US20020037972A1 - Free-flowing transparent polyamide molding composition - Google Patents
Free-flowing transparent polyamide molding composition Download PDFInfo
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- US20020037972A1 US20020037972A1 US09/768,286 US76828601A US2002037972A1 US 20020037972 A1 US20020037972 A1 US 20020037972A1 US 76828601 A US76828601 A US 76828601A US 2002037972 A1 US2002037972 A1 US 2002037972A1
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- acid
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- molding composition
- graft copolymer
- polyamide
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 39
- 229920002647 polyamide Polymers 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000000465 moulding Methods 0.000 title claims abstract description 26
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 150000003951 lactams Chemical class 0.000 claims abstract description 8
- 150000007513 acids Chemical class 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 28
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 10
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 claims description 8
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 8
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 claims description 8
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 8
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 6
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 claims description 4
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 239000000412 dendrimer Substances 0.000 claims description 2
- 229920000736 dendritic polymer Polymers 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 8
- 229920006020 amorphous polyamide Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- -1 aliphatic diamines Chemical class 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 description 1
- 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 1
- RLEQVGMLDNITBW-UHFFFAOYSA-N 2,4,4-trimethylhexanedioic acid Chemical compound OC(=O)C(C)CC(C)(C)CC(O)=O RLEQVGMLDNITBW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WAXJSQREIWGYCB-UHFFFAOYSA-N 2-[4-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1CCC(CC(O)=O)CC1 WAXJSQREIWGYCB-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910003953 H3PO2 Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OTKFKCIRTBTDKK-UHFFFAOYSA-N [3-(aminomethyl)-5-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1C(CN)C2C(CN)CC1C2 OTKFKCIRTBTDKK-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the invention relates to free-flowing transparent polyamide molding compositions having substantially unimpaired mechanical properties.
- Transparent copolyamides are generally distinguished over other materials by good low-temperature impact strength and good chemical resistance; in addition, they have high light transparency together with an amorphous structure, which provides good shrinkage behavior. Such materials can be used to produce molded articles having superior properties.
- transparent polyamide compositions have a high melt viscosity, which makes processing them considerably more difficult than other types of molding compositions.
- thin-walled injection-molded articles can be produced from transparent copolyamides only with difficulty.
- Plastics can usually be rendered more free-flowing by lowering the number average molecular weight. However, this generally also results in a significant impairment of the mechanical properties. In the case of polyamides, the impact strength in particular is drastically reduced by lowering the number average molecular weight of the polymer below a critical value.
- CA-A 2,039,136 describes amorphous polyamides having improved flow behavior which are obtained by adding certain types of carbon black to the polyamides.
- DE-A 3728 334 describes the improvement in the flow of amorphous polyamides by addition of polyolefins grafted with maleic anhydride.
- A. Siegmann et al. (Polymer, 1985, 26(9), 1325-1330) were able to reduce the melt viscosity of amorphous polyamides by the addition of liquid crystalline polyesters. In all of these cases however, the additives destroy the transparency of the amorphous polyamides.
- U.S. Pat. No. 3,442,975 suggests that a polyethyleneimine-PA 6 graft copolymer can be used as flow aid for PA 6.
- this is a crystalline, opaque polyamide, and the mixture of polyethyleneimine-PA 6 graft copolymer with PA 6 is also opaque.
- the object of the present invention is to develop free-flowing transparent polyamide molding compositions which do not have the above-mentioned disadvantages of the prior art, and whose mechanical properties, in particular tensile strength, modulus of elasticity, flexural strength and impact strength, are only slightly impaired compared to the unmodified transparent polyamides. This is achieved by blending the transparent polyamide with a graft copolymer formed from a branched polyarnine and polyamide-forming monomers.
- the molding composition of the present invention comprises the following components:
- polyamide-forming monomers selected from lactams, ⁇ -aminocarboxylic acids and/or equivalent combinations of diamine and dicarboxylic acid,
- Transparent polyamides are known (Kunststoffhandbuch [Plastics Handbook] 3/4, Editors G. W. Becker and G. Braun, pp. 803 ff., Carl Hanser Verlag Kunststoff, Vienna, 1998). Transparent polyamides which are suitable for the purposes of the invention are also described, for example, in the following publications: U.S. Pat. No.
