WO2014141978A1 - ポリアミド樹脂の製造方法 - Google Patents
ポリアミド樹脂の製造方法 Download PDFInfo
- Publication number
- WO2014141978A1 WO2014141978A1 PCT/JP2014/055699 JP2014055699W WO2014141978A1 WO 2014141978 A1 WO2014141978 A1 WO 2014141978A1 JP 2014055699 W JP2014055699 W JP 2014055699W WO 2014141978 A1 WO2014141978 A1 WO 2014141978A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide resin
- polyamide
- kneading
- vacuum
- oligomer
- Prior art date
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims description 62
- 239000004952 Polyamide Substances 0.000 claims abstract description 113
- 229920002647 polyamide Polymers 0.000 claims abstract description 113
- 238000004898 kneading Methods 0.000 claims abstract description 95
- 238000002156 mixing Methods 0.000 claims description 47
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- 125000004437 phosphorous atom Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 238000006068 polycondensation reaction Methods 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 21
- 125000004427 diamine group Chemical group 0.000 claims description 18
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 17
- -1 phosphorus compound Chemical class 0.000 claims description 13
- 239000005022 packaging material Substances 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000012770 industrial material Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000006157 aromatic diamine group Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 27
- 239000011347 resin Substances 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 238000011049 filling Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 28
- 238000001125 extrusion Methods 0.000 description 28
- 238000011144 upstream manufacturing Methods 0.000 description 21
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 18
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 150000004985 diamines Chemical class 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001339 alkali metal compounds Chemical class 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 6
- 150000004984 aromatic diamines Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 6
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 5
- 229940064002 calcium hypophosphite Drugs 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 4
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 4
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000005819 Potassium phosphonate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical class NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000011955 best available control technology Methods 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910001383 lithium hypophosphite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-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
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-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
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FLBFODZVDUPBLV-UHFFFAOYSA-L P([O-])([O-])=O.[Li+].P(O)(O)O.[Li+] Chemical compound P([O-])([O-])=O.[Li+].P(O)(O)O.[Li+] FLBFODZVDUPBLV-UHFFFAOYSA-L 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- KIXBZFKSFFHEBZ-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine benzene-1,4-dicarboxamide Chemical compound NCC1CCCC(CN)C1.NC(=O)c1ccc(cc1)C(N)=O KIXBZFKSFFHEBZ-UHFFFAOYSA-N 0.000 description 1
- ZFQPIZJVUYGCOH-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine decanediamide Chemical compound NCC1CCC(CN)CC1.NC(=O)CCCCCCCCC(N)=O ZFQPIZJVUYGCOH-UHFFFAOYSA-N 0.000 description 1
- APCDJRHDYGQKBD-UHFFFAOYSA-N [Ca++].[O-]P[O-] Chemical compound [Ca++].[O-]P[O-] APCDJRHDYGQKBD-UHFFFAOYSA-N 0.000 description 1
- IXRFQWWRSJGLAD-UHFFFAOYSA-L [Li+].[Li+].[O-]P([O-])=O Chemical compound [Li+].[Li+].[O-]P([O-])=O IXRFQWWRSJGLAD-UHFFFAOYSA-L 0.000 description 1
- RKQCWKUKEODNIO-UHFFFAOYSA-N [Mg++].[O-]P[O-] Chemical compound [Mg++].[O-]P[O-] RKQCWKUKEODNIO-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- PHIBEYMUALDAQI-UHFFFAOYSA-N benzylphosphinic acid Chemical compound OP(=O)CC1=CC=CC=C1 PHIBEYMUALDAQI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- OMAAXMJMHFXYFY-UHFFFAOYSA-L calcium trioxidophosphanium Chemical compound [Ca+2].[O-]P([O-])=O OMAAXMJMHFXYFY-UHFFFAOYSA-L 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- DRXDBDATOLWSNZ-UHFFFAOYSA-L dilithium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(=O)C1=CC=CC=C1 DRXDBDATOLWSNZ-UHFFFAOYSA-L 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- ZYAPDAASNUBTSQ-UHFFFAOYSA-N dipotassium dioxidophosphane Chemical compound [K+].[K+].[O-]P[O-] ZYAPDAASNUBTSQ-UHFFFAOYSA-N 0.000 description 1
- CVFJNXQOIZKPMG-UHFFFAOYSA-L dipotassium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [K+].[K+].[O-]P([O-])(=O)C1=CC=CC=C1 CVFJNXQOIZKPMG-UHFFFAOYSA-L 0.000 description 1
- WCPNHDCBQKJBDD-UHFFFAOYSA-L dipotassium;ethyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [K+].[K+].CCP([O-])([O-])=O WCPNHDCBQKJBDD-UHFFFAOYSA-L 0.000 description 1
- JOQAMSDLZYQHMX-UHFFFAOYSA-L disodium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Na+].[Na+].[O-]P([O-])(=O)C1=CC=CC=C1 JOQAMSDLZYQHMX-UHFFFAOYSA-L 0.000 description 1
- FFEOZYZNEUVLSW-UHFFFAOYSA-N disodium;dioxidophosphane Chemical compound [Na+].[Na+].[O-]P[O-] FFEOZYZNEUVLSW-UHFFFAOYSA-N 0.000 description 1
- ZRRLFMPOAYZELW-UHFFFAOYSA-N disodium;hydrogen phosphite Chemical compound [Na+].[Na+].OP([O-])[O-] ZRRLFMPOAYZELW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- DJHASRVNBMMHLB-UHFFFAOYSA-N ethoxy(phenyl)phosphinite Chemical compound CCOP([O-])C1=CC=CC=C1 DJHASRVNBMMHLB-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 235000021056 liquid food Nutrition 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- GGBCFSSSAXHPPM-UHFFFAOYSA-N lithium;phenoxyphosphinite Chemical compound [Li+].[O-]POC1=CC=CC=C1 GGBCFSSSAXHPPM-UHFFFAOYSA-N 0.000 description 1
- ISPMIYRVKUAKMX-UHFFFAOYSA-N magnesium hydrogen phosphite Chemical compound [Mg++].OP([O-])[O-] ISPMIYRVKUAKMX-UHFFFAOYSA-N 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- DXCSBPNCZRYVDN-UHFFFAOYSA-N phenoxyphosphinous acid Chemical compound OPOC1=CC=CC=C1 DXCSBPNCZRYVDN-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- CMCWULILUYLGQL-UHFFFAOYSA-N potassium;phenoxyphosphinite Chemical compound [K+].[O-]POC1=CC=CC=C1 CMCWULILUYLGQL-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- IYYIUOWKEMQYNV-UHFFFAOYSA-N sodium;ethoxy-oxido-oxophosphanium Chemical compound [Na+].CCO[P+]([O-])=O IYYIUOWKEMQYNV-UHFFFAOYSA-N 0.000 description 1
- AMALSQNGRLASSJ-UHFFFAOYSA-N sodium;phenoxyphosphinite Chemical compound [Na+].[O-]POC1=CC=CC=C1 AMALSQNGRLASSJ-UHFFFAOYSA-N 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CELVKTDHZONYFA-UHFFFAOYSA-N trilithium;phosphite Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])[O-] CELVKTDHZONYFA-UHFFFAOYSA-N 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
- B29K2077/10—Aromatic polyamides [polyaramides] or derivatives thereof
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Definitions
- the present invention relates to a method for producing a polyamide resin from a polyamide oligomer using an extruder composed of a co-rotating meshing twin screw.
- Polyamide is excellent in mechanical properties and processability and has a relatively high gas barrier property, so it can be used not only as an injection molding material for automobiles and electrical and electronic parts, but also for packaging materials such as food, beverages, chemicals and electronic parts. It is also widely used as an industrial material.
- a polyamide obtained from a polycondensation reaction between xylylenediamine and an aliphatic dicarboxylic acid has high strength and elastic modulus, and low permeability to gaseous substances such as oxygen, carbon dioxide, odor and flavor. Therefore, it is widely used as a gas barrier material in the field of packaging materials. Further, since it has resistance and gas barrier properties against alcohol, weakly alkaline chemicals, weakly acidic chemicals, fuel, various organic solvents, industrial gases, etc., it is also widely used in industrial fields.
- a polyamide resin for example, after polycondensation of a dicarboxylic acid component and a diamine component to obtain a polyamide, the polyamide is polymerized by a solid-phase polymerization method in a heat drying apparatus such as a tumble dryer.
- a heat drying apparatus such as a tumble dryer.
- the solid-phase polymerization method has a problem in that a resin having a high melting point is produced and there is a limit to increasing the molecular weight of a resin having low crystallinity, and a resin having a high melting point cannot be obtained.
- a method of obtaining a polyamide resin by melt-kneading a polyamide oligomer obtained by polycondensation of a dicarboxylic acid component and a diamine component using an extruder having a twin screw and further polycondensing it is also known.
- an extruder having a twin screw an oligomer can be melt-kneaded in a short time, and a polyamide resin having a high melting point can be produced, and further, a self-cleaning property enables handling of a small variety of products. is there. Therefore, various methods for producing various types of polyamide resins by an extruder using a twin screw have been studied.
- the polymerization of polyamide oligomer is dehydration polycondensation, and a large amount of water is generated in the reaction process. Therefore, depending on the molecular weight and moisture content of the oligomer, when the polymerization reaction is carried out by a normal kneading operation using a twin screw extruder, a large amount of water may flow backward. Moreover, in the vacuum vent for making the inside of a cylinder into a negative pressure, troubles, such as clogging by the raw material sucked with water, may occur.
- the present invention has been made in view of the above problems, and an object of the present invention is to polymerize a polyamide oligomer without causing problems in the process when an extruder composed of a twin screw is used.
- an object of the present invention is to polymerize a polyamide oligomer without causing problems in the process when an extruder composed of a twin screw is used.
- it is to provide a method for producing a polyamide capable of producing a polyamide resin having an appropriate molecular weight and a low yellowness.
- the present invention provides the following (1) to (10).
- a polyamide resin is produced by polycondensation by melt kneading
- a method for producing a polyamide resin wherein a pressure-lowering element is provided at a position closer to a supply unit than a position where the vacuum vent is provided, and a range of 30% or less of the total screw length is a vacuum region of 300 torr or less.
- n represents an integer of 2 to 18.
- Ar represents an arylene group.
- the manufacturing method of the polyamide resin of description (9) The polyamide according to any one of (1) to (8), wherein a kneading part for kneading the polyamide oligomer is provided at a position closer to the supply part than the vacuum region, and the kneading part includes a kneading element having strong dispersion and mixing properties. Manufacturing method of resin. (10) Molded from the polyamide resin produced by the method for producing a polyamide resin according to any one of (1) to (9) above, and selected from the group consisting of packaging materials, packaging containers, industrial materials and industrial parts Goods.
- a polyamide resin can be produced from a polyamide oligomer having a predetermined molecular weight and moisture content without causing problems in the process.
- FIG. 3A and 3B are perspective views showing a rotor used in the present invention, in which FIG. 3A shows a continuous rotor and FIG. 3B shows a discontinuous rotor. It is sectional drawing and the side view which show the SME mixing element used by this invention. It is a side view which shows the mixing gear used by this invention. It is sectional drawing and the side view which show the ZME mixing element used by this invention.
- 1 is a schematic view showing an extruder used in Examples 1 to 6 and Comparative Example 1.
