JP7056015B2 - polyamide - Google Patents
polyamide Download PDFInfo
- Publication number
- JP7056015B2 JP7056015B2 JP2017110287A JP2017110287A JP7056015B2 JP 7056015 B2 JP7056015 B2 JP 7056015B2 JP 2017110287 A JP2017110287 A JP 2017110287A JP 2017110287 A JP2017110287 A JP 2017110287A JP 7056015 B2 JP7056015 B2 JP 7056015B2
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- JP
- Japan
- Prior art keywords
- structural unit
- mol
- polyamide
- formula
- polyamine
- Prior art date
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- 239000004952 Polyamide Substances 0.000 title claims description 75
- 229920002647 polyamide Polymers 0.000 title claims description 75
- 229920000768 polyamine Polymers 0.000 claims description 37
- 239000000470 constituent Substances 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 125000000962 organic group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- -1 Aminophenoxy Chemical group 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000002516 radical scavenger Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000005456 alcohol based solvent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-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
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-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
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- KHUPHKVFRLSDQQ-UHFFFAOYSA-N 2-piperazin-2-ylethanamine Chemical compound NCCC1CNCCN1 KHUPHKVFRLSDQQ-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- DVXYMCJCMDTSQA-UHFFFAOYSA-N 3-[2-(3-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=CC(N)=C1 DVXYMCJCMDTSQA-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- JERFEOKUSPGKGV-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 JERFEOKUSPGKGV-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- SXTPNMJRVQKNRN-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1SC(C=C1)=CC=C1OC1=CC=C(N)C=C1 SXTPNMJRVQKNRN-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、ポリアミドに関する。 The present invention relates to polyamide.
ポリアミドは、高い耐熱性及び溶融成形の容易さから、優れたエンジニアリングプラスチックとして広く知られている。その一方で、ポリアミドは、アルコール系溶剤に対する溶解性に乏しいため、溶剤塗工によるフィルム成形に適用できないという問題がある。そのため、アルコール系溶剤に対する溶解性に優れたポリアミドの開発が望まれている。 Polyamide is widely known as an excellent engineering plastic because of its high heat resistance and ease of melt molding. On the other hand, polyamide has a problem that it cannot be applied to film molding by solvent coating because it has poor solubility in alcohol-based solvents. Therefore, it is desired to develop a polyamide having excellent solubility in an alcohol solvent.
アルコール系溶剤に対するポリアミドの溶解性を向上させる方法として、ポリアミドの構成単位にフッ素原子を導入する方法が知られている（例えば、非特許文献１参照）。しかし、フッ素原子を導入したポリアミドは非常に高価であるため、適用できる分野が限定されてしまう傾向にある。 As a method for improving the solubility of polyamide in an alcohol solvent, a method of introducing a fluorine atom into a constituent unit of polyamide is known (see, for example, Non-Patent Document 1). However, since polyamides into which fluorine atoms have been introduced are very expensive, the fields in which they can be applied tend to be limited.
本発明は、上記事情に鑑みてなされたものであり、アルコール系溶剤に対する溶解性に優れるポリアミドを提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyamide having excellent solubility in an alcohol solvent.
本発明は、ポリアミンに由来する構成単位と、ジカルボン酸に由来する構成単位と、を含み、ポリアミンに由来する構成単位のうち少なくとも一部が、下記一般式（１）で表される構成単位又は下記一般式（２）で表される構成単位の少なくとも一方である、ポリアミドを提供する。このようなポリアミドは、アルコール系溶剤に対する溶解性に優れる。
［式（１）中、Ｒ１はアルキレン基を示し、ｎは１～５の整数を示す。複数存在するＲ１は互いに同一であっても異なっていてもよい。］
［式（２）中、Ｒ２及びＲ３はそれぞれ独立にアルキレン基を示す。］
The present invention includes a structural unit derived from a polyamine and a structural unit derived from a dicarboxylic acid, and at least a part of the structural units derived from the polyamine is a structural unit represented by the following general formula (1) or Provided is a polyamide which is at least one of the structural units represented by the following general formula (2). Such polyamides have excellent solubility in alcohol solvents.
[In the formula (1), R 1 represents an alkylene group and n represents an integer of 1 to 5. A plurality of R 1s may be the same or different from each other. ]
[In formula (2), R 2 and R 3 each independently represent an alkylene group. ]
一般式（１）で表される構成単位及び一般式（２）で表される構成単位の合計の含有量は、ポリアミンに由来する構成単位全量を基準として、５モル％以上であってもよい。一般式（１）で表される構成単位及び一般式（２）で表される構成単位の合計の含有量がこのような範囲にあると、アルコール系溶剤に対するポリアミドの溶解性がより一層優れる傾向にある。 The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) may be 5 mol% or more based on the total amount of the structural unit derived from polyamine. .. When the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is in such a range, the solubility of the polyamide in an alcohol solvent tends to be further excellent. It is in.
ポリアミンに由来する構成単位又はジカルボン酸に由来する構成単位の少なくとも一方は、芳香族基を含む２価の有機基を有する構成単位を含んでいてもよい。このような構成単位を含むポリアミドは、耐熱性により優れる傾向にある。 At least one of the structural units derived from polyamines or dicarboxylic acids may contain a structural unit having a divalent organic group including an aromatic group. Polyamides containing such structural units tend to be more excellent in heat resistance.
芳香族基を含む２価の有機基は、下記式で表される基のいずれかであってもよい。
［式中、ｍは１～１０の整数を示す。］
The divalent organic group containing an aromatic group may be any of the groups represented by the following formula.
[In the formula, m represents an integer from 1 to 10. ]
本発明によれば、アルコール系溶剤に対する溶解性に優れるポリアミドを提供することができる。いくつかの形態に係るポリアミドは、耐熱性の点でも優れる。 According to the present invention, it is possible to provide a polyamide having excellent solubility in an alcohol solvent. Polyamides according to some forms are also excellent in heat resistance.
以下、本発明の実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
本明細書において、「ポリアミン」は、分子内に２以上のアミノ基を有する化合物を意味する。 As used herein, "polyamine" means a compound having two or more amino groups in the molecule.
一実施形態のポリアミドは、ポリアミンに由来する構成単位と、ジカルボン酸に由来する構成単位と、を含む。ポリアミドは、ポリアミンに由来する構成単位のうち少なくとも一部が、下記一般式（１）で表される構成単位（以下、「式（１）の構成単位」という場合がある。）又は下記一般式（２）で表される構成単位（以下、「式（２）の構成単位」という場合がある。）の少なくとも一方である。 The polyamide of one embodiment contains a structural unit derived from a polyamine and a structural unit derived from a dicarboxylic acid. In polyamide, at least a part of the constituent units derived from polyamine is represented by the following general formula (1) (hereinafter, may be referred to as “constituent unit of formula (1)”) or the following general formula. It is at least one of the structural units represented by (2) (hereinafter, may be referred to as “constituent unit of equation (2)”).
