CN1329430C - 聚酰胺 - Google Patents
聚酰胺 Download PDFInfo
- Publication number
- CN1329430C CN1329430C CNB2004800124441A CN200480012444A CN1329430C CN 1329430 C CN1329430 C CN 1329430C CN B2004800124441 A CNB2004800124441 A CN B2004800124441A CN 200480012444 A CN200480012444 A CN 200480012444A CN 1329430 C CN1329430 C CN 1329430C
- Authority
- CN
- China
- Prior art keywords
- polymeric amide
- hexanolactam
- acid
- alkyl
- preferred
- 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.)
- Expired - Lifetime
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- 239000004952 Polyamide Substances 0.000 title abstract description 8
- 229920002647 polyamide Polymers 0.000 title abstract description 8
- -1 and to fibres Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 150000001408 amides Chemical class 0.000 claims description 60
- 239000000178 monomer Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 14
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 8
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- SZMLDVKZMIXAJF-UHFFFAOYSA-N 1-(2-methylpropyl)azepan-2-one Chemical compound CC(C)CN1CCCCCC1=O SZMLDVKZMIXAJF-UHFFFAOYSA-N 0.000 claims 1
- VGZOTUWVGXUNRC-UHFFFAOYSA-N 1-butylazepan-2-one Chemical compound CCCCN1CCCCCC1=O VGZOTUWVGXUNRC-UHFFFAOYSA-N 0.000 claims 1
- BWISIXSYQURMMY-UHFFFAOYSA-N 1-propylazepan-2-one Chemical compound CCCN1CCCCCC1=O BWISIXSYQURMMY-UHFFFAOYSA-N 0.000 claims 1
- ZNAUAYFPKFKGBT-UHFFFAOYSA-N 1-tert-butylazepan-2-one Chemical compound CC(C)(C)N1CCCCCC1=O ZNAUAYFPKFKGBT-UHFFFAOYSA-N 0.000 claims 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical group CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 18
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000003951 lactams Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000005219 aminonitrile group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 3
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 description 3
