JP2003292616A - Method for producing polyamide resin - Google Patents
Method for producing polyamide resinInfo
- Publication number
- JP2003292616A JP2003292616A JP2002105652A JP2002105652A JP2003292616A JP 2003292616 A JP2003292616 A JP 2003292616A JP 2002105652 A JP2002105652 A JP 2002105652A JP 2002105652 A JP2002105652 A JP 2002105652A JP 2003292616 A JP2003292616 A JP 2003292616A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- pressure
- polyester resin
- diamine compound
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- -1 diamine compound Chemical class 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001225 polyester resin Polymers 0.000 claims abstract description 39
- 239000004645 polyester resin Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 1
- CZMUOQBVCQWEHG-UHFFFAOYSA-N 4-(4-propan-2-ylphenyl)aniline Chemical compound C1=CC(C(C)C)=CC=C1C1=CC=C(N)C=C1 CZMUOQBVCQWEHG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- ZWPIVPCBQJHQKP-UHFFFAOYSA-N 4-[2,5-di(propan-2-yl)phenyl]cyclohexan-1-amine Chemical compound CC(C)C1=CC=C(C(C)C)C(C2CCC(N)CC2)=C1 ZWPIVPCBQJHQKP-UHFFFAOYSA-N 0.000 description 1
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- 102100024406 60S ribosomal protein L15 Human genes 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 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
- 101001117935 Homo sapiens 60S ribosomal protein L15 Proteins 0.000 description 1
- 101100121112 Oryza sativa subsp. indica 20ox2 gene Proteins 0.000 description 1
- 101100121113 Oryza sativa subsp. japonica GA20OX2 gene Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 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
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 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
- 239000000463 material Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Polyamides (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエステル樹脂
廃棄物のリサイクル技術として有用な、ポリエステル樹
脂からポリアミド樹脂を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a polyamide resin from a polyester resin, which is useful as a recycling technique for waste polyester resin.
【０００２】[0002]
【従来の技術】資源の有効利用を図るとともに、廃棄物
処理に伴う環境への負荷を低減するため、プラスチック
廃棄物をリサイクルする技術が盛んに検討されている。
その代表的なものが、ポリエステル樹脂の原料モノマー
への還元技術であり、メタノール分解法、エチレングリ
コール分解法、エステル交換法といった様々な技術が開
発されている。2. Description of the Related Art Techniques for recycling plastic waste have been actively studied in order to effectively use resources and reduce the environmental load associated with waste treatment.
A typical example thereof is a reduction technique of a polyester resin to a raw material monomer, and various techniques such as a methanol decomposition method, an ethylene glycol decomposition method, and a transesterification method have been developed.
【０００３】しかしながら、このような方法で再生した
モノマーは、バージン材に比べ価格が高くなる場合が多
く、事業化しても採算性に乏しいものとなる。そして、
このことが、リサイクル化の普及を妨げる大きな要因と
なっている。However, the price of the monomer regenerated by such a method is often higher than that of the virgin material, and the profitability is poor even if it is commercialized. And
This is a major factor preventing the spread of recycling.
【０００４】このようななかで、ポリエステル樹脂の１
種であり、繊維、ボトル、フィルム、シート等に大量に
消費され、したがってリサイクル化の要求も高いポリエ
チレンテレフタレートから直接ポリアミド樹脂を合成す
る方法が考案され、上記問題を解決するものとして注目
されている。Among these, one of the polyester resins
It is a kind, and is consumed in large quantities in fibers, bottles, films, sheets, etc., and therefore a method of directly synthesizing a polyamide resin from polyethylene terephthalate, which is highly demanded for recycling, was devised, and it has been noted as a solution to the above problems .
【０００５】この方法は、基本的にエステル−アミド置
換反応を利用するもので、ポリエチレンテレフタレート
とジアミン化合物とを特定の溶媒を反応媒体として反応
させることにより、ポリエチレンテレフタレートのエス
テル基をアミド基に置換してポリアミド化するものであ
る。This method basically utilizes an ester-amide substitution reaction, in which the ester group of polyethylene terephthalate is replaced with an amide group by reacting polyethylene terephthalate with a diamine compound in a specific solvent as a reaction medium. And then polyamidized.
【０００６】しかしながら、これまでに報告されている
この種の方法では、いずれも反応溶媒として有機溶媒を
使用しているため、環境への負荷が大きいという問題が
あった。また、高分子量のポリアミド樹脂を得ようとす
ると、ポリエチレンテレフタレートとジアミン化合物と
の反応後に、さらに重縮合の工程が必要になるという問
題もあった。However, all of the methods of this type that have been reported so far have a problem that the load on the environment is large because an organic solvent is used as a reaction solvent. Further, when trying to obtain a high-molecular weight polyamide resin, there is a problem that a step of polycondensation is further required after the reaction of the polyethylene terephthalate and the diamine compound.