式（１）中、Ｒ１はアルキレン基を示す。複数存在するＲ１は互いに同一であっても異なっていてもよいが、同一であることが好ましい。アルキレン基は、メチレン基、エチレン基、又はプロピレン基のような炭素数１～３のアルキレン基であってもよく、エチレン基であってもよい。 In formula (1), R 1 represents an alkylene group. A plurality of R 1s may be the same or different from each other, but are preferably the same. The alkylene group may be an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, or a propylene group, or may be an ethylene group.
式（１）中、ｎは１～５の整数を示す。ｎは１～３の整数であってもよい。 In equation (1), n represents an integer of 1 to 5. n may be an integer of 1 to 3.
式（１）の構成単位を与えるポリアミンとしては、例えば、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等が挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。これらのうち、式（１）の構成単位を与えるポリアミンは、ジエチレントリアミン、トリエチレンテトラミン、又はテトラエチレンペンタミンであってもよく、ジエチレントリアミンであってもよい。 Examples of the polyamine that gives the structural unit of the formula (1) include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. These can be used alone or in combination of two or more. Of these, the polyamine that gives the structural unit of the formula (1) may be diethylenetriamine, triethylenetetramine, or tetraethylenepentamine, or may be diethylenetriamine.
式（２）中、Ｒ２及びＲ３はそれぞれ独立にアルキレン基を示す。Ｒ２及びＲ３は互いに同一であっても異なっていてもよいが、同一であることが好ましい。Ｒ２及びＲ３は、メチレン基、エチレン基、プロピレン基、ブチレン基、又はペンチレン基のような炭素数１～５のアルキレン基であってもよく、プロピレン基であってもよい。 In formula (2), R 2 and R 3 each independently represent an alkylene group. R 2 and R 3 may be the same or different from each other, but are preferably the same. R 2 and R 3 may be an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group, or may be a propylene group.
式（２）の構成単位を与えるポリアミンとしては、例えば、１，４－ビス（３－アミノプロピル）ピペラジン、１，４－ビス（３－アミノエチル）ピペラジン、１，４－ビス（３－アミノメチル）ピペラジン等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。これらのうち、式（２）の構成単位を与えるポリアミンは、１，４－ビス（３－アミノプロピル）ピペラジンであってもよい。 Examples of the polyamine that gives the structural unit of the formula (2) include 1,4-bis (3-aminopropyl) piperazine, 1,4-bis (3-aminoethyl) piperazine, and 1,4-bis (3-amino). Methyl) piperazine and the like can be mentioned. These can be used alone or in combination of two or more. Of these, the polyamine that gives the structural unit of formula (2) may be 1,4-bis (3-aminopropyl) piperazine.
式（１）の構成単位及び式（２）の構成単位の合計の含有量は、ポリアミンに由来する構成単位全量を基準として、５モル％以上であってもよい。これらの構成単位の含有量がこのような範囲にあると、アルコール系溶剤に対するポリアミドの溶解性がより一層優れる傾向にある。式（１）の構成単位及び式（２）の構成単位の含有量は、１０モル％以上、２０モル％以上、又は３０モル％以上であってもよく、また、１００モル％以下、９０モル％以下、又は８０モル％以下であってもよい。 The total content of the constituent units of the formula (1) and the constituent units of the formula (2) may be 5 mol% or more based on the total amount of the constituent units derived from polyamines. When the content of these constituent units is in such a range, the solubility of the polyamide in an alcohol-based solvent tends to be even better. The content of the structural unit of the formula (1) and the structural unit of the formula (2) may be 10 mol% or more, 20 mol% or more, or 30 mol% or more, and 100 mol% or less, 90 mol. % Or less, or 80 mol% or less.
本実施形態のポリアミドは、式（１）の構成単位及び式（２）の構成単位以外のポリアミンに由来する構成単位を含んでいてもよい。 The polyamide of the present embodiment may contain a structural unit derived from a polyamine other than the structural unit of the formula (1) and the structural unit of the formula (2).
このような構成単位を与えるポリアミンとしては、例えば、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、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、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メタン、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルメタン、ビス（４－アミノ－３，５－ジメチルフェニル）メタン、ビス（４－アミノ－３，５－ジイソプロピルフェニル）メタン、３，３’－ジアミノジフェニルスルホン、３，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルフィド、３，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルフィド、３，３’－ジアミノジフェニルケトン、３，４’－ジアミノジフェニルケトン、４，４’－ジアミノジフェニルケトン、２，２－ビス（３－アミノフェニル）プロパン、２，２’－（３，４’－ジアミノジフェニル）プロパン、２，２－ビス（４－アミノフェニル）プロパン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，４－ビス（３－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、３，３’－（１，４－フェニレンビス（１－メチルエチリデン））ビスアニリン、３，４’－（１，４－フェニレンビス（１－メチルエチリデン））ビスアニリン、４，４’－（１，４－フェニレンビス（１－メチルエチリデン））ビスアニリン、２，２－ビス（４－（３－アミノフェノキシ）フェニル）プロパン、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）スルフィド、ビス（４－（４－アミノフェノキシ）フェニル）スルフィド、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、３，５－ジアミノ安息香酸等の芳香族基を含む２価の有機基を有するジアミン；１，２－ジアミノエタン、１，３－ジアミノプロパン、１，４－ジアミノブタン、１，５－ジアミノペンタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン、１，１１－ジアミノウンデカン、１，１２－ジアミノドデカン、１，２－ジアミノシクロヘキサン等の脂肪族基を有するジアミン；ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、ポリオキシテトラメチレンジアミン等のポリオキシアルキレンジアミン；脂肪族不飽和カルボン酸の二量体（ダイマー酸）から誘導されるダイマージアミンなどが挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。 Examples of the polyamine giving such a structural unit include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diamino. Diphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5) -Diisopropylphenyl) methane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide , 4,4'-Diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 2,2-bis (3-aminophenyl) propane, 2,2'-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-) Aminophenoxy) Benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4'-(1,4-phenylene) Bis (1-methylethylidene)) bisaniline, 4,4'-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2 , 2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (4- (4-aminophenoxy) phenyl) sulfide Diamines with divalent organic groups including aromatic groups such as 3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 3,5-diaminobenzoic acid; 1,2- Diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane , 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane , Diamines having an aliphatic group such as 1,2-diaminocyclohexane; polyoxyalkylenediamines such as polyoxyethylenediamine, polyoxypropylenediamine and polyoxytetramethylenediamine; dimers of aliphatic unsaturated carboxylic acids (dimer acid) ) Derived from dimer diamine and the like. These can be used alone or in combination of two or more.