- the transparent polyamides used in accordance with the present invention which can also be in the form of copolyamides, are prepared, for example, from the following monomers:
- branched or unbranched aliphatic diamines having 6 to 14 carbon atoms for example, 1,6-hexamethylenediamine, 2-methyl-1,5-diaminopentane, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine or 1,12-dodecamethylenediamine;
- cycloaliphatic diamines having 6 to 22 carbon atoms for example, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylpropane, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,6-bis(aminomethyl)norbornane or 3-aminomethyl-3,5,5-trimethylcyclohexylamine;
- araliphatic diamines having 8 to 22 carbon atoms, for example, m- or p-xylylenediamine or bis(4-aminophenyl)propane;
- branched or unbranched aliphatic dicarboxylic acids having 6 to 22 carbon atoms for example, adipic acid, 2,2,4- or 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid or 1,12-dodecanedioic acid;
- cycloalipbatic dicarboxylic acids having 6 to 22 carbon atoms for example, cyclohexane-1,4-dicarboxylic acid, 4,4′-dicarboxydicyclohexylmethane, 3,3′-dimethyl-4,4′-dicarboxydicyclohexylmethane, 4,4′-dicarboxydicyclohexylpropane and 1,4-bis(carboxymethyl)cyclohexane;
- araliphatic dicarboxylic acids having 8 to 22 carbon atoms for example, 4,4′-diphenylmethanedicarboxylic acid;
- aromatic dicarboxylic acids having 8 to 22 carbon atoms, for example isophthalic acid, tributylisophthalic acid, terephthalic acid, 1,4-, 1,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenic acid or 4,4′-oxybis(benzoic acid),
- lactams having 6 to 12 carbon atoms or the corresponding aminocarboxylic acids such as, for example, 6-caprolactam, 6-aminocaproic acid, caprylolactam, ⁇ -aminocaprylic acid, -aminoundecanoic acid, laurolactam or ⁇ -aminododecanoic acid.
- transparent polyamides which can be used in accordance with the invention are as follows:
- polyamide made from isophthalic acid and 1,6-hexamethylenediamine
- copolyamide made from a mixture of terephthalic acid/isophthalic acid and 1,6-hexamethylenediamine
- copolyamide made from isophthalic acid, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and laurolactam or caprolactam,
- polyamide or copolyamide made from 1,12-dodecanedioic acid, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and, if desired, laurolactam or caprolactam,
- copolyamide made from isophthalic acid, 4,4′-diaminodicyclohexylmethane and laurolactam or caprolactam,
- polyamide made from 1,12-dodecanedioic acid and 4,4′-diaminodicyclohexylmethane,
- the copolyamide made from a terephthalic acid/isophthalic acid mixture, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and laurolactam.
- the branched polyamine can be, for example, any of the following classes of polyamines:
- dendrimers for example,
- branched polyethyleneimines which are obtainable by polymerization of aziridines (Houben-Weyl, Methoden der Organischen Chemie ⁇ Methods of Organic Chemistry ⁇ , Volume E20, pages 1482-1487, Georg Thieme Verlag Stuttgart, 1987) and which generally have the following amino group distribution:
- the polyamine has a number average molecular weight M n of at most 20,000 g/mol, particularly preferably of at most 10,000 g/mol and particularly preferably of at most 5000 g/mol.
- the polyamide-forming monomers employed can be any of the monomers mentioned above for the transparent polyamide, in particular lactams and/or ⁇ -aminocarboxylic acids. Particular preference is given to ⁇ -caprolactam, ⁇ -aminoundecanoic acid and/or laurolactam, the latter primarily if the transparent polyamide comprises a substantial proportion of copolymerized laurolactam. However, it is also possible to employ an equivalent combination of diamine and dicarboxylic acid, if desired, together with a lactam and/or an ⁇ -aminocarboxylic acid.
- the graft copolymer may be prepared with the additional use of an oligocarboxylic acid selected from 0.015 to about 3 mol % of dicarboxylic acid and 0.01 to about 1.2 mol % of tricarboxylic acid, in each case based on the sum of the moles of the other polyamide-forming monomers.