- FIG. 6 is a schematic view showing an extruder used in Comparative Example 2.
- FIG. 1 is a schematic view showing an extruder used in Examples 1 to 6 and Comparative Example 1.
- FIG. 6 is a schematic view showing an extruder used in Comparative Example 2.
- FIG. 6 is a schematic view showing an extruder used in Comparative Example 2.
- the present invention is a method for producing a polyamide by polycondensing a polyamide oligomer to produce a polyamide resin having a higher molecular weight than that of the polyamide oligomer.
- the polyamide oligomer used as a raw material in the present invention contains a diamine unit and a dicarboxylic acid unit.
- the proportion of the content of the diamine unit and the dicarboxylic acid unit is preferably substantially the same from the viewpoint of the polymerization reaction, and the content of the dicarboxylic acid unit is ⁇ 2 mol% of the content of the diamine unit. More preferred.
- the polyamide oligomer may further contain a constituent unit other than the diamine unit and the dicarboxylic acid unit as long as the effects of the present invention are not impaired.
- the diamine unit in the polyamide oligomer is a diamine unit selected from an aromatic diamine unit represented by the following general formula (I-1) and an alicyclic diamine unit represented by the following general formula (I-2): It contains 70 mol% or more in total in the diamine unit. The content is preferably 80 mol% or more, more preferably 90 mol% or more, and the upper limit is 100 mol%.
- Examples of the compound that can constitute the aromatic diamine unit represented by the general formula (I-1) include orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine. These can be used alone or in combination of two or more.
- Examples of the compound that can constitute the alicyclic diamine unit represented by the general formula (I-2) include bis (amino) such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane. Methyl) cyclohexanes. These can be used alone or in combination of two or more.
- the cis-isomer content ratio in the bis (aminomethyl) cyclohexane is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.
- the trans content in the bis (aminomethyl) cyclohexane is preferably 50 mol% or more, more preferably 60 mol% or more, and most preferably 70 mol% or more.
- the diamine unit in the polyamide oligomer contains at least one of an aromatic diamine unit represented by the general formula (I-1) and an alicyclic diamine unit represented by the general formula (I-2).
- an aromatic diamine unit represented by the general formula (I-1) it preferably contains an aromatic diamine unit represented by the general formula (I-1).
- the diamine unit in the polyamide oligomer contains 70 mol% or more of metaxylylenediamine units from the viewpoint of facilitating the moldability of a general-purpose thermoplastic resin in addition to exhibiting excellent gas barrier properties in the polyamide resin.
- the content is more preferably 80 mol% or more, still more preferably 90 mol% or more, and the upper limit is 100 mol%.
- Examples of the compound that can constitute a diamine unit other than the diamine unit represented by any one of formulas (I-1) and (I-2) include ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, Straight chain aliphatic diamines having 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms, such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine; Aromatic diamines such as paraphenylenediamine; alicyclic diamines such as 1,3-diaminocyclohexane and 1,4-diaminocyclohexane; N-methylethylenediamine, 2-methyl-1,5-pentanediamine, 1-amino-3 -Aminomethyl-3,5,5-tri Aliphatic diamines other than linear aliphatic diamine
- the dicarboxylic acid unit in the polyamide oligomer is a linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) from the viewpoint of reactivity during polymerization, crystallinity and moldability of the polyamide resin, and A total of 50 mol% or more of dicarboxylic acid units selected from aromatic dicarboxylic acid units represented by the general formula (II-2) are contained in the dicarboxylic acid units.
- the content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and the upper limit is 100 mol%.
- n represents an integer of 2 to 18.
- Ar represents an arylene group.
- the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) gives an appropriate glass transition temperature and crystallinity to the polyamide resin obtained by the present production method, for example, a packaging material or a packaging container. It is preferable at the point which can provide required softness.
- n represents an integer of 2 to 18, preferably 3 to 16, more preferably 4 to 12, and still more preferably 4 to 8.
- Examples of the compound that can constitute the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10 Examples include, but are not limited to, decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid and the like. These can be used alone or in combination of two or more.
- the kind of the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) is appropriately determined according to the use.
- the linear aliphatic dicarboxylic acid unit in addition to imparting excellent gas barrier properties to the polyamide resin, from the viewpoint of maintaining heat resistance after heat sterilization of packaging materials and packaging containers, adipic acid units, sebacic acid units, and It is preferable that at least one selected from the group consisting of 1,12-dodecanedicarboxylic acid units is contained in a total of 50 mol% or more in the linear aliphatic dicarboxylic acid units, and the content is more preferably 70 mol%. Above, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and the upper limit is 100 mol%.
- the linear aliphatic dicarboxylic acid unit in the polyamide oligomer is 50 parts of the adipic acid unit in the linear aliphatic dicarboxylic acid unit from the viewpoint of the gas barrier property of the polyamide resin and the thermal properties such as an appropriate glass transition temperature and melting point. It is preferable to contain more than mol%. Further, the linear aliphatic dicarboxylic acid unit in the polyamide oligomer is 50 mol% or more of the sebacic acid unit in the linear aliphatic dicarboxylic acid unit from the viewpoint of imparting appropriate gas barrier properties and moldability to the polyamide resin. It is preferable to include.
- the linear aliphatic dicarboxylic acid unit may contain 50 mol% or more of 1,12-dodecanedicarboxylic acid units. preferable.
- the aromatic dicarboxylic acid unit represented by the general formula (II-2) is capable of facilitating molding processability of packaging materials and packaging containers in addition to imparting further gas barrier properties to the polyamide resin.
- Ar represents an arylene group.
- the arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
- Examples of the compound that can constitute the aromatic dicarboxylic acid unit represented by the general formula (II-2) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like, but are not limited thereto. Absent. These can be used alone or in combination of two or more.
- the type of the aromatic dicarboxylic acid unit represented by the general formula (II-2) is appropriately determined according to the use.
- the aromatic dicarboxylic acid unit in the polyamide oligomer contains at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit in a total of 50 moles in the aromatic dicarboxylic acid unit.
- the content is 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and the upper limit is 100 mol%.
- at least one of isophthalic acid and terephthalic acid is preferably included in the aromatic dicarboxylic acid unit.
- the content ratio of the isophthalic acid unit to the terephthalic acid unit is not particularly limited and is appropriately determined according to the application.
- the molar ratio is preferably 0/100 to 100/0, more preferably 0/100 to 60/40, More preferably, it is 0/100 to 40/60, and most preferably 0/100 to 30/70.
- the content ratio of the linear aliphatic dicarboxylic acid unit and the aromatic dicarboxylic acid unit is not particularly limited, It is determined appropriately according to the application.
- the total of both units of the linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit is 100.
- the molar ratio is preferably 0/100 to 60/40, more preferably 0/100 to 40/60, and still more preferably 0/100 to 30/70.
- the linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit is 100
- the molar ratio is preferably 40/60 to 100/0, more preferably 60/40 to 100/0, still more preferably 70/30 to 100/0.
- Compounds that can constitute dicarboxylic acid units other than the dicarboxylic acid unit represented by the general formula (II-1) or (II-2) include oxalic acid, malonic acid, fumaric acid, maleic acid, 1,3-benzene.
- Examples of the dicarboxylic acid include diacetic acid and 1,4-benzenediacetic acid, but are not limited thereto.
- relative viscosity and moisture content of polyamide oligomer As an index representing the molecular weight of the polyamide oligomer or the polyamide resin described later, there is a relative viscosity.
- the relative viscosity of the polyamide oligomer is 1.1 to 1.3.
- the polyamide oligomer has a water content of 3% by mass or less. In the present invention, when the relative viscosity and the water content are within the above ranges, the polyamide oligomer can be polymerized and the polyamide resin can be produced without causing problems in the process by the production method described later.
- the moisture content of the polyamide oligomer as a raw material is preferably 2.5% by mass or less, more preferably 1.8% by mass or less.
- the moisture content is not particularly limited, but is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more from the viewpoint of increasing the efficiency of the process, such as drying the oligomer in a short time.
- the yellowness degree of the polyamide oligomer which is a raw material of the present invention is preferably 10 or less, more preferably 7 or less. By reducing the yellowness of the raw material polyamide oligomer, the yellowness of the produced polyamide resin can be improved.
- the polyamide oligomer in the present invention is obtained by polycondensation reaction of a diamine component corresponding to the diamine unit of the polyamide resin and a dicarboxylic acid component corresponding to the dicarboxylic unit.
- the polycondensation reaction is performed by, for example, a melt polycondensation method. Specifically, a method of performing a polycondensation reaction by heating a nylon salt composed of a dicarboxylic acid component and a diamine component in the presence of water under pressure. At this time, the reaction may be performed while dehydrating the condensed water as necessary.
- the obtained polyamide oligomer can be finally separated from water by flashing or the like to obtain a powdery polyamide oligomer.
- the melt polycondensation method may also include a method in which a diamine component is directly added to a molten dicarboxylic acid component and polycondensed. In this case, in order to keep the reaction system in a uniform liquid state, the diamine component is continuously added to the dicarboxylic acid component, while the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated polyamide oligomer. The polycondensation proceeds. Moreover, you may pressurize a reaction system while dripping a diamine component. Further, the polyamide oligomer may be appropriately dried after the polycondensation reaction and adjusted so as to have the above moisture content.
- the polyamide oligomer used as a raw material is preferably obtained by polycondensation of a dicarboxylic acid component and a diamine component in the presence of a phosphorus atom-containing compound.
- a phosphorus atom containing compound is mix
- Examples of the phosphorus atom-containing compound include phosphinic acid compounds such as dimethylphosphinic acid and phenylmethylphosphinic acid; hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, Diphosphite compounds such as calcium hypophosphite and ethyl hypophosphite; phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, potassium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphone Phosphonic acid compounds such as acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate; phosphonous acid, sodium phosphonite, phosphorous acid Lithium phosphonate, potassium
- Phosphonic acid compounds Phosphonic acid compounds; phosphorous acid, sodium hydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, pyro-subite
- Examples thereof include phosphorous acid compounds such as phosphoric acid.
- hypophosphorous acid metal salts such as sodium hypophosphite, calcium hypophosphite, potassium hypophosphite, lithium hypophosphite, etc. are particularly effective in promoting the polycondensation reaction, and also in preventing coloration. Since it is excellent, it is preferably used, and sodium hypophosphite is particularly preferable.
- the phosphorus atom containing compound which can be used by this invention is not limited to these compounds.
- the compounding amount of the phosphorus atom-containing compound is preferably 10 to 500 ppm, more preferably 20 to 300 ppm in terms of phosphorus atom concentration in the polyamide oligomer. If it is 10 ppm or more, the polycondensation reaction proceeds at an appropriate rate, and coloring is unlikely to occur during the polycondensation reaction. If it is 500 ppm or less, the polyamide oligomer and the polyamide resin are not easily gelled, and it is possible to reduce the mixing of fish eyes considered to be caused by the phosphorus atom-containing compound, and the appearance of the molded product is improved.
- the polyamide oligomer as a raw material may be obtained by polycondensation in the presence of an alkali metal compound in addition to the phosphorus atom-containing compound.
- an alkali metal compound in addition to the phosphorus atom-containing compound.