- 150000003948 formamides Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XHSHBZYAHLVSGW-UHFFFAOYSA-N C1(=CC=CC=C1)N(C1=CC=C(C=C1)NC=O)C=O Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)NC=O)C=O XHSHBZYAHLVSGW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000001261 hydroxy acids Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- WPXQWTBMMKQBDE-UHFFFAOYSA-N 2-aminoundecanamide Chemical compound CCCCCCCCCC(N)C(N)=O WPXQWTBMMKQBDE-UHFFFAOYSA-N 0.000 description 1
- FJJJJJASZCGAJW-UHFFFAOYSA-N 2-aminoundecanenitrile Chemical compound CCCCCCCCCC(N)C#N FJJJJJASZCGAJW-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZLHYDRXTDZFRDZ-UHFFFAOYSA-N epsilon-aminocaproamide Chemical compound NCCCCCC(N)=O ZLHYDRXTDZFRDZ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- YJDGPHNALRFFGD-UHFFFAOYSA-N methyl 2-aminoundecanoate Chemical class CCCCCCCCCC(N)C(=O)OC YJDGPHNALRFFGD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
本发明涉及主链含有化学键合的N-烷基内酰胺的聚酰胺。本发明还涉及制备该聚酰胺的方法以及包含该聚酰胺的纤维、膜和模制品。
Description
本发明涉及主链含有化学键合的N-烷基内酰胺的聚酰胺。
本发明进一步涉及一种制备该聚酰胺的方法以及包含至少一种该聚酰胺的纤维、膜和模制品。
聚酰胺,尤其是尼龙-6和尼龙-6,6是工业上重要的聚合物。它们通常由在水存在下反应的合适单体如己内酰胺、己二酸或六亚甲基二胺制备。
通常将聚酰胺聚合物成型为成型材料如纤维、膜或模制品。
该类成型材料在使用中通常暴露于力的作用;这些力可能导致成型材料破裂并因此导致成型材料损坏。
衡量标准是根据DIN EN ISO 10350-1并结合DIN EN ISO 527-1的断裂拉伸应变εB或标称应变εt。
断裂拉伸应变表示在达到屈服点以前发生断裂时的断裂应力下的相对伸长率;标称应变表示在达到屈服点以后的相对伸长率。直到屈服点伸长都是可逆的,并且在超过屈服点后伸长不可逆。
高断裂拉伸应变是成型材料的所需性能,因为这表示成型材料能够弹性吸收施加的力,并且在该力逐渐消失以后回复到原始形状。
本发明的目的是提供一种与现有技术的聚酰胺相比具有改进的DINEN ISO 527-1断裂拉伸应变的聚酰胺以及一种制备该聚酰胺的方法。
我们发现该目的由开头所定义的聚酰胺、一种制备它的方法以及包含至少一种该聚酰胺的纤维、膜和模制品实现。
聚酰胺在本发明中应理解为在聚合物主链中具有作为基本成分的重复酰胺基团的合成长链聚酰胺的均聚物、共聚物、共混物和接枝聚合物。该类聚酰胺的实例是尼龙-6(聚己内酰胺)、尼龙-6,6(聚己二酰己二胺)、尼龙-4,6(聚己二酰丁二胺)、尼龙-6,10(聚癸二酰己二胺)、尼龙-7(聚庚内酰胺)、尼龙-11(聚十一烷内酰胺)、尼龙-12(聚十二烷内酰胺)。除了已知属名为尼龙的聚酰胺外,聚酰胺进一步包括芳族聚酰胺,如聚(间-苯二甲酰间-苯二胺)(NOMEX纤维,US-A-3,287,324)或聚(对-苯二甲酰对-苯二胺)(KEVLAR纤维,US-A-3,671,542)。
聚酰胺原则上可以由两种方法制备。
在由二羧酸和二胺进行的聚合中以及在由氨基酸或其衍生物如氨基腈、氨基酰胺、氨基羧酸酯或氨基羧酸盐进行的聚合中,原料单体或原料低聚体的氨基和羧基端基相互反应形成酰胺基团和水。随后可以将水从聚合物中除去。在由氨基酰胺进行的聚合中,原料单体或原料低聚体的氨基和酰胺端基相互反应形成酰胺基团和氨。随后可以将氨从聚合物中除去。当聚合氨基羧酸酯时,原料单体或原料低聚体的氨基和酯端基相互反应形成酰胺基团和醇。随后可以将醇从聚合物中除去。在氨基腈的聚合中,腈基可以首先与水反应形成酰胺或羧基且所得氨基酰胺或氨基羧酸可以如上所述进行反应。该聚合反应通常已知为缩聚。