- an oligocarboxylic acid selected from 0.015 to about 3 mol % of dicarboxylic acid and 0.01 to about 1.2 mol % of tricarboxylic acid, in each case based on the sum of the moles of the other polyamide-forming monomers.
- each monomer in the combination of diamine and dicarboxylic acid is considered individually.
- the amount added to the graft copolymer is preferably from 0.03 to 2.2 mol %, particularly preferably from 0.05 to 1.5 mol %, very particularly preferably from 0.1 to 1 mol % and in particular from 0.15 to 0.65 mol %.
- the amount added to the graft copolymer is preferably from 0.02 to 0.9 mol %, particularly preferably from 0.025 to 0.6 mol %, very particularly preferably from 0.03 to 0.4 mol % and in particular from 0.04 to 0.25 mol %.
- the concomitant use of the oligocarboxylic acid significantly improves the solvent and hydrolysis resistance of the graft copolymer.
- the oligocarboxylic acid employed can be any desired di- or tricarboxylic acid having 6 to 24 carbon atoms, for example adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, trimesic acid and/or trimellitic acid.
- aliphatic, alicyclic, aromatic, aralkyl- and/or alkylaryl-substituted monocarboxylic acids having 3 to 50 carbon atoms such as, for example, lauric acid, unsaturated fatty acids, acrylic acid or benzoic acid, can be employed as a regulator.
- these regulators the concentration of amino groups can be reduced without changing the shape of the molecule.
- the graft copolymers according to the invention can be prepared by various processes.
- One possibility is to initially introduce the lactam or ⁇ -aminocarboxylic acid and polyamine together and to carry out the polymerization or polycondensation.
- the oligocarboxylic acid can be added either at the beginning or during the reaction.
- a preferred two-step process comprises first carrying out the lactam cleavage and prepolymerization in the presence of water (alternatively, the corresponding ⁇ -aminocarboxylic acids or diamines and dicarboxylic acids are employed and prepolymerized directly).
- the polyamine is added, while any oligocarboxylic acid used concomitantly is metered in before, during or after the prepolymerization.
- the mixture is then held under reduced pressure at temperatures of from 200 to 290° C. and polycondensed in a stream of nitrogen or under reduced pressure.
- a further preferred process comprises the hydrolytic degradation of a polyamide to a prepolymer and the simultaneous or subsequent reaction with the polyamine. Preference is given to polyamides in which the end group difference is approximately zero or in which any oligocarboxylic acid used concomitantly has already been copolycondensed. However, the oligocarboxylic acid can also be added at the beginning or during the degradation reaction.
- this can be followed, in a further process step, by holding the graft copolymer thus formed under vacuum for a number of hours. Fir example, this step may last at least four hours, preferably at least six hours and particularly preferably at least eight hours at a temperature of from 200 to 290° C. After an induction period of several hours, an increase in the melt viscosity of the polymer is then observed, which is probably attributable to a reaction of amino end groups with one another, together with elimination of ammonia and the formation of crosslinks.
- the graft copolymer can also be post-condensed in the solid phase by conventional methods for polyamides.
- the transparent polyamide and the graft copolymer can be mixed with one another by any conventional method.
- the mixing may be carried out in the melt in a compounding unit.
- the molding composition according to the invention can also contain conventional auxiliaries and additives used in transparent polyamides, for example, flame retardants, stabilizers, plasticizers, glass fibers or other polymers which do not impair the transparency of the molding composition.
- the amount of all additives is in total a maximum of 40 parts by weight, preferably a maximum of 30 parts by weight and particularly preferably a maximum of 20 parts by weight.
- Moldings can be produced from the molding composition by any conventional method, for example by extrusion, blow molding, thermoforming and, in particular, injection molding.
- the molding composition according to the present invention is also excellently suited for the extrusion coating of any desired surface.
- Example 2 but with 90 parts by weight of the polyamide and 10 parts by weight of the graft copolymer. Here too, transparent test specimens were obtained.
- Table 1 shows that the mechanical properties of the molding compositions according to the invention are at the same level as those of the unmodified polyamide.
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Abstract
Description
- 1. Field of the Invention
- The invention relates to free-flowing transparent polyamide molding compositions having substantially unimpaired mechanical properties.