【０００７】[0007]
【発明が解決しようとする課題】このように、ポリエチ
レンテレフタレートからポリアミド樹脂を直接合成する
方法は、大量に消費されているプラスチックのリサイク
ル化を促進するものとして大いに期待されるが、環境へ
の負荷が大きい、高分子量のポリアミド樹脂を得ようと
すると工程が煩雑になる、などの問題があった。As described above, the method of directly synthesizing a polyamide resin from polyethylene terephthalate is highly expected to promote the recycling of plastics that are consumed in large quantities, but the load on the environment is great. There is a problem that the process becomes complicated when trying to obtain a high molecular weight polyamide resin.
【０００８】本発明はこのような点に対処してなされた
もので、ポリエステル樹脂あるいはその廃棄物から有用
な高分子量のポリアミド樹脂を簡単なプロセスで容易に
製造することができ、しかも、環境への負荷も少ないポ
リアミド樹脂の製造方法を提供することを目的とする。The present invention has been made in consideration of such a point, and a useful high-molecular weight polyamide resin can be easily produced from a polyester resin or a waste thereof by a simple process, and moreover, it is environmentally friendly. It is an object of the present invention to provide a method for producing a polyamide resin that has a low load.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するた
め、本発明のポリアミド樹脂の製造方法は、ポリエステ
ル樹脂とジアミン化合物とを、超臨界水または亜臨界水
中で反応させてポリアミド樹脂を生成することを特徴と
する。In order to achieve the above object, in the method for producing a polyamide resin of the present invention, a polyester resin and a diamine compound are reacted in supercritical water or subcritical water to produce a polyamide resin. It is characterized by
【００１０】ここで、反応温度を350℃〜450℃とし、か
つ、反応圧力を10MPa〜50MPaとしてもよい。The reaction temperature may be 350 ° C. to 450 ° C., and the reaction pressure may be 10 MPa to 50 MPa.
【００１１】また、ポリアミド樹脂生成後、反応容器内
を超臨界二酸化炭素で満たし、その後、降温降圧してポ
リアミド樹脂を回収するようにしてもよい。After the polyamide resin is produced, the reaction vessel may be filled with supercritical carbon dioxide, and then the temperature may be lowered and the pressure may be reduced to recover the polyamide resin.
【００１２】さらに、ポリエステル樹脂が廃棄物からの
回収物であってもよく、また、ポリエステル樹脂がポリ
アルキレンテレフタレートであってもよい。Further, the polyester resin may be a product recovered from waste, and the polyester resin may be polyalkylene terephthalate.
【００１３】本発明においては、十分に高分子量のポリ
アミド樹脂をポリエステル樹脂から実質的に一工程で製
造することができ、しかも、反応溶媒として超臨界水ま
たは亜臨界水を使用するため、有機溶剤を使用する従来
の方法に比べ、環境への負荷も低減される。In the present invention, a sufficiently high molecular weight polyamide resin can be produced from a polyester resin in substantially one step, and since supercritical water or subcritical water is used as a reaction solvent, an organic solvent is used. The load on the environment is also reduced as compared with the conventional method using the.
【００１４】[0014]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明において原料として使用されるポリエステ
ル樹脂は、ジカルボン酸またはその誘導体化合物と多価
アルコールの脱水縮合反応により得られたものである。
ジカルボン酸またはその誘導体化合物としては、テレフ
タル酸、イソフタル酸、フタル酸、テレフタル酸ジメチ
ル、テレフタル酸ジクロライド、ジフェニルジカルボン
酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸お
よびその誘導体、シュウ酸、コハク酸、アジピン酸、セ
バシン酸、マレイン酸、フマル酸等の脂肪族ジカルボン
酸およびその誘導体が挙げられる。また、多価アルコー
ルとしては、エチレングリコール、プロピレングリコー
ル、ブタン-1,3-ジオール、ブタン-1,4-ジオール、テト
ラメチレングリコール等のアルキレングリコール、シク
ロヘキサンジオール、ビスフェノールＡ、ビスフェノー
ルＦ等の芳香族２価アルコール等が挙げられる。これら
のポリエステル樹脂は、廃棄物から回収されたものであ
ってもよい。本発明においては、特に、廃棄物から回収
されたポリブチレンテレフタレートの使用が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The polyester resin used as a raw material in the present invention is obtained by a dehydration condensation reaction of a dicarboxylic acid or its derivative compound and a polyhydric alcohol.
Examples of the dicarboxylic acid or its derivative compound include terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, terephthalic acid dichloride, diphenyldicarboxylic acid, naphthalenedicarboxylic acid, and other aromatic dicarboxylic acids and their derivatives, oxalic acid, succinic acid, and adipine. Examples thereof include aliphatic dicarboxylic acids such as acids, sebacic acid, maleic acid and fumaric acid, and their derivatives. Examples of the polyhydric alcohol include alkylene glycols such as ethylene glycol, propylene glycol, butane-1,3-diol, butane-1,4-diol and tetramethylene glycol, and aromatic compounds such as cyclohexanediol, bisphenol A and bisphenol F. Dihydric alcohol etc. are mentioned. These polyester resins may be recovered from waste. In the present invention, it is particularly preferable to use polybutylene terephthalate recovered from waste.
