CN1169718A - Method of obtaining caprolactam by cracking of molten polycaprolactam - Google Patents
Method of obtaining caprolactam by cracking of molten polycaprolactam Download PDFInfo
- Publication number
- CN1169718A CN1169718A CN95196756.8A CN95196756A CN1169718A CN 1169718 A CN1169718 A CN 1169718A CN 95196756 A CN95196756 A CN 95196756A CN 1169718 A CN1169718 A CN 1169718A
- Authority
- CN
- China
- Prior art keywords
- hexanolactam
- weight
- polycaprolactam
- polymkeric substance
- alkali
- 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.)
- Pending
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 36
- 238000005336 cracking Methods 0.000 title description 10
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000000975 dye Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 6
- 239000012860 organic pigment Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 21
- 150000001408 amides Chemical class 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 7
- 239000012764 mineral filler Substances 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 230000009089 cytolysis Effects 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 229960005141 piperazine Drugs 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920006097 Ultramide® Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- WVNFFHLXDXOSGO-UHFFFAOYSA-N n-hexylpropanamide Chemical compound CCCCCCNC(=O)CC WVNFFHLXDXOSGO-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical class C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000002406 phosphoroclastic effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Caprolactam is obtained from caprolactam-containing polymers in the presence of a base under reduced pressure by depolymerizing polymers which contain the repeating unit -[-N(H)-(CH2)5-C(O)-] or mixtures consisting essentially of from 50 to 99.99% by weight of a polymer containing the repeating unit -[-N(H)-(CH2)5-C(O)-]- from 0.01 to 50% by weight of additives selected from the group consisting of inorganic fillers, organic and inorganic pigments and dyes, from 0 to 10% by weight of organic and/or inorganic additives, from 0 to 40% by weight of non-polyamide-containing polymers and from 0 to 20% by weight of polyamides, with the exception of polycaprolactam and copolyamides prepared from caprolactam, in at least two depolymerization reactors connected in series.
Description
The present invention relates to a kind of under reduced pressure in the presence of alkali by the method for the polymer manufacture hexanolactam that contains hexanolactam.
The invention still further relates to a kind of equipment of implementing this method, this method is used to reclaim the application of the waste material that contains hexanolactam and the application that is prepared the equipment of hexanolactam by polycaprolactam.
Journal of applied (J.Appl.P.Sci.) 22 (1978), 361～368 described under reduced pressure, the cracking of polycaprolactam (PA6) in the presence of alkali.But for industrial application extensive, that require economic benefit, 90.5% productive rate is not enough.
In addition, disclose the method that the PA6 cracking prepares hexanolactam as JP50131979 and JP551002, reaction under reduced pressure, carry out in the presence of acid in these methods.But in these cases, for Economic Application, being respectively 89% and 69% productive rate can not be satisfactory.In addition, all publication has all only been described the depolymerization of pure polycaprolactam.
In addition, US5169870 openly uses the method processing treatment carpet waste of phosphoroclastic cleavage.The shortcoming of this method is the high flow rate amount of phosphoric acid, because the lime carbonate that exists in phosphoric acid and the carpet reacts.
An object of the present invention is to provide a kind of higher hexanolactam productive rate arranged prepare the method for hexanolactam by polycaprolactam.In addition, it also provides a kind of method that can utilize the waste material production hexanolactam that contains polycaprolactam.And used catalyzer should be an inert to the most normally used additive.
We find, this purpose can with a kind of under reduced pressure, in the presence of the alkali by the polymkeric substance that contains hexanolactam at least two placed in-line depolymerizing reactors, the method that makes hexyl propionamide by the polymkeric substance depolymerization reaches, this polymkeric substance contains following repeating unit
-[N (H)-(CH
2)
5-C (O)-]-or being main mixture composed of the following components: 50～99.99% (weight) contain repeating unit-[N (H)-(CH
2)
5-C (O)-]-polymkeric substance, 0.01～50% (weight) is selected from mineral filler, organic or inorganic pigment and the additive of dyestuff, organic and/or the inorganic additive of 0～10% (weight), 0～40% (weight) contains the polymkeric substance of non-polymeric amide, and 0～20% (weight) is except that polycaprolactam that is prepared by hexanolactam and the polymeric amide the copolyamide.
