CA2525137A1 - Polyamides - Google Patents
Polyamides Download PDFInfo
- Publication number
- CA2525137A1 CA2525137A1 CA002525137A CA2525137A CA2525137A1 CA 2525137 A1 CA2525137 A1 CA 2525137A1 CA 002525137 A CA002525137 A CA 002525137A CA 2525137 A CA2525137 A CA 2525137A CA 2525137 A1 CA2525137 A1 CA 2525137A1
- Authority
- CA
- Canada
- Prior art keywords
- polyamide
- group
- acid
- amino
- ester
- 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.)
- Abandoned
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 73
- 229920002647 polyamide Polymers 0.000 title claims abstract description 73
- 125000003368 amide group Chemical group 0.000 claims abstract description 15
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 7
- 150000001733 carboxylic acid esters Chemical group 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 10
- -1 and to fibres Substances 0.000 abstract description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 9
- 150000003951 lactams Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 4
- 239000000049 pigment Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- 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
- GDYYIJNDPMFMTB-UHFFFAOYSA-N 2-[3-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC(CC(O)=O)=C1 GDYYIJNDPMFMTB-UHFFFAOYSA-N 0.000 description 3
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 3
- NSMYBPIHVACKQG-UHFFFAOYSA-N 2-aminocyclopentene-1-carbonitrile Chemical compound NC1=C(C#N)CCC1 NSMYBPIHVACKQG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- 229960002684 aminocaproic acid Drugs 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 2
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 2
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- OMMWHZACYMWERD-UHFFFAOYSA-N 11-aminoundecanenitrile Chemical compound NCCCCCCCCCCC#N OMMWHZACYMWERD-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical group CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 1
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZLHYDRXTDZFRDZ-UHFFFAOYSA-N epsilon-aminocaproamide Chemical compound NCCCCCC(N)=O ZLHYDRXTDZFRDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- QVGONMHQKGSFOB-UHFFFAOYSA-N methyl 11-aminoundecanoate Chemical compound COC(=O)CCCCCCCCCCN QVGONMHQKGSFOB-UHFFFAOYSA-N 0.000 description 1
- TZJVWRXHKAXSEA-UHFFFAOYSA-N methyl 6-aminohexanoate Chemical compound COC(=O)CCCCCN TZJVWRXHKAXSEA-UHFFFAOYSA-N 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 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
- 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
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 238000007363 ring formation reaction Methods 0.000 description 1
- 102220085978 rs141230910 Human genes 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000013638 trimer Substances 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived 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
-
- 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
-
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
Abstract
The invention relates to a polyamide, the main chain thereof containing a chemically bonded amine selected from the group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyclopent-1-ene, wherein R represents a functional group that can react with an amino group to form an amide group.
The invention also relates to a method for producing one such polyamide, and to fibres, films and moulded bodies containing the same.
The invention also relates to a method for producing one such polyamide, and to fibres, films and moulded bodies containing the same.
Description
~yC cJ~, .r'y, z,.1, CA 02525137 2005-11-08 Polyamides Description The present invention relates to a polyamide whose main claim contains a chemically bound amine selected from the group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, or mixtures thereof.
The present invention further relates to a process for preparing such a polyamide and also to fibers, films and moldings comprising at least one such polyamide.
Polyamides, especially nylon-6 and nylon-6,6, are industrially important polymers. They are typically prepared from suitable monomers, such as caprolactam, adipic acid or hexamethylenediamine, which are reacted in the presence of water.
Polyamide polymers are typically shaped, for example into fibers, films or moldings.
Such fibers or textile entities manufactured therefrom, such as apparel or carpet, films or moldings are then typically dyed. This can be accomplished for example by means of dyebaths in the case of fibers or textile entities manufactured therefrom or by printing in the case of textile entities, films or moldings.
It is desirable for the polyamide to have a high rate of dyeing in order that a high rate of processing may be achieved.
It is an object of the present invention to provide a polyamide which has a higher rate of dyeing than prior art polyamides and also a process for preparing such a polyamide.
We have found that this object is achieved by the polyamide defined at the beginning, a process for preparing it and also fibers, films and moldings comprising at least one such polyamide.
Polyamides are herein to be understood as being homopolymers, copolymers, blends and grafts of synthetic long-chain polyamides having recurring amide groups in the polymer main chain as an essential constituent. Examples of such poiyamides are nylon-6 (polycaprolactam), nylon-6,6 (polyhexamethyleneadipamide), nylon-4,6 (polytetramethyleneadipamide), nylon-6,10 (polyhexamethylenesebacamide), nylon-(polyenantholactam), nylon-11 (poly- undecanolactam), nylon-12 (polydodecanolactam). As well as polyamides known by the generic name of nylon, PF 5.524 CA 02525137 2005-11-08 polyamides further include the aramids (aromatic polyamides), such as poly-meta-phenyleneisophthalamide (NOMEX~ fiber, US-A-3,287,324) or poly-para-phenyleneterephthalamide (KEVLAR~ fiber, US-A-3,671,542).
Polyamides can in principle be prepared by two methods.
fn a polymerization from dicarboxylic acids and diamines and also in a polymerization from amino acids or their derivatives, such as aminocarbonitrifes, aminocarboxamides, aminocarboxylate esters or aminocarboxylate salts, the amino and carboxyl end groups of the starting monomers or starting oligomers react with one another to form an amide group and water. The water can subsequently be removed from the polymer. In a polymerization from aminocarboxamides, the amino and amide end groups of the starting monomers or starting oligomers react with one another to form an amide group and ammonia. The ammonia can subsequently be removed from the polymer. When aminocarboxylic esters are polymerized, the amino and ester end groups of the starting monomers or oligomers react with each other to form an amide group and alcohol. The alcohol can subsequently be removed from the polymer mass. In the polymerization of aminocarboxylic nitrites, the nitrite groups can first react with water to form amid or carboxyl groups and the resulting aminocarboxylic amides or acids reacted as described.
This polymerization reaction is customarily known as a polycondensation.
A polymerization from lactams as starting monomers or starting oligomers is customarily known as a polyaddition.