由内酰胺作为原料单体或原料低聚体的聚合通常已知为加聚。
该类聚酰胺可以通过常规方法由选自如下的单体得到:内酰胺,ω-氨基羧酸,ω-氨基腈,ω-氨基酰胺,ω-氨基羧酸盐,ω-氨基羧酸酯,二胺和二羧酸、二羧酸/二胺盐、二腈与二胺的等摩尔混合物或其混合物,所述常规方法例如描述于DE-A-1495198,DE-A-2558480,EP-A-129196中或Polymerization Processes,Interscience,New York,1977,第424-467页,尤其是第444-446页所述。
有用的单体包括:
C2-C20,优选C2-C18芳脂族或优选脂族内酰胺如庚内酰胺、十一烷内酰胺、十二烷内酰胺或己内酰胺的单体或低聚体,
C2-C20,优选C3-C18氨基羧酸如6-氨基己酸或11-氨基十一烷酸及其盐如碱金属盐,例如锂、钠或钾盐的单体或低聚体,
C2-C20,优选C3-C18氨基腈如6-氨基己腈或11-氨基十一烷腈的单体或低聚体,
C2-C20氨基酰胺如6-氨基己酰胺或11-氨基十一烷酰胺的单体或低聚体,
C2-C20,优选C3-C18氨基羧酸的酯,优选C1-C4烷基酯,如甲基、乙基、正丙基、异丙基、正丁基、异丁基或仲丁基酯,如6-氨基己酸酯,例如6-氨基己酸甲酯,或11-氨基十一烷酸酯,例如11-氨基十一烷酸甲酯,
C2-C20,优选C2-C12烷基二胺如四亚甲基二胺或优选六亚甲基二胺与C2-C20,优选C2-C14脂族二羧酸或其单腈或二腈如癸二酸、十二烷二酸、己二酸、癸二腈、癸烷-1,10-二腈或己二腈的单体或低聚体,
C2-C20,优选C2-C12烷基二胺如四亚甲基二胺或优选六亚甲基二胺与C8-C20,优选C8-C12芳族二羧酸或其衍生物如氯化物,如萘-2,6-二羧酸,优选间-苯二甲酸或对-苯二甲酸的单体或低聚体,
C2-C20,优选C2-C12烷基二胺如四亚甲基二胺或优选六亚甲基二胺与C9-C20,优选C9-C18芳脂族二羧酸或其衍生物如氯化物,如邻-苯二乙酸、间-苯二乙酸或对-苯二乙酸的单体或低聚体,
Cx-C20,优选C6-C10芳族二胺如间-苯二胺或对-苯二胺与C2-C20,优选C2-C14脂族二羧酸或其单腈或二腈如癸二酸、十二烷二酸、己二酸、癸二腈、癸烷-1,10-二腈或己二腈的单体或低聚体,
C6-C20,优选C6-C10芳族二胺如间-苯二胺或对-苯二胺与C8-C20,优选C8-C12芳族二羧酸或其衍生物如氯化物,如萘-2,6-二羧酸,优选间-苯二甲酸或对-苯二甲酸的单体或低聚体,
C6-C20,优选C6-C10芳族二胺如间-苯二胺或对-苯二胺与C9-C20,优选C9-C18芳脂族二羧酸或其衍生物如氯化物,如邻-苯二乙酸、间-苯二乙酸或对-苯二乙酸的单体或低聚体,
C7-C20,优选C8-C18芳脂族二胺如间-苯二甲胺或对-苯二甲胺与C2-C20,优选C2-C14脂族二羧酸或其单腈或二腈如癸二酸、十二烷二酸、己二酸、癸二腈、癸烷-1,10-二腈或己二腈的单体或低聚体,
C7-C20,优选C8-C18芳脂族二胺如间-苯二甲胺或对-苯二甲胺与C6-C20,优选C6-C10芳族二羧酸或其衍生物如氯化物,如萘-2,6-二羧酸,优选间-苯二甲酸或对-苯二甲酸的单体或低聚体,
C7-C20,优选C8-C18芳脂族二胺如间-苯二甲胺或对-苯二甲胺与C9-C20,优选C9-C18芳脂族二羧酸或其衍生物如氯化物,如邻-苯二乙酸、间-苯二乙酸或对-苯二乙酸的单体或低聚体,
以及这类原料单体或原料低聚体的均聚物、共聚物、共混物和接枝聚合物。
有用的低聚体尤其包括所述单体或所述单体混合物的二聚体、三聚体、四聚体、五聚体或六聚体。
在优选的实施方案中,所用内酰胺为己内酰胺,所用二胺为四亚甲基二胺、六亚甲基二胺或其混合物且所用二羧酸为己二酸、癸二酸、十二烷二酸、对-苯二甲酸、间-苯二甲酸或其混合物。特别优选内酰胺为己内酰胺,二胺为六亚甲基二胺且二羧酸为己二酸或对-苯二甲酸或其混合物。
特别优选聚合时得到尼龙-6、尼龙-6,6、尼龙-4,6、尼龙-6,10、尼龙-6,12、尼龙-7、尼龙-11或尼龙-12的聚酰胺或聚(间-苯二甲酰间-苯二胺)或聚(对-苯二甲酰对-苯二胺)的芳族聚酰胺,尤其是得到尼龙-6或尼龙-6,6的那些原料单体或原料低聚体。
在优选的实施方案中,聚酰胺可以使用一种或多种链长调节剂制备。有用的链长调节剂有利地包括具有一个或多个如2、3或4个,优选在纤维形式的体系情况下为2个,在聚酰胺形成中具有反应性的氨基或一个或多个如2、3或4个,优选在纤维形式的体系情况下为2个,在聚酰胺形成中具有反应性的羧基的化合物。