We also find a kind of equipment of implementing this novel method, and the application of this equipment and recovery contain the application of novel method of the waste material of polycaprolactam.
According to the present invention, used raw material is to contain repeating unit-[N (H)-(CH
2)
5-C (O)-]-polymkeric substance or main mixture composed of the following components, 50～99.9% (weight), preferred 60～99.99% (weight) contain repeating unit-[N (H)-(CH
2)
5-C (O)-]-polymkeric substance, 0～50% (weight), preferred 0～40% (weight) are selected from mineral filler, organic and inorganic pigment and the additive of dyestuff, 0～10% (weight), the organic and/or inorganic additive of preferred 0～5% (weight), 0.01～40% (weight), preferred 0.01～20% (weight) contain the polymkeric substance and 0～20% (weight) of non-polymeric amide, preferred 0～15% (weight) except that polycaprolactam that is prepared by hexanolactam and the polymeric amide the copolyamide.
The preferred polymkeric substance that uses as relative viscosity be 1～5, preferred 2.0～4.0 polycaprolactam (under 25 ℃, in per 100 milliliter of 96% (weight) sulfuric acid, contain 1 restrain under the concentration of polymkeric substance measure).The polycaprolactam that uses the oligopolymer residue or contain oligopolymer also is possible; By total amount, wherein each contains oligopolymer 0.01～100% (weight), preferred 0.05～10% (weight), preferred especially 1～5% (weight).
In addition, also can use the copolyamide that is made by hexanolactam and other monomers that generates polymeric amide, other monomers for example are salt, preferred AH salt (being made by hexanodioic acid and hexamethylene-diamine) and lactams and the lauryl lactams that is generated by di-carboxylic acid (as hexanodioic acid, sebacic acid and terephthalic acid) and diamine (as hexamethylene-diamine and tetramethylene-diamine).
Present observed result shows, the all available the inventive method of all known polycaprolactams changes into hexanolactam, for example even the polycaprolactam that in the presence of monocarboxylic acid or dicarboxylic acid or amine (as triacetonediamine and hexamethylene-diamine), makes, they are as chain regulator, as acetate, propionic acid, phenylformic acid, C
4～C
10The alkane dicarboxylic acid is as hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid and composition thereof, C
5～C
8The cycloalkanes dicarboxylic acid, as pentamethylene-1,3-dicarboxylic acid, hexanaphthene-1,4-dicarboxylic acid and composition thereof, benzene dicarboxylic acid and naphthalene dicarboxylic acids, they can have two sulfo groups at the most, comprise corresponding alkali metal salt, its carboxyl is non-conterminous, for example terephthalic acid, m-phthalic acid, naphthalene-2,6-dicarboxylic acid, 5-sulfoisophthalic acid and sodium salt and lithium salts, and their mixture, 1,4-piperazine two (C
1-C
6The alkane dicarboxylic acid), as 1,4-piperazine oxalic acid, 1,4-piperazine dipropionic acid, 1,4-piperazine two butyric acid, 1,4-piperazine two valeric acids and 1,4-piperazine two caproic acids.
For those skilled in the art, corresponding copolyamide is known, and is available as disclosed method preparation among WO93/25736, DE-A1495198 and the DE-A2558480.
Present observed result shows that all fillers that are generally used in the polymeric amide preparation all can be used as mineral filler, as glass fibre, lime carbonate and talcum.Present observed result shows, is generally used for all pigment of colored polyamide and dyestuff and all can be used as inorganic and organically pigment and dyestuff, and as titanium dioxide, ferric oxide and carbon black, and conventional spinning dyestuff, as chromium or copper complex.
Conventional stablizer and oxidation inhibitor, thermo-stabilizer and UV stablizer, static inhibitor and fire retardant can be used as organic and inorganic additive.
Oxidation inhibitor and thermo-stabilizer for example are phenols, hydroquinones, phosphorous acid esters and the derivatives thereof that is obstructed in the space, and the mixture of these compounds, and copper compound, as cupric iodide (II) and venus crystals (II).