ダイマージアミンは、例えば、下記式（Ａ－１）で表される化合物、下記式（Ａ－２）で表される化合物、下記式（Ａ－３）で表される化合物等であってもよい。ダイマージアミンは、「ＰＲＩＡＭＩＮＥ １０７４」、「ＰＲＩＡＭＩＮＥ １０７３」、「ＰＲＩＡＭＩＮＥ １０７５」（いずれもクローダジャパン株式会社製）等の市販品を使用することができる。 The diamine diamine may be, for example, a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), a compound represented by the following formula (A-3), or the like. .. As the diamine diamine, commercially available products such as "PRIAMINE 1074", "PRIAMINE 1073", and "PRIAMINE 1075" (all manufactured by Croda Japan Co., Ltd.) can be used.
ジイソシアネートは、加水分解によってジアミンを生じ得る。そのため、式（１）の構成単位及び式（２）の構成単位以外のポリアミンに由来する構成単位を与える化合物として、ジイソシアネートを用いることができる。ジイソシアネートとしては、例えば、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキシルメタンジイソシアネート、２，２，４－又は２，４，４－トリメチルヘキサメチレンジイソシアネート、イソプロピリデンビス（４－シクロヘキシルイソシアネート）、メチルシクロヘキサンジイソシアネート、イソホロンジイソシアネート等の脂肪族又は脂環式ジイソシアネート；２，４－又は２，６－トリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、３－メチルジフェニルメタン－４，４’－ジイソシアネート、ｍ－又はｐ－フェニレンジイソシアネート、クロロフェニレン－２，４－ジイソシアネート、ナフタレン－１，５－ジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ジイソシアネートなどが挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。 Diisocyanates can produce diamines by hydrolysis. Therefore, diisocyanate can be used as a compound that gives a structural unit derived from a polyamine other than the structural unit of the formula (1) and the structural unit of the formula (2). Examples of the diisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexylmethane diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, and isopropyridenebis (4-cyclohexyl). Isocyanates), aliphatic or alicyclic diisocyanates such as methylcyclohexane diisocyanate and isophorone diisocyanate; 2,4- or 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4,4' Examples thereof include aromatic diisocyanates such as -diisocyanate, m- or p-phenylenediocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These can be used alone or in combination of two or more.
本実施形態のポリアミドは、ポリアミンに由来する構成単位として、ポリオキシアルキレンジアミンに由来する構成単位を含んでいてもよい。このような構成単位を含むことによって、ポリアミドに柔軟性が付与され、アルコール系溶剤に対するポリアミドの溶解性がより優れる傾向にある。ポリオキシアルキレンジアミンに由来する構成単位の含有量は、ポリアミンに由来する構成単位全量を基準として、１モル％以上、３モル％以上、又は５モル％以上であってもよく、８０モル％以下、５０モル％以下、又は３０モル％以下であってもよい。 The polyamide of the present embodiment may contain a structural unit derived from polyoxyalkylene diamine as a structural unit derived from polyamine. By including such a structural unit, flexibility is imparted to the polyamide, and the solubility of the polyamide in an alcohol solvent tends to be more excellent. The content of the structural unit derived from polyoxyalkylene diamine may be 1 mol% or more, 3 mol% or more, or 5 mol% or more, and 80 mol% or less, based on the total amount of the structural unit derived from polyamine. , 50 mol% or less, or 30 mol% or less.
本実施形態のポリアミドは、ポリアミンに由来する構成単位として、ダイマージアミンに由来する構成単位を含んでいてもよい。このような構成単位を含むことによって、アルコール系溶剤に対するポリアミドの溶解性がより優れる傾向にある。ダイマージアミンに由来する構成単位の含有量は、ポリアミンに由来する構成単位全量を基準として、１モル％以上、３モル％以上、又は５モル％以上であってもよく、８０モル％以下、５０モル％以下、又は３０モル％以下であってもよい。 The polyamide of the present embodiment may contain a structural unit derived from dimer diamine as a structural unit derived from polyamine. By including such a structural unit, the solubility of the polyamide in an alcohol solvent tends to be more excellent. The content of the constituent units derived from dimer diamine may be 1 mol% or more, 3 mol% or more, or 5 mol% or more, based on the total amount of the constituent units derived from polyamines, and may be 80 mol% or less, 50. It may be 1 mol% or less, or 30 mol% or less.
本実施形態のポリアミドは、ジカルボン酸に由来する構成単位を含む。ジカルボン酸としては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸等の芳香族基を含む２価の有機基を有するジカルボン酸；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、ノナンジカルボン酸、ドデカンジカルボン酸、１，４－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸等の脂肪族基又は脂環式基を有するジカルボン酸；これらの炭素数１～１０のアルキルエステル；これらの塩化物などが挙げられる。これらは１種単独で又は２種以上組み合わせて用いることができる。 The polyamide of the present embodiment contains a structural unit derived from a dicarboxylic acid. Examples of the dicarboxylic acid include a dicarboxylic acid having a divalent organic group including an aromatic group such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid; , Azelaic acid, sebacic acid, nonandicarboxylic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other dicarboxylic acids having aliphatic or alicyclic groups; ~ 10 Alkyl esters; these chlorides and the like can be mentioned. These can be used alone or in combination of two or more.
ポリアミンに由来する構成単位又はジカルボン酸に由来する構成単位の少なくとも一方は、芳香族基を含む２価の有機基を有する構成単位を含んでいてもよい。このような構成単位を含むポリアミドは、耐熱性により優れる傾向にある。 At least one of the structural units derived from polyamines or dicarboxylic acids may contain a structural unit having a divalent organic group including an aromatic group. Polyamides containing such structural units tend to be more excellent in heat resistance.
芳香族基を含む２価の有機基は、下記式で表される基のいずれかであってもよい。 The divalent organic group containing an aromatic group may be any of the groups represented by the following formula.
式中、ｍは１～１０の整数を示す。ｍは１～５の整数であってもよい。 In the formula, m represents an integer from 1 to 10. m may be an integer of 1 to 5.
芳香族基を含む２価の有機基を有する構成単位の含有量は、ポリアミドの全構成単位を基準として、３０モル％以上、４０モル％以上、又は５０モル％以上であってもよく、８０モル％以下、７０モル％以下、又は６０モル％以下であってもよい。芳香族基を含む２価の有機基を有する構成単位の含有量がこのような範囲にあると、耐熱性により一層優れる傾向にある。 The content of the constituent unit having a divalent organic group including an aromatic group may be 30 mol% or more, 40 mol% or more, or 50 mol% or more, based on all the constituent units of polyamide, and may be 80 mol% or more. It may be 100 mol% or less, 70 mol% or less, or 60 mol% or less. When the content of the structural unit having a divalent organic group including an aromatic group is in such a range, the heat resistance tends to be further improved.
