tube, a thermometer, and a nitrogen introduction tube, 9.2 g of isophthalic acid, 1.3 g of terephthalic acid, polyoxypropylenediamine (JEFFAMINE (registered trademark) D-2000, (Made by HUNTSMAN) 12.6 g, 1,4-bisaminopropylpiperazine 8.8 g, 4,4′-diaminodicyclohexylmethane 2.7 g, purified iron oxide (III) (α form 99.9%) 50 mg and γ -64 g of butyrolactone were added. Polymerization was performed at 200 ° C. for 6 hours under a nitrogen flow of 0.75 L / min to obtain a polyamide resin varnish.
（比較例１）
撹拌機、ディーンスターク管、温度計及び窒素導入管を備えた４つ口セパラブルフラスコに、テレフタル酸１０．５ｇ、ポリプロピレンオキサイドジアミン（ＪＥＦＦＡＭＩＮＥ（登録商標）Ｄ−２０００、ＨＵＮＴＳＭＡＮ社製）１２．６ｇ、１，４−ビスアミノプロピルピペラジン８．８ｇ、４，４’−ジアミノジシクロヘキシルメタン２．７ｇ及びγ−ブチロラクトン７３ｇを加えた。毎分０．７５Ｌの窒素の気流下、２００℃で７時間反応させたが、重合物は得られなかった。
(Comparative Example 1)
In a four-necked separable flask equipped with a stirrer, Dean-Stark tube, thermometer and nitrogen inlet tube, 10.5 g of terephthalic acid, polypropylene oxide diamine (JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN) 12.6 g 1,4-bisaminopropylpiperazine (8.8 g), 4,4′-diaminodicyclohexylmethane (2.7 g) and γ-butyrolactone (73 g) were added. The reaction was carried out at 200 ° C. for 7 hours under a nitrogen stream of 0.75 L / min, but no polymer was obtained.
表１に示すように、鉄系触媒を用いることにより、効率よくイミド、アミド結合を形成でき、対応する樹脂が製造可能である。 As shown in Table 1, by using an iron-based catalyst, imide and amide bonds can be formed efficiently, and corresponding resins can be produced.
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