The example of UV stablizer is Resorcinol, salicylate, benzotriazole, benzophenone and HALS (hindered amine light stabilizer) the type compound that replaces, and manganese (II) compound also is applicable to this.
Conventional material such as polyoxyalkylene and derivative thereof can be used as static inhibitor.
Conventional chlorine-containing compound and nitrogenous compound are as melamine cyanurate and Dechlorane
, and aluminium hydroxide can be used as fire retardant.
Conventional thermoplasticity engineering polymers, as based on ethene, propylene, cinnamic polymkeric substance, and the multipolymer of they and divinyl can be used as the polymkeric substance that contains non-polymeric amide.
Polymeric amide except that polycaprolactam that is made by hexanolactam and copolyamide for example is polyamide 66, polyamide 6 10 and polymeric amide 46.
Preferred raw material is a polycaprolactam to be processed or in polycaprolactam production and the waste material that obtains in processing long filament, film and articles injection-moulded or extrusion molding parts, and articles for use to be processed, as film, packing articles, fabric, carpet fiber, long filament and extrusion molding parts.
According to the present invention, used alkali is the compound that is selected from alkalimetal oxide, alkali metal hydroxide, alkaline carbonate, alkali metal alcoholates, alkaline earth metal oxide, alkaline earth metal hydroxides and alkaline earth metal carbonate, as sodium oxide, potassium oxide, magnesium oxide, calcium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash, salt of wormwood, sodium methylate, lime carbonate and magnesiumcarbonate, the mixture of preferred sodium hydroxide, potassium hydroxide and sodium hydroxide and potassium hydroxide.
The consumption of alkali is main relevant with the alkalescence of the alkali that will use, and for example when use sodium hydroxide and potassium hydroxide, every kilogram of polycaprolactam or the polymkeric substance alkali charge that contains hexanolactam be 0.001～0.5, preferred 0.005～0.05 kilogram.
Alkali can be before the fusion step, add in the process, after preferred.
According to the present invention, depolymerization is carried out at least two, preferred two placed in-line depolymerizing reactors.Depolymerization also can be carried out in a depolymerizing reactor, and preferably in oar formula reactor, still the productive rate of hexanolactam is higher at least two depolymerizing reactors.
Conventional stirring tank can be used as depolymerizing reactor.In first step, cracking is carried out under 240～350 ℃ (preferred 250～310 ℃), 0.05～8 kPa (preferred 0.1～5 kPa) usually, preferably uses continuation method.
Under the situation of operate continuously, the residence time in each depolymerizing reactor is generally 10～300, preferred 20～200 minutes.
Usually, in the first depolymerizing reactor D1, have 40～98%, the used polycaprolactam cracking of preferred 65～85% (weight).
In an embodiment preferred, as second depolymerizing reactor, used reaction conditions is identical with the reaction conditions that uses in first depolymerizing reactor usually with oar formula reactor; If desired, can select higher temperature range, preferred 260～320 ℃.If desired, for example available metering outfit adds other alkali in second reactor.In principle, it is possible using two above depolymerizing reactors, and still, technical thus complicacy has also increased, so preferably only use two placed in-line depolymerizing reactors.
In another embodiment preferred, separate in the hexanolactam that the hexanolactam oligomer that may exist after depolymerization makes from depolymerization, and deliver at least one depolymerizing reactor.
In another embodiment preferred, carry out following steps (referring to Fig. 1): (a) will contain repeating unit-[N (H)-(CH
2)
5-C (O)-]-polymkeric substance or main mixture fusion composed of the following components, 50～99.9% (weight) contain repeating unit-[N (H)-(CH
2)
5-C (O)-]-polymkeric substance, 0.01～50% (weight) is selected from mineral filler, organic and the inorganic pigment and the additive of dyestuff, organic and/or the inorganic additive of 0～10% (weight), 0～40% (weight) contains the polymeric amide of polymkeric substance and 0～20% (weight) except that polycaprolactam that is made by hexanolactam and copolyamide of non-polymeric amide, (b) melt A is sent among the maintenance depolymerizing reactor D1 under reduced pressure, obtain steam B1 and still bottom product S1, (c) from depolymerizing reactor D1, remove the steam B1 that contains hexanolactam, and (d) if desired, still bottom product S1 is transferred among the maintenance second depolymerizing reactor D2 under reduced pressure, obtain containing the steam B2 and the still bottom product S2 of hexanolactam; Before the fusion step, in the process or afterwards, but before the depolymerization step, be added to alkali in the polymkeric substance, in the mixture or in the melt; And preferably carry out step (d).