式（１）の構成単位及び式（２）の構成単位の合計に対する、芳香族基を含む２価の有機基を有する構成単位のモル比（芳香族基を含む２価の有機基を有する構成単位のモル量／式（１）の構成単位及び式（２）の構成単位の合計のモル量）は、０．８以上、１．０以上、又は１．２以上であってもよく、２．０以下、１．９以下、又は１．８以下であってもよい。モル比がこのような範囲にあると、アルコール系溶剤に対する溶解性と耐熱性とを高水準で両立することが可能である。 The molar ratio of the structural unit having a divalent organic group containing an aromatic group to the total of the structural units of the formula (1) and the structural unit of the formula (2) (a configuration having a divalent organic group including an aromatic group). The molar amount of the unit / the total molar amount of the structural unit of the formula (1) and the structural unit of the formula (2)) may be 0.8 or more, 1.0 or more, or 1.2 or more. It may be 0.0 or less, 1.9 or less, or 1.8 or less. When the molar ratio is in such a range, it is possible to achieve both solubility in an alcohol solvent and heat resistance at a high level.
本実施形態のポリアミドの重量平均分量は、２０００以上又は５０００以上であってもよい。重量平均分量がこのような範囲にあると、ポリアミドの耐熱性及びフィルム成形性がより優れる傾向にある。ポリアミドの重量平均分量は、２０００００以下又は１０００００以下であってもよい。重量平均分量がこのような範囲にあると、アルコール系溶剤に対するポリアミドの溶解性及び他の材料との相溶性に優れ、かつ取扱い性に優れる傾向にある。なお、重量平均分量は、ゲルパーミエーションクロマトグラフィー法により測定し、標準ポリスチレン検量線に基づき換算した値を意味する。 The weight average amount of the polyamide of this embodiment may be 2000 or more or 5000 or more. When the weight average amount is in such a range, the heat resistance and film formability of the polyamide tend to be more excellent. The weight average amount of the polyamide may be 200,000 or less or 100,000 or less. When the weight average amount is in such a range, the solubility of the polyamide in an alcohol solvent and the compatibility with other materials tend to be excellent, and the handleability tends to be excellent. The weight average amount means a value measured by a gel permeation chromatography method and converted based on a standard polystyrene calibration curve.
本実施形態のポリアミドは、２５℃で固形状であってもよい。ポリアミドが固形状であると、取扱い性に優れる傾向にある。 The polyamide of the present embodiment may be solid at 25 ° C. When the polyamide is in a solid state, it tends to be easy to handle.
本実施形態のポリアミドは、２５℃において、アルコール系溶剤に対して可溶である。なお、本明細書中、「アルコール系溶剤」は、溶剤全量を基準として、アルコールを２５質量％以上含む溶剤を意味する。アルコールは、メタノール、エタノール、１－プロパノール、又は２－プロパノールであってもよい。溶剤に含まれる非アルコール溶剤は、水、アセトン、テトラヒドロフラン、メチルエチルケトン、メチルイソブチルケトン、ベンゼン、トルエン、酢酸メチル、酢酸エチル、酢酸ブチル、シクロヘキサノン、１－メチル－２－ピロリドン、γ－ブチロラクトン、Ｎ，Ｎ－ジメチルアセトアミド、又はＮ，Ｎ－ジメチルホルムアミドであってもよい。 The polyamide of the present embodiment is soluble in an alcohol solvent at 25 ° C. In the present specification, "alcohol-based solvent" means a solvent containing 25% by mass or more of alcohol based on the total amount of the solvent. The alcohol may be methanol, ethanol, 1-propanol, or 2-propanol. Non-alcoholic solvents contained in the solvent include water, acetone, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, 1-methyl-2-pyrrolidone, γ-butyrolactone, N, It may be N-dimethylacetamide or N, N-dimethylformamide.
本実施形態のポリアミドは、ポリアミドの原料（例えば、等モル量のポリアミン及びジカルボン酸等）を通常の方法によって重合することによって得ることができる。 The polyamide of the present embodiment can be obtained by polymerizing a raw material of the polyamide (for example, an equimolar amount of a polyamine and a dicarboxylic acid) by a conventional method.
重合反応は、溶媒中で又は無溶媒条件下で行ってもよいが、均一なポリアミドが得られる観点から、溶媒中で行うことが好ましい。溶媒は、ポリアミドの原料を溶解させることができるものであれば特に制限されないが、１－メチル－２－ピロリドン、γ－ブチロラクトン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド等であってもよい。 The polymerization reaction may be carried out in a solvent or under solvent-free conditions, but is preferably carried out in a solvent from the viewpoint of obtaining a uniform polyamide. The solvent is not particularly limited as long as it can dissolve the raw material of polyamide, but is 1-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. May be good.
ポリアミドの原料として、ポリアミン及びジカルボン酸二塩化物を用いる場合、重合反応時に反応熱を生じることから、重合反応は冷却しながら行うことが好ましい。また、同様の観点から、重合反応は溶媒中で行うことが好ましく、ポリアミン又はジカルボン酸二塩化物のいずれか一方を滴下しながら行うこと好ましい。さらに、重合反応は系中に発生する塩酸を捕捉するために、塩酸捕捉剤を共存させて行うことが好ましい。 When polyamine and dicarboxylic acid dichloride are used as raw materials for the polyamide, the reaction heat is generated during the polymerization reaction, so that the polymerization reaction is preferably carried out while cooling. From the same viewpoint, the polymerization reaction is preferably carried out in a solvent, and it is preferable to carry out the polymerization reaction while dropping either polyamine or dicarboxylic acid dichloride. Further, in order to capture the hydrochloric acid generated in the system, the polymerization reaction is preferably carried out in the coexistence of a hydrochloric acid scavenger.
塩酸捕捉剤は、トリエチルアミン、ピリジン等であってもよい。塩酸捕捉剤は、ジカルボン酸二塩化物に対して、１．０～１．５当量であってもよい。塩酸捕捉剤が１．０当量以上であると、充分に塩酸を捕捉でき、重合反応が促進される傾向にある。塩酸捕捉剤が１．５当量以下であると、ポリアミドの重量平均分子量が充分に大きくなる傾向にある。 The hydrochloric acid scavenger may be triethylamine, pyridine or the like. The hydrochloric acid scavenger may be 1.0 to 1.5 equivalents with respect to the dicarboxylic acid dichloride. When the amount of the hydrochloric acid scavenger is 1.0 equivalent or more, hydrochloric acid can be sufficiently trapped and the polymerization reaction tends to be promoted. When the amount of the hydrochloric acid scavenger is 1.5 equivalents or less, the weight average molecular weight of the polyamide tends to be sufficiently large.