- 2. Discussion of the Background
- Transparent copolyamides are generally distinguished over other materials by good low-temperature impact strength and good chemical resistance; in addition, they have high light transparency together with an amorphous structure, which provides good shrinkage behavior. Such materials can be used to produce molded articles having superior properties. However, transparent polyamide compositions have a high melt viscosity, which makes processing them considerably more difficult than other types of molding compositions. For example, thin-walled injection-molded articles can be produced from transparent copolyamides only with difficulty.
- Plastics can usually be rendered more free-flowing by lowering the number average molecular weight. However, this generally also results in a significant impairment of the mechanical properties. In the case of polyamides, the impact strength in particular is drastically reduced by lowering the number average molecular weight of the polymer below a critical value.
- Another way of improving the flow behavior of plastics is to add so-called flow improvers. Low molecular weight additives are frequently employed for this purpose. In the case of transparent plastics, however, additives of this type frequently result in a loss in transparency or in the formation of deposits in the mold during processing.
- CA-A 2,039,136 describes amorphous polyamides having improved flow behavior which are obtained by adding certain types of carbon black to the polyamides. DE-A 3728 334 describes the improvement in the flow of amorphous polyamides by addition of polyolefins grafted with maleic anhydride. A. Siegmann et al. (Polymer, 1985, 26(9), 1325-1330) were able to reduce the melt viscosity of amorphous polyamides by the addition of liquid crystalline polyesters. In all of these cases however, the additives destroy the transparency of the amorphous polyamides.
- C. F. Frihart et al. (Plast. Copd. 1990, 13(3), 109-110) were able to reduce the melt viscosity of an amorphous polyamide by adding at least 1% by weight of an additional amorphous polyamide based on a dimeric fatty acid (C36-dicarboxylic acid). However, this procedure results in a significant reduction in the modulus of elasticity of the blend.
- U.S. Pat. No. 3,442,975 suggests that a polyethyleneimine-PA 6 graft copolymer can be used as flow aid for PA 6. However, this is a crystalline, opaque polyamide, and the mixture of polyethyleneimine-PA 6 graft copolymer with PA 6 is also opaque.
- The object of the present invention is to develop free-flowing transparent polyamide molding compositions which do not have the above-mentioned disadvantages of the prior art, and whose mechanical properties, in particular tensile strength, modulus of elasticity, flexural strength and impact strength, are only slightly impaired compared to the unmodified transparent polyamides. This is achieved by blending the transparent polyamide with a graft copolymer formed from a branched polyarnine and polyamide-forming monomers.
- The molding composition of the present invention comprises the following components:
- I) from 50 to 99 parts by weight, preferably from 75 to 98 parts by weight and particularly preferably from 85 to 97 parts by weight, of a transparent polyamide, and
- II) from 1 to 50 parts by weight, preferably from 2 to 25 parts by weight and particularly preferably from 3 to 15 parts by weight, of a graft copolymer prepared from the following monomers:
- a) from 0.5 to 25% by weight, preferably from 1 to 20% by weight and particularly preferably from 1.5 to 16% by weight, based on the graft copolymer, of a branched polyamine having at least 4, preferably at least 8 and particularly preferably at least 11 nitrogen atoms and having a number average molecular weight Mn of at least 146 g/mol and preferably of at least 500 g/mol, and
- b) polyamide-forming monomers selected from lactams, ω-aminocarboxylic acids and/or equivalent combinations of diamine and dicarboxylic acid,
- where the sum of the parts by weight of I) and II) is 100.
- Transparent polyamides are known (Kunststoffhandbuch [Plastics Handbook] 3/4, Editors G. W. Becker and G. Braun, pp. 803 ff., Carl Hanser Verlag Munich, Vienna, 1998). Transparent polyamides which are suitable for the purposes of the invention are also described, for example, in the following publications: U.S. Pat. No. 2,742,496, CH-B-480 381, CH-B-679 861, DE-A-22 25 938, DE-A-26 42 244, DE-A-27 43 515, DE-A-29 36 759, DE-A-27 32 928, DE-A-43 10 970, EP-A-0 053 876, EP-A-0 271 308, EP-A-0 313 436, EP-A-0 725 100 and EP-A-0 725 101.