In another particularly preferred embodiment, also can carry out following steps: (e) if desired, all send into steam B1 and B2 in one equipment respectively, remove any hexanolactam oligomer that may exist, obtain hexanolactam oligomer and hexanolactam, or (f) if desired, steam B1 and B2 are merged, subsequently the steam that merges is passed through an equipment, remove the hexanolactam oligomer that may exist, obtain hexanolactam oligomer and hexanolactam, (g) will in sending at least one reactor among depolymerizing reactor D1 and the D2, (e) or the oligopolymer that (f) obtains (h) if desired, will merge at (e) or the hexanolactam that (f) obtains, and (i) if desired, the hexanolactam that obtains in the step (h) is delivered in the purification step.
Want the polymkeric substance or the corresponding mixture (, only being called polycaprolactam below) of depolymerization in the known conventional fusion apparatus of those skilled in the art,, to obtain melt A 240～350 ℃, preferred 250～310 ℃ of following fusions for for simplicity.Extruding machine, particularly devolatilization extruding machine are preferred for this purpose, preferably the polycaprolactam of pulverizing are sent in the described extruding machine.
In an embodiment preferred, alkali is added in the fused polycaprolactam; After the fusion step, preferably melt A is sent in the mixing equipment that is fit to this purposes, in stirring tank; When adding alkali, stir, obtain melt B.
In another embodiment preferred, before depolymerization,, from alkaliferous melt B, remove the water of existence by melt B being remained under 0.05～50 kPa the decompression and 240～320 ℃ of temperature.For example can in extruding machine, under reduced pressure dewater by devolatilization.Certainly, in melting process,, also can be used for melt A is dewatered by vacuum apparatus decompression at one or more extruding machine nibs place.
In dehydration, water-content preferably is depressurized less than 0.1% (weight).According to the present invention, melt B (if desired) is sent among the depolymerizing reactor D1 then through dehydration.
According to the present invention, melt A (containing alkali) reduces pressure in depolymerizing reactor D1.The hexanolactam that generates is removed from first reactor usually continuously, and it contains any other volatile constituent, as hexanolactam oligomer (steam B1).
Can not cracked and uncracked component (still bottom product S1) preferably deliver among the same maintenance second parallel off reactor D2 under reduced pressure; If desired, also other alkali can be added in second depolymerizing reactor.
As under the situation of steam B1, the steam B2 that obtains from second reactor contains hexanolactam usually, also can contain other volatile constituent, as hexanolactam oligomer.The still bottom product S2 of the second depolymerizing reactor D2 is preferred processedly to be fallen.
Cracking obtains in depolymerizing reactor D1 (also having D2 if desired) the steam B1 and the B2 that contain caprolactam deliver in the purification step usually.
The still bottom product S1 that cracking obtains in the first depolymerizing reactor D1 is usually by a kind of like this bath component, and this melt mainly is rich in inorganic residue and other polymkeric substance, does not promptly contain repeating unit-[N (H)-(CH)
2-C (O)-]-polymkeric substance, and melt also contains 2～60% usually, the used hexanolactam in preferred 15～35% (weight) first depolymerizing reactor D1 upstream.
In another preferred embodiment, the temperature among the depolymerizing reactor D1 is controlled by external heat exchanger and then the method that is recycled in the reactor (referring to Fig. 1) with a part of reactor content.
The volatile constituent that obtains in the second depolymerizing reactor D2 (steam B2) preferably merges with steam B1, sends in the purification step of hexanolactam.The depolymerization product that the still bottom product S2 of the second depolymerizing reactor D2 contains 0.5～50% (weight) hexanolactam usually and exists with equilibrium state under reaction conditions, it is usually as disposing in incinerator.
In an embodiment preferred, before these steam were delivered to the hexanolactam purification step, the oligopolymer that will contain the component of non-hexanolactam, particularly hexanolactam was removed from steam B1 and B2; If desired they are merged.The component of telling that contains non-hexanolactam is preferably recycled at least one depolymerizing reactor.