重合反応には、必要に応じて、活性触媒を添加してもよい。活性触媒としては、例えば、ホウ酸、鉄粉等を挙げられる。 An active catalyst may be added to the polymerization reaction, if necessary. Examples of the active catalyst include boric acid, iron powder and the like.
重合反応の温度は、ポリアミドの原料の種類に応じて、適宜選択することができる。重合温度は、１２０～３００℃であってもよく、１５０～２００℃であってもよい。重合温度が１２０℃以上であると、重合反応が促進される傾向にあり、重合反応が３００℃以下であると、特殊な設備を必要することなく、ポリアミドを製造することができる。 The temperature of the polymerization reaction can be appropriately selected depending on the type of the raw material of the polyamide. The polymerization temperature may be 120 to 300 ° C. or 150 to 200 ° C. When the polymerization temperature is 120 ° C. or higher, the polymerization reaction tends to be promoted, and when the polymerization reaction is 300 ° C. or lower, polyamide can be produced without the need for special equipment.
以下、本発明について実施例を挙げてより具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
［ポリアミドの合成］
（実施例１）
窒素雰囲気下において、窒素導入管付滴下漏斗、還流冷却器、温度計、及び撹拌機を備えた３００ｍＬのセパラブルフラスコに、ジカルボン酸二塩化物として二塩化イソフタロイル２０．３ｇ（０．１０ｍｏｌ）及び溶媒としてＮＭＰ（Ｎ－メチル－２－ピロリドン）７０．０ｇを加え、氷浴を用いて１０℃まで冷却しながら１５分間撹拌した。続いて、ポリアミンとして、ダイマージアミン（炭素数３６、クローダジャパン株式会社製、「ＰＲＩＡＭＩＮＥ １０７４」）１０．７ｇ（０．０２ｍｏｌ）、１，４－ビス（３－アミノプロピル）ピペラジン（式（２）の構成単位を与えるポリアミン）１６．０ｇ（０．０８ｍｏｌ）、及び発生する塩酸捕捉剤としてトリエチルアミン２２．３ｇ（０．２２ｍｏｌ）をＮＭＰ３９．８ｇに溶解し、滴下漏斗に導入した。滴下漏斗からジアミン化合物及び塩酸捕捉剤のＮＭＰ溶液を、フラスコ内の温度が３０～３５℃になるように調節しながら滴下し、ポリアミド（ＰＡ－１）のＮＭＰ溶液を得た。得られたＰＡ－１のＮＭＰ溶液を水中に投入し、析出物を回収した。この析出物を粉砕及び乾燥して２５℃で固形状のＰＡ－１を得た。
[Synthesis of polyamide]
(Example 1)
In a nitrogen atmosphere, in a 300 mL separable flask equipped with a dropping funnel with a nitrogen introduction tube, a reflux condenser, a thermometer, and a stirrer, 20.3 g (0.10 mol) of isophthaloyl dichloride as dicarboxylic acid dichloride and 70.0 g of NMP (N-methyl-2-pyrrolidone) was added as a solvent, and the mixture was stirred for 15 minutes while cooling to 10 ° C. using an ice bath. Subsequently, as polyamines, 10.7 g (0.02 mol) of dimer diamine (36 carbon atoms, manufactured by Claude Japan Co., Ltd., "PRIAMINE 1074"), 1,4-bis (3-aminopropyl) piperazine (formula (2)). 16.0 g (0.08 mol) of polyamine giving the constituent unit of the above and 22.3 g (0.22 mol) of triethylamine as a generated hydrochloric acid scavenger were dissolved in 39.8 g of NMP and introduced into a dropping funnel. An NMP solution of a diamine compound and a hydrochloric acid scavenger was added dropwise from the dropping funnel while adjusting the temperature in the flask to 30 to 35 ° C. to obtain an NMP solution of polyamide (PA-1). The obtained NMP solution of PA-1 was put into water, and the precipitate was recovered. This precipitate was pulverized and dried to obtain a solid PA-1 at 25 ° C.
（実施例２）
窒素雰囲気下において、窒素導入管付滴下漏斗、還流冷却器、温度計、及び撹拌機を備えた３００ｍＬのセパラブルフラスコに、ジカルボン酸二塩化物として二塩化イソフタロイル２０．３ｇ（０．１０ｍｏｌ）及び溶媒としてＮＭＰ１００．０ｇを加え、氷浴を用いて１０℃まで冷却しながら１５分間撹拌した。続いて、ポリアミンとして、ポリオキシプロピレンジアミン（ＨＵＮＴＳＭＡＮ社製、「ジェファーミン Ｄ－２０００」）２０．０ｇ（０．０１ｍｏｌ）、１，４－ビス（３－アミノプロピル）ピペラジン（式（２）の構成単位を与えるポリアミン）１４．０ｇ（０．０７ｍｏｌ）、２、２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン８．２ｇ（０．０２ｍｏｌ）、及び発生する塩酸捕捉剤としてトリエチルアミン２２．３ｇ（０．２２ｍｏｌ）をＮＭＰ４５．９ｇに溶解し、滴下漏斗に導入した。滴下漏斗からジアミン化合物及び塩酸捕捉剤のＮＭＰ溶液を、フラスコ内の温度が３０～３５℃になるように調節して滴下しながら、ポリアミド（ＰＡ－２）のＮＭＰ溶液を得た。得られたＰＡ－２のＮＭＰ溶液を水中に投入し、析出物を回収した。この析出物を粉砕及び乾燥して２５℃で固形状のＰＡ－２を得た。
(Example 2)
In a nitrogen atmosphere, in a 300 mL separable flask equipped with a dropping funnel with a nitrogen introduction tube, a reflux condenser, a thermometer, and a stirrer, 20.3 g (0.10 mol) of isophthaloyl dichloride as dicarboxylic acid dichloride and 100.0 g of NMP was added as a solvent, and the mixture was stirred for 15 minutes while cooling to 10 ° C. using an ice bath. Subsequently, as polyamines, polyoxypropylene diamine (manufactured by HUNTSMAN, "Jeffamine D-2000") 20.0 g (0.01 mol), 1,4-bis (3-aminopropyl) piperazine (formula (2)) Polyamines giving building blocks) 14.0 g (0.07 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 8.2 g (0.02 mol), and triethylamine 22 as a generated hydrochloric acid scavenger .3 g (0.22 mol) was dissolved in NMP 45.9 g and introduced into a dropping funnel. An NMP solution of a polyamide (PA-2) was obtained by dropping an NMP solution of a diamine compound and a hydrochloric acid scavenger from a dropping funnel while adjusting the temperature in the flask to 30 to 35 ° C. The obtained NMP solution of PA-2 was put into water, and the precipitate was recovered. This precipitate was pulverized and dried to obtain a solid PA-2 at 25 ° C.