- The transparent polyamides used in accordance with the present invention, which can also be in the form of copolyamides, are prepared, for example, from the following monomers:
- branched or unbranched aliphatic diamines having 6 to 14 carbon atoms, for example, 1,6-hexamethylenediamine, 2-methyl-1,5-diaminopentane, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine or 1,12-dodecamethylenediamine;
- cycloaliphatic diamines having 6 to 22 carbon atoms, for example, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylpropane, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,6-bis(aminomethyl)norbornane or 3-aminomethyl-3,5,5-trimethylcyclohexylamine;
- araliphatic diamines having 8 to 22 carbon atoms, for example, m- or p-xylylenediamine or bis(4-aminophenyl)propane;
- branched or unbranched aliphatic dicarboxylic acids having 6 to 22 carbon atoms, for example, adipic acid, 2,2,4- or 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid or 1,12-dodecanedioic acid;
- cycloalipbatic dicarboxylic acids having 6 to 22 carbon atoms, for example, cyclohexane-1,4-dicarboxylic acid, 4,4′-dicarboxydicyclohexylmethane, 3,3′-dimethyl-4,4′-dicarboxydicyclohexylmethane, 4,4′-dicarboxydicyclohexylpropane and 1,4-bis(carboxymethyl)cyclohexane;
- araliphatic dicarboxylic acids having 8 to 22 carbon atoms, for example, 4,4′-diphenylmethanedicarboxylic acid;
- aromatic dicarboxylic acids having 8 to 22 carbon atoms, for example isophthalic acid, tributylisophthalic acid, terephthalic acid, 1,4-, 1,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenic acid or 4,4′-oxybis(benzoic acid),
- lactams having 6 to 12 carbon atoms or the corresponding aminocarboxylic acids, such as, for example, 6-caprolactam, 6-aminocaproic acid, caprylolactam, ω-aminocaprylic acid, -aminoundecanoic acid, laurolactam or ω-aminododecanoic acid.
- Examples of transparent polyamides which can be used in accordance with the invention are as follows:
- the copolyamide made from terephthalic acid and the isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine,
- the polyamide made from isophthalic acid and 1,6-hexamethylenediamine,
- the copolyamide made from a mixture of terephthalic acid/isophthalic acid and 1,6-hexamethylenediamine,
- the copolyamide made from isophthalic acid, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and laurolactam or caprolactam,
- the polyamide or copolyamide made from 1,12-dodecanedioic acid, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and, if desired, laurolactam or caprolactam,
- the copolyamide made from isophthalic acid, 4,4′-diaminodicyclohexylmethane and laurolactam or caprolactam,
- the polyamide made from 1,12-dodecanedioic acid and 4,4′-diaminodicyclohexylmethane,
- the copolyamide made from a terephthalic acid/isophthalic acid mixture, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and laurolactam.
- The branched polyamine can be, for example, any of the following classes of polyamines:
- dendrimers, for example,
- ((H2N—(CH2)3)2N—(CH2)3)2—N(CH2)2-N((CH2)2-N((CH2)3-NH2)2)2 (DE-A-196 54179) or tris(2-aminoethyl)amine, N, N-bis(2-aminoethyl)-N,N′-bis{2-{bis(2-aminoethyl)amino}ethyl}-1,2-ethanediamine or
- 3,15-bis(2-aminoethyl)-6,12-bis{2-{bis{2-aminoethyl)amino}ethyl}-9-{2{bis{2-bis(2-aminoethyl)amino}ethyl}amino}ethyl}-3,6,9,12,15-pentaazaheptadecane-1,17-diamine (J. M. Warakomski, Chem. Mat. 1992, 4, 1000-1004);
- branched polyethyleneimines, which are obtainable by polymerization of aziridines (Houben-Weyl, Methoden der Organischen Chemie {Methods of Organic Chemistry}, Volume E20, pages 1482-1487, Georg Thieme Verlag Stuttgart, 1987) and which generally have the following amino group distribution:
- from 25 to 46% of primary amino groups,
- from 30 to 45% of secondary amino groups and
- from 16 to 40% of tertiary amino groups.
- In the preferred case, the polyamine has a number average molecular weight Mn of at most 20,000 g/mol, particularly preferably of at most 10,000 g/mol and particularly preferably of at most 5000 g/mol.