- the gelation of the polyamide oligomer or the polyamide resin may be caused in some cases. There is a risk of inviting. Therefore, by blending an alkali metal compound in addition to the phosphorus atom-containing compound, the amidation reaction rate can be adjusted and gelation can be prevented.
- alkali metal hydroxide alkali metal hydroxide, alkali metal acetate, alkali metal carbonate, alkali metal alkoxide, and the like are preferable.
- Specific examples of the alkali metal compound that can be used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate.
- Sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium carbonate and the like but can be used without being limited to these compounds.
- the range of .05 to 1.0 / 1.5 is preferable, more preferably 1.0 / 0.1 to 1.0 / 1.2, and still more preferably 1.0 / 0.2 to 1.0. /1.1.
- the polyamide resin obtained in the production method of the present invention has the same diamine unit as that of the polyamide oligomer and a dicarboxylic acid unit. Moreover, units other than the diamine unit and the dicarboxylic acid unit may optionally be included as in the polyamide oligomer.
- the polyamide resin can be sufficiently polymerized and its relative viscosity can be increased.
- the relative viscosity of the polyamide resin obtained by the production method of the present invention is preferably 1.8 to 4.0, more preferably 2.0 to 3.5. If the relative viscosity is 1.8 or more, the polyamide resin obtained in the present invention can be used without causing the problem of moldability due to insufficient melt viscosity during molding. Moreover, if relative viscosity is 4.0 or less, the polyamide resin obtained by this invention can be utilized, without producing the problem of the moldability by the melt viscosity at the time of a shaping
- Mw / Mn molecular weight distribution
- the polyamide resin obtained in the present invention has a relatively low degree of dispersion.
- Mw / Mn is preferably 1.8 to 2.5, and more preferably 1.8 to 2.3. If the molecular weight distribution is 1.8 or more, there is no particular problem in moldability, and if the molecular weight distribution is 2.5 or less, there are few low molecular weight components, etc., color changes during molding at high temperatures, and molding There is little color change during high-temperature processing of the body, and it has excellent heat resistance and impact resistance.
- the polyamide resin obtained in the present invention is sufficiently dehydrated and has a low moisture content.
- the moisture content is preferably 0.3% or less, more preferably 0.1% or less.
- a moisture content will be 0.01% or more, for example.
- the moisture content mentioned here is a value measured in the case of cooling by air cooling (air cooling type).
- the cooling method of the strand-shaped resin obtained by extruding from the extruder mentioned later includes an air cooling type and a water cooling type cooling with a water bath, it is not limited to these.
- the water cooling type it is possible to rapidly cool, but a drying step may be required.
- the drying process can be omitted, but a cooling distance is required.
- the polyamide resin obtained by the present invention has little heat history due to heating, and can suppress the yellowness to a low value.
- the yellowness is preferably 30 or less, and more preferably 25 or less.
- melting point of polyamide resin In the present invention, even a polyamide resin having a high melting point can be produced by the production method described later.
- the melting point of the polyamide resin is, for example, 220 ° C. or higher. However, in the present invention, a polyamide resin having a melting point of 300 ° C. or higher can be produced.
- the melting point of the polyamide resin is usually 380 ° C. or lower, preferably 360 ° C. or lower. In the present specification, the melting point refers to the temperature of the peak on the high temperature side unless otherwise specified when the polyamide resin has two melting point peaks.
- the polyamide resin of the present invention is a packaging container for storing and storing various products such as various liquid beverages, various liquid foods, liquid pharmaceuticals, liquid daily necessities, etc .; various foods, various pharmaceuticals, various daily necessities, various electronic materials , Gasoline, various agricultural chemicals, various organic solvents and other packaging materials, industrial materials such as fibers and CFRP; fuel tanks for automobiles, fuel tubes, connectors, sliding parts, radiator tanks, engine mounts, connectors It can be molded into articles such as parts, backlight light sources for liquid crystal displays, semiconductor substrate parts, casings of mobile phones and personal computers, and industrial parts such as metal substitute parts.
- the polyamide oligomer is polycondensed using an extruder to obtain a polyamide resin.
- the extruder used in the present invention is an extruder comprising a co-rotating meshing twin screw and has at least one open vent and at least one vacuum vent.
- the extruder has a pressure-lowering element that increases the filling rate of the resin or oligomer in a portion closer to the supply unit than the position where the vacuum vent is provided, and the range of 30% or less of the total screw length is 300 torr or less. It is intended to be a vacuum region.
- FIG. 1 is a schematic view showing an example of an extruder used in the present invention.
- the extruder used in the present invention includes a supply unit A having a supply port such as a hopper at the most upstream position, and a plurality of kneading units B1 disposed downstream of the supply unit A for kneading or mixing the resin. To B4 and a die D arranged at the most downstream position.
- the extruder has conveying units E1 to E5 for conveying the resin between the supply unit A and the kneading unit B1, between the kneading units B1 to B4, and between the kneading unit B4 and the die D. .
- FIG. 1 is a schematic view showing an example of an extruder used in the present invention.
- the extruder used in the present invention includes a supply unit A having a supply port such as a hopper at the most upstream position, and a plurality of kneading
- kneading parts B1 to B4 are shown, but the present invention is not limited to this. However, it is preferable that one or more kneading parts are present upstream from the vacuum area VA described later, more preferably two or more kneading parts are present, and there may be three or more kneading parts. . Specifically, the number may be three as shown in FIG. 1, four, or more. Moreover, it is preferable that the vacuum area VA also has one or more kneading parts.
- an extruder composed of a co-rotating meshing type twin screw is an extruder having a self-cleaning property in which two screws rotate in the same direction in a cylinder and the meshing ratio is 1.2 to 1.7. Machine.
- the polyamide oligomer as a raw material is supplied from the supply unit A, and the raw material supplied from the supply unit A is heated and sent to the die D through the conveying units E1 to E5 and the kneading units B1 to B4. It is done.
- the polyamide oligomer is heated and melted in the conveying parts E1 to E5 and the kneading parts B1 to B4, and is polycondensed by being kneaded in the kneading parts B1 to B4, thereby increasing the degree of polymerization.
- the polyamide oligomer used as a raw material is supplied from the supply part A in a powder form, a particle form, or a pellet form.
- the interior of the extruder is at least partially set at a temperature higher than the melting point of the polyamide resin to be produced, and from the die D
- the resin temperature to be extruded is set higher than the melting point of the produced polyamide resin.
- the internal temperature of the extruder may all be set constant, but may have a relatively low temperature region and a relatively high temperature region. For example, as the polymerization reaction proceeds, the softening temperature of the polyamide increases and the heat resistance also improves, so the most upstream region is set to a relatively low temperature, and the other regions are set to relatively high temperatures. It may be set.
- the temperature on the upstream side should be slightly higher, the temperature on the middle part should be lower, and the downstream side should be set higher than the upstream side. Also good. Furthermore, when it is necessary to prevent heat degradation of the polyamide as much as possible, the resin pressure is stabilized by lowering the temperature on the downstream side to near the softening temperature at which there is no problem with the polyamide, so that the strand can be pulled out. May be stabilized.
- the portion corresponding to each of the kneading parts B1 to B4 includes a kneading element X and a pressure-lowering element Y downstream of the kneading element X.
- the kneading element X is appropriately selected from a kneading disk, a rotor, a mixing element, or a mixing gear.
- the kneading element X may be a single kneading element X by combining two or more of these elements.
- the pressure-lowering element Y has a pressure-lowering ability and increases the filling rate of the resin or oligomer in the kneading element X in each of the kneading parts B1 to B4, and is constituted by a reverse screw type full flight, a sealing disk, or the like. In each kneading part, the pressure-lowering element Y increases the filling rate of the resin or oligomer in the portion corresponding to the kneading element X, so that the kneading element X can appropriately mix and disperse the resin or oligomer.
- voltage fall element Y can be made into a vacuum area
- the part corresponding to the conveying units E1 to E5 is composed of a feed screw such as a full flight screw element.
- the screw shape may be a single thread, a double thread, or a triple thread, but the double thread is the most versatile.
- the extruder includes open vents OV1 and OV2 and vacuum vents VV1 and VV2.
- the open vents OV1 and OV2 are arranged on the upstream side (supply part A side), and the vacuum vents VV1 and VV2 are arranged on the downstream side (die D side).
- the vacuum vent is sucked by a vacuum pump or the like, and makes the inside of the extruder have a negative pressure.
- the vacuum vent VV1 is disposed in the transport unit E4 between the kneading units B3 and B4, and the vacuum vent VV2 is disposed in the transport unit E5 between the kneading unit B4 and the die D.
- the region downstream of the pressure-lowering element Y of the kneading unit B3 and from the conveying unit E4 to the end on the die D side is made the vacuum region VA by the vacuum vents VV1 and VV2.
- the number and arrangement position of the vacuum vents in FIG. 1 are merely examples, and the present invention is not limited to this. The number and arrangement positions may be such that the vacuum area VA can have a predetermined length and a predetermined degree of vacuum. Good.
- At least one of the vacuum vents is 25% or less of the total screw length from the end of the die D side of the extruder. It is preferable to be provided within the range.
- the open vents OV1 and OV2 are provided between the kneading units B1 and B2 and the conveying units E2 and E3 between the kneading units B2 and B3, but at a position closer to the supply unit A than the vacuum region VA. If it exists and it arrange
- two vents that are upstream from the vacuum region VA are open vented to the two most upstream transport units.
- an open vent may be provided in each subsequent transport unit.
- the two upstream conveying parts are not provided with oven vents, while the two downstream conveying parts
- An open vent may be provided in the part.
- the polyamide oligomer in the present invention has a low molecular weight, the reaction proceeds relatively fast in the upstream portion of the extruder, and a large amount of water is generated. Since a large amount of water is extracted from the oven vents OV1 and OV2 provided on the upstream side, dehydration proceeds appropriately, and the presence of water prevents the polycondensation reaction from being hindered.
- the resin or oligomer has a low moisture content and a high molecular weight in the downstream portion of the extruder, but the downstream portion of the extruder is in the vacuum region VA, so that the moisture content is appropriately lowered under the negative pressure. The reaction proceeds.
- the polyamide oligomer is completely melted before reaching at least the most upstream open vent OV1. In this way, the polyamide oligomer is melted before reaching the open vent OV1, so that water can be actively removed from the open vent OV1 without blocking the open vent with the powdered oligomer.
- the vacuum region VA is in a range of 30% or less of the total screw length.
- the range of the vacuum area VA is larger than 30%, the oligomer or resin is sent to the vacuum area VA without being melted or dehydrated, and the vacuum vent may be clogged.
- the length of the vacuum region VA is more preferably 27% or less of the total screw length.
- the length of the vacuum region VA is preferably 10% or more of the total screw length.
- the degree of vacuum in the vacuum region VA is kept at 300 torr or less.
- the degree of vacuum in the vacuum region VA is greater than 300 torr, the oligomer is not sufficiently dehydrated and the water content of the resulting polyamide resin cannot be sufficiently reduced.
- the polycondensation reaction of the polyamide resin cannot proceed appropriately, and the molecular weight may not be sufficiently increased.
- the yellowness (YI) of the polyamide resin may be increased.
- the degree of vacuum in the vacuum region VA is preferably 200 torr or less, and more preferably 180 torr or less. By setting the degree of vacuum below these upper limit values, the moisture content of the polyamide resin can be further reduced, and the polycondensation reaction can be further promoted.