Such polyamides are obtainable by conventional processes, as described for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, lnterscience, New York, 1977, pages 424-467, especially pages 444-446, from monomers selected from the group consisting of lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylate salts, omega-aminocarboxylate esters, equimolar mixtures of diamines and dicarboxylic acids, dicarboxylic acidldiamine salts, dinitriles and diamines or mixtures thereof.
Useful monomers include monomers or oligomers of a C2 to C2o, preferably C2 to C,B, arylaiiphatic or, preferably, aliphatic lactam such as enantholactam, undecanolactam, dodecanolactam or caprolactam, monomers or oligomers of CZ to C2o, preferably C3 to C,B, aminocarboxylic acids such as 6-aminocaproic acid or 11-aminoundecanoic acid, and salts thereof such as alkali metal salts, for example lithium, sodium or potassium salts, monomers or oligomers of Cz to C2o, preferably C3 to C,B, aminocarbonitriles such as 6-aminocapronitrile or 11-aminoundecanonitrile, monomers or oligomers of C2 to CZO amino acid amides such as 6-aminocapronamide or 11-aminoundecanomide, esters, preferably C,-CQ alkyl esters, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl esters, of CZ to C2o, preferably C3 to C,B, aminocarboxylic acids, such as 6-aminocaproic acid esters, for example methyl 6-aminocaproate, or 11-aminoundecanoic acid esters, for example methyl 11-aminoundecanoate, monomers or oligomers of a Cz to C2a, preferably C2 to C,2, alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine, with a CZ to CZO, preferably CZ to C,4, aliphatic dicarboxylic acid or mono-or dinitriles thereof, such as sebacic acid, dodecanedioic acid, adipic acid, sebacic acid dinitrile, decanoic acid 1,10-dinitriie or adiponitrile, monomers or oligomers of a Cz to C2o, preferably C2 to C~2, alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine, with a C8 to C2a, preferably Ca to C,Z, aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as naphthalene-2,6-dicarboxylic acid, preferably isophthalic acid or terephthalic acid, monomers or oligomers of a C2 to CZO, preferably CZ to C,2, alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine, with a C9 to C2o, preferably C9 to C,B, arylaliphatic dicarboxylic acid or derivatives PI' x4524 CA 02525137 2005-11-08 thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid, monomers or oligomers of a C6 to C2o, preferably C6 to C,o, aromatic diamine, such as m- or p-phenylenediamine, with a CZ to C2o, preferably CZ to C,4, aliphatic dicarboxylic acid or mono-or dinitriles thereof, such as sebacic acid, dodecanedioic acid, adipic acid, sebacic acid dinitrile, decane-1,10-dinitrile oradiponitrile, monomers or oligomers of a C6 to C2o, preferably C6 to C,o, aromatic diamine, such as m- or p-phenylenediamine, with a C8 to C2o, preferably CB to C,z, aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as naphthalene-2,6-dicarboxylic acid, preferably isophthalic acid or terephthalic acid, monomers or oligomers of a C6 to C2o, preferably C6 to C,o, aromatic diamine, such as m- or p-phenylenediamine, with a C9 to CZO, preferably C9 to C,B, arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid, monomers or oligomers of a C, to C2o, preferably CS to C,B, arylaliphatic diamine, such as m- or p-xylylenediamine, with a C2 to C2o, preferably C2 to C,4, aliphatic dicarboxylic acid or mono-or dinitriles thereof, such as sebacic acid, dodecanedioic acid, adipic acid, sebacic acid dinitrile, decane-1,10-dinitrile or adiponitrile, monomers or oligomers of a C~ to C2o, preferably CB to C,B, arylaliphatic diamine, such as m- or p-xylylenediamine, with a C6 to CZO, preferably C6 to C,o, aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as naphthalene-2,6-dicarboxylic acid, preferably isophthalic acid or terephthalic acid, monomers or oligomers of a C~ to C2o, preferably C8 to C,$, arylaliphatic diamine, such as m- or p-xylylenediamine, with a C9 to CZO, preferably C9 to C,B, arylaliphatic dicarboxylic acid or derivatives PF 5.524 CA 02525137 2005-11-08 thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid, and homopolymers, copolymers, blends and grafts of such starting monomers or starting oligomers.
The present invention further relates to a process for preparing such a polyamide and also to fibers, films and moldings comprising at least one such polyamide.
Polyamides, especially nylon-6 and nylon-6,6, are industrially important polymers. They are typically prepared from suitable monomers, such as caprolactam, adipic acid or hexamethylenediamine, which are reacted in the presence of water.
Polyamide polymers are typically shaped, for example into fibers, films or moldings.
Such fibers or textile entities manufactured therefrom, such as apparel or carpet, films or moldings are then typically dyed. This can be accomplished for example by means of dyebaths in the case of fibers or textile entities manufactured therefrom or by printing in the case of textile entities, films or moldings.
It is desirable for the polyamide to have a high rate of dyeing in order that a high rate of processing may be achieved.
It is an object of the present invention to provide a polyamide which has a higher rate of dyeing than prior art polyamides and also a process for preparing such a polyamide.
We have found that this object is achieved by the polyamide defined at the beginning, a process for preparing it and also fibers, films and moldings comprising at least one such polyamide.
Polyamides are herein to be understood as being homopolymers, copolymers, blends and grafts of synthetic long-chain polyamides having recurring amide groups in the polymer main chain as an essential constituent. Examples of such poiyamides are nylon-6 (polycaprolactam), nylon-6,6 (polyhexamethyleneadipamide), nylon-4,6 (polytetramethyleneadipamide), nylon-6,10 (polyhexamethylenesebacamide), nylon-(polyenantholactam), nylon-11 (poly- undecanolactam), nylon-12 (polydodecanolactam). As well as polyamides known by the generic name of nylon, PF 5.524 CA 02525137 2005-11-08 polyamides further include the aramids (aromatic polyamides), such as poly-meta-phenyleneisophthalamide (NOMEX~ fiber, US-A-3,287,324) or poly-para-phenyleneterephthalamide (KEVLAR~ fiber, US-A-3,671,542).