- The polyamide-forming monomers employed can be any of the monomers mentioned above for the transparent polyamide, in particular lactams and/or ω-aminocarboxylic acids. Particular preference is given to ε-caprolactam, ω-aminoundecanoic acid and/or laurolactam, the latter primarily if the transparent polyamide comprises a substantial proportion of copolymerized laurolactam. However, it is also possible to employ an equivalent combination of diamine and dicarboxylic acid, if desired, together with a lactam and/or an ω-aminocarboxylic acid.
- In one possible embodiment, the graft copolymer may be prepared with the additional use of an oligocarboxylic acid selected from 0.015 to about 3 mol % of dicarboxylic acid and 0.01 to about 1.2 mol % of tricarboxylic acid, in each case based on the sum of the moles of the other polyamide-forming monomers. In this connection, each monomer in the combination of diamine and dicarboxylic acid is considered individually.
- If a dicarboxylic acid is used, the amount added to the graft copolymer is preferably from 0.03 to 2.2 mol %, particularly preferably from 0.05 to 1.5 mol %, very particularly preferably from 0.1 to 1 mol % and in particular from 0.15 to 0.65 mol %. If a tricarboxylic acid is used, the amount added to the graft copolymer is preferably from 0.02 to 0.9 mol %, particularly preferably from 0.025 to 0.6 mol %, very particularly preferably from 0.03 to 0.4 mol % and in particular from 0.04 to 0.25 mol %. The concomitant use of the oligocarboxylic acid significantly improves the solvent and hydrolysis resistance of the graft copolymer.
- The oligocarboxylic acid employed can be any desired di- or tricarboxylic acid having 6 to 24 carbon atoms, for example adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, trimesic acid and/or trimellitic acid.
- In addition, if desired, aliphatic, alicyclic, aromatic, aralkyl- and/or alkylaryl-substituted monocarboxylic acids having 3 to 50 carbon atoms, such as, for example, lauric acid, unsaturated fatty acids, acrylic acid or benzoic acid, can be employed as a regulator. By means of these regulators, the concentration of amino groups can be reduced without changing the shape of the molecule.
- The graft copolymers according to the invention can be prepared by various processes. One possibility is to initially introduce the lactam or ω-aminocarboxylic acid and polyamine together and to carry out the polymerization or polycondensation. The oligocarboxylic acid can be added either at the beginning or during the reaction. However, a preferred two-step process comprises first carrying out the lactam cleavage and prepolymerization in the presence of water (alternatively, the corresponding ω-aminocarboxylic acids or diamines and dicarboxylic acids are employed and prepolymerized directly). In the second step, the polyamine is added, while any oligocarboxylic acid used concomitantly is metered in before, during or after the prepolymerization. The mixture is then held under reduced pressure at temperatures of from 200 to 290° C. and polycondensed in a stream of nitrogen or under reduced pressure.
- A further preferred process comprises the hydrolytic degradation of a polyamide to a prepolymer and the simultaneous or subsequent reaction with the polyamine. Preference is given to polyamides in which the end group difference is approximately zero or in which any oligocarboxylic acid used concomitantly has already been copolycondensed. However, the oligocarboxylic acid can also be added at the beginning or during the degradation reaction.
- These processes allow the preparation of ultra-highly branched polyamides having acid numbers of less than 40 mmol/kg, preferably less than 20 mmol/kg and particularly preferably less than 10 mmol/kg. After a reaction time of only from one to five hours at temperatures of from 200° C. to 290° C., approximately complete conversion is achieved.
- If desired, this can be followed, in a further process step, by holding the graft copolymer thus formed under vacuum for a number of hours. Fir example, this step may last at least four hours, preferably at least six hours and particularly preferably at least eight hours at a temperature of from 200 to 290° C. After an induction period of several hours, an increase in the melt viscosity of the polymer is then observed, which is probably attributable to a reaction of amino end groups with one another, together with elimination of ammonia and the formation of crosslinks.
- If it is not desired to continue the reaction to completion in the melt, the graft copolymer can also be post-condensed in the solid phase by conventional methods for polyamides.
- The transparent polyamide and the graft copolymer can be mixed with one another by any conventional method. For example, the mixing may be carried out in the melt in a compounding unit.