- the lower limit of the degree of vacuum is not particularly limited, but is usually 1 torr or more depending on the characteristics of the apparatus.
- the region upstream of the vacuum region VA in the extruder is a region where the pressure is higher than 300 torr, but is usually a normal pressure region that is not substantially negative pressure. In this region, an inert gas such as nitrogen is usually supplied from the supply unit A.
- the degree of vacuum is measured at each vacuum vent.
- the vacuum vent VV1 uses a negative pressure at the transport unit E4 and the kneading unit B4, and the degree of vacuum measured at the vacuum vent VV1 is the vacuum of the transport unit E4 and the kneading unit B4.
- the vacuum vent VV2 has a negative pressure inside the conveyance unit E5 and the die D, and the degree of vacuum measured by the vacuum vent VV2 is the degree of vacuum inside the conveyance unit E5 and the die D.
- substance mixing is divided into dispersive mixing and distributed mixing.
- Dispersive mixing refers to mixing with particle size reduction, i.e., particle fragmentation
- distributed mixing refers to mixing by position exchange between particles.
- strong dispersion mixing means mixing where the mixing mode involving crushing of the polyamide oligomer or resin is dominant
- strong distribution mixing means mixing mode by position exchange of the polyamide oligomer or resin. Means dominant mixing but does not mean that dispersive mixing does not occur when dispersive mixing occurs, or that dispersive mixing does not occur when distributive mixing occurs.
- elements having strong dispersion and mixing include kneading disks having a wide disk width (see FIG. 2), rotors (see FIG. 3), etc., but are not limited thereto. Absent.
- the kneading disk is a combination of a plurality of disks, and the kneading disk having a wide disk width has a ratio W / D of the disk width W to the screw diameter D of 0.15 or more. 5 or less.
- the mixing element shown in FIG. 4 and the mixing gear shown in FIG. 5 can be mentioned, but the invention is not limited to these.
- the mixing element shown in FIG. 4 is an SME mixing element provided with a notch in a full-flight disk with a positive thread, but the mixing element is a ZME provided with a notch in a full-flight disk with a reverse thread shown in FIG. It may be a mixing element. Further, the mixing gear may or may not have a self-cleaning property.
- the rotor has a feature that it can apply a uniform shear stress to the material, although the maximum shear stress applied to the material is smaller than that of the kneading disk. Therefore, as described above, both the distribution mixing property and the dispersion mixing property are relatively strong.
- the rotor is a continuous type formed so that the cross section is smoothly continuous as shown in FIG. 3A, the cross section is formed discontinuously as shown in FIG. 3B. It may be a discontinuous type.
- the kneading element X in the kneading section (kneading sections B1 to B3 in FIG. 1) upstream from the vacuum area VA is preferably selected from the elements having strong dispersion and mixing properties described above.
- a wide kneading disk is more preferable.
- one or more kneading parts may be constituted by a kneading disk having a wide disk width, but all the kneading parts are constituted by a kneading disk having a wide disk width.
- a kneading disk having a wide disk width used in the kneading element X upstream of the vacuum region VA preferably has a ratio W / D of 0.2 or more, and more preferably 0.3 or more.
- W / D a ratio of 0.2 or more, and more preferably 0.3 or more.
- the kneading element X of the kneading part (kneading part B4 in FIG. 1) in the vacuum region VA is preferably an element having a strong distribution and mixing property as described above, and more preferably a rotor.
- the kneading part in the vacuum region VA a screw having a strong distribution and mixing property, it is possible to prevent excessive heat generation by applying excessive shearing force to the polyamide resin or oligomer, and thereby, YI Can be suppressed.
- gelation etc. are prevented and molecular weight falls are also prevented.
- kneading parts composed of elements with strong distribution and mixing properties
- region VA for example, is the kneading part B4 in the example of FIG.
- an element having a strong distribution mixing property is provided at a predetermined position on the downstream side, so that the balance between the dispersion mixing and the distribution mixing becomes good. Therefore, as described above, an excessive shearing force is prevented from being applied to the resin, and a high-quality polyamide resin having a high molecular weight, a low moisture content, and a moderately narrow molecular weight distribution can be produced.
- the relative viscosity, moisture content, yellowness, glass transition temperature and melting point of the polyamide oligomer and polyamide resin, and the molecular weight and molecular weight distribution of the polyamide resin were measured as follows.
- Relative viscosity 0.2 g of polyamide oligomer or polyamide resin was precisely weighed and dissolved in 20 ml of 96% sulfuric acid at 20-30 ° C. with stirring. After completely dissolving, 5 ml of the solution was quickly taken into a Cannon Fenceke viscometer, and allowed to stand in a constant temperature bath at 25 ° C. for 10 minutes, and then the drop time (t) was measured. Further, the dropping time (t 0 ) of 96% sulfuric acid itself was measured in the same manner.
- the relative viscosity was calculated from t and t 0 according to the following formula.
- Relative viscosity t / t 0
- Moisture content Using a trace moisture measuring device AQ-2000 manufactured by Hiranuma Sangyo Co., Ltd., measurement was performed under a nitrogen atmosphere at 230 ° C. for 30 minutes.
- Mw / Mn The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) can be determined by gel permeation chromatography (GPC). Specifically, “HLC-8320GPC” manufactured by Tosoh Corporation was used as an apparatus, and two “TSK gel Super HM-H” manufactured by Tosoh Corporation were used as columns.
- hexafluoroisopropanol having a sodium trifluoroacetate concentration of 10 mmol / L is used as the eluent, the resin or oligomer concentration is 0.02% by mass, the column temperature is 40 ° C., the flow rate is 0.3 ml / min, and the refractive index is detected.
- the molecular weight distribution was measured under the conditions of the vessel (RI). In addition, the molecular weight of resin and oligomer was calculated
- the polyamide oligomer used as a raw material for the polyamide resin was produced by the methods of Production Examples 1 to 7 below.
- Production Example 1 (Production of polyamide oligomer 1) Pressure capacity of internal volume 50L equipped with stirrer, partial pressure reducer, total pressure reducer, pressure regulator, thermometer, dripping tank and pump, aspirator, nitrogen introduction pipe, bottom exhaust valve, and receiving pot for flushing oligomer
- the temperature was raised to 220 ° C.
- the internal pressure at this time was 2.3 MPa. Stirring was continued for 2 hours while maintaining the internal pressure at 2.3 MPa at 220 ° C. Then, after the stirring was stopped, the ball valve of the bottom discharge valve was opened to normal pressure in 90 seconds, and the slurry-like oligomer was flushed and taken out into the receiving pot. Thereafter, it was dried in a vacuum dryer at 150 ° C. for 5 hours to obtain 18 kg of powdered N-1,4-BAC6 oligomer (polyamide oligomer 1). The concentration of the phosphorus atom-containing compound in the polyamide oligomer 1 was 300 ppm in terms of phosphorus atom concentration.
- Production Example 2 (Production of polyamide oligomer 2) Production Example 1 except that sebacic acid (produced by Ito Oil Co., Ltd.) was used as the dicarboxylic acid component, and 1,4-bisaminomethylcyclohexane (produced by Guangei Chemical Industry Co., Ltd.) having a trans ratio of 80 mol% was used as the diamine component. Similarly, a powdery N-1,4-BAC10 oligomer was obtained (polyamide oligomer 2). The concentration of the phosphorus atom-containing compound in the polyamide oligomer 2 was 300 ppm in terms of phosphorus atom concentration.
- Production Example 3 (Production of polyamide oligomer 3) 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Inc.) having a cis ratio of 70 mol% was used as the diamine component, sodium hypophosphite was used instead of calcium hypophosphite, and sodium hypophosphite 15.8 g (0.149 mol) and powdered N-1,3-BAC6 oligomer was obtained in the same manner as in Production Example 1 except that sodium acetate was used in an amount of 9.76 g (0.119 mol) (polyamide oligomer 3).
- the concentration of the phosphorus atom-containing compound in the polyamide oligomer 3 was 300 ppm in terms of phosphorus atom concentration.
- Production Example 4 (Production of polyamide oligomer 4) Powdered N-PXD10 oligomer in the same manner as in Production Example 1 except that paraxylylenediamine (manufactured by Showa Denko KK) was used as the diamine component, and sebacic acid (manufactured by Ito Oil Co., Ltd.) was used as the dicarboxylic acid component. (Polyamide oligomer 4) was obtained. The concentration of the phosphorus atom-containing compound in the polyamide oligomer 4 was 300 ppm in terms of phosphorus atom concentration.
- Production Example 5 (Production of polyamide oligomer 5) Except for using 1,3-bisaminomethylcyclohexane (Mitsubishi Gas Chemical Co., Ltd.) with a cis ratio of 70 mol% as the diamine component and using high-purity terephthalic acid (Mizukushima Aroma Co., Ltd.) as the dicarboxylic acid component.
- a powdered N-1,3-BACT oligomer was obtained (polyamide oligomer 5).
- the concentration of the phosphorus atom-containing compound in the polyamide oligomer 5 was 300 ppm in terms of phosphorus atom concentration.
- Production Example 6 (Production of polyamide oligomer 6) Metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) is used as the diamine component, adipic acid (Asahi Kasei Co., Ltd.) is used as the dicarboxylic acid component, and sodium hypophosphite is used instead of calcium hypophosphite.
- a powdered N-MXD6 oligomer was obtained in the same manner as in Production Example 1 except that 0.0735 mol of sodium acid and 0.0588 mol of sodium acetate were used (polyamide oligomer 6).
- the concentration of the phosphorus atom-containing compound in the polyamide oligomer 6 was 150 ppm in terms of phosphorus atom concentration.
- Production Example 7 (Production of polyamide oligomer 7) A powdered N-1,4-BAC6 oligomer was obtained (polyamide oligomer 7) in the same manner as in Production Example 1, except that the drying condition in the vacuum dryer was 150 ° C. for 2 hours.
- Table 1 shows the measurement results of the relative viscosity, moisture content, and yellowness of polyamide oligomers 1-7.
- the polyamide oligomers 1 to 7 were polycondensed by melt kneading using an extruder to obtain a polyamide resin.
- HYPERTKTX30 manufactured by Kobe Steel, Ltd. in which a plurality of barrels are assembled to form one extruder, was used.
- This extruder is composed of a co-rotating meshing type twin screw, L / D (L: screw length, D: screw diameter) is 74.4, and the cylinder major axis ⁇ when the cylinder is viewed from the front is It was 30 mm.
- Example 1 As shown in FIG. 7, the extruder is formed by connecting 20 barrels (including the die D) to a barrel provided with a hopper and provided with a supply unit A. Open vents OV1 to OV3 are provided in the sixth, seventh, and tenth barrels from the part A side, and vacuum vents VV1 and VV2 are provided in the sixteenth and eighteenth barrels, respectively.
- the 3, 5, and 9 barrels were each provided with a kneading disk element having a wide disk width on the screw, and a reverse screw type full flight was connected downstream thereof to form kneading parts B1 to B3.
- the 13th to 15th barrels were provided with kneading disk elements on their screws, and a reverse screw type full flight was connected to the most downstream side to form one kneading section B4.
- the seventeenth barrel was provided with a rotor on its screw and connected with a reverse screw type full flight on the downstream side thereof to form a kneading part B5.