【００１５】また、上記ポリエステル樹脂の加水分解物
と反応させるジアミン化合物としては、エチレンジアミ
ン、トリメチレンジアミン、1,2-プロパンジアミン、テ
トラメチレンジアミン、ペンタメチレンジアミン、ヘキ
サメチレンジアミン、オクタメチレンジアミン、ドデカ
メチレンジアミン、2,2,4-トリメチルヘキサメチレンジ
アミン等の脂肪族ジアミン化合物；p-フェニレンジアミ
ン、o-フェニレンジアミン、m-フェニレンジアミン、m-
トルイレンジアミン、p-キシリレンジアミン、m-キシリ
レンジアミン、4,4’-ジアミノビフェニール、3,3’-ジ
メチル-4,4’-ジアミノビフェニール、3,3’-ジクロロ-
4,4’-ジアミノビフェニール、4,4’-ジアミノジフェニ
ルエーテル、3,4’-ジアミノジフェニルエーテル、4,
4’-ジアミノジフェニルプロパン、4,4’-ジアミノジフ
ェニルスルホン、4,4’-ジアミノジフェニルエスルファ
イド、4,4’-ジアミノベンズアニリド、3,3’-ジメチル
-4,4’-ジアミノジフェニルメタン、3,3’-ジエチル-4,
4’-ジアミノジフェニルメタン、4,4’-ジアミノアント
ラキノン、3,3’-ジメトキシベンチジン、α,α’-ビス
(4-アミノフェニル)-p-イソプロピルベンゼン、1,5-ジ
アミノナフタレン、2,6-ジアミノナフタレン等の芳香族
ジアミン化合物；1,3-ジアミノシクロヘキサン、1,4-ジ
アミノシクロヘキサン、1,3-ビス(アミノメチル)シクロ
ヘキサン、イソホロンジアミン、ピペラジン、2,5-ジメ
チルピペラジン、ビス(4-アミノシクロヘキシル)メタ
ン、ビス(4-アミノシクロヘキシル)プロパン、4,4’-ジ
アミノ-3,3’-ジメチルジシクロヘキシルメタン、α,
α’-ビス(4-アミノシクロヘキシル)-p-ジイソプロピル
ベンゼン、α,α’-ビス(4-アミノシクロヘキシル)-m-
ジイソプロピルベンゼン、メンタンジアミン等の脂環式
ジアミン化合物；両末端にアミノ基を有するポリジメチ
ルシロキサン等のポリマー等が挙げられる。これらは1
種を単独で使用してもよく2種以上を混合して使用して
もよい。本発明においては、なかでもテトラメチレンジ
アミン、ヘキサメチレンジアミン、p-フェニレンジアミ
ンの使用が好ましい。The diamine compound to be reacted with the hydrolyzate of the polyester resin is ethylenediamine, trimethylenediamine, 1,2-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, dodeca. Aliphatic diamine compounds such as methylenediamine and 2,2,4-trimethylhexamethylenediamine; p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, m-
Toluylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-
4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl esulfide, 4,4'-diaminobenzanilide, 3,3'-dimethyl
-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,
4'-diaminodiphenylmethane, 4,4'-diaminoanthraquinone, 3,3'-dimethoxybenzidine, α, α'-bis
Aromatic diamine compounds such as (4-aminophenyl) -p-isopropylbenzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene; 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3- Bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyl Dicyclohexylmethane, α,
α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -m-
Examples thereof include alicyclic diamine compounds such as diisopropylbenzene and menthanediamine; polymers such as polydimethylsiloxane having amino groups at both ends. These are 1
The seeds may be used alone or in combination of two or more. In the present invention, it is preferable to use tetramethylenediamine, hexamethylenediamine, and p-phenylenediamine.
【００１６】このジアミン化合物の使用量は、ポリエス
テル樹脂の繰返し単位1モルに対し1モル〜10モルの範囲
が好ましい。ジアミン化合物の使用量が1モル未満で
は、ジアミン化合物自身の分解や装置系内の圧力維持の
ために反応容器から排出される分などもあるため、ポリ
エステル樹脂との反応が十分に進まず、また、10モルを
超えると、ジアミン化合物の分解物の量が増え、この分
解物がポリエステル樹脂やその加水分解成分と反応する
ことにより低分子量のポリアミド成分が増加する。より
好ましい範囲は、ポリエステル樹脂の繰返し単位1モル
に対し2〜5モルの範囲である。The amount of the diamine compound used is preferably in the range of 1 mol to 10 mol per 1 mol of the repeating unit of the polyester resin. If the amount of the diamine compound used is less than 1 mol, there is also a portion such as the amount of the diamine compound discharged from the reaction vessel for the purpose of decomposing the diamine compound or maintaining the pressure in the apparatus system, so that the reaction with the polyester resin does not proceed sufficiently, When the amount exceeds 10 mol, the amount of the decomposed product of the diamine compound increases, and the decomposed product reacts with the polyester resin or its hydrolyzed component to increase the low molecular weight polyamide component. A more preferable range is 2 to 5 mol per 1 mol of the repeating unit of the polyester resin.