Polyamides can in principle be prepared by two methods.
fn a polymerization from dicarboxylic acids and diamines and also in a polymerization from amino acids or their derivatives, such as aminocarbonitrifes, aminocarboxamides, aminocarboxylate esters or aminocarboxylate salts, the amino and carboxyl end groups of the starting monomers or starting oligomers react with one another to form an amide group and water. The water can subsequently be removed from the polymer. In a polymerization from aminocarboxamides, the amino and amide end groups of the starting monomers or starting oligomers react with one another to form an amide group and ammonia. The ammonia can subsequently be removed from the polymer. When aminocarboxylic esters are polymerized, the amino and ester end groups of the starting monomers or oligomers react with each other to form an amide group and alcohol. The alcohol can subsequently be removed from the polymer mass. In the polymerization of aminocarboxylic nitrites, the nitrite groups can first react with water to form amid or carboxyl groups and the resulting aminocarboxylic amides or acids reacted as described.
This polymerization reaction is customarily known as a polycondensation.
A polymerization from lactams as starting monomers or starting oligomers is customarily known as a polyaddition.
Such polyamides are obtainable by conventional processes, as described for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, lnterscience, New York, 1977, pages 424-467, especially pages 444-446, from monomers selected from the group consisting of lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylate salts, omega-aminocarboxylate esters, equimolar mixtures of diamines and dicarboxylic acids, dicarboxylic acidldiamine salts, dinitriles and diamines or mixtures thereof.
Useful monomers include monomers or oligomers of a C2 to C2o, preferably C2 to C,B, arylaiiphatic or, preferably, aliphatic lactam such as enantholactam, undecanolactam, dodecanolactam or caprolactam, monomers or oligomers of CZ to C2o, preferably C3 to C,B, aminocarboxylic acids such as 6-aminocaproic acid or 11-aminoundecanoic acid, and salts thereof such as alkali metal salts, for example lithium, sodium or potassium salts, monomers or oligomers of Cz to C2o, preferably C3 to C,B, aminocarbonitriles such as 6-aminocapronitrile or 11-aminoundecanonitrile, monomers or oligomers of C2 to CZO amino acid amides such as 6-aminocapronamide or 11-aminoundecanomide, esters, preferably C,-CQ alkyl esters, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl esters, of CZ to C2o, preferably C3 to C,B, aminocarboxylic acids, such as 6-aminocaproic acid esters, for example methyl 6-aminocaproate, or 11-aminoundecanoic acid esters, for example methyl 11-aminoundecanoate, monomers or oligomers of a Cz to C2a, preferably C2 to C,2, alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine, with a CZ to CZO, preferably CZ to C,4, aliphatic dicarboxylic acid or mono-or dinitriles thereof, such as sebacic acid, dodecanedioic acid, adipic acid, sebacic acid dinitrile, decanoic acid 1,10-dinitriie or adiponitrile, monomers or oligomers of a Cz to C2o, preferably C2 to C~2, alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine, with a C8 to C2a, preferably Ca to C,Z, aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as naphthalene-2,6-dicarboxylic acid, preferably isophthalic acid or terephthalic acid, monomers or oligomers of a C2 to CZO, preferably CZ to C,2, alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine, with a C9 to C2o, preferably C9 to C,B, arylaliphatic dicarboxylic acid or derivatives PI' x4524 CA 02525137 2005-11-08 thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid, monomers or oligomers of a C6 to C2o, preferably C6 to C,o, aromatic diamine, such as m- or p-phenylenediamine, with a CZ to C2o, preferably CZ to C,4, aliphatic dicarboxylic acid or mono-or dinitriles thereof, such as sebacic acid, dodecanedioic acid, adipic acid, sebacic acid dinitrile, decane-1,10-dinitrile oradiponitrile, monomers or oligomers of a C6 to C2o, preferably C6 to C,o, aromatic diamine, such as m- or p-phenylenediamine, with a C8 to C2o, preferably CB to C,z, aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as naphthalene-2,6-dicarboxylic acid, preferably isophthalic acid or terephthalic acid, monomers or oligomers of a C6 to C2o, preferably C6 to C,o, aromatic diamine, such as m- or p-phenylenediamine, with a C9 to CZO, preferably C9 to C,B, arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid, monomers or oligomers of a C, to C2o, preferably CS to C,B, arylaliphatic diamine, such as m- or p-xylylenediamine, with a C2 to C2o, preferably C2 to C,4, aliphatic dicarboxylic acid or mono-or dinitriles thereof, such as sebacic acid, dodecanedioic acid, adipic acid, sebacic acid dinitrile, decane-1,10-dinitrile or adiponitrile, monomers or oligomers of a C~ to C2o, preferably CB to C,B, arylaliphatic diamine, such as m- or p-xylylenediamine, with a C6 to CZO, preferably C6 to C,o, aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as naphthalene-2,6-dicarboxylic acid, preferably isophthalic acid or terephthalic acid, monomers or oligomers of a C~ to C2o, preferably C8 to C,$, arylaliphatic diamine, such as m- or p-xylylenediamine, with a C9 to CZO, preferably C9 to C,B, arylaliphatic dicarboxylic acid or derivatives PF 5.524 CA 02525137 2005-11-08 thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid, and homopolymers, copolymers, blends and grafts of such starting monomers or starting oligomers.
Useful oligomers include, in particular, the dimers, trimers, tetramers, pentamers or hexamers of said monomers or of mixtures of such monomers.
In a preferred embodiment, the lactam used is caprolactam, the diamine used is tetramethylenediamine, hexamethylenediamine or their mixtures and the dicarboxylic acid used is adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof. Particular preference is given to the lactam being caprolactam, the diamine being hexamethylenediamine and the dicarboxylic acid being adipic acid or terephthalic acid or their mixtures.
Particular preference is given to those starting monomers or starting oligomers which on polymerization lead to the polyamides nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-6,12, nylon-7, nylon-11 or nylon-12 or the aramids poly-meta-phenyieneisophthalamide or poly-para-phenyleneterephthalamide, especially to nylon-6 or nylon-6,6.