- the barrel 16 to the barrel 20 became the vacuum region VA, and the length thereof was 25% of the total screw length.
- the screw in the barrel other than the kneading parts B1 to B5 was a double-threaded flight screw element, and constituted a conveying part.
- the polyamide oligomer 1 was introduced from the hopper of the supply unit A using a feeder, and further, dry nitrogen was constantly flowed from the hopper to carry out reactive extrusion, whereby a polyamide resin 1 was obtained.
- the resin outlet temperature was 306 ° C.
- the extrusion conditions were as follows.
- Example 2 A polyamide resin 2 was obtained in the same manner as in Example 1 except that the polyamide oligomer 2 was used and the reactive extrusion was carried out under the following extrusion conditions.
- the resin outlet temperature was 316 ° C.
- ⁇ Extrusion conditions> Feeder amount: 20 kg / h Screw rotation speed: 200rpm
- Set temperature (° C.): C1 / C2 / C3 to C16 / C17 to C19 / C20 240/300/300/290/290 Vacuum degree of vacuum vents VV1 and VV2: 100 torr
- Example 3 A polyamide resin 3 was obtained in the same manner as in Example 1 except that the polyamide oligomer 3 was used and reactive extrusion was carried out under the following extrusion conditions.
- the resin outlet temperature was 245 ° C.
- ⁇ Extrusion conditions> Feeder amount: 10 kg / h Screw rotation speed: 100rpm
- Set temperature (° C.): C1 / C2 / C3 to C16 / C17 to C19 / C20 220/250/250/240/240 Vacuum degree of vacuum vents VV1 and VV2: 100 torr
- Example 4 A polyamide resin 4 was obtained in the same manner as in Example 1 except that the polyamide oligomer 4 was used and reactive extrusion was carried out under the following extrusion conditions.
- the resin outlet temperature was 302 ° C.
- ⁇ Extrusion conditions> Feeder amount: 20 kg / h Screw rotation speed: 200rpm
- Set temperature (° C.): C1 / C2 / C3 to C16 / C17 to C19 / C20 260/300/300/290/290 Vacuum vent VV1, VV2: 90 torr
- Example 5 A polyamide resin 5 was obtained in the same manner as in Example 1 except that the polyamide oligomer 5 was used and reactive extrusion was carried out under the following extrusion conditions.
- the resin outlet temperature was 362 ° C.
- ⁇ Extrusion conditions> Feeder amount: 10 kg / h Screw rotation speed: 100rpm
- Set temperature (° C.): C1 / C2 / C3 to C16 / C17 to C19 / C20 320/350/350/350/350 Vacuum degree of vacuum vents VV1 and VV2: 160 torr
- Example 6 A polyamide resin 6 was obtained in the same manner as in Example 1 except that the polyamide oligomer 6 was used and reactive extrusion was carried out under the following extrusion conditions.
- the resin outlet temperature was 262 ° C.
- ⁇ Extrusion conditions> Feeder amount: 30 kg / h Screw rotation speed: 200rpm
- Set temperature (° C.): C1 / C2 / C3 to C16 / C17 to C19 / C20 240/260/260/240/240 Vacuum degree of vacuum vents VV1 and VV2: 96 torr
- Comparative Example 1 Reactive extrusion was attempted in the same manner as in Example 1 except that polyamide oligomer 7 was used and reactive extrusion was performed under the following extrusion conditions. However, due to the large amount of water in the polyamide oligomer, a large amount of water is ejected from the open vent, and water vapor flows backward in the hopper direction, so that the powdered oligomer is vented up in the extruder and solidified and extruded. There wasn't.
- the extruder is formed by connecting 20 barrels (including the die D) to a barrel provided with a hopper and provided with a supply unit A.
- the open vent VO1 was provided with vacuum vents VV1 to VV4 in the seventh, tenth, thirteenth and sixteenth barrels, respectively.
- the third, sixth, ninth and twelfth barrels are each provided with a kneading disk element having a wide disk width on the screw, and connected with a reverse screw type full flight downstream thereof to form kneading sections B1 to B4. .
- a rotor was provided on the screw at the 15th barrel position, and a reverse screw type full flight was connected downstream thereof to obtain a kneading part B5.
- the barrels 7 to 20 became the vacuum region VA, and the length thereof was 70% of the total screw length.
- the screw in the barrel other than the kneading parts B1 to B5 was a double-threaded flight screw element.
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Abstract
Description
一方で、ジカルボン酸成分と、ジアミン成分を重縮合して得たポリアミドオリゴマーを、二軸スクリューを有する押出機を用いて溶融混練して、さらに重縮合させてポリアミド樹脂を得る方法も知られている(例えば、特許文献1参照)。二軸スクリューを有する押出機では、短時間でオリゴマーが溶融混練できるとともに、高融点のポリアミド樹脂でも生産可能であり、さらには、セルフクリーニング性により少量多品種の製品を取り扱うことができるというメリットがある。そのため、様々な種類のポリアミド樹脂に対して、二軸スクリューを用いた押出機により製造する方法が種々検討されている。
(1)下記一般式(I-1)で表される芳香族ジアミン単位、及び下記一般式(I-2)で表わされる脂環族ジアミン単位から選択されるジアミン単位を70モル%以上含むジアミン単位と、下記一般式(II-1)で表される直鎖脂肪族ジカルボン酸単位、及び下記一般式(II-2)で表わされる芳香族ジカルボン酸単位から選択されるジカルボン酸単位を50モル%以上含むジカルボン酸単位を含有するポリアミドオリゴマーを重縮合して、ポリアミド樹脂を製造するポリアミド樹脂の製造方法であって、
該製造方法では、相対粘度が1.1~1.3で、水分率が3質量%以下であるポリアミドオリゴマーを、少なくとも1つ以上のオープンベント及び少なくとも1つ以上の真空ベントを有し、同方向回転かみ合い型二軸スクリューを備える押出機を用いて、溶融混練により、重縮合してポリアミド樹脂を製造し、
前記真空ベントを設けた位置よりも供給部側の位置に降圧エレメントを設け、かつ全スクリュー長さの30%以下の範囲を300torr以下の真空領域とする、ポリアミド樹脂の製造方法。
(2)ポリアミド樹脂の相対粘度が1.8~4.0となる上記(1)に記載のポリアミド樹脂の製造方法。
(3)ポリアミド樹脂の分子量分布(Mw/Mn)が1.8~2.5となる上記(1)又は(2)に記載のポリアミド樹脂の製造方法。
(4)前記ポリアミドオリゴマーが、リン原子濃度10~500ppmでリン化合物が配合されたものである上記(1)~(3)のいずれかに記載のポリアミド樹脂の製造方法。
(5)前記オープンベントを前記真空領域よりも供給部側に配置する上記(1)~(4)のいずれかに記載のポリアミド樹脂の製造方法。
(6)前記真空領域、及び前記真空領域よりも供給部側の位置それぞれに前記ポリアミドオリゴマーを混練する混練部を設ける上記(1)~(5)のいずれかに記載のポリアミド樹脂の製造方法。
(7)前記押出機のダイ側端部から全スクリュー長さの25%以下の範囲内に、少なくとも1つ以上の真空ベントを設ける上記(1)~(6)のいずれかに記載のポリアミド樹脂の製造方法。
(8)前記押出機のダイ側端部から全スクリュー長さの25%以下の範囲内に、分配混合性の強い混練エレメントを有する混練部を設ける上記(1)~(7)のいずれかに記載のポリアミド樹脂の製造方法。
(9)前記真空領域よりも供給部側の位置に前記ポリアミドオリゴマーを混練する混練部を設け、該混練部が分散混合性の強い混練エレメントを備える上記(1)~(8)に記載のポリアミド樹脂の製造方法。