Separate and carry out in distillation plant usually, preferably carry out in separation column, steam B1 and/or B2 are cooled to 50～200 ℃, preferred 100～160 ℃, pressure is usually corresponding to the pressure among depolymerizing reactor D1 and the D2.
The purifying of the hexanolactam that the present invention makes can carry out with the method for routine, for example hexanolactam is delivered to the hexanolactam purification step that is used for producing hexanolactam.If desired, another possibility method of the hexanolactam that makes of purifying the present invention is for example at EP-A568882 and 570 843 open.Purified hexanolactam usually for further using, particularly prepares PA6 then.
Present device (referring to Fig. 1) is mainly by fusion apparatus (1), the mixing equipment (2) (being used for alkali and polycaprolactam melt-mixing), depolymerizing reactor D1 (3) (downstreams in mixing equipment (2)) and the depolymerizing reactor D2 (4) (in the downstream of described reactor D1) that link to each other with (1).
Equipment of the present invention is used to reclaim the waste material that contains hexanolactam, preferably reclaims with the inventive method.
The inventive method is preferred for reclaiming the waste material that contains polycaprolactam.
The advantage that the inventive method surpasses the prior art method is that the cracking productive rate is up to 99%; In treating processes, it is few to need to handle depleted waste material amount.
Embodiment 1 (interrupter method)-contrast
In 1 liter of autoclave, under 2 kPas, with 250 gram polyamide 6 (Ultramid
BS700 (BASF), relative viscosity=2.7 (measuring under 25 ℃ of concentration that contain down 1 gram polymkeric substance in per 100 milliliter of 96% (weight) sulfuric acid), content of residual water is 0.01% (weight)) and 5.0 restrain sodium hydroxide and be heated to 280 ℃.In 2 hours, from autoclave, remove 232.6 lactan of restraining oneself by distillation.Productive rate: 93%, oligomer: 0.8% (measuring) with HPLC.
According to table 1, with 1 kilogram of/hour polycaprolactam or the mixture that contains polycaprolactam in extruding machine (Barmag, L/D was than 12: 1) 280 ℃ of fusions.Then with 20 Grams Per Hour potassium hydroxide in mixing tank (280 ℃, 50 kPas) with the melt-mixing of from extruding machine, discharging, under described condition, remove the water of deentrainment simultaneously.To deliver among the depolymerizing reactor D1 that remains under the decompression (1.5 kPas) with the melt of alkali then, and at 273 ℃ be following cracking in 60 minutes at mean residence time.Still bottom product S1 is delivered in second depolymerizing reactor (oar formula reactor) (1.5 kPas, 273 ℃, the residence time with first reactor in identical), steam B1 and steam B2 from the second depolymerizing reactor D2 are merged.Steam B1 and B2 with gc analysis merges measure its caprolactam content.By the used hexanolactam or the polycaprolactam of copolymerization, productive rate is listed table 1 in.
Table 1
| Embodiment | Used raw material | Hexanolactam [Grams Per Hour] | Productive rate [%] | Oligopolymer 2)????[％] |
| ????2 | Ultramid BS700 | ????994 | ??99 | ????- |
| ????3 | The polycaprolactam enriched material 1), obtain by carpeting, contain the poly-hexyl propionamide of 75% (weight) | ????701 | ??93 | ????- |
| ????4 | Copolyamide 6/66 (is made by 85% (weight) hexanolactam and 15% (weight) AH salt; Ultramid C35, relative viscosity=3.25) | ????807 | ??95 | ????- |
| ????5 | Ultramid RC6000 (contains 30.2% (weight) staple glass fibre; Relative viscosity=2.7) | ????672 | ??96 | ????- |
1) removes non-polyamide component in the carpeting, until gather in oneself by mixture
Amide content is 75% (weight)
2) measure with HPLC
Claims (8)
- One kind in the presence of alkali, at least two placed in-line depolymerizing reactors, under reduced pressure by the method for the polymer manufacture hexanolactam that contains hexanolactam, this method comprises making and contains repeating unit-[N (H)-(CH 2) 5-C (O)-]-polymkeric substance or main mixture depolymerization composed of the following components, 50～99.9% (weight) contain repeating unit-[N (H)-(CH 2) 5-C (O)-]-polymkeric substance, 0.01～50% (weight) is selected from mineral filler, organic and inorganic pigment and the additive of dyestuff, organic and/or the inorganic additive of 0～10% (weight), 0～40% (weight) contain the polymeric amide of polymkeric substance and 0～20% (weight) except that polycaprolactam that is made by hexanolactam and copolyamide of non-polymeric amide.