第一种情况提供的聚酰胺中用于制备所述聚酰胺的单体和链长调节剂具有的用于形成所述聚合物链的氨基或其等价物的数目高于用于形成所述聚合物链的羧酸基团或其等价物。
第二种情况提供的聚酰胺中用于制备所述聚酰胺的单体和链长调节剂具有的用于形成所述聚合物链的羧酸基团或其等价物的数目高于用于形成所述聚合物链的氨基或其等价物。
有用的链长调节剂有利地包括单羧酸,如链烷烃羧酸,例如乙酸、丙酸,如苯或萘的单羧酸,例如苯甲酸;二羧酸,如C4-C10链烷烃二羧酸,例如己二酸、壬二酸、癸二酸、十二烷二酸,C5-C8环烷烃二羧酸,例如环己烷-1,4-二羧酸,苯或萘的二羧酸,例如对-苯二甲酸、间-苯二甲酸、萘-2,6-二羧酸;C2-C20,优选C2-C12烷基胺,如环己胺;C6-C20,优选C6-C10芳族单胺,如苯胺;或C7-C20,优选C8-C18芳脂族单胺,如苄基胺;二胺,如C4-C10链烷烃二胺,例如六亚甲基二胺。
链长调节剂可以是未取代或例如被如下基团取代:脂族基团,优选C1-C8-烷基,如甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、正戊基、正己基、正庚基、正辛基、2-乙基己基;OH、=O、C1-C8烷氧基、COOH、C2-C6烷酯基、C1-C10酰氧基;或C1-C8-烷基氨基、磺酸或其盐如碱金属盐或碱土金属盐、氰基或卤素如氟、氯、溴。取代的链长调节剂的实例是磺基-间-苯二甲酸及其碱金属盐或碱土金属盐如锂、钠或钾盐,例如与C1-C16链烷醇形成的磺基-间-苯二甲酸酯,或尤其是与适合形成聚酰胺且带有至少一个氨基的单体如六亚甲基二胺或6-氨基己酸形成的磺基-间-苯二甲酸单酰胺或二酰胺。
优选的链长调节剂是下式的空间位阻哌啶衍生物:
其中
R1为能够与聚酰胺的聚合物链形成酰胺的官能团,
优选基团-(NH)R5,其中R5为氢或C1-C8烷基,或羧基官能团或羧基衍生物;或基团-(CH2)x(NH)R5,其中x为1-6且R5为氢或C1-C8烷基;或基团-(CH2)yCOOH,其中y为1-6;或-(CH2)yCOOH酸衍生物,其中y为1-6,尤其为基团-NH2,
R2为烷基,优选C1-C4烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基,尤其是甲基,
R3为氢、C1-C4烷基或O-R4,其中R4为氢或C1-C7烷基,R3尤其为氢。
在该类化合物中,空间位阻通常防止哌啶环体系中的叔氨官能团,尤其是仲氨官能团发生反应。
特别优选的空间位阻哌啶衍生物是4-氨基-2,2,6,6-四甲基哌啶。
基于聚酰胺的1mol酰胺基团,链长调节剂可以有利地以不低于0.001mol%,优选不低于0.01mol%,尤其是不低于0.03mol%,更优选不低于0.08mol%的量使用。
基于聚酰胺的1mol酰胺基团,链长调节剂可以有利地以不超过2.0mol%,优选不超过1mol%,尤其不超过0.6mol%,更优选不超过0.5mol%的量使用。
按照本发明,聚酰胺的主链含有化学键合的N-烷基内酰胺。
每当本发明提到N-烷基内酰胺时,该术语不仅应理解为该N-烷基内酰胺,而且还有该N-烷基内酰胺的混合物。
在优选的实施方案中,N-烷基内酰胺是N-C1-C10烷基内酰胺,优选N-烷基内酰胺选自N-甲基内酰胺、N-乙基内酰胺、N-正丙基内酰胺、N-异丙基内酰胺、N-正丁基内酰胺、N-异丁基内酰胺和N-叔丁基内酰胺,尤其是N-乙基内酰胺。
有用的N-烷基内酰胺还有在内酰胺环中具有3-10个碳原子的那些,优选其中内酰胺环选自吡咯烷酮、哌啶酮和己内酰胺,尤其是己内酰胺的那些。
内酰胺环可以例如被一个或多个烷基,优选C1-C10-烷基,尤其是甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基;卤素如氟、氯、溴;卤代烷基如三氟甲基取代。在优选的实施方案中,内酰胺环未被取代。
在特别优选的实施方案中,N-烷基内酰胺为N-乙基己内酰胺。
该N-烷基内酰胺及其制备本身是已知的。
基于聚酰胺的1mol酰胺基团,N-烷基内酰胺的含量可以有利地不低于0.001mol%,优选不低于0.01mol%,尤其不低于0.03mol%,更优选不低于0.08mol%。
基于聚酰胺的1mol酰胺基团,N-烷基内酰胺的含量可以有利地不超过2.0mol%,优选不超过1mol%,尤其不超过0.6mol%,更优选不超过0.5mol%。
本发明的聚酰胺可以由这样的方法得到:其包括在N-烷基内酰胺或在制备聚酰胺的反应条件下从中释放出N-烷基内酰胺的化合物存在下将适合形成聚酰胺的单体、低聚体或其混合物转化成聚酰胺。