(10)上記(1)~(9)のいずれかに記載のポリアミド樹脂の製造方法により製造されたポリアミド樹脂から成形され、包装材料、包装容器、工業材料及び工業用部品からなる群から選択される物品。
以下、本発明についてさらに詳細に説明する。
<ポリアミドオリゴマー>
本発明において原料となるポリアミドオリゴマーは、ジアミン単位と、ジカルボン酸単位を含有するものである。
ジアミン単位とジカルボン酸単位との含有量の割合は、重合反応の観点から、ほぼ同量であることが好ましく、ジカルボン酸単位の含有量がジアミン単位の含有量の±2モル%であることがより好ましい。ジカルボン酸単位の含有量がジアミン単位の含有量の±2モル%の範囲となると、ポリアミド樹脂の重合度が上がりやすく、重合が比較的短時間で済み、熱劣化が生じにくい。
ポリアミドオリゴマーは、本発明の効果を損なわない範囲で、ジアミン単位及びジカルボン酸単位以外の構成単位を更に含んでいてもよい。
ポリアミドオリゴマー中のジアミン単位は、下記一般式(I-1)で表される芳香族ジアミン単位、及び下記一般式(I-2)で表される脂環族ジアミン単位から選ばれるジアミン単位を、ジアミン単位中に合計で70モル%以上含む。当該含有量は、好ましくは80モル%以上、より好ましくは90モル%以上であり、その上限値は100モル%である。
一般式(I-2)で表される脂環族ジアミン単位を構成しうる化合物としては、1,3-ビス(アミノメチル)シクロヘキサン、1,4-ビス(アミノメチル)シクロヘキサン等のビス(アミノメチル)シクロヘキサン類が挙げられる。これらは単独で又は2種以上を組み合わせて用いることができる。
ビス(アミノメチル)シクロヘキサン類は、構造異性体を持つが、cis体比率を高くすることで、ポリアミド樹脂は、結晶性が高くなり、成形性も良好となる。一方、cis体比率を低くすれば、結晶性が低い、透明なポリアミド樹脂が得られる。したがって、結晶性を高くしたい場合は、ビス(アミノメチル)シクロヘキサン類におけるcis体含有比率を70モル%以上とすることが好ましく、より好ましくは80モル%以上、更に好ましくは90モル%以上とする。一方、結晶性を低くしたい場合は、ビス(アミノメチル)シクロヘキサン類におけるtrans体含有比率を50モル%以上とすることが好ましく、より好ましくは60モル%以上、最も好ましくは70モル%以上とする。
ポリアミドオリゴマー中のジカルボン酸単位は、重合時の反応性、並びにポリアミド樹脂の結晶性及び成形性の観点から、下記一般式(II-1)で表される直鎖脂肪族ジカルボン酸単位、及び下記一般式(II-2)で表される芳香族ジカルボン酸単位から選ばれるジカルボン酸単位を、ジカルボン酸単位中に合計で50モル%以上含む。当該含有量は、好ましくは70モル%以上、より好ましくは80モル%以上、更に好ましくは90モル%以上であり、その上限値は100モル%である。
一般式(II-1)中、nは2~18の整数を表し、好ましくは3~16、より好ましくは4~12、更に好ましくは4~8である。
一般式(II-1)で表される直鎖脂肪族ジカルボン酸単位を構成しうる化合物としては、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、1,10-デカンジカルボン酸、1,11-ウンデカンジカルボン酸、1,12-ドデカンジカルボン酸等を例示できるが、これらに限定されるものではない。これらは単独で又は2種以上を組み合わせて用いることができる。
一般式(II-2)中、Arはアリーレン基を表す。アリーレン基は、好ましくは炭素数6~30、より好ましくは炭素数6~15のアリーレン基であり、例えば、フェニレン基、ナフチレン基等が挙げられる。
一般式(II-2)で表される芳香族ジカルボン酸単位を構成しうる化合物としては、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸等を例示できるが、これらに限定されるものではない。これらは単独で又は2種以上を組み合わせて用いることができる。
また、ポリアミド樹脂のガラス転移温度を下げてポリアミド樹脂に柔軟性を付与することを目的とした場合、直鎖脂肪族ジカルボン酸単位/芳香族ジカルボン酸単位は、両単位の合計を100としたとき、モル比で好ましくは40/60~100/0、より好ましくは60/40~100/0、更に好ましくは70/30~100/0である。
ポリアミドオリゴマーや後述するポリアミド樹脂の分子量を表す指標としては、相対粘度がある。本発明において、ポリアミドオリゴマーの相対粘度は1.1~1.3となるものである。また、ポリアミドオリゴマーは、その水分率が3質量%以下となるものである。本発明では、相対粘度及び水分率が上記範囲内になることで、後述する製造方法により工程上の不具合を生じさせることなく、ポリアミドオリゴマーを高分子化して、ポリアミド樹脂を製造することができる。
例えば、水分率が3質量%より高くなる場合や相対粘度を1.1より低くすると、ポリアミド樹脂の製造過程で、押出機のオープンベントから大量の水が噴出したり、供給部側に水蒸気が逆流したりし、さらにはオリゴマーがシリンダー内で固化して押出ができなくなる等の不具合が生じる。また、相対粘度1.3より大きくなるようにオリゴマーの分子量を簡便な方法で上げるのは難しい。
本発明において、原料となるポリアミドオリゴマーの水分率は、好ましくは2.5質量%以下、より好ましくは1.8質量%以下である。また、この水分率は、特に限定されないが、オリゴマーの乾燥を短時間にできる等、工程の効率化の観点から、0.5質量%以上が好ましく、1.0質量%以上がより好ましい。
本発明の原料であるポリアミドオリゴマーの黄色度は、好ましくは10以下、より好ましくは7以下である。原料ポリアミドオリゴマーの黄色度を低くすることで、製造されるポリアミド樹脂の黄色度も良好なものとすることができる。
本発明におけるポリアミドオリゴマーは、ポリアミド樹脂のジアミン単位に対応するジアミン成分と、ジカルボン単位に対応するジカルボン酸成分とを、重縮合反応することにより得られるものである。
重縮合反応は例えば溶融重縮合法により行われる。具体的には、ジカルボン酸成分と、ジアミン成分とからなるナイロン塩を、水の存在下、加圧下で加熱して重縮合反応を行う方法が挙げられる。このとき、必要に応じて縮合水を脱水しつつ反応を行ってもよい。また、得られたポリアミドオリゴマーは、最終的に、フラッシュ等により水から分離して、粉状のポリアミドオリゴマーを得ることが可能である。
また、溶融重縮合法としては、ジアミン成分を溶融状態のジカルボン酸成分に直接加えて、重縮合する方法を挙げることもできる。この場合、反応系を均一な液状状態に保つために、ジアミン成分をジカルボン酸成分に連続的に加え、その間、反応温度が生成するポリアミドオリゴマーの融点よりも下回らないように反応系を昇温しつつ重縮合が進められる。また、ジアミン成分を滴下する間、反応系を加圧してもよい。
また、ポリアミドオリゴマーは、重縮合反応の後に適宜乾燥等されて、上記した水分率となるように調整されてもよい。
原料となるポリアミドオリゴマーは、ジカルボン酸成分と、ジアミン成分が、リン原子含有化合物存在下、重縮合して得られたものであることが好ましい。このように、ポリアミドオリゴマー製造前にリン原子含有化合物が配合されると、ポリアミドオリゴマー及びポリアミド樹脂を製造する際の重合性を良好にできるとともに、ポリアミドオリゴマー及びポリアミド樹脂の着色を防止することができる。
リン原子含有化合物としては、ジメチルホスフィン酸、フェニルメチルホスフィン酸等のホスフィン酸化合物;次亜リン酸、次亜リン酸ナトリウム、次亜リン酸カリウム、次亜リン酸リチウム、次亜リン酸マグネシウム、次亜リン酸カルシウム、次亜リン酸エチル等のジ亜リン酸化合物;ホスホン酸、ホスホン酸ナトリウム、ホスホン酸カリウム、ホスホン酸リチウム、ホスホン酸カリウム、ホスホン酸マグネシウム、ホスホン酸カルシウム、フェニルホスホン酸、エチルホスホン酸、フェニルホスホン酸ナトリウム、フェニルホスホン酸カリウム、フェニルホスホン酸リチウム、フェニルホスホン酸ジエチル、エチルホスホン酸ナトリウム、エチルホスホン酸カリウム等のホスホン酸化合物;亜ホスホン酸、亜ホスホン酸ナトリウム、亜ホスホン酸リチウム、亜ホスホン酸カリウム、亜ホスホン酸マグネシウム、亜ホスホン酸カルシウム、フェニル亜ホスホン酸、フェニル亜ホスホン酸ナトリウム、フェニル亜ホスホン酸カリウム、フェニル亜ホスホン酸リチウム、フェニル亜ホスホン酸エチル等の亜ホスホン酸化合物;亜リン酸、亜リン酸水素ナトリウム、亜リン酸ナトリウム、亜リン酸リチウム、亜リン酸カリウム、亜リン酸マグネシウム、亜リン酸カルシウム、亜リン酸トリエチル、亜リン酸トリフェニル、ピロ亜リン酸等の亜リン酸化合物等が挙げられる。
これらの中でも特に次亜リン酸ナトリウム、次亜リン酸カルシウム、次亜リン酸カリウム、次亜リン酸リチウム等の次亜リン酸金属塩が、重縮合反応を促進する効果が高くかつ着色防止効果にも優れるため好ましく用いられ、特に次亜リン酸ナトリウムが好ましい。なお、本発明で使用できるリン原子含有化合物はこれらの化合物に限定されない。
ポリアミド樹脂及びポリアミドオリゴマーの着色を防止するためには、十分な量のリン原子含有化合物を存在させる必要があるが、リン原子含有化合物があると、場合によってはポリアミドオリゴマーやポリアミド樹脂のゲル化を招くおそれがある。そのため、リン原子含有化合物に加えてアルカリ金属化合物を配合することで、アミド化反応速度を調整し、ゲル化を防ぐことができる。
アルカリ金属化合物としては、アルカリ金属水酸化物やアルカリ金属酢酸塩、アルカリ金属炭酸塩、アルカリ金属アルコキシド等が好ましい。本発明で用いることのできるアルカリ金属化合物の具体例としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸ルビジウム、酢酸セシウム、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムプロポキシド、ナトリウムブトキシド、カリウムメトキシド、リチウムメトキシド、炭酸ナトリウム等が挙げられるが、これらの化合物に限定されることなく用いることができる。なお、ポリアミドオリゴマーにおけるリン原子含有化合物とアルカリ金属化合物の比率(モル比)は、重合速度制御の観点や、黄色度を低減する観点から、リン原子含有化合物/アルカリ金属化合物=1.0/0.05~1.0/1.5の範囲が好ましく、より好ましくは、1.0/0.1~1.0/1.2、更に好ましくは、1.0/0.2~1.0/1.1である。
本発明の製造方法において得られるポリアミド樹脂は、ポリアミドオリゴマーと同様のジアミン単位と、ジカルボン酸単位とを有する。また、ポリアミドオリゴマーと同様に、任意でジアミン単位及びジカルボン酸単位以外の単位も含んでいてもよい。
本発明の後述する製造方法によれば、ポリアミド樹脂は、十分に高分子化でき、その相対粘度を高めることができる。本発明の製造方法で得たポリアミド樹脂の相対粘度は、好ましくは1.8~4.0であり、より好ましくは2.0~3.5である。相対粘度が1.8以上であれば、成形加工時の溶融粘度不足に起因する成形性の問題を生じさせることなく、本発明で得たポリアミド樹脂を利用できる。また、相対粘度が4.0以下であれば、成形加工時の溶融粘度が高すぎることによる成形性の問題を生じさせることなく、本発明で得たポリアミド樹脂を利用できる。
ポリアミド樹脂の分散度を示す指標としては分子量分布(Mw/Mn)がある。本発明で得られるポリアミド樹脂は、その分散度が比較的低くなるものである。具体的には、Mw/Mnは、好ましくは1.8~2.5となるものであり、より好ましくは1.8~2.3である。分子量分布が1.8以上であれば、成形性に特に問題がなく、分子量分布が2.5以下であれば、低分子量成分等が少なく、高温下での成形時の色の変化や、成形体の高温加工における色の変化が少ないと共に耐熱性や耐衝撃性に優れる。
本発明で得られるポリアミド樹脂は、後述するように、脱水が十分に進み水分率が低くなる。水分率は、具体的には、好ましくは0.3%以下、より好ましくは0.1%以下である。また、水分率は、効率的にポリアミド樹脂を製造するために、例えば0.01%以上となるものである。ここで言う水分率は空冷による冷却を行った場合(空冷式)において測定した値である。
なお、後述する押出機から押し出して得られたストランド状の樹脂の冷却方法には、空冷式と水浴により冷却する水冷式などが挙げられるが、これらに限定されるものではない。水冷式の場合、急冷することが可能であるが、乾燥工程が必要になる場合がある。空冷式の場合、乾燥工程を省くことが可能であるが、冷却距離が必要となる。
本発明で得られるポリアミド樹脂は、加熱による熱履歴が少なく、その黄色度を低い値に抑えることができる。具体的には、黄色度は30以下が好ましく、25以下がより好ましい。