- 2. according to the process of claim 1 wherein that any hexanolactam oligomer with existing separates from hexanolactam after depolymerization, and deliver to further depolymerization at least one depolymerizing reactor.
- One kind in the presence of alkali, under reduced pressure, wherein carry out following steps: (a) make and contain repeating unit-[N (H)-(CH by the method for the polymer manufacture hexanolactam that contains hexanolactam 2) 5-C (O)-]-polymkeric substance or main mixture fusion composed of the following components, obtain melt A50～99.9% (weight) and contain repeating unit-[N (H)-(CH 2) 5-C (O)-]-polymkeric substance, 0.01～50% (weight) is selected from mineral filler, organic and the inorganic pigment and the additive of dyestuff, organic and/or the inorganic additive of 0～10% (weight), 0～40% (weight) contains the polymkeric substance of non-polymeric amide, and 0～20% (weight) polymeric amide except that polycaprolactam that makes by hexanolactam and copolyamide, (b) melt A is sent among the maintenance depolymerizing reactor D1 under reduced pressure, obtain steam B1 and still bottom product S1, (c) from depolymerizing reactor D1, remove the steam B1 that contains hexanolactam, and (d) if desired, still bottom product S1 is delivered among the maintenance second depolymerizing reactor D2 under reduced pressure, obtain containing the steam B2 and the still bottom product S2 of hexanolactam; Before the fusion step, in the process or after the step, but before depolymerization, be added to alkali in the polymkeric substance, be added in the mixture or be added in the melt.
- 4. removed any water that may exist according to the process of claim 1 wherein in the past in depolymerization.
- 5. according to the process of claim 1 wherein that used alkali is selected from alkalimetal oxide, alkali metal hydroxide, alkaline carbonate, alkali metal alcoholates, alkaline earth metal oxide, alkaline earth metal hydroxides and alkaline earth metal carbonate.
- 6. equipment that under reduced pressure prepares hexanolactam with alkaline lysis fused polycaprolactam, this equipment is mainly by forming with the lower section: fusion apparatus (1), the mixing equipment (2) that is used to make alkali and polycaprolactam melt-mixing that links to each other with it, at the depolymerizing reactor D1 (3) in mixing equipment (2) downstream and at the depolymerizing reactor D2 (4) in described reactor D1 downstream.
- 7. the equipment of claim 6 is used to reclaim the application of the waste material that contains polycaprolactam.
- 8. the method for claim 1 is used to reclaim the application of the waste material that contains polycaprolactam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95196756.8A CN1169718A (en) | 1994-12-12 | 1995-12-01 | Method of obtaining caprolactam by cracking of molten polycaprolactam |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/355,285 | 1994-12-12 | ||
| CN95196756.8A CN1169718A (en) | 1994-12-12 | 1995-12-01 | Method of obtaining caprolactam by cracking of molten polycaprolactam |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892511A (en) * | 2014-09-26 | 2015-09-09 | 江苏弘盛新材料股份有限公司 | System for improving recovery quality of caprolactam monomer |
| CN114591240A (en) * | 2021-12-22 | 2022-06-07 | 浙江恒逸锦纶有限公司 | Polyamide-6 oligomer depolymerization residue treatment process |
-
1995
- 1995-12-01 CN CN95196756.8A patent/CN1169718A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892511A (en) * | 2014-09-26 | 2015-09-09 | 江苏弘盛新材料股份有限公司 | System for improving recovery quality of caprolactam monomer |
| CN114591240A (en) * | 2021-12-22 | 2022-06-07 | 浙江恒逸锦纶有限公司 | Polyamide-6 oligomer depolymerization residue treatment process |
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