【００１７】さらに、上記のようなポリエステル樹脂を
加水分解させるとともに、この加水分解によって生じた
ジカルボン酸成分とジアミン化合物の重縮合反応を進行
させる反応溶媒として使用される超臨界水は、臨界温度
（374.2℃）および臨界圧力（22.1MPa）を超えた非凝縮
性の高密度水であり、また、亜臨界水は、臨界温度（37
4.2℃）および臨界圧力（22.1MPa）に近い温度、圧力で
超臨界に近い状態にある水である。Further, the supercritical water used as a reaction solvent for hydrolyzing the polyester resin as described above and for proceeding the polycondensation reaction of the dicarboxylic acid component and the diamine compound produced by the hydrolysis is a critical temperature ( Non-condensable dense water above 374.2 ° C) and critical pressure (22.1MPa), and subcritical water has a critical temperature (37
4.2 ℃) and water at a temperature and pressure close to the critical pressure (22.1MPa), which is near supercritical.
【００１８】本発明においては、上記したようなポリエ
ステル樹脂とジアミン化合物とを超臨界水または亜臨界
水中で反応させ、ポリアミド樹脂を生成する。ポリアミ
ド樹脂生成のメカニズムは未だ明確には解明されていな
いが、超臨界水または亜臨界水中でポリエステル樹脂分
子鎖中のエステル結合部分にジアミン化合物が直接反応
することによりエステル基がアミド基に置換される、い
わゆるエステル−アミド置換反応と、ポリエステル樹脂
が超臨界水または亜臨界水と接触、反応して加水分解さ
れ、この加水分解によって生じたジカルボン酸成分とジ
アミン化合物が重縮合するという、2つの反応が平行し
て進行しているものと考えられる。In the present invention, the above polyester resin and diamine compound are reacted in supercritical water or subcritical water to produce a polyamide resin. The mechanism of polyamide resin formation has not been clarified yet, but the ester group is replaced with an amide group by the direct reaction of the diamine compound with the ester bond in the polyester resin molecular chain in supercritical water or subcritical water. A so-called ester-amide substitution reaction, and the polyester resin is contacted with supercritical water or subcritical water, and is hydrolyzed by reaction, and the dicarboxylic acid component and the diamine compound produced by this hydrolysis are polycondensed. It is considered that the reactions proceed in parallel.
【００１９】上記反応を進行させるための温度および圧
力は、本発明の効果に大きく影響し、それぞれ350℃〜4
50℃および10MPa〜50MPaの範囲で調整することが好まし
い。反応温度が350℃より低いとポリエステル樹脂の加
水分解が進みすぎ、ジアミン化合物との反応が十分に進
行しないおそれがある。ちなみに、ポリエステル樹脂が
完全に加水分解されて生じるジカルボン酸モノマーは、
カルボキシル基部分が会合して安定化してしまい、ジア
ミン化合物とはほとんど反応することはない。また、反
応温度が450℃より高いと、ポリエステル樹脂のエステ
ル結合以外の部分での分解が進み、また、ジアミン化合
物の分解も進むようになる。一方、反応圧力が10MPaよ
り低いとポリエステル樹脂の加水分解速度が低下し、非
効率的となる。また、反応圧力が50MPaより高いと、反
応温度が350℃より低い場合と同様、ポリエステル樹脂
の加水分解が進みすぎ、ジアミン化合物との反応が十分
に進行しないおそれがある。より好ましい範囲は、反応
温度が375℃〜430℃、反応圧力が20MPa〜30Mpaの範囲で
ある。The temperature and pressure for advancing the above reaction have a great influence on the effect of the present invention.
It is preferable to adjust the temperature in the range of 50 ° C. and 10 MPa to 50 MPa. When the reaction temperature is lower than 350 ° C., the hydrolysis of the polyester resin proceeds too much, and the reaction with the diamine compound may not proceed sufficiently. By the way, the dicarboxylic acid monomer produced by the complete hydrolysis of the polyester resin is
The carboxyl groups are associated and stabilized, and hardly react with the diamine compound. Further, when the reaction temperature is higher than 450 ° C., the decomposition of the polyester resin other than the ester bond proceeds, and the diamine compound also decomposes. On the other hand, when the reaction pressure is lower than 10 MPa, the hydrolysis rate of the polyester resin decreases, which is inefficient. When the reaction pressure is higher than 50 MPa, the hydrolysis of the polyester resin may proceed too much, and the reaction with the diamine compound may not proceed sufficiently, as in the case where the reaction temperature is lower than 350 ° C. More preferable ranges are a reaction temperature of 375 ° C to 430 ° C and a reaction pressure of 20 MPa to 30 MPa.
【００２０】本発明においては、このような反応を、例
えば図１に示すようなセミバッチ式の装置を用いて行う
ことができる。In the present invention, such a reaction can be carried out using, for example, a semi-batch type apparatus as shown in FIG.