本発明では、後述する製造方法により、融点が高いポリアミド樹脂であっても製造可能となる。ポリアミド樹脂の融点は、例えば220℃以上であるが、本発明では、融点が300℃以上のポリアミド樹脂を製造することもできる。ポリアミド樹脂の融点は、通常、380℃以下、好ましくは360℃以下である。なお、本明細書でいう融点とは、ポリアミド樹脂が2つの融点ピークを有する場合、特に言及のない限り、高温側のピークの温度をいう。
本発明では、押出機を用いて上記のポリアミドオリゴマーを重縮合して、ポリアミド樹脂を得るものである。本発明で使用される押出機は、同方向回転かみ合い型二軸スクリューからなる押出機であって、少なくとも1つ以上のオープンベント及び少なくとも1つ以上の真空ベントを有する。また、押出機は、その真空ベントを設けた位置よりも供給部側の部分に樹脂ないしオリゴマーの充満率を高める降圧エレメントを有し、かつ全スクリュー長さの30%以下の範囲を300torr以下の真空領域とするものである。以下、本発明の製造方法を図面を参照しつつより詳細に説明する。
本発明で使用する押出機は、最も上流側の位置にホッパー等の供給口を備える供給部Aと、供給部Aより下流側に配置され、樹脂を混練ないし混合するための複数の混練部B1~B4と、最も下流側の位置に配置されるダイDとを有する。また、押出機は、供給部Aと混練部B1の間、各混練部B1~B4の間、及び混練部B4とダイDとの間に、樹脂を搬送するための搬送部E1~E5を有する。なお、図1の例では、混練部B1~B4を4つ示すがこれに限定されるわけではなく、1つ以上であればいくつあってもよい。
ただし、後述する真空領域VAより上流側に、1つ以上の混練部があることが好ましく、2つ以上の混練部があることがより好ましく、3つ以上の多数の混練部があってもよい。具体的には、図1のように3つであってもよいし、4つであってもよいし、それ以上であってもよい。また、真空領域VAにも、1つ以上の混練部があることが好ましい。
本発明では、特に限定されないが、原料となるポリアミドオリゴマーは、粉状、粒子状、あるいは、ペレット状で供給部Aより供給される。
押出機の内部温度は、全て一定に設定されていてもよいが、相対的に低い温度の領域と、相対的に高い温度の領域を有してもよい。例えば、重合反応が進むとともに、ポリアミドの軟化温度が上昇し、耐熱性も向上するため、最も上流側の領域が相対的に低い温度に設定されるとともに、その他の領域が相対的に高い温度に設定されてもよい。また、上流側でポリアミドオリゴマーを素早く軟化させ、スクリュー内に充満させる必要がある場合は、上流側の温度をやや高めにし、中間部の温度を低くし、下流側を上流側より高く設定されてもよい。さらに、できる限りポリアミドへの熱による劣化を防ぐ必要がある場合は、下流側の温度をポリアミドの問題ない軟化温度付近まで温度を下げることで、樹脂圧を安定化させ、ストランドでの抜出性を安定させてもよい。
降圧エレメントYは、降圧能力を有し、各混練部B1~B4において、混練エレメントXにおける樹脂ないしオリゴマーの充満率を大きくするものであり、逆ネジ型フルフライト、シーリングディスク等で構成される。各混練部において、降圧エレメントYが、混練エレメントXに対応する部分の樹脂ないしオリゴマーの充満率を高めることにより、混練エレメントXが、樹脂ないしオリゴマーを適切に混合・分散できるようになる。また、降圧エレメントYは、後述するように、その下流にある真空ベントとともに、降圧エレメントYよりも下流側の領域を負圧にして真空領域とすることができる。
また、前記スクリューにおいて、搬送部E1~E5に対応する部位は、例えばフルフライトスクリューエレメント等の送りスクリューからなる。そのスクリュー形状は一条ネジであっても二条ネジ、又は三条ネジであっても良いが、二条ネジが最も汎用的である。
より具体的には、真空ベントVV1は、混練部B3、B4の間の搬送部E4に、真空ベントVV2は、混練部B4とダイDの間の搬送部E5に配置される。これにより、押出機では、混練部B3の降圧エレメントYよりも下流側の領域であって、搬送部E4からダイD側の端部までの領域が、真空ベントVV1、VV2によって真空領域VAとされる。
なお、図1における真空ベントの数及び配置位置は一例であって、これに限定されるわけではなく、真空領域VAを所定の長さと所定の真空度にできるような数と配置位置であればよい。
ただし、下流側の領域の真空度を確保するとともに、ポリアミド樹脂又はオリゴマーの分子量を上げるために、真空ベントは、少なくとも1つが押出機のダイD側の端部から全スクリュー長さの25%以下の範囲内に設けられることが好ましい。
また、真空領域VAより上流側に、混練部及び搬送部それぞれが多数(例えば、4つ以上)ある場合には、真空領域VAより上流側においては、最も上流側の2つの搬送部にオープンベントが設けられない一方で、それ以降の各搬送部にオープンベントが設けられてもよい。例えば、真空領域VAより上流側に混練部が4つあって、搬送部が4つある場合には、上流側の2つの搬送部にオーブンベントが設けられない一方で、下流側の2つの搬送部にオープンベントが設けられてもよい。
このように、ポリアミドオリゴマーは、オープンベントOV1に到達する前に溶融されることで、オープンベントを粉状オリゴマーで閉塞させることなく、オープンベントOV1から積極的に水を抜くことができる。
また、真空領域VAの長さは、全スクリュー長さの10%以上であることが好ましい。真空領域VAの長さを10%以上とすることで、脱水を十分に行うことが可能になり、得られるポリアミド樹脂の含水率を低くできる。また、重縮合反応を十分に進行させて、得られるポリアミド樹脂の分子量を十分に大きくすることも可能になる。このような観点から、上記真空領域VAの長さは、15%以上であることが好ましく、20%以上であることがより好ましい。
真空領域VAの真空度は、200torr以下にすることが好ましく、180torr以下がより好ましい。真空度をこれら上限値以下とすることで、ポリアミド樹脂の含水率を更に低くすることができ、重縮合反応もより進行させやすくなる。
なお、真空度の下限値は、特に限定されないが、装置の特性等により、通常1torr以上となる。
なお、本発明では、押出機内部において、真空領域VAよりも上流側の領域は、300torrより圧力が高い領域となるが、通常、実質的に負圧にされない常圧の領域となる。この領域には、通常、供給部Aから窒素等の不活性ガスが流されている。
なお、真空領域VAより上流にある混練エレメントXで使用されるディスク幅の広いニーディングディスクは、比W/Dが、好ましくは0.2以上、さらに好ましくは0.3以上である。このように、比W/Dを大きくすることで、より分散混合性を強くすることができる。
本発明では、真空領域VAより上流にある混練エレメントXを分散混合性の強いスクリューとすることで、剪断力が高くなり、粉状等である原料ポリアミドコポリマーを、比較的上流側の位置で均一な混合状態とすることができる。
なお、以下の実施例において、
ポリ1,3-ビスアミノメチルシクロヘキサンアジパミドを「N-1,3-BAC6」、
ポリ1,4-ビスアミノメチルシクロヘキサンアジパミドを「N-1,4-BAC6」、
ポリ1,4-ビスアミノメチルシクロヘキサンセバカミドを「N-1,4-BAC10」、
ポリ1,3-ビスアミノメチルシクロヘキサンテレフタラミドを「N-1,3-BACT」
ポリメタキシリレンアジパミドを「N-MXD6」、及び
ポリパラキシリレンセバカミドを「N-PXD10」という。
(1)相対粘度
ポリアミドオリゴマー又はポリアミド樹脂0.2gを精秤し、96%硫酸20mlに20~30℃で撹拌溶解した。完全に溶解した後、速やかにキャノンフェンスケ型粘度計に溶液5mlを取り、25℃の恒温漕中で10分間放置後、落下時間(t)を測定した。また、96%硫酸そのものの落下時間(t0)も同様に測定した。t及びt0から次式により相対粘度を算出した。
相対粘度=t/t0
(2)水分率
平沼産業株式会社製微量水分測定装置AQ-2000を用いて、窒素雰囲気下、230℃30分の条件で測定を行った。
(3)黄色度(YI)
日本電色工業株式会社製Z-Σ80色差計を用いてASTM D1003に準じて透過法で測定した。
(4)分子量分布(Mw/Mn)
数平均分子量(Mn)、重量平均分子量(Mw)、分子量分布(Mw/Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)により求めることができる。具体的には、装置として東ソー社製「HLC-8320GPC」、カラムとして、東ソー社製「TSK gel Super HM-H」2本を使用した。また、溶離液としてトリフルオロ酢酸ナトリウム濃度が10mmol/Lのヘキサフルオロイソプロパノール(HFIP)を使用し、樹脂またはオリゴマー濃度0.02質量%、カラム温度40℃、流速0.3ml/分、屈折率検出器(RI)の条件で分子量分布を測定した。なお、樹脂およびオリゴマーの分子量は標準ポリメチルメタクリレート換算の値として求めた。
(5)ガラス転移温度及び融点
示差走査熱量計((株)島津製作所製、商品名:DSC-60)を用い、昇温速度10℃/分で窒素気流下にDSC測定(示差走査熱量測定)を行い、ガラス転移温度(Tg)及び融点(Tm)を求めた。
撹拌機、分縮器、全縮器、圧力調整器、温度計、滴下槽及びポンプ、アスピレーター、窒素導入管、底排弁、及びオリゴマーをフラッシュさせるための受け釜を備えた内容積50Lの耐圧反応容器に、精秤したアジピン酸(旭化成ケミカルズ(株)製)9000g(61.58mol)、trans比率62mol%の1,4-ビスアミノメチルシクロヘキサン(広栄化学工業(株)製)8759.8g(61.58mol)、次亜リン酸カルシウム12.7g(0.0746mol)、酢酸ナトリウム4.90g(0.0597mol)、蒸留水6241gを入れ、十分に窒素置換した後、反応容器内を密閉し、撹拌下220℃まで昇温した。このときの内圧は2.3MPaであった。220℃で内圧を2.3MPaで保持した状態で2時間撹拌を続けた。その後、撹拌を停止した後、底排弁のボールバルブを90秒で常圧に開放して、スラリー状のオリゴマーをフラッシュさせて受け釜に取り出した。その後、真空乾燥機にて、150℃、5時間乾燥して18kgの粉状N-1,4-BAC6オリゴマーを得た(ポリアミドオリゴマー1)。ポリアミドオリゴマー1におけるリン原子含有化合物濃度はリン原子濃度換算で300ppmであった。
ジカルボン酸成分としてセバシン酸(伊藤製油(株)製)、ジアミン成分としてtrans比率80mol%の1,4-ビスアミノメチルシクロヘキサン(広栄化学工業(株)製)を用いたこと以外は製造例1と同様にして、粉状N-1,4-BAC10オリゴマーを得た(ポリアミドオリゴマー2)。ポリアミドオリゴマー2におけるリン原子含有化合物濃度はリン原子濃度換算で300ppmであった。
ジアミン成分としてcis比率70mol%の1,3-ビスアミノメチルシクロヘキサン(三菱ガス化学(株)製)を用い、次亜リン酸カルシウムの代わりに次亜リン酸ナトリウムを用い,次亜リン酸ナトリウム15.8g(0.149mol)、酢酸ナトリウムを9.76g(0.119mol)としたこと以外は、製造例1と同様にして、粉状N-1,3-BAC6オリゴマーを得た(ポリアミドオリゴマー3)。ポリアミドオリゴマー3におけるリン原子含有化合物濃度はリン原子濃度換算で300ppmであった。
ジアミン成分としてパラキシリレンジアミン(昭和電工(株)製)、ジカルボン酸成分としてセバシン酸(伊藤製油(株)製)を用いたこと以外は製造例1と同様にして、粉状N-PXD10オリゴマーを得た(ポリアミドオリゴマー4)。ポリアミドオリゴマー4におけるリン原子含有化合物濃度はリン原子濃度換算で300ppmであった。
ジアミン成分としてcis比率70mol%の1,3-ビスアミノメチルシクロヘキサン(三菱ガス化学(株)製)を用い、ジカルボン酸成分として高純度テレフタル酸(水島アロマ(株)製)を用いたこと以外は、製造例1と同様にして、粉状N-1,3-BACTオリゴマーを得た(ポリアミドオリゴマー5)。ポリアミドオリゴマー5におけるリン原子含有化合物濃度はリン原子濃度換算で300ppmであった。
ジアミン成分としてメタキシリレンジアミン(三菱ガス化学(株)製)、ジカルボン酸成分としてアジピン酸(旭化成(株)製)を用い、次亜リン酸カルシウムの代わりに次亜リン酸ナトリウムを用い、次亜リン酸ナトリウム0.0735mol、酢酸ナトリウムを0.0588molとしたこと以外は製造例1と同様にして、粉状N-MXD6オリゴマーを得た(ポリアミドオリゴマー6)。ポリアミドオリゴマー6におけるリン原子含有化合物濃度はリン原子濃度換算で150ppmであった。
真空乾燥機での乾燥条件が150℃2時間としたこと以外は、製造例1と同様にして粉状N-1,4-BAC6オリゴマーを得た(ポリアミドオリゴマー7)。