（実施例３）
窒素雰囲気下において、窒素導入管付滴下漏斗、還流冷却器、温度計、及び撹拌機を備えた３００ｍＬのセパラブルフラスコに、ジカルボン酸二塩化物として二塩化イソフタロイル２５．４ｇ（０．１２ｍｏｌ）及び溶媒としてＮＭＰ１３０．０ｇを加え、氷浴を用いて１０℃まで冷却しながら１５分間撹拌した。続いて、ポリアミンとして、ポリオキシプロピレンジアミン（ＨＵＮＴＳＭＡＮ社製、「ジェファーミン Ｄ－２０００」）２５．０ｇ（０．０１ｍｏｌ）、１，４－ビス（３－アミノプロピル）ピペラジン（式（２）の構成単位を与えるポリアミン）１７．５ｇ（０．０９ｍｏｌ）、３，４’－ジアミノジフェニルエーテル５．０ｇ（０．０２ｍｏｌ）、及び発生する塩酸捕捉剤としてトリエチルアミン２７．８ｇ（０．２７ｍｏｌ）をＮＭＰ４０．１ｇに溶解し、滴下漏斗に導入した。滴下漏斗からジアミン化合物及び塩酸捕捉剤のＮＭＰ溶液を、フラスコ内の温度が３０～３５℃になるように調節しながら滴下し、ポリアミド（ＰＡ－３）のＮＭＰ溶液を得た。得られたＰＡ－３のＮＭＰ溶液を水中に投入し、析出物を回収した。この析出物を粉砕及び乾燥して２５℃で固形状のＰＡ－３を得た。
(Example 3)
In a nitrogen atmosphere, in a 300 mL separable flask equipped with a dropping funnel with a nitrogen inlet tube, a reflux condenser, a thermometer, and a stirrer, 25.4 g (0.12 mol) of isophthaloyl dichloride as dicarboxylic acid dichloride and 130.0 g of NMP was added as a solvent, and the mixture was stirred for 15 minutes while cooling to 10 ° C. using an ice bath. Subsequently, as polyamines, polyoxypropylene diamine (manufactured by HUNTSMAN, "Jeffamine D-2000") 25.0 g (0.01 mol), 1,4-bis (3-aminopropyl) piperazine (formula (2)) 17.5 g (0.09 mol) of polyamine giving a structural unit, 5.0 g (0.02 mol) of 3,4'-diaminodiphenyl ether, and 27.8 g (0.27 mol) of triethylamine as a generated hydrochloric acid scavenger were added to NMP40. It was dissolved in 1 g and introduced into a dropping funnel. An NMP solution of a diamine compound and a hydrochloric acid scavenger was added dropwise from the dropping funnel while adjusting the temperature in the flask to 30 to 35 ° C. to obtain an NMP solution of polyamide (PA-3). The obtained NMP solution of PA-3 was put into water, and the precipitate was recovered. This precipitate was pulverized and dried to obtain a solid PA-3 at 25 ° C.
（実施例４）
窒素雰囲気下において、ディーンスターク還流冷却器、温度計、及び撹拌機を備えた３００ｍＬのセパラブルフラスコに、ジアミン化合物としてダイマージアミン（クローダジャパン株式会社製、「ＰＲＩＡＭＩＮＥ １０７４」）１５０．１ｇ（０．２８ｍｏｌ）、ジエチレントリアミン（式（１）の構成単位を与えるポリアミン）７．２ｇ（０．０７ｍｏｌ）、ジカルボン酸化合物としてアジピン酸５１．２ｇ（０．３５ｍｏｌ）、及び活性触媒としてホウ酸０．６５ｇを加え、室温で１５分間攪拌した。その後、２００℃まで昇温し、ディーンスターク還流冷却器により析出する水を除去しながら６時間反応させた。フラスコの加温を停止し、１５０℃以上の高温のままフラスコ内から粘性状樹脂をかき出し、２５℃で固形状のポリアミド（ＰＡ－４）を得た。
(Example 4)
In a nitrogen atmosphere, dimerdiamine (“PRIAMINE 1074” manufactured by Claude Japan Co., Ltd.) 150.1 g (0.) was placed in a 300 mL separable flask equipped with a Dean Stark reflux condenser, a thermometer, and a stirrer. 28 mol), 7.2 g (0.07 mol) of diethylenetriamine (polyamine giving the structural unit of the formula (1)), 51.2 g (0.35 mol) of adipic acid as a dicarboxylic acid compound, and 0.65 g of boric acid as an active catalyst. In addition, the mixture was stirred at room temperature for 15 minutes. Then, the temperature was raised to 200 ° C., and the reaction was carried out for 6 hours while removing the water precipitated by the Dean-Stark reflux condenser. The heating of the flask was stopped, and the viscous resin was scraped out from the inside of the flask at a high temperature of 150 ° C. or higher to obtain a solid polyamide (PA-4) at 25 ° C.
（比較例１）
窒素雰囲気下において、ディーンスターク還流冷却器、温度計、及び撹拌機を備えた３００ｍＬのセパラブルフラスコに、ポリアミンとしてダイマージアミン（クローダジャパン株式会社製、「ＰＲＩＡＭＩＮＥ １０７４」）１８７．６ｇ（０．３５ｍｏｌ）、ジカルボン酸としてアジピン酸５１．２ｇ（０．３５ｍｏｌ）、及び活性触媒としてホウ酸０．６５ｇを加え、室温で１５分間攪拌した。その後、２００℃まで昇温し、ディーンスターク還流冷却器により析出する水を除去しながら６時間反応させた。フラスコの加温を停止し、１５０℃以上の高温のままフラスコ内から粘性状樹脂をかき出し、２５℃で固形状のポリアミド（ＰＡ－５）を得た。
(Comparative Example 1)
187.6 g (0.35 mol) of dimerdiamine (“PRIAMINE 1074” manufactured by Claude Japan Co., Ltd.) as a polyamine in a 300 mL separable flask equipped with a Dean Stark reflux condenser, a thermometer, and a stirrer under a nitrogen atmosphere. ), 51.2 g (0.35 mol) of adipic acid as a dicarboxylic acid, and 0.65 g of boric acid as an active catalyst were added, and the mixture was stirred at room temperature for 15 minutes. Then, the temperature was raised to 200 ° C., and the reaction was carried out for 6 hours while removing the water precipitated by the Dean-Stark reflux condenser. The heating of the flask was stopped, and the viscous resin was scraped out from the inside of the flask at a high temperature of 150 ° C. or higher to obtain a solid polyamide (PA-5) at 25 ° C.