In a preferred embodiment, the polyamides may be prepared using one or more chain regulators. Useful chain regulators advantageously include compounds having one or more, such as two, three or four, preferably two in the case of systems in the form of fibers, amino groups reactive in polyamide formation or one or more, such as two, three or four, preferably two in the case of systems in the form of fibers, carboxyl groups reactive in polyamide formation.
The first case provides polyamides wherein the monomers and chain regulators used for preparing said polyamide have a higher number of amino groups, or their equivalents, used for forming said polymer chain than carboxylic acid groups, or their equivalents, used for forming said polymer chain.
The second case provides polyamides wherein the monomers and chain regulators used for preparing said polyamide have a higher number of carboxylic acid groups, or their equivalents, used for forming said polymer chain than amino groups, or their equivalents, used for forming said polymer chain.
Useful chain regulators advantageously include monocarboxyfic acids, such as alkanecarboxylic acids, for example acetic acid, propionic acid, such as benzene- or naphthalene-monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C4-C,o-alkanedicarboxylic acid, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, CS-C8-cycloalkanedicarboxylic acids, for example cyclohexane-1,4-dicarboxylic acid, benzene- or naphthalenedicarboxylic acid, for example terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, Cz to CZO, preferably C2 to C,2, alkylamines, such as cyclohexylamine, C6 to C2o, preferably C6 to C,o, aromatic monoamines, such as aniline, or C7 to C2p, preferably C8 to C,a, arylaliphatic monoamines, such as benzylamine, diamines, such as C4-C,o-alkanediamines, for example hexamethylenediamine.
The chain regulators rnay be unsubstituted or substituted, for example by aliphatic groups, preferably C,-C8-alkyl groups, such as methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, s-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, OH, =O, C,-C8-alkoxy, COOH, CZ-C6-carbalkoxy, C,-C,o-acyloxy, or C,-C8-alkylamino, sulfonic acid or salts thereof, such as alkali or alkaline earth metal salts, cyano or halogens, such as fluorine, chlorine, bromine. Examples of substituted chain regulators are sulfoisophthalic acid and alkali or alkaline earth metal salts thereof, such as lithium, sodium or potassium salts, sulfoisophthalic esters, for example with C,-C,6-alkanols, or sulfoisophthalic acid mono- or diamides, especially with monomers suitable for forming polyamides and bearing at least one amino group, such as hexamethylenediamine or 6-aminocaproic acid.
Preferred chain regulators are sterically hindered piperidine derivatives of the formula Rz R' IV-R3 R2~R2 where R' is a functional group capable of amide formation with the polymer chain of the polyamide, preferably a group -(NH)R5, in which R5 is hydrogen or C,-CE alkyl, or a carboxyl group, or a carboxyl derivative, or a group -(CHZ)X(NH)R5, in which x is 1 to 6 and R5 is hydrogen or C,-C8 alkyl, or a group -(CHZ)yCOOH, in which y is 1 to 6, or a -(CH2)YCOOH acid derivative, in which y is 1 to 6, especially a group -NH2, RZ is an alkyl group, preferably a C,-C4 alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, especially a methyl group, R3 is hydrogen, C,-C4 alkyl or O-R4, in which R4 is hydrogen or C,-C~ alkyl, R3 being hydrogen in particular.
In such compounds, steric hindrance usually prevents the tertiary amino groups, and especially the secondary amino groups, of the piperidine ring systems from reacting.
A particularly preferred sterically hindered piperidine derivative is 4-amino-2,2,6,6-tetramethylpiperidine.
A chain regulator may advantageously be used in amounts of not less than 0.001 mol%, preferably not less than 0.01 mol%, especially not less than 0.03 mol%
and more preferably not less than 0.08 mol%, based on 1 mot of acid amide groups of the polyamide.
A chain regulator may advantageously be used in amounts of not more than 2.0 mol%, preferably not more than 1 mol%, especially not more than 0.6 mol%, and more preferably not more than 0.5 mol%, based on 1 mol of acid amide groups of the polyamide.
In accordance with the present invention, the main chain of the polyamide contains a chemically bound amine selected from the group consisting of 2-methyl-1,5-diamino-pentane and 1-amino-2-R-cyclopent-1-ene, where R is a functions! group capable of combining with an amino group to form an amide group.
~F ~4r~~4 CA 02525137 2005-11-08 Whenever the present invention refers to the amine mentioned, the term shall comprehend not only such an amine but also a mixture of such amines.
2-Methyl-1,5-diaminopentane and processes for preparing this compound are known.
For instance, 2-methyl-1,5-diaminopentane may be obtained by hydrogenation of 2-methylglutaronitrile, which in turn is by-produced in appreciable amounts in industrial adiponitrile synthesis by double hydrocyanation of butadiene.
According to the present invention, R in the amine 1-amino-2-R-cyclopent-1-ene is a functional group capable of combining with an amino group to form an amide group.
Advantageously, R is a functional group selected from the group consisting of carboxylic acid (COOH), carboxylic ester, carboxylic amide and nitrite (CN), especially nitrite, or mixtures thereof.
When R represents a carboxylic ester, such as an ester of an aromatic and preferably aliphatic alcohol, especially C, to C,6 alcohol, it is a particularly preferred embodiment for R to be able to represent a carboxylic ester selected from the group consisting of methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, s-butyl ester, i-butyl ester and t-butyl ester or mixtures thereof, especially methyl ester.
When R represents carboxylic amide, the carboxylic amide may be unsubstituted and thus R may represent the group CONH2, or be substituted by one or two aromatic and preferably aliphatic radicals, especially C, to C,6 radicals, more preferably selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl or mixtures thereof, especially methyl, such as N-methylamide or N,N-dimethylamide.
The preparation of amine 1-amino-2-R-cyclopent-1-ene having the designated meanings for R is known per se. For instance, 1-amino-2-cyanocyclopent-1-ene may be obtained by internal cyclization of adiponitrile. The other suitable compounds may be obtained for example by converting the cyano group in 1-amino-2-cyanocyclopent-1-ene by conventional methods, as by partial or complete hydrolysis of the cyano group.