図7に示すように、押出機は、ホッパーが設けられ供給部Aを設けたバレルに、20個(ダイDを含む)のバレルを接続してなるものであって、それらバレルのうち、供給部A側から6、7、10個目のバレルそれぞれにオープンベントOV1~OV3を設け、16、18個目のバレルそれぞれに真空ベントVV1、VV2を設けた。また、3、5,9個のバレルは、それぞれスクリューにディスク幅の広いニーディングディスクのエレメントを設け、かつその下流に逆ネジ型フルフライトを接続し、混練部B1~B3とした。また、13~15個目のバレルは、そのスクリューにニーディングディスクのエレメントを設け、その最下流側に逆ネジ型フルフライトを接続し、1つの混練部B4とした。17個目のバレルは、そのスクリューにローターを設け、かつその下流側に逆ネジ型フルフライトを接続し、混練部B5とした。これにより、バレル16~バレル20が真空領域VAとなり、その長さは全スクリュー長さの25%であった。混練部B1~B5以外の他のバレルにおけるスクリューは、二条ネジのフライトスクリューエレメントであり、搬送部を構成した。
〈押出条件〉
フィーダー量:10kg/h
スクリュー回転数:200rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=260/320/310/300/300
真空ベントVV1,VV2の真空度:150torr
※なお、C1~C20それぞれは、1~20個目それぞれのバレルにおける設定温度を示す。
ポリアミドオリゴマー2を用い、下記押出条件にて反応押出を実施したこと以外は、実施例1と同様にポリアミド樹脂2を得た。樹脂出口温度は、316℃であった。
〈押出条件〉
フィーダー量:20kg/h
スクリュー回転数:200rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=240/300/300/290/290
真空ベントVV1,VV2の真空度:100torr
ポリアミドオリゴマー3を用い、下記押出条件にて反応押出を実施したこと以外は、実施例1と同様にポリアミド樹脂3を得た。樹脂出口温度は、245℃であった。
〈押出条件〉
フィーダー量:10kg/h
スクリュー回転数:100rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=220/250/250/240/240
真空ベントVV1,VV2の真空度:100torr
ポリアミドオリゴマー4を用い、下記押出条件にて反応押出を実施したこと以外は、実施例1と同様にポリアミド樹脂4を得た。樹脂出口温度は、302℃であった。
〈押出条件〉
フィーダー量:20kg/h
スクリュー回転数:200rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=260/300/300/290/290
真空ベントVV1,VV2:90torr
ポリアミドオリゴマー5を用い、下記押出条件にて反応押出を実施したこと以外は、実施例1と同様にポリアミド樹脂5を得た。樹脂出口温度は、362℃であった。
〈押出条件〉
フィーダー量:10kg/h
スクリュー回転数:100rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=320/350/350/350/350
真空ベントVV1,VV2の真空度:160torr
ポリアミドオリゴマー6を用い、下記押出条件にて反応押出を実施したこと以外は、実施例1と同様にポリアミド樹脂6を得た。樹脂出口温度は、262℃であった。
〈押出条件〉
フィーダー量:30kg/h
スクリュー回転数:200rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=240/260/260/240/240
真空ベントVV1,VV2の真空度:96torr
ポリアミドオリゴマー7を用い、下記押出条件にて反応押出を実施したこと以外は、実施例1と同様の方法にて、反応押出を試みた。しかしながら、ポリアミドオリゴマーの水分量が多いことに起因して、オープンベントから大量の水が噴出するとともに、ホッパー方向へ水蒸気が逆流して、粉状オリゴマーが押出機内でベントアップして固まり押出ができなかった。
〈押出条件〉
フィーダー量:10kg/h
スクリュー回転数:200rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=260/320/310/300/300
真空ベントVV1,VV2の真空度:真空引きできず
図8に示すように、押出機は、ホッパーが設けられ供給部Aを設けたバレルに、20個(ダイDを含む)のバレルを接続してなるものであって、4個目のバレルにオープンベントVO1を、7、10、13、16個目のバレルそれぞれに真空ベントVV1~VV4を設けた。また、3、6、9、12個目のバレルは、それぞれスクリューにディスク幅の広いニーディングディスクのエレメントを設け、かつその下流に逆ねじ型フルフライトを接続し、混練部B1~B4とした。また、15個目のバレル位置のスクリューにローターを設け、その下流に逆ねじ型フルフライトを接続し、混練部B5とした。これにより、バレル7~バレル20が真空領域VAとなり、その長さは全スクリュー長さの70%であった。混練部B1~B5以外の他のバレルにおけるスクリューは、二条ネジのフライトスクリューエレメントとした。
〈押出条件〉
フィーダー量:10kg/h
スクリュー回転数:200rpm
設定温度(℃):C1/C2/C3~C16/C17~C19/C20
=260/320/310/300/300
真空ベントの真空度:真空ベント閉塞
B1~B5 混練部
D ダイ
E1~E4 搬送部
OV1~OV3 オーブンベント
VA 真空領域
VV1~VV4 真空ベント
X 混練エレメント
Y 降圧エレメント
Claims (10)
- 下記一般式(I-1)で表される芳香族ジアミン単位、及び下記一般式(I-2)で表わされる脂環族ジアミン単位から選択されるジアミン単位を70モル%以上含むジアミン単位と、下記一般式(II-1)で表される直鎖脂肪族ジカルボン酸単位、及び下記一般式(II-2)で表わされる芳香族ジカルボン酸単位から選択されるジカルボン酸単位を50モル%以上含むジカルボン酸単位を含有するポリアミドオリゴマーを重縮合して、ポリアミド樹脂を製造するポリアミド樹脂の製造方法であって、
該製造方法では、相対粘度が1.1~1.3で、水分率が3質量%以下であるポリアミドオリゴマーを、少なくとも1つ以上のオープンベント及び少なくとも1つ以上の真空ベントを有し、同方向回転かみ合い型二軸スクリューを備える押出機を用いて、溶融混練により、重縮合してポリアミド樹脂を製造し、
前記真空ベントを設けた位置よりも供給部側の位置に降圧エレメントを設け、かつ全スクリュー長さの30%以下の範囲を300torr以下の真空領域とする、ポリアミド樹脂の製造方法。
- 前記ポリアミド樹脂の相対粘度が1.8~4.0となる請求項1に記載のポリアミド樹脂の製造方法。
- 前記ポリアミド樹脂の分子量分布(Mw/Mn)が1.8~2.5となる請求項1又は2に記載のポリアミド樹脂の製造方法。
- 前記ポリアミドオリゴマーが、リン原子濃度10~500ppmでリン化合物が配合されたものである請求項1~3のいずれかに記載のポリアミド樹脂の製造方法。
- 前記オープンベントを前記真空領域よりも供給部側に配置する請求項1~4のいずれかに記載のポリアミド樹脂の製造方法。
- 前記真空領域、及び前記真空領域よりも供給部側の位置それぞれに前記ポリアミドオリゴマーを混練する混練部を設ける請求項1~5のいずれかに記載のポリアミド樹脂の製造方法。
- 前記押出機のダイ側端部から全スクリュー長さの25%以下の範囲内に、少なくとも1つ以上の真空ベントを設ける請求項1~6のいずれかに記載のポリアミド樹脂の製造方法。
- 前記押出機のダイ側端部から全スクリュー長さの25%以下の範囲内に、分配混合性の強い混練エレメントを有する混練部を設ける請求項1~7のいずれかに記載のポリアミド樹脂の製造方法。
- 前記真空領域よりも供給部側の位置に前記ポリアミドオリゴマーを混練する混練部を設け、該混練部が分散混合性の強い混練エレメントを備える請求項1~8のいずれかに記載のポリアミド樹脂の製造方法。
- 請求項1~9のいずれかに記載のポリアミド樹脂の製造方法により製造されたポリアミド樹脂から成形され、包装材料、包装容器、工業材料及び工業用部品からなる群から選択される物品。
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- 2014-03-05 US US14/775,515 patent/US9540485B2/en active Active
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017054957A1 (de) * | 2015-10-01 | 2017-04-06 | Technip Zimmer Gmbh | Verfahren und vorrichtung zur kontinuierlichen modifikation einer polymerschmelze aus unextrahiertem polyamid 6 mit einem oder mehreren additiven |
CN108463319A (zh) * | 2015-10-01 | 2018-08-28 | 特尼吉玛有限责任公司 | 利用一种或多种添加剂连续改性由未萃取的聚酰胺6形成的聚合物熔体的方法和装置 |
US10899060B2 (en) | 2015-10-01 | 2021-01-26 | Technip Zimmer Gmbh | Method and device for continuously modifying a polymer melt made of non-extracted polyamide 6 with one or more additives |
CN108463319B (zh) * | 2015-10-01 | 2021-02-02 | 特尼吉玛有限责任公司 | 利用一种或多种添加剂连续改性由未萃取的聚酰胺6形成的聚合物熔体的方法和装置 |
EA038444B1 (ru) * | 2015-10-01 | 2021-08-30 | Технип Зиммер Гмбх | Способ и устройство для непрерывного модифицирования полимерного расплава неэтилированного полиамида 6 с одной или несколькими добавками |
WO2017090556A1 (ja) * | 2015-11-27 | 2017-06-01 | 三菱瓦斯化学株式会社 | ポリアミド樹脂、成形品およびポリアミド樹脂の製造方法 |
JPWO2017090556A1 (ja) * | 2015-11-27 | 2018-09-13 | 三菱瓦斯化学株式会社 | ポリアミド樹脂、成形品およびポリアミド樹脂の製造方法 |
US11225552B2 (en) * | 2016-02-02 | 2022-01-18 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin, molded article, and method for manufacturing polyamide resin |
WO2017141969A1 (ja) * | 2016-02-16 | 2017-08-24 | 三菱瓦斯化学株式会社 | 多層容器およびその応用 |
US11911341B2 (en) | 2016-02-16 | 2024-02-27 | Mitsubishi Gas Chemical Company, Inc. | Multilayer vessel, and application thereof |
Also Published As
Publication number | Publication date |
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RU2015138704A (ru) | 2017-04-18 |
KR102124415B1 (ko) | 2020-06-18 |
US20160046765A1 (en) | 2016-02-18 |
CN105073832A (zh) | 2015-11-18 |
JPWO2014141978A1 (ja) | 2017-02-16 |
EP2975075A4 (en) | 2016-10-19 |
EP2975075B1 (en) | 2019-01-30 |
EP2975075A1 (en) | 2016-01-20 |
US9540485B2 (en) | 2017-01-10 |
TWI605074B (zh) | 2017-11-11 |
JP6311699B2 (ja) | 2018-04-18 |
KR20150128696A (ko) | 2015-11-18 |
CN105073832B (zh) | 2017-12-22 |
TW201441279A (zh) | 2014-11-01 |
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