可以使用由相应单体制备聚酰胺的常用工艺条件制备本发明的聚酰胺,例如在DE-A-1495198、DE-A-2558480、EP-A-129196、DE-A-19709390、DE-A-3534817、WO99/38908、WO99/43734、WO99/43732、WO00/24808、WO01/56984中或在Polymerization Processes(聚合工艺),Interscience,New York,1977,第424-467页,尤其是第444-446页中所述。
在优选的实施方案中,本发明方法的聚合或缩聚可以在至少一种颜料存在下进行。优选的颜料是二氧化钛,优选锐钛矿或金红石晶型,或者有机或无机类有色化合物。在每种情况下基于100重量份的聚酰胺,颜料的加入量优选为0-5重量粉,尤其是0.02-2重量份。颜料可以与原料一起或单独加入反应器中。
此外,聚酰胺不仅可以由上述的两种优选方法制备,还可以由阴离子聚合制备。
阴离子聚合方法通常包括使下列化合物相互反应以得到聚酰胺:
a)内酰胺或内酰胺的混合物,
b)内酰胺盐或由a)的内酰胺释放出内酰胺盐的化合物,或该组分的混合物,和
c)聚合调节活化剂
内酰胺的阴离子聚合方法,也已知为内酰胺的碱性聚合,以及还有合适化合物a)、b)和c)是公知技术,例如由US-A-3,206,418、US-A-3,207,713、US-A-3,494,999、US-A-3,793,255、US-A-4,233,433、US-A-4,393,193、US-A-4,503,014、US-A-5,747,634、WO-A-00/58387、WO-A-01/49906、International Polymer Processing 16(2)(2001)172-182或Fourné,Synthetische Fasern,Carl Hanser Verlag,Munich/Vienna,1995,第38-39页已知。
本发明的聚酰胺可以有利地用于生产含有该聚酰胺或更具体来讲由该聚酰胺组成的纤维、膜和模制品。
实施例
按照DIN51562-1至4作为在96%硫酸中的相对溶液粘度测量实施例中报告的溶液粘度。
具体而言,每100ml溶液称取1g聚合物,并在乌氏粘度计中测量其相对于纯溶剂的流动时间。
发明实施例1
在压力容器中,在氮气下将500kg(4419mol)己内酰胺、50kg完全无离子水和1271g(9mol)N-乙基己内酰胺加热到270℃的内部温度,然后立即在1小时内降至大气压,补充缩合60分钟并卸料。
萃取卸出的聚酰胺、干燥并以固态进行热处理至RV=2.72的相对溶液粘度。
对比例1
重复发明实施例1,不同的是不加入N-乙基己内酰胺。热处理后的相对溶液粘度RV=2.73。
实施例2
在挤出机中将按照发明实施例1和对比例1制备的聚合物与30重量%OCF123D10P玻璃纤维(购自OCF)和7重量%Lupolen KR1270橡胶(购自BASF Aktiengesellschaft)配混(百分含量基于完成配混后的材料)。在这两种情况下,配混后的相对溶液粘度均为2.80。
按照ISO527对两种配混材料进行断裂拉伸应变测量。得到下列结果:
发明实施例1的聚合物的归一化断裂拉伸应变:6%
对比例1的聚合物的归一化断裂拉伸应变:4%
因此,按照发明实施例1制备的聚合物比按照对比例1制备的聚合物的断裂拉伸应变高50%。
Claims (8)
1.一种主链含有化学键合的N-烷基己内酰胺的聚酰胺。
2.根据权利要求1的聚酰胺,其中N-烷基己内酰胺为N-(C1-C10)烷基己内酰胺。
3.根据权利要求1的聚酰胺,其中N-烷基己内酰胺选自N-甲基己内酰胺、N-乙基己内酰胺、N-正丙基己内酰胺、N-异丙基己内酰胺、N-正丁基己内酰胺、N-异丁基己内酰胺和N-叔丁基己内酰胺。
4.根据权利要求1的聚酰胺,其中N-烷基己内酰胺为N-乙基己内酰胺。
5.根据权利要求1-4中任何一项的聚酰胺,其中基于聚酰胺的1mol酰胺基团,化学键合的N-烷基己内酰胺含量为0.001-2mol%。
6.一种制备聚酰胺的方法,包括在根据权利要求1-5中任何一项的N-烷基己内酰胺存在下将适合形成聚酰胺的单体转化成聚酰胺。
7.一种制备聚酰胺的方法,包括在根据权利要求1-5中任何一项的N-烷基己内酰胺存在下将适合形成聚酰胺的低聚体转化成聚酰胺。
8.包含根据权利要求1-5中任何一项的聚酰胺的纤维、膜和模制品。
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CA (1) | CA2525136A1 (zh) |