The level of amine selected from group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, may advantageously be not less than 0.001 mot%, preferably not less than 0.01 mot%, especially not less than 0.03 mol%
and more preferably not less than 0.08 mot%, based on 1 mot of acid amide groups of the pofyamide.
I-'~~' ~4~,~C4 CA 02525137 2005-11-08 The level of arnine selected from group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyciopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, may advantageously be not more than 2.0 mol%, preferably not more than 1 mol%, especially not more than 0.6 mol%
and more preferably not more than 0.5 mol%, based on 1 mol of acid amide groups of the polyamide.
The polyamides of the present invention are obtainable in a process which comprises converting monomers, oligomers or mixtures thereof suitable for forming a polyamide into a polyamide in the presence of an amine selected from the group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group.
The polyamides of the present invention may be prepared using the process conditions customary for preparing polyamides from the corresponding monomers, as described for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196, DE-A-19 709 390, DE-A-35 34 817, WO 99/38908, WO 99/43734, WO 99/43732, WO 00/24808, WO 01/56984 or in Polymerization Processes, Interscience, New York, 1977, pages 424-467, especially pages 444-446.
In a preferred embodiment, the polymerization or polycondensation of the process according to the present invention may be carried out in the presence of at least one pigment. Preferred pigments are titanium dioxide, preferably in the anatase or rutile crystal form, or inorganic or organic colored compounds. The pigments are preferably added in an amount from 0 to 5 parts by weight and especially from 0.02 to 2 parts by weight, based in each case on 100 parts by weight of polyamide. The pigments may be added to the reactor with the starting materials or separately therefrom.
Furthermore, the polyamides may be prepared not only by the two, preferred processes mentioned but also by anionic polymerization.
An anionic polymerization process typically comprises reacting a) a lactam or a mixture of lactams, b) a lactamate or a compound which releases a lactamate from a lactam as per a), or mixtures of such components, and P~ 'rJ~~~4 CA 02525137 2005-11-08 c) a polymerization-regulating activator mixed with one another to obtain a polyamide.
Processes for anionic polymerization of lactams, also known as alkaline polymerization 5 of lactams, and also suitable compounds a), b) and c) are general common knowledge, for example from 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 or Fourne, Synthetische Fasern, Carl Hanser Verlag, Munich/Vienna, 1995, pages 38-39.
The polyamides of the present invention may advantageously be used for producing fibers, films and moldings comprising such a polyamide or, more specifically, consisting of such a polyamide.
Examples The solution viscosity reported in the examples was measured as a relative solution viscosity in 96% sulfuric acid as per DIN 51562-1 to -4.
Specifically, 1 g of polymer was weighed out per 100 ml of solution and the flow time was measured in a Ubbelohde viscometer against the pure solvent.
Inventive example 1 In a pressure vessel, 500 kg (4 419 mol) of caprolactam, 50 kg of completely ion-free water and 1 046 g (9 mol) of 2-methyl-1,5-diaminopentane were heated under nitrogen to an internal temperature of 270°C, immediately thereafter let down to atmospheric over an hour, supplementarily condensed for 60 minutes and discharged. The discharged polyamide was extracted, dried and heat-treated in the solid state to a relative solution viscosity of RV = 2.70.
Comparative example 1 Inventive example 1 was repeated except that 1 046 g (9 mol) of hexamethylene-diamine were added instead of 2-methyl-1,5-diaminopentane. The solution viscosity after heat treatment was RV = 2.71.
Inventive example 2 inventive example 1 was repeated except that 973 g (9 mol) of 1-amino-2-cyanocyclopent-1-ene were added instead of 2-methyl-1,5-diaminopentane. The solution viscosity after heat treatment was RV = 2.69.
Comparative example 2 Inventive example 1 was repeated except that 1 081 g (9 mol) of 6-aminocaproic acid were added instead of 2-methyl-1,5-diaminopentane. The solution viscosity after heat treatment was RV = 2.70.
Example 3 The polymers from inventive examples 1 and 2 and from comparative examples 1 and 2 were spun into standard 44 dtex 12 filament round profile yarn at 5 500 mlmin on an Inventa pilot spinning plant by the H4S process at identical machine settings.
The draw ratio was 1.40 : 1. The textile yarns thus produced were each then processed on a Lawson Hemphill FAK 3.5 circular knitting machine into a knit tube having the same yarn weight. The knit tube specimens of inventive example 1 and comparative example 1 and also of inventive example 2 and comparative example 2 were then each dyed jointly in a single dyebath with a commercially available metallized dye (0.3% of Acidol black MSRL, liquor ratio 20 : 1, 1.0% of Uniperol AC, pH 7, starting temperature 40°C, heating to 98°C at 1.5°/min, 60 min at 98°C, rinsing with warm water, drying).
The relative depth of shade (color intensity) of the two knits was subsequently determined using an Optronic Colorflash C22S spectrophotometer by the Kubelka-Munk method in line with DIN 53234 "Determination of relative color intensityn.
Tab. 1: Relative color intensity of yarns [%] after competitive dyeing Inventive Comparative Inventive Comparative example example 1 example 2 example 2 250 100 * 260 100 Table 1 reveals that yarns produced from polyamides of inventive examples 1 and 2 are dyed distinctly deeper in a competitive dyeing with yarns of the polyamides from the respective comparative examples 1 and 2.
To achieve a predetermined depth of shade on yarns, yarns from polyamides as per inventive examples 1 and 2 accordingly need shorter residence times in dyebaths by virtue of their higher rate of dyeing than yarns from polyamides as per the prior art.
Thus, higher processing speeds are achievable when dyeing yarns from polyamides as t~l' 54.~~4 CA 02525137 2005-11-08 'i 2 per inventive examples 1 and 2 than for yarns from poiyamides as per the prior art. It was an object of the present invention to provide a polyamide which has a higher rate of dyeing than prior art polyamides and also a process for preparing such a polyamide.
In a preferred embodiment, the lactam used is caprolactam, the diamine used is tetramethylenediamine, hexamethylenediamine or their mixtures and the dicarboxylic acid used is adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof. Particular preference is given to the lactam being caprolactam, the diamine being hexamethylenediamine and the dicarboxylic acid being adipic acid or terephthalic acid or their mixtures.