（比較例２）
窒素雰囲気下において、窒素導入管付滴下漏斗、還流冷却器、温度計、及び撹拌機を備えた３００ｍＬのセパラブルフラスコに、ジカルボン酸二塩化物として二塩化イソフタロイル２０．３ｇ（０．１０ｍｏｌ）及び溶媒としてＮＭＰ１４０．０ｇを加え、氷浴を用いて１０℃まで冷却しながら１５分間撹拌した。続いて、ポリアミンとして、ポリオキシプロピレンジアミン（ＨＵＮＴＳＭＡＮ社製、「ジェファーミン Ｄ－２０００」）２０．０ｇ（０．０１ｍｏｌ）、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン３７．０ｇ（０．０９ｍｏｌ）、及び発生する塩酸捕捉剤としてトリエチルアミン２２．３ｇ（０．２２ｍｏｌ）をＮＭＰ４０．３ｇに溶解し、滴下漏斗に導入した。滴下漏斗からジアミン化合物及び塩酸捕捉剤のＮＭＰ溶液を、フラスコ内の温度が３０～３５℃になるように調節しながら滴下し、ポリアミド（ＰＡ－６）のＮＭＰ溶液を得た。得られたＰＡ－６のＮＭＰ溶液を水中に投入し、析出物を回収した。この析出物を粉砕及び乾燥して２５℃で固形状のＰＡ－６を得た。
(Comparative Example 2)
In a nitrogen atmosphere, in a 300 mL separable flask equipped with a dropping funnel with a nitrogen introduction tube, a reflux condenser, a thermometer, and a stirrer, 20.3 g (0.10 mol) of isophthaloyl dichloride as dicarboxylic acid dichloride and 140.0 g of NMP was added as a solvent, and the mixture was stirred for 15 minutes while cooling to 10 ° C. using an ice bath. Subsequently, as polyamines, polyoxypropylene diamine (manufactured by HUNTSMAN, "Jeffamine D-2000") 20.0 g (0.01 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 37. 0.0 g (0.09 mol) and 22.3 g (0.22 mol) of triethylamine as a generated hydrochloric acid scavenger were dissolved in 40.3 g of NMP and introduced into a dropping funnel. An NMP solution of a diamine compound and a hydrochloric acid scavenger was added dropwise from the dropping funnel while adjusting the temperature in the flask to 30 to 35 ° C. to obtain an NMP solution of polyamide (PA-6). The obtained NMP solution of PA-6 was put into water, and the precipitate was recovered. This precipitate was pulverized and dried to obtain a solid PA-6 at 25 ° C.
［溶解性評価］
容量が２０ｍＬのガラス瓶に、得られたポリアミド３．０ｇ、トルエン３．５ｇ、及びメタノール３．５ｇを加え、ポリアミドの固形分が３０質量％となるようにポリアミドのトルエン／メタノール溶液を調製した。２５℃で２４時間撹拌し、不溶物の有無を目視にて確認した。結果を表１に示す。また、メタノールをエタノール又は２－プロプロパノールに変更した以外は、同様にして、不溶物の有無を目視にて確認した。結果を表１に示す。
[Solubility evaluation]
3.0 g of the obtained polyamide, 3.5 g of toluene, and 3.5 g of methanol were added to a glass bottle having a capacity of 20 mL, and a toluene / methanol solution of the polyamide was prepared so that the solid content of the polyamide was 30% by mass. The mixture was stirred at 25 ° C. for 24 hours, and the presence or absence of insoluble matter was visually confirmed. The results are shown in Table 1. In addition, the presence or absence of insoluble matter was visually confirmed in the same manner except that methanol was changed to ethanol or 2-propanol. The results are shown in Table 1.
［耐熱性評価］
得られたポリアミドに関して、粘弾性測定装置（ＴＡ Ｉｎｓｔｒｕｍｅｎｔ社製レオメータＡＲＥＳ－Ｇ２、昇温速度：１０℃／分、測定周波数：１Ｈｚ、応力ひずみ：５％）を用いて１８０℃から４０℃までの貯蔵弾性率を測定した。得られた貯蔵弾性率のうち、１６０℃、１２０℃、及び８０℃の値を読み取った。結果を表１に示す。
[Heat resistance evaluation]
The obtained polyamide was measured from 180 ° C. to 40 ° C. using a viscoelasticity measuring device (TA Instrument rheometer ARES-G2, heating rate: 10 ° C./min, measurement frequency: 1 Hz, stress strain: 5%). The storage elastic modulus was measured. Of the obtained storage elastic moduli, the values at 160 ° C, 120 ° C, and 80 ° C were read. The results are shown in Table 1.
特定の構成単位を含む実施例１～４のポリアミドは、各種アルコールとトルエンとの混合溶液（アルコール系溶剤）に対して優れた溶解性を有していた。これに対して、そのような構成単位を含まない比較例１及び２のポリアミドは、不溶物が観測され、アルコール系溶剤に対する溶解性が充分ではなかった。また、芳香族炭化水素基を含む２価の有機基を有する構成単位を含む実施例１～３のポリアミドは、そのような構成単位を含まない実施例４のポリアミドに比べて、耐熱性により優れることが判明した。これらの結果から、本発明のポリアミドがアルコール系溶剤に対する溶解性に優れることが確認された。 The polyamides of Examples 1 to 4 containing a specific structural unit had excellent solubility in a mixed solution (alcohol-based solvent) of various alcohols and toluene. On the other hand, insoluble substances were observed in the polyamides of Comparative Examples 1 and 2 not containing such a structural unit, and the solubility in alcohol-based solvents was not sufficient. Further, the polyamides of Examples 1 to 3 containing a structural unit having a divalent organic group containing an aromatic hydrocarbon group are more excellent in heat resistance than the polyamide of Example 4 not containing such a structural unit. It has been found. From these results, it was confirmed that the polyamide of the present invention has excellent solubility in alcohol solvents.
Claims (2)
前記ポリアミンに由来する構成単位が、下記一般式（２）で表される構成単位及びダイマー酸から誘導されるダイマージアミンに由来する構成単位を含み、
前記一般式（２）で表される構成単位の含有量が、前記ポリアミンに由来する構成単位全量を基準として、３０モル％以上９０モル％以下であり、
前記ダイマージアミンに由来する構成単位の含有量が、前記ポリアミンに由来する構成単位全量を基準として、１モル％以上３０モル％以下であり、
前記ポリアミンに由来する構成単位又は前記ジカルボン酸に由来する構成単位の少なくとも一方が、芳香族基を含む２価の有機基を有する構成単位を含み、
前記芳香族基を含む２価の有機基を有する構成単位の含有量が、ポリアミドの全構成単位を基準として、３０モル％以上７０モル％以下であり、
前記式（２）の構成単位に対する前記芳香族基を含む２価の有機基を有する構成単位のモル比が、１．０以上１．８以下である、ポリアミド。
［式（２）中、Ｒ２及びＲ３はそれぞれ独立にアルキレン基を示す。］ Containing a constituent unit derived from a polyamine and a constituent unit derived from a dicarboxylic acid,
The structural unit derived from the polyamine includes a structural unit represented by the following general formula (2) and a structural unit derived from dimerdiamine derived from dimer acid .