DE (2) | DE10321789A1 (zh) |
ES (1) | ES2293254T3 (zh) |
MX (1) | MXPA05011465A (zh) |
MY (1) | MY136466A (zh) |
PL (1) | PL1631615T3 (zh) |
TW (1) | TW200505964A (zh) |
WO (1) | WO2004101647A1 (zh) |
Families Citing this family (2)
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KR100937086B1 (ko) * | 2006-12-20 | 2010-01-15 | 주식회사 효성 | 형상기억성 폴리아미드 및 그를 이용한 형상기억성폴리아미드 원단의 제조방법 |
EP2460847A1 (de) * | 2010-12-02 | 2012-06-06 | Basf Se | Schaum mit Füllung |
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CS175888B1 (zh) * | 1975-02-18 | 1977-05-31 | ||
EP0602241A1 (en) * | 1992-04-09 | 1994-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Acrylic resin composition |
CN1169720A (zh) * | 1994-12-12 | 1998-01-07 | 巴斯福股份公司 | 熔融聚己内酰胺解聚制己内酰胺 |
CN1491250A (zh) * | 2000-12-20 | 2004-04-21 | 东丽株式会社 | 聚酰胺预聚物、聚酰胺及其制造方法 |
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FR2137175B1 (zh) * | 1971-05-14 | 1974-03-08 | Aquitaine Total Organico | |
FR2261266B1 (zh) * | 1974-02-19 | 1977-03-18 | Ato Chimie | |
DE2637010A1 (de) * | 1976-08-17 | 1978-02-23 | Bayer Ag | Aktivierte anionische polymerisation |
DE3932949A1 (de) * | 1989-10-03 | 1991-04-11 | Bayer Ag | Elasthanfasern hoher dehnbarkeit und festigkeit und ein verfahren zu ihrer herstellung |
JPH1160983A (ja) * | 1997-08-11 | 1999-03-05 | Amcol Internatl Corp | モノマー、オリゴマー及び/またはポリマーインターカラントならびに表面修飾剤と層状物とのコインターカレーションによって形成したインターカレーション物及び当該インターカレーションで調製したナノ合成物 |
DE10039750C1 (de) * | 2000-08-16 | 2002-05-08 | Bayer Ag | Schlichtezusammensetzung für Glasfasern sowie deren Verwendung |
JP4443176B2 (ja) * | 2002-09-27 | 2010-03-31 | 日本化薬株式会社 | 接着補助剤組成物 |
-
2003
- 2003-05-14 DE DE10321789A patent/DE10321789A1/de not_active Withdrawn
-
2004
- 2004-05-06 EP EP04731364A patent/EP1631615B1/de not_active Expired - Lifetime
- 2004-05-06 BR BRPI0410243-6B1A patent/BRPI0410243B1/pt not_active IP Right Cessation
- 2004-05-06 KR KR1020057021522A patent/KR100989235B1/ko not_active IP Right Cessation