【００２１】すなわち、図１は、本発明に使用される装
置の一例を概略的に示したものである。図１に示すよう
に、この装置は、電気炉１ａを備えた耐圧反応容器１
と、液体二酸化炭素ボンベ２と、この液体二酸化炭素ボ
ンベ２から耐圧反応容器１内に加圧した二酸化炭素を送
り込む送液ポンプ３と、供給される二酸化炭素を予熱す
る二酸化炭素予熱器４と、純水貯溜槽５と、この純水貯
溜槽５から耐圧反応容器１内に加圧した純水を送り込む
送水ポンプ６と、供給される純水を予熱する水予熱器７
と、耐圧反応容器１から排出される成分から固形物を分
離除去する固液分離器８と、これらの各機器を接続する
配管９とを備えている。また、二酸化炭素予熱器４と耐
圧反応容器１との間、水予熱器７と耐圧反応容器１との
間、および耐圧反応容器１と固液分離器８の間の各配管
９には、ラインヒータ１０が付設されている。なお、耐
圧反応容器１と固液分離器８間の配管９に付設されたラ
インヒータ１０は、ポリエステル樹脂の加水分解物が耐
圧反応容器１から排出される際に析出するのを防止する
ために設けられている。図中、１１は液体二酸化炭素ボ
ンベ２から送り出される二酸化炭素を脱水する脱水剤、
１２は流量計、１３は温度測定用熱電対、１４は温度制
御用の熱電対、１５は減圧弁をそれぞれ示している。That is, FIG. 1 schematically shows an example of an apparatus used in the present invention. As shown in FIG. 1, this apparatus has a pressure-resistant reaction container 1 equipped with an electric furnace 1a.
A liquid carbon dioxide cylinder 2, a liquid feed pump 3 for feeding pressurized carbon dioxide from the liquid carbon dioxide cylinder 2 into the pressure resistant reaction container 1, and a carbon dioxide preheater 4 for preheating supplied carbon dioxide, Pure water storage tank 5, water pump 6 for feeding pressurized pure water from this pure water storage tank 5 into pressure resistant reaction vessel 1, and water preheater 7 for preheating supplied pure water
And a solid-liquid separator 8 that separates and removes solids from the components discharged from the pressure-resistant reaction container 1, and a pipe 9 that connects these devices. Further, a line is provided in each pipe 9 between the carbon dioxide preheater 4 and the pressure resistant reaction vessel 1, between the water preheater 7 and the pressure resistant reaction vessel 1, and between the pressure resistant reaction vessel 1 and the solid-liquid separator 8. A heater 10 is attached. The line heater 10 attached to the pipe 9 between the pressure-resistant reaction vessel 1 and the solid-liquid separator 8 prevents the hydrolysis product of the polyester resin from being deposited when discharged from the pressure-resistant reaction vessel 1. It is provided. In the figure, 11 is a dehydrating agent for dehydrating the carbon dioxide sent from the liquid carbon dioxide cylinder 2,
12 is a flow meter, 13 is a thermocouple for temperature measurement, 14 is a thermocouple for temperature control, and 15 is a pressure reducing valve.
【００２２】このような装置においては、まず、耐圧反
応容器１にポリエステル樹脂およびジアミン化合物を投
入する。ポリエステル樹脂が廃棄物からの回収物であ
り、大きさなどが不均一な場合には、予め裁断するなど
して大きさや形状をできるだけ均一にしたうえで投入す
ることが好ましい。また、汚れやゴミなどが付着してい
る場合には、反応への影響や回収後の精製工程の負荷を
少なくするため、予め除去しておくことが好ましい。In such an apparatus, first, a polyester resin and a diamine compound are put into the pressure resistant reaction vessel 1. When the polyester resin is a product recovered from waste and has a non-uniform size, it is preferable to cut the product in advance to make the size and shape as uniform as possible. Further, if dirt or dust is attached, it is preferable to remove it in advance in order to reduce the influence on the reaction and the load of the purification step after the collection.
【００２３】次いで、純水貯溜槽５から予熱器７および
ラインヒータ１０により加熱された純水を連続的に供給
するとともに、耐圧反応容器１を加熱して、反応容器１
内を前述したような温度および圧力範囲とする。温度お
よび圧力の上昇にともない、ポリエステル樹脂とジアミ
ン化合物が直接反応し、あるいは、ポリエステル樹脂の
加水分解が進み、この加水分解によって生じたジカルボ
ン酸成分とジアミン化合物の重縮合反応し、ポリアミド
樹脂が生成される。Then, the pure water heated by the preheater 7 and the line heater 10 is continuously supplied from the pure water storage tank 5, and the pressure-resistant reaction container 1 is heated to react with the reaction container 1.
The inside is the temperature and pressure range as described above. Polyester resin and diamine compound react directly with increase in temperature and pressure, or hydrolysis of polyester resin proceeds and polycondensation reaction of dicarboxylic acid component and diamine compound generated by this hydrolysis, resulting in polyamide resin. To be done.