- The molding composition according to the invention can also contain conventional auxiliaries and additives used in transparent polyamides, for example, flame retardants, stabilizers, plasticizers, glass fibers or other polymers which do not impair the transparency of the molding composition. The amount of all additives is in total a maximum of 40 parts by weight, preferably a maximum of 30 parts by weight and particularly preferably a maximum of 20 parts by weight.
- Moldings can be produced from the molding composition by any conventional method, for example by extrusion, blow molding, thermoforming and, in particular, injection molding. The molding composition according to the present invention is also excellently suited for the extrusion coating of any desired surface.
- Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.
- 56.58 kg of ε-caprolactam and 0.094 kg of dodecanedioic acid were melted at from 180 to 210° C. in a heated kettle and metered into a pressure-tight polycondensation reactor. 5% by weight of water and 57 ppm of H3PO2 were then added. The pressure imposed on the mixture was then reduced to a residual steam pressure of 3 bar over the course of 3 hours, and 5% by weight of polyethyleneimine (Lupasol G100, BASF AG, Ludwigshafen) were metered in. The polyethyleneimine was incorporated at the ambient pressure established under these conditions. The mixture was subsequently decompressed to atmospheric pressure, and the reaction was continued to completion over the course of 5 hours at 240° C. while nitrogen was passed over the mixture. The clear melt was discharged as an extrudate via a spinning wheel pump, cooled in a water bath and granulated. The graft copolymer thus formed had the following properties:
- ηrel: 1.23
- Melting point Tm: 209° C.
- The granules were opaque.
- 95 parts by weight of a transparent polyamide made from 50 mol % of terephthalic acid and 50 mol % of an isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine were mixed in the melt with 5 parts by weight of the graft copolymer prepared in Example 1, during which the material temperature was held within the range from 280° C. to 320° C. The product was extruded and granulated. Transparent standard test specimens were produced from the granules by injection molding. The results are shown in Table 1. For comparison, the table also contains the corresponding data for the unmodified polyamide, which was not mixed with a graft copolymer.
- As Example 2, but with 90 parts by weight of the polyamide and 10 parts by weight of the graft copolymer. Here too, transparent test specimens were obtained.
- Table 1 shows that the mechanical properties of the molding compositions according to the invention are at the same level as those of the unmodified polyamide.
- The priority document of the present application, German patent application 10002948.5 filed Jan. 25, 2000, is incorporated herein by reference.
- Obviously, numerous modifications and variations on the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
TABLE 1 Basic mechanical properties For comparison: transparent polyamide Property Method Unit Example 2 Example 3 employed Impact strength (CHARPY) ISO 179/IeU 23° C. kJ/m2 no break no break no break −30° C. kJ/m2 no break 4/10 no break no break −30° C. kJ/m2 no break no break no break Notched impact strength (CHARPY) ISO 179/IeA 23° C. kJ/m2 10 9 11 0° C. kJ/m2 9 9 10 −30° C. kJ/m2 6 6 7 Shore hardness D DIN 53505 87 88 87 Ball impression hardness H 30 ISO 2039 N/mm2 165 172 178 Tensile test 50 mm/min ISO 527 Yield stress N/mm2 91 95 88 Elongation % 7 7 8 Tensil strength N/mm2 65 63 63 Tensil elongation % >150 >150 >100 Modulus of elasticity (tensile test) DIN 53457-t N/mm2 3140 3200 2670 Flexural test 5 mm/min ISO 178 Flexural strength N/mm2 154 156 155 3.5% flexural stress N/mm2 100 103 107 Outer fiber strain at flexural strength % 10 9 9 Modulus of elasticity (flexural test) DIN 53457-B3 N/mm2 2900 3080 3085 Melt viscosity at 280° C. and a shear rate of 10 [l/s] 100 [l/s] High-pressure capillary [Pas] 4100 2850 8250 rheometry [Pas] 2050 1800 3500