- 2004-05-06 JP JP2006529747A patent/JP4586023B2/ja not_active Expired - Fee Related
- 2004-05-06 PL PL04731364T patent/PL1631615T3/pl unknown
- 2004-05-06 CN CNB2004800124441A patent/CN1329430C/zh not_active Expired - Lifetime
- 2004-05-06 US US10/556,674 patent/US7393913B2/en active Active
- 2004-05-06 MX MXPA05011465A patent/MXPA05011465A/es active IP Right Grant
- 2004-05-06 CA CA002525136A patent/CA2525136A1/en not_active Abandoned
- 2004-05-06 WO PCT/EP2004/004816 patent/WO2004101647A1/de active IP Right Grant
- 2004-05-06 DE DE502004005565T patent/DE502004005565D1/de not_active Expired - Lifetime
- 2004-05-06 ES ES04731364T patent/ES2293254T3/es not_active Expired - Lifetime
- 2004-05-11 TW TW093113208A patent/TW200505964A/zh unknown
- 2004-05-12 MY MYPI20041753A patent/MY136466A/en unknown
- 2004-05-14 AR ARP040101637A patent/AR044326A1/es unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CS175888B1 (zh) * | 1975-02-18 | 1977-05-31 | ||
EP0602241A1 (en) * | 1992-04-09 | 1994-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Acrylic resin composition |
CN1169720A (zh) * | 1994-12-12 | 1998-01-07 | 巴斯福股份公司 | 熔融聚己内酰胺解聚制己内酰胺 |
CN1491250A (zh) * | 2000-12-20 | 2004-04-21 | 东丽株式会社 | 聚酰胺预聚物、聚酰胺及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
MXPA05011465A (es) | 2005-12-15 |
EP1631615B1 (de) | 2007-11-21 |
US20070027295A1 (en) | 2007-02-01 |
KR20060009334A (ko) | 2006-01-31 |
WO2004101647A1 (de) | 2004-11-25 |
CN1784451A (zh) | 2006-06-07 |
BRPI0410243A (pt) | 2006-05-16 |
BRPI0410243B1 (pt) | 2013-11-19 |
JP4586023B2 (ja) | 2010-11-24 |
DE502004005565D1 (en) | 2008-01-03 |
JP2006528269A (ja) | 2006-12-14 |
AR044326A1 (es) | 2005-09-07 |
DE10321789A1 (de) | 2004-12-09 |
TW200505964A (en) | 2005-02-16 |
KR100989235B1 (ko) | 2010-10-20 |
MY136466A (en) | 2008-10-31 |
CA2525136A1 (en) | 2004-11-25 |
ES2293254T3 (es) | 2008-03-16 |
EP1631615A1 (de) | 2006-03-08 |
PL1631615T3 (pl) | 2008-05-30 |
US7393913B2 (en) | 2008-07-01 |
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