【００２４】この後、耐圧反応容器１内の温度および圧
力を維持したまま、液体二酸化炭素ボンベ２から予熱器
４およびラインヒータ１０により加熱された二酸化炭素
を連続的に供給し、耐圧反応容器１内を超臨界二酸化炭
素で置換する。耐圧反応容器１内が超臨界二酸化炭素で
完全に置換されたところで、加熱を中止し、耐圧反応容
器１内を常温常圧に戻し、生成されたポリアミド樹脂を
回収する。なお、このように耐圧反応容器１内を超臨界
二酸化炭素で置換するのは、耐圧反応容器１内を常温常
圧に戻す過程で、ポリアミド樹脂が加水分解されて低分
子量化するのを防止するためである。すなわち、生成さ
れたポリアミド樹脂は、超臨界水または亜臨界水中では
加水分解を受けることはなく安定であるが（これは、水
が超臨界乃至亜臨界状態ではイオン積が小さく非プロト
ン性の溶媒の性質を示すことによる）、そのまま反応容
器１内の温度および圧力を低下させると、ポリアミド樹
脂は、イオン積が増大しプロトン性の溶媒に変わった水
との接触が避けられず、加水分解が進行する。反応容器
１内の温度および圧力を維持したまま、反応容器１内を
超臨界二酸化炭素によって置換することにより、このよ
うなポリアミド樹脂の加水分解を防止することができ、
低分子量化を防止することができる。回収したポリアミ
ド樹脂は、その後、精製され、製品とされる。After that, the carbon dioxide heated by the preheater 4 and the line heater 10 is continuously supplied from the liquid carbon dioxide cylinder 2 while maintaining the temperature and pressure inside the pressure resistant reaction vessel 1, and the pressure resistant reaction vessel 1 is operated. The inside is replaced with supercritical carbon dioxide. When the inside of the pressure resistant reaction vessel 1 is completely replaced with supercritical carbon dioxide, heating is stopped, the pressure resistant reaction vessel 1 is returned to normal temperature and pressure, and the produced polyamide resin is recovered. The replacement of the pressure-resistant reaction vessel 1 with supercritical carbon dioxide prevents the polyamide resin from being hydrolyzed to lower the molecular weight in the process of returning the pressure-resistant reaction vessel 1 to the normal temperature and pressure. This is because. That is, the produced polyamide resin is stable without being hydrolyzed in supercritical water or subcritical water (this is because an ionic product is small and an aprotic solvent is used when water is in a supercritical or subcritical state). When the temperature and pressure inside the reaction vessel 1 are lowered as they are, the polyamide resin is inevitably contacted with water, which increases the ionic product and is changed to a protic solvent, and hydrolysis is not possible. proceed. By replacing the inside of the reaction vessel 1 with supercritical carbon dioxide while maintaining the temperature and pressure inside the reaction vessel 1, it is possible to prevent such hydrolysis of the polyamide resin,
It is possible to prevent lowering of the molecular weight. The recovered polyamide resin is then refined into a product.
【００２５】なお、本発明においては、耐圧反応容器１
内にポリエステル樹脂およびジアミン化合物を投入した
後、系内を一旦純水で満たして内部の酸素を除去し、そ
の後、加熱加圧を開始するようにすることが望ましい。
これによって、溶存酸素による副反応を防止することが
できる。また、同様の観点から、耐圧反応容器１に供給
する水には、窒素ガスによるバブリング処理を施すなど
して、溶存する酸素を除去したものを用いるようにする
ことが望ましい。さらに、反応の制御を容易にするた
め、耐圧反応容器１内の圧力を所定の圧力まで昇圧した
うえで、加熱を開始することが望ましい。In the present invention, the pressure resistant reactor 1
It is desirable that after the polyester resin and the diamine compound have been charged therein, the system is once filled with pure water to remove oxygen inside, and then heating and pressurization is started.
This can prevent side reactions due to dissolved oxygen. From the same viewpoint, it is desirable that the water supplied to the pressure-resistant reaction vessel 1 be one from which dissolved oxygen has been removed, such as by bubbling with nitrogen gas. Furthermore, in order to facilitate control of the reaction, it is desirable to raise the pressure in the pressure resistant reaction vessel 1 to a predetermined pressure and then start heating.
【００２６】本発明は、上述したようないわゆるセミバ
ッチ式の装置によらず、連続反応式の装置を用いて行う
こともできる。The present invention can be carried out not by using the so-called semi-batch type apparatus as described above but by using a continuous reaction type apparatus.
【００２７】[0027]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明は以下の実施例に限定されるものでは
ない。EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
【００２８】実施例
市販のポリエチレンテレフタレート（ＰＥＴ）製の飲料
用ボトルを回収し、数mm角の大きさのチップ状に裁断し
た後、約4ｇを量り取り、図1に示す装置の耐圧反応容器
（内容積10ml）１内に投入した。さらに、ジアミン化合
物としてヘキサメチレンジアミンを約3ｇと脱気した純
水を投入し、耐圧反応容器１を密封した。Example A commercially available beverage bottle made of polyethylene terephthalate (PET) was collected and cut into chips each having a size of several mm square, and then about 4 g was weighed and the pressure-resistant reaction container of the apparatus shown in FIG. (Internal volume 10 ml) 1 was charged. Further, deaerated pure water of about 3 g of hexamethylenediamine was added as a diamine compound, and the pressure resistant reaction vessel 1 was sealed.