Particular preference is given to those starting monomers or starting oligomers which on polymerization lead to the polyamides nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-6,12, nylon-7, nylon-11 or nylon-12 or the aramids poly-meta-phenyieneisophthalamide or poly-para-phenyleneterephthalamide, especially to nylon-6 or nylon-6,6.
In a preferred embodiment, the polyamides may be prepared using one or more chain regulators. Useful chain regulators advantageously include compounds having one or more, such as two, three or four, preferably two in the case of systems in the form of fibers, amino groups reactive in polyamide formation or one or more, such as two, three or four, preferably two in the case of systems in the form of fibers, carboxyl groups reactive in polyamide formation.
The first case provides polyamides wherein the monomers and chain regulators used for preparing said polyamide have a higher number of amino groups, or their equivalents, used for forming said polymer chain than carboxylic acid groups, or their equivalents, used for forming said polymer chain.
The second case provides polyamides wherein the monomers and chain regulators used for preparing said polyamide have a higher number of carboxylic acid groups, or their equivalents, used for forming said polymer chain than amino groups, or their equivalents, used for forming said polymer chain.
Useful chain regulators advantageously include monocarboxyfic acids, such as alkanecarboxylic acids, for example acetic acid, propionic acid, such as benzene- or naphthalene-monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C4-C,o-alkanedicarboxylic acid, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, CS-C8-cycloalkanedicarboxylic acids, for example cyclohexane-1,4-dicarboxylic acid, benzene- or naphthalenedicarboxylic acid, for example terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, Cz to CZO, preferably C2 to C,2, alkylamines, such as cyclohexylamine, C6 to C2o, preferably C6 to C,o, aromatic monoamines, such as aniline, or C7 to C2p, preferably C8 to C,a, arylaliphatic monoamines, such as benzylamine, diamines, such as C4-C,o-alkanediamines, for example hexamethylenediamine.
The chain regulators rnay be unsubstituted or substituted, for example by aliphatic groups, preferably C,-C8-alkyl groups, such as methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, s-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, OH, =O, C,-C8-alkoxy, COOH, CZ-C6-carbalkoxy, C,-C,o-acyloxy, or C,-C8-alkylamino, sulfonic acid or salts thereof, such as alkali or alkaline earth metal salts, cyano or halogens, such as fluorine, chlorine, bromine. Examples of substituted chain regulators are sulfoisophthalic acid and alkali or alkaline earth metal salts thereof, such as lithium, sodium or potassium salts, sulfoisophthalic esters, for example with C,-C,6-alkanols, or sulfoisophthalic acid mono- or diamides, especially with monomers suitable for forming polyamides and bearing at least one amino group, such as hexamethylenediamine or 6-aminocaproic acid.
Preferred chain regulators are sterically hindered piperidine derivatives of the formula Rz R' IV-R3 R2~R2 where R' is a functional group capable of amide formation with the polymer chain of the polyamide, preferably a group -(NH)R5, in which R5 is hydrogen or C,-CE alkyl, or a carboxyl group, or a carboxyl derivative, or a group -(CHZ)X(NH)R5, in which x is 1 to 6 and R5 is hydrogen or C,-C8 alkyl, or a group -(CHZ)yCOOH, in which y is 1 to 6, or a -(CH2)YCOOH acid derivative, in which y is 1 to 6, especially a group -NH2, RZ is an alkyl group, preferably a C,-C4 alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, especially a methyl group, R3 is hydrogen, C,-C4 alkyl or O-R4, in which R4 is hydrogen or C,-C~ alkyl, R3 being hydrogen in particular.
In such compounds, steric hindrance usually prevents the tertiary amino groups, and especially the secondary amino groups, of the piperidine ring systems from reacting.
A particularly preferred sterically hindered piperidine derivative is 4-amino-2,2,6,6-tetramethylpiperidine.
A chain regulator may advantageously be used in amounts of not less than 0.001 mol%, preferably not less than 0.01 mol%, especially not less than 0.03 mol%
and more preferably not less than 0.08 mol%, based on 1 mot of acid amide groups of the polyamide.
A chain regulator may advantageously be used in amounts of not more than 2.0 mol%, preferably not more than 1 mol%, especially not more than 0.6 mol%, and more preferably not more than 0.5 mol%, based on 1 mol of acid amide groups of the polyamide.
In accordance with the present invention, the main chain of the polyamide contains a chemically bound amine selected from the group consisting of 2-methyl-1,5-diamino-pentane and 1-amino-2-R-cyclopent-1-ene, where R is a functions! group capable of combining with an amino group to form an amide group.
~F ~4r~~4 CA 02525137 2005-11-08 Whenever the present invention refers to the amine mentioned, the term shall comprehend not only such an amine but also a mixture of such amines.
2-Methyl-1,5-diaminopentane and processes for preparing this compound are known.
For instance, 2-methyl-1,5-diaminopentane may be obtained by hydrogenation of 2-methylglutaronitrile, which in turn is by-produced in appreciable amounts in industrial adiponitrile synthesis by double hydrocyanation of butadiene.
According to the present invention, R in the amine 1-amino-2-R-cyclopent-1-ene is a functional group capable of combining with an amino group to form an amide group.
Advantageously, R is a functional group selected from the group consisting of carboxylic acid (COOH), carboxylic ester, carboxylic amide and nitrite (CN), especially nitrite, or mixtures thereof.
When R represents a carboxylic ester, such as an ester of an aromatic and preferably aliphatic alcohol, especially C, to C,6 alcohol, it is a particularly preferred embodiment for R to be able to represent a carboxylic ester selected from the group consisting of methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, s-butyl ester, i-butyl ester and t-butyl ester or mixtures thereof, especially methyl ester.
When R represents carboxylic amide, the carboxylic amide may be unsubstituted and thus R may represent the group CONH2, or be substituted by one or two aromatic and preferably aliphatic radicals, especially C, to C,6 radicals, more preferably selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl or mixtures thereof, especially methyl, such as N-methylamide or N,N-dimethylamide.