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Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2696482A (en) * | 1951-07-19 | 1954-12-07 | Du Pont | Transparent synthetic linear polyamide and process for producing same |
NL131009C (en) * | 1959-10-29 | |||
US3442975A (en) * | 1967-01-11 | 1969-05-06 | Allied Chem | Polyimine/polycarbonamide graft polymers |
DE2652465A1 (en) * | 1976-11-18 | 1978-05-24 | Bayer Ag | TRANSPARENT COPOLYAMID |
CH671022A5 (en) * | 1986-08-26 | 1989-07-31 | Inventa Ag | |
US5321079A (en) | 1986-08-26 | 1994-06-14 | Ems - Inventa Ag | Impact resistant polyamide compositions |
EP0345648B2 (en) * | 1988-06-07 | 2000-04-05 | Ems-Inventa Ag | Thermoplastically processable polyamides |
CA2039136A1 (en) | 1991-01-10 | 1992-07-11 | G. Fred Willard | Amorphous polyamide compositions containing a carbon black compound exhibiting improved melt flow |
US5321118A (en) | 1993-09-30 | 1994-06-14 | Eastman Chemical Company | 1-acetoacetamido-2,3-propane diol monomer and polyesters prerpared therefrom |
BE1008134A3 (en) * | 1994-03-16 | 1996-01-23 | Dsm Nv | Preparation of star-branched polymers. |
WO1996035739A1 (en) * | 1995-05-03 | 1996-11-14 | Dsm N.V. | Star-shaped branched polyamide |
-
2000
- 2000-01-25 DE DE10002948A patent/DE10002948A1/en not_active Withdrawn
- 2000-12-01 DE DE50010279T patent/DE50010279D1/en not_active Expired - Lifetime
- 2000-12-01 EP EP00126328A patent/EP1120443B1/en not_active Expired - Lifetime
- 2000-12-01 AT AT00126328T patent/ATE295393T1/en not_active IP Right Cessation
-
2001
- 2001-01-22 JP JP2001013676A patent/JP4713748B2/en not_active Expired - Fee Related
- 2001-01-23 CA CA002332064A patent/CA2332064A1/en not_active Abandoned
- 2001-01-25 US US09/768,286 patent/US6407182B1/en not_active Expired - Lifetime
Cited By (11)
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US6726999B2 (en) | 2000-12-21 | 2004-04-27 | Degussa Ag | Free flowing polyester molding composition |
US20040166342A1 (en) * | 2003-02-25 | 2004-08-26 | Degussa Ag | Transparent molding composition for optical applications |
US7133209B2 (en) | 2003-02-25 | 2006-11-07 | Degussa Ag | Transparent molding composition for optical applications |
CN110606948A (en) * | 2012-09-04 | 2019-12-24 | 阿克马法国公司 | Copolyamide, composition comprising such a copolyamide and use thereof |
CN106866980A (en) * | 2017-03-22 | 2017-06-20 | 中国科学院理化技术研究所 | Semi-aromatic polyamide resin and preparation method thereof |
EP3670576A1 (en) * | 2018-12-19 | 2020-06-24 | EMS-Patent AG | Polyamide moulding material for glass compositions |
EP3670577A1 (en) | 2018-12-19 | 2020-06-24 | EMS-Patent AG | Polyamide moulding material for glass compositions |
US20200199362A1 (en) * | 2018-12-19 | 2020-06-25 | Ems-Patent Ag | Polyamide moulding compositions for glass composites |
CN111334034A (en) * | 2018-12-19 | 2020-06-26 | Ems 专利股份公司 | Polyamide moulding compositions for glass composites |
US11807718B2 (en) * | 2018-12-19 | 2023-11-07 | Ems-Patent Ag | Polyamide moulding compositions for glass composites |
CN111072953A (en) * | 2019-12-23 | 2020-04-28 | 中国纺织科学研究院有限公司 | Method for the continuous production of lactam copolymers |
Also Published As
Publication number | Publication date |
---|---|
US6407182B1 (en) | 2002-06-18 |
JP2001226584A (en) | 2001-08-21 |
DE50010279D1 (en) | 2005-06-16 |
EP1120443A2 (en) | 2001-08-01 |
ATE295393T1 (en) | 2005-05-15 |
EP1120443A3 (en) | 2003-02-05 |
EP1120443B1 (en) | 2005-05-11 |
JP4713748B2 (en) | 2011-06-29 |
DE10002948A1 (en) | 2001-07-26 |
CA2332064A1 (en) | 2001-07-25 |
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