【００２９】次いで、耐圧反応容器１と固液分離器８を
接続する配管９に付設したラインヒータ１０の温度を35
0℃に設定するとともに、純水貯溜槽５から脱気した純
水を連続的に送液し、耐圧反応容器1内の内圧を30MPaま
で昇圧した後、その圧力を保持しながら約45分かけて耐
圧反応容器1内を390℃まで昇温し、1分間保持した。そ
の後、耐圧反応容器1内に脱水した超臨界二酸化炭素を5
ml/minの流量で連続的に圧入し、耐圧反応容器1内の内
温内圧を維持しつつ、耐圧反応容器1内を超臨界水から
超臨界二酸化炭素に置換した。置換後、空冷して、耐圧
反応容器1内の内温内圧を常温常圧に戻し、耐圧反応容
器1内の固形物を回収した。Next, the temperature of the line heater 10 attached to the pipe 9 connecting the pressure-resistant reaction vessel 1 and the solid-liquid separator 8 is set to 35
After setting the temperature to 0 ° C and continuously feeding deaerated pure water from the pure water storage tank 5, the internal pressure in the pressure resistant reaction vessel 1 was increased to 30 MPa, and then the pressure was maintained for about 45 minutes. The temperature inside the pressure resistant reactor 1 was raised to 390 ° C. and kept for 1 minute. After that, the dehydrated supercritical carbon dioxide 5
The pressure was continuously injected at a flow rate of ml / min, and the pressure inside the pressure resistant reaction vessel 1 was replaced with supercritical carbon dioxide while maintaining the internal temperature and internal pressure inside the pressure resistant reaction vessel 1. After the replacement, the mixture was air-cooled, the internal temperature inside the pressure-resistant reaction vessel 1 was returned to room temperature and atmospheric pressure, and the solid matter in the pressure-resistant reaction vessel 1 was recovered.
【００３０】この回収された固形物を80℃で5時間真空
乾燥（10mmHg以下）させた後、ジメチルホルムアミドに
溶解した。この溶液をろ過し、ろ液にクロロホルムを添
加したところ、析出物が現れた。The recovered solid was vacuum dried (10 mmHg or less) at 80 ° C. for 5 hours and then dissolved in dimethylformamide. When this solution was filtered and chloroform was added to the filtrate, a precipitate appeared.
【００３１】この析出物をろ過回収し、60℃で5時間乾
燥させた後、赤外分光分析および１Ｈ−ＮＭＲ分析を行
い、析出物がポリアミド６Ｔであることを確認した。ま
た、ＧＰＣ（ゲルパーミエーションクロマトグラフ）分
析により、析出物の重量平均分子量（Ｍｗ）が約10000
であることを確認した。The precipitate was collected by filtration, dried at 60 ° C. for 5 hours, and then subjected to infrared spectroscopic analysis and 1H-NMR analysis to confirm that the precipitate was polyamide 6T. The weight average molecular weight (Mw) of the precipitate was about 10,000 by GPC (gel permeation chromatograph) analysis.
Was confirmed.
【００３２】[0032]
【発明の効果】以上説明したように、本発明によれば、
ポリエステル樹脂とジアミン化合物とを、超臨界水また
は亜臨界水中で反応させてポリアミドを生成するので、
ポリエステル樹脂あるいはその廃棄物から有用な高分子
量のポリアミド樹脂を簡単でしかも環境への負荷の少な
いプロセスで製造することが可能となる。As described above, according to the present invention,
Since polyester resin and diamine compound are reacted in supercritical water or subcritical water to produce polyamide,
It becomes possible to produce a useful high-molecular-weight polyamide resin from a polyester resin or its waste by a simple and environmentally-friendly process.
【図１】本発明の実施に使用される装置の一例を概略的
に示す図。FIG. 1 is a diagram schematically showing an example of an apparatus used for carrying out the present invention.
１………耐圧反応容器 １ａ………電気炉 ２………液体二酸化炭素ボンベ ３………送液ポンプ ５………純水貯溜槽 ７………送水ポンプ ９………配管 1 ... Pressure resistant reactor 1a ......... electric furnace 2 ... Liquid carbon dioxide cylinder 3 ... Liquid delivery pump 5: Pure water storage tank 7 ... Water pump 9 ………… Piping
───────────────────────────────────────────────────── フロントページの続き (72)発明者 古村 清司 愛知県名古屋市緑区大高町字北関山20番地 の１ 中部電力株式会社電力技術研究所内 (72)発明者 渡邉 彰三 愛知県名古屋市緑区大高町字北関山20番地 の１ 中部電力株式会社電力技術研究所内 (72)発明者 平井 進 神奈川県川崎市川崎区小田栄２丁目１番１ 号 昭和電線電纜株式会社内 (72)発明者 仲本 隆男 神奈川県川崎市川崎区小田栄２丁目１番１ 号 昭和電線電纜株式会社内 (72)発明者 新舘 均 神奈川県川崎市川崎区小田栄２丁目１番１ 号 昭和電線電纜株式会社内 (72)発明者 森田 広昭 神奈川県川崎市川崎区小田栄２丁目１番１ 号 昭和電線電纜株式会社内 Ｆターム(参考） 4J001 DA03 DB02 DB04 DC03 DC14 EB75 EC04 EC05 EC06 EC07 EC08 EC09 EC13 EC14 EC29 EC38 EC44 EC45 EC46 EC47 EC48 EC55 EC56 EC66 EC67 EC69 EC70 EC81 ED66 FA01 FB01 GA12 GA20 GB02 GB03 JA01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kiyoshi Furumura 20 Kitakanzan, Otakamachi, Midori-ku, Nagoya-shi, Aichi No. 1 Chubu Electric Power