The preparation of amine 1-amino-2-R-cyclopent-1-ene having the designated meanings for R is known per se. For instance, 1-amino-2-cyanocyclopent-1-ene may be obtained by internal cyclization of adiponitrile. The other suitable compounds may be obtained for example by converting the cyano group in 1-amino-2-cyanocyclopent-1-ene by conventional methods, as by partial or complete hydrolysis of the cyano group.
The level of amine selected from group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, may advantageously be not less than 0.001 mot%, preferably not less than 0.01 mot%, especially not less than 0.03 mol%
and more preferably not less than 0.08 mot%, based on 1 mot of acid amide groups of the pofyamide.
I-'~~' ~4~,~C4 CA 02525137 2005-11-08 The level of arnine selected from group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyciopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, may advantageously be not more than 2.0 mol%, preferably not more than 1 mol%, especially not more than 0.6 mol%
and more preferably not more than 0.5 mol%, based on 1 mol of acid amide groups of the polyamide.
The polyamides of the present invention are obtainable in a process which comprises converting monomers, oligomers or mixtures thereof suitable for forming a polyamide into a polyamide in the presence of an amine selected from the group consisting of 2-methyl-1,5-diaminopentane and 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group.
The polyamides of the present invention may be prepared using the process conditions customary for preparing polyamides from the corresponding monomers, as described for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196, DE-A-19 709 390, DE-A-35 34 817, WO 99/38908, WO 99/43734, WO 99/43732, WO 00/24808, WO 01/56984 or in Polymerization Processes, Interscience, New York, 1977, pages 424-467, especially pages 444-446.
In a preferred embodiment, the polymerization or polycondensation of the process according to the present invention may be carried out in the presence of at least one pigment. Preferred pigments are titanium dioxide, preferably in the anatase or rutile crystal form, or inorganic or organic colored compounds. The pigments are preferably added in an amount from 0 to 5 parts by weight and especially from 0.02 to 2 parts by weight, based in each case on 100 parts by weight of polyamide. The pigments may be added to the reactor with the starting materials or separately therefrom.
Furthermore, the polyamides may be prepared not only by the two, preferred processes mentioned but also by anionic polymerization.
An anionic polymerization process typically comprises reacting a) a lactam or a mixture of lactams, b) a lactamate or a compound which releases a lactamate from a lactam as per a), or mixtures of such components, and P~ 'rJ~~~4 CA 02525137 2005-11-08 c) a polymerization-regulating activator mixed with one another to obtain a polyamide.
Processes for anionic polymerization of lactams, also known as alkaline polymerization 5 of lactams, and also suitable compounds a), b) and c) are general common knowledge, for example from 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 or Fourne, Synthetische Fasern, Carl Hanser Verlag, Munich/Vienna, 1995, pages 38-39.
The polyamides of the present invention may advantageously be used for producing fibers, films and moldings comprising such a polyamide or, more specifically, consisting of such a polyamide.
Examples The solution viscosity reported in the examples was measured as a relative solution viscosity in 96% sulfuric acid as per DIN 51562-1 to -4.
Specifically, 1 g of polymer was weighed out per 100 ml of solution and the flow time was measured in a Ubbelohde viscometer against the pure solvent.
Inventive example 1 In a pressure vessel, 500 kg (4 419 mol) of caprolactam, 50 kg of completely ion-free water and 1 046 g (9 mol) of 2-methyl-1,5-diaminopentane were heated under nitrogen to an internal temperature of 270°C, immediately thereafter let down to atmospheric over an hour, supplementarily condensed for 60 minutes and discharged. The discharged polyamide was extracted, dried and heat-treated in the solid state to a relative solution viscosity of RV = 2.70.
Comparative example 1 Inventive example 1 was repeated except that 1 046 g (9 mol) of hexamethylene-diamine were added instead of 2-methyl-1,5-diaminopentane. The solution viscosity after heat treatment was RV = 2.71.
Inventive example 2 inventive example 1 was repeated except that 973 g (9 mol) of 1-amino-2-cyanocyclopent-1-ene were added instead of 2-methyl-1,5-diaminopentane. The solution viscosity after heat treatment was RV = 2.69.
Comparative example 2 Inventive example 1 was repeated except that 1 081 g (9 mol) of 6-aminocaproic acid were added instead of 2-methyl-1,5-diaminopentane. The solution viscosity after heat treatment was RV = 2.70.
Example 3 The polymers from inventive examples 1 and 2 and from comparative examples 1 and 2 were spun into standard 44 dtex 12 filament round profile yarn at 5 500 mlmin on an Inventa pilot spinning plant by the H4S process at identical machine settings.
The draw ratio was 1.40 : 1. The textile yarns thus produced were each then processed on a Lawson Hemphill FAK 3.5 circular knitting machine into a knit tube having the same yarn weight. The knit tube specimens of inventive example 1 and comparative example 1 and also of inventive example 2 and comparative example 2 were then each dyed jointly in a single dyebath with a commercially available metallized dye (0.3% of Acidol black MSRL, liquor ratio 20 : 1, 1.0% of Uniperol AC, pH 7, starting temperature 40°C, heating to 98°C at 1.5°/min, 60 min at 98°C, rinsing with warm water, drying).
The relative depth of shade (color intensity) of the two knits was subsequently determined using an Optronic Colorflash C22S spectrophotometer by the Kubelka-Munk method in line with DIN 53234 "Determination of relative color intensityn.
Tab. 1: Relative color intensity of yarns [%] after competitive dyeing Inventive Comparative Inventive Comparative example example 1 example 2 example 2 250 100 * 260 100 Table 1 reveals that yarns produced from polyamides of inventive examples 1 and 2 are dyed distinctly deeper in a competitive dyeing with yarns of the polyamides from the respective comparative examples 1 and 2.
To achieve a predetermined depth of shade on yarns, yarns from polyamides as per inventive examples 1 and 2 accordingly need shorter residence times in dyebaths by virtue of their higher rate of dyeing than yarns from polyamides as per the prior art.