The content of the structural unit represented by the general formula (2) is 30 mol% or more and 90 mol% or less based on the total amount of the structural unit derived from the polyamine.
The content of the structural unit derived from the dimer diamine is 1 mol% or more and 30 mol% or less based on the total amount of the structural unit derived from the polyamine.
At least one of the constituent units derived from the polyamine or the dicarboxylic acid comprises a constituent unit having a divalent organic group containing an aromatic group.
The content of the constituent unit having a divalent organic group including an aromatic group is 30 mol% or more and 70 mol% or less based on all the constituent units of the polyamide.
A polyamide having a molar ratio of a structural unit having a divalent organic group containing the aromatic group to the structural unit of the formula (2) of 1.0 or more and 1.8 or less .
[In formula (2), R 2 and R 3 each independently represent an alkylene group. ]
［式中、ｍは１～１０の整数を示す。］ The polyamide according to claim 1 , wherein the divalent organic group containing the aromatic group is one of the groups represented by the following formula.
[In the formula, m represents an integer from 1 to 10. ]
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5154760A (en) | 1990-11-27 | 1992-10-13 | Union Camp Corporation | Polyamide resin compositions for use as laminating ink resin binders |
| JP2009522460A (en) | 2005-12-29 | 2009-06-11 | ナルコ カンパニー | Creping adhesive comprising a mixture of polyaminoamide epihalohydrin resin and polyamide |
| JP2010202853A (en) | 2009-02-06 | 2010-09-16 | Hitachi Chem Co Ltd | Adhesion improver for glass, resin composition, and method for producing laminate of the same and glass |
| JP2011116937A (en) | 2009-11-04 | 2011-06-16 | Hitachi Chem Co Ltd | Adhesive composition, circuit connection structure, and semiconductor device |
| WO2012141267A1 (en) | 2011-04-12 | 2012-10-18 | 日立化成工業株式会社 | Pressure-sensitive adhesive, pressure-sensitive adhesive material using same, and method for using said adhesive and material |
| JP2013047355A (en) | 2011-04-12 | 2013-03-07 | Hitachi Chemical Co Ltd | Adhesive, adhesive material using the same, and use thereof |
| JP2013204023A (en) | 2012-03-29 | 2013-10-07 | Hitachi Chemical Co Ltd | Adhesive composition, film-like adhesive, and method for peeling adhered material |
| JP2013209484A (en) | 2012-03-30 | 2013-10-10 | Hitachi Chemical Co Ltd | Adhesive composition, filmy adhesive and method for peeling adherend |
| JP2013245243A (en) | 2012-05-23 | 2013-12-09 | Hitachi Chemical Co Ltd | Pressure-sensitive adhesive, method for producing glass substrate and method for producing image display element |
| JP2013245245A (en) | 2012-05-23 | 2013-12-09 | Hitachi Chemical Co Ltd | Pressure-sensitive adhesive for reinforcing copper-clad laminate or flexible wiring board, pressure-sensitive adhesive sheet for reinforcing copper-clad laminate or flexible wiring board and method for using the same |
| JP2015199793A (en) | 2014-04-04 | 2015-11-12 | 日立化成株式会社 | Pressure-sensitive adhesive and method for using the same, and pressure-sensitive adhesive material and method for using the same |
| JP2017129660A (en) | 2016-01-19 | 2017-07-27 | 東洋紡株式会社 | Photosensitive resin composition for relief printing plate precursor and relief printing plate precursor obtained from the composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4218351A (en) * | 1978-07-17 | 1980-08-19 | Minnesota Mining And Manufacturing Company | Impact resistant, thermoplastic polyamides |
| US5139677A (en) * | 1991-11-18 | 1992-08-18 | Texaco Inc. | Membrane separation method |
| JP3127652B2 (en) * | 1993-01-26 | 2001-01-29 | 日本ピー・エム・シー株式会社 | Method for producing aqueous solution of cationic thermosetting resin |
-
2017
- 2017-06-02 JP JP2017110287A patent/JP7056015B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5154760A (en) | 1990-11-27 | 1992-10-13 | Union Camp Corporation | Polyamide resin compositions for use as laminating ink resin binders |
| JP2009522460A (en) | 2005-12-29 | 2009-06-11 | ナルコ カンパニー | Creping adhesive comprising a mixture of polyaminoamide epihalohydrin resin and polyamide |
| JP2010202853A (en) | 2009-02-06 | 2010-09-16 | Hitachi Chem Co Ltd | Adhesion improver for glass, resin composition, and method for producing laminate of the same and glass |
| JP2011116937A (en) | 2009-11-04 | 2011-06-16 | Hitachi Chem Co Ltd | Adhesive composition, circuit connection structure, and semiconductor device |
| WO2012141267A1 (en) | 2011-04-12 | 2012-10-18 | 日立化成工業株式会社 | Pressure-sensitive adhesive, pressure-sensitive adhesive material using same, and method for using said adhesive and material |
| JP2013047355A (en) | 2011-04-12 | 2013-03-07 | Hitachi Chemical Co Ltd | Adhesive, adhesive material using the same, and use thereof |
| JP2013204023A (en) | 2012-03-29 | 2013-10-07 | Hitachi Chemical Co Ltd | Adhesive composition, film-like adhesive, and method for peeling adhered material |
| JP2013209484A (en) | 2012-03-30 | 2013-10-10 | Hitachi Chemical Co Ltd | Adhesive composition, filmy adhesive and method for peeling adherend |
| JP2013245243A (en) | 2012-05-23 | 2013-12-09 | Hitachi Chemical Co Ltd | Pressure-sensitive adhesive, method for producing glass substrate and method for producing image display element |
| JP2013245245A (en) | 2012-05-23 | 2013-12-09 | Hitachi Chemical Co Ltd | Pressure-sensitive adhesive for reinforcing copper-clad laminate or flexible wiring board, pressure-sensitive adhesive sheet for reinforcing copper-clad laminate or flexible wiring board and method for using the same |
| JP2015199793A (en) | 2014-04-04 | 2015-11-12 | 日立化成株式会社 | Pressure-sensitive adhesive and method for using the same, and pressure-sensitive adhesive material and method for using the same |
| JP2017129660A (en) | 2016-01-19 | 2017-07-27 | 東洋紡株式会社 | Photosensitive resin composition for relief printing plate precursor and relief printing plate precursor obtained from the composition |
Non-Patent Citations (1)
| Title |
|---|
| Journal of Microencapsulation, 1995, Vol.12, p.425-435 |
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