Co., Inc. (72) Inventor Shozo Watanabe 20 Kitakanzan, Otakamachi, Midori-ku, Nagoya-shi, Aichi No. 1 Chubu Electric Power Co., Inc. (72) Inventor Susumu Hirai 2-1-1 Oda Sakae, Kawasaki-ku, Kawasaki-shi, Kanagawa No. Showa Densen Denki Co., Ltd. (72) Inventor Takao Nakamoto 2-1-1 Oda Sakae, Kawasaki-ku, Kawasaki-shi, Kanagawa No. Showa Densen Denki Co., Ltd. (72) Inventor Hitoshi Shindate 2-1-1 Oda Sakae, Kawasaki-ku, Kawasaki-shi, Kanagawa No. Showa Densen Denki Co., Ltd. (72) Inventor Hiroaki Morita 2-1-1 Oda Sakae, Kawasaki-ku, Kawasaki-shi, Kanagawa No. Showa Densen Denki Co., Ltd. F-term (reference) 4J001 DA03 DB02 DB04 DC03 DC14 EB75 EC04 EC05 EC06 EC07 EC08 EC09 EC13 EC14 EC29 EC38 EC44 EC45 EC46 EC47 EC48 EC55 EC56 EC66 EC67 EC69 EC70 EC81 ED66 FA01 FB01 GA12 GA20 GB02 GB03 JA01
Claims (5)
を、超臨界水または亜臨界水中で反応させてポリアミド
樹脂を生成することを特徴とするポリアミド樹脂の製造
方法。1. A method for producing a polyamide resin, which comprises reacting a polyester resin and a diamine compound in supercritical water or subcritical water to produce a polyamide resin.
応圧力を10Mpa〜50Mpaとすることを特徴とする請求項１
記載のポリアミド樹脂の製造方法。2. The reaction temperature is 350 ° C. to 450 ° C. and the reaction pressure is 10 MPa to 50 MPa.
A method for producing the described polyamide resin.
臨界二酸化炭素で満たし、その後、降温降圧してポリア
ミド樹脂を回収することを特徴とする請求項１または２
記載のポリアミド樹脂の製造方法。3. The method according to claim 1, wherein after the polyamide resin is produced, the reaction vessel is filled with supercritical carbon dioxide, and then the temperature is lowered and the pressure is reduced to recover the polyamide resin.
A method for producing the described polyamide resin.
であることを特徴とする請求項１乃至３のいずれか１項
記載のポリアミド樹脂の製造方法。4. The method for producing a polyamide resin according to claim 1, wherein the polyester resin is a product recovered from waste.
フタレートであることを特徴とする請求項１乃至４のい
ずれか１項記載のポリアミド樹脂の製造方法。5. The method for producing a polyamide resin according to any one of claims 1 to 4, wherein the polyester resin is polyalkylene terephthalate.
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|---|---|---|---|
| JP2002105652A JP4187456B2 (en) | 2002-04-08 | 2002-04-08 | Method for producing polyamide resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002105652A JP4187456B2 (en) | 2002-04-08 | 2002-04-08 | Method for producing polyamide resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2005077515A1 (en) * | 2004-02-12 | 2007-10-18 | 帝人株式会社 | Polycarbonate decomposition method |
| EP1608717B2 (en) † | 2003-04-01 | 2013-05-15 | De-Bonding Limited | Method and apparatus for bonding and debonding adhesive interface surfaces |
| CN111905652A (en) * | 2020-07-16 | 2020-11-10 | 华峰集团上海工程有限公司 | Continuous polymerization reaction process of polyamide |
| WO2022118557A1 (en) * | 2020-12-04 | 2022-06-09 | ユニチカ株式会社 | Polyamide manufacturing method and polyamide manufactured by said manufacturing method |
-
2002
- 2002-04-08 JP JP2002105652A patent/JP4187456B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1608717B2 (en) † | 2003-04-01 | 2013-05-15 | De-Bonding Limited | Method and apparatus for bonding and debonding adhesive interface surfaces |
| JPWO2005077515A1 (en) * | 2004-02-12 | 2007-10-18 | 帝人株式会社 | Polycarbonate decomposition method |
| JP4500774B2 (en) * | 2004-02-12 | 2010-07-14 | 帝人株式会社 | Method for decomposing polycarbonate |
| CN111905652A (en) * | 2020-07-16 | 2020-11-10 | 华峰集团上海工程有限公司 | Continuous polymerization reaction process of polyamide |
| CN111905652B (en) * | 2020-07-16 | 2021-06-04 | 华峰集团上海工程有限公司 | Continuous polymerization reaction process of polyamide |
| WO2022118557A1 (en) * | 2020-12-04 | 2022-06-09 | ユニチカ株式会社 | Polyamide manufacturing method and polyamide manufactured by said manufacturing method |
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| Publication number | Publication date |
|---|---|
| JP4187456B2 (en) | 2008-11-26 |
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