Thus, higher processing speeds are achievable when dyeing yarns from polyamides as t~l' 54.~~4 CA 02525137 2005-11-08 'i 2 per inventive examples 1 and 2 than for yarns from poiyamides as per the prior art. It was an object of the present invention to provide a polyamide which has a higher rate of dyeing than prior art polyamides and also a process for preparing such a polyamide.
Claims (11)
1. A polyamide whose main chain comprises chemically bound 1-amino-2-R-cyclopent-1-ene is, where R is a functional group capable of combining with an amino group to form an amide group.
2. The polyamide according to claim 1 wherein R is selected from the group consisting of carboxylic acid, carboxylic ester, carboxylic amide and nitrile.
3. The polyamide according to claim 1 wherein R represents nitrile.
4. The polyamide according to claim 1 wherein R represents carboxylic acid.
5. The polyamide according to claim 1 wherein R represents carboxylic ester.
6. The polyamide according to claim 5 wherein R represents a carboxylic ester selected from the group consisting of methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, s-butyl ester, i-butyl ester and t-butyl ester.
7. The polyamide according to claim 1 wherein the main chain of said polyamide comprises chemically bound 2-methyl-1,5-diaminopentane.
8. The polyamide according to any of claims 1 to 7, wherein the main chain of said polyamide comprises chemically bound 1-amino-2-R-cyclopent-1-ene is, where R
is a functional group capable of combining with an amino group to form an amide group, at a level in the range from 0.001 mol% to 2 mol%, based on 1 mol of acid amide groups of said polyamide.
is a functional group capable of combining with an amino group to form an amide group, at a level in the range from 0.001 mol% to 2 mol%, based on 1 mol of acid amide groups of said polyamide.
9. A process for preparing a polyamide, which comprises converting monomers suitable for forming a polyamide into a polyamide in the presence of 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, according to any of claims 1 to 8.
10. A process for preparing a polyamide, which comprises converting oligomers suitable for forming a polyamide into a polyamide in the presence of 1-amino-2-R-cyclopent-1-ene, where R is a functional group capable of combining with an amino group to form an amide group, according to any of claims 1 to 8.
11. Fibers, films and moldings comprising a polyamide as per any of claims 1 to 8.
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DE10321788.6 | 2003-05-14 | ||
DE10321788A DE10321788A1 (en) | 2003-05-14 | 2003-05-14 | polyamides |
PCT/EP2004/004817 WO2004101648A1 (en) | 2003-05-14 | 2004-05-06 | Polyamides |
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EP (1) | EP1625173B1 (en) |
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CN (1) | CN100365042C (en) |
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WO2009010405A1 (en) | 2007-07-18 | 2009-01-22 | Basf Se | Laser-sensitive coating formulation |
WO2010049282A1 (en) | 2008-10-27 | 2010-05-06 | Basf Se | Coating composition for marking substrates |
EP2596047B1 (en) * | 2010-07-20 | 2014-06-25 | Basf Se | Polyamide shaped parts containing micro-encapsulated latent heat-storage material |
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GB1429776A (en) * | 1972-08-18 | 1976-03-24 | Ici Ltd | Purification of adiponitrile |
GB1452904A (en) * | 1973-04-24 | 1976-10-20 | Ici Ltd | Purification of adiponitrile |
EP0083907A1 (en) * | 1981-12-23 | 1983-07-20 | Ciba-Geigy Ag | Process for the preparation of pigmented or coloured compositions |
US4739035A (en) * | 1986-08-27 | 1988-04-19 | The Standard Oil Company | Two-step process for the manufacture of polyamide from diamine and dinitrile |
JPH06504304A (en) * | 1991-01-10 | 1994-05-19 | デユポン・カナダ・インコーポレーテツド | polyamide composition |
US5270437A (en) * | 1992-11-13 | 1993-12-14 | E. I. Du Pont De Nemours And Company | Process for making partially aromatic polyamides containing 2-methylpentamethylenediamine units |
JP3481951B2 (en) * | 1996-09-11 | 2003-12-22 | デュポン カナダ インコーポレイテッド | Dimensionally stable tubular plastic heat exchanger |
US6094816A (en) | 1996-09-11 | 2000-08-01 | E. I. Du Pont De Nemours And Company | Method of making a dimensionally stable tube type plastic heat exchangers |
SG76540A1 (en) * | 1997-03-13 | 2000-11-21 | Mitsui Chemicals Inc | Semiaromatic polyamide resin composition |
JP3453057B2 (en) * | 1997-03-13 | 2003-10-06 | 三井化学株式会社 | Semi-aromatic polyamide resin composition |
DE19809687A1 (en) * | 1998-03-06 | 1999-09-09 | Basf Ag | Hydrogenation catalyst |
DE19809688A1 (en) * | 1998-03-06 | 1999-09-09 | Basf Ag | Process for the preparation of aliphatic alpha-, omega-diamines |
DE19839346A1 (en) * | 1998-08-28 | 2000-03-02 | Basf Ag | Improved process for the production of hexamethylenediamine |
US6094817A (en) * | 1998-10-15 | 2000-08-01 | Acoust-A-Fiber Research And Development, Inc. | Method for filling a silencer with sound insulating material |
US6075117A (en) * | 1998-12-21 | 2000-06-13 | E.I. Dupont De Nemours & Company | Process for the hydrolysis of adiponitrile and the production of nylon 6,6 using dicarboxylic acids as the sole catalyst |
DE19923894A1 (en) * | 1999-05-25 | 2000-11-30 | Basf Ag | Process for the production of polyamides |
JP3589088B2 (en) * | 1999-05-27 | 2004-11-17 | 宇部興産株式会社 | Sequential biaxially stretched film |
DE10058292A1 (en) * | 2000-11-23 | 2002-05-29 | Basf Ag | polyamides |
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ATE370181T1 (en) | 2007-09-15 |
WO2004101648A1 (en) | 2004-11-25 |
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MXPA05010878A (en) | 2005-11-25 |
PL1625173T3 (en) | 2008-01-31 |
CN1788035A (en) | 2006-06-14 |
US20060223974A1 (en) | 2006-10-05 |
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MY144349A (en) | 2011-09-15 |
JP4566998B2 (en) | 2010-10-20 |
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