CA2024729A1 - Stabilized thermoplastic molding materials based on polyphenylene ethers and polyamides - Google Patents
Stabilized thermoplastic molding materials based on polyphenylene ethers and polyamidesInfo
- Publication number
- CA2024729A1 CA2024729A1 CA002024729A CA2024729A CA2024729A1 CA 2024729 A1 CA2024729 A1 CA 2024729A1 CA 002024729 A CA002024729 A CA 002024729A CA 2024729 A CA2024729 A CA 2024729A CA 2024729 A1 CA2024729 A1 CA 2024729A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- acid
- thermoplastic molding
- molding material
- ether
- 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
- 239000012778 molding material Substances 0.000 title claims abstract description 32
- 238000009757 thermoplastic moulding Methods 0.000 title claims abstract description 11
- 229920001955 polyphenylene ether Polymers 0.000 title claims description 27
- 239000004952 Polyamide Substances 0.000 title description 25
- 229920002647 polyamide Polymers 0.000 title description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 poly-phenylene ether Chemical class 0.000 claims abstract description 42
- 229920001971 elastomer Polymers 0.000 claims abstract description 26
- 239000005060 rubber Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 8
- 229920006345 thermoplastic polyamide Polymers 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 6
- 239000005083 Zinc sulfide Substances 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000003951 lactams Chemical class 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000010456 wollastonite Substances 0.000 claims description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000000306 component Substances 0.000 description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 27
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229940063559 methacrylic acid Drugs 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920006024 semi-aromatic copolyamide Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- SSIZLKDLDKIHEV-UHFFFAOYSA-N 2,6-dibromophenol Chemical compound OC1=C(Br)C=CC=C1Br SSIZLKDLDKIHEV-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 229940063557 methacrylate Drugs 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical class C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- WQJUBZMZVKITBU-UHFFFAOYSA-N (3,4-dimethyl-4-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)C(C)(CC)C1=CC=CC=C1 WQJUBZMZVKITBU-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- VMEZXMFPKOMWHR-UHFFFAOYSA-N (dimethylamino)methyl prop-2-enoate Chemical compound CN(C)COC(=O)C=C VMEZXMFPKOMWHR-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- PYEQMLYFGNRZIP-UHFFFAOYSA-N 2,3,3-triphenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C(C)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C)C1=CC=CC=C1 PYEQMLYFGNRZIP-UHFFFAOYSA-N 0.000 description 1
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- HYBLFDUGSBOMPI-UHFFFAOYSA-N octa-1,4-diene Chemical compound CCCC=CCC=C HYBLFDUGSBOMPI-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- 150000003012 phosphoric acid amides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- KMNONFBDPKFXOA-UHFFFAOYSA-N prop-2-enamide;styrene Chemical compound NC(=O)C=C.C=CC1=CC=CC=C1 KMNONFBDPKFXOA-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
- 27 - O.Z. 0050/41085 Abstract of the Disclosure: Thermoplastic molding materials containing, as essential components, A) from 10 to 89.9 % by weight of a thermoplastic polyamide, B) from 10 to 89.9 % by weight of a modified poly-phenylene ether, C) from 0.1 to 8 % by weight of a metal sulfide and, in addition, D) from n to 40 % by weight of a fibrous or particulate filler or a mixture thereof, E) from 0 to 25 % by weight of an impact-modifying rubber and F) from 0 to 25 % by weight of a flameproofing agent.
Description
2~72~
o.z. 0050/41085 Stabilized thermop~astic moldin~ material~ based on polyphenylene ether~ and polyamides The present invention xelate~ to thermopla~tic molding material~ containing, as essential components, S A) from 10 to 89.9 % by weight of a thermoplastic polyamide, B) from 10 to 89.9 ~ by weight of a modif_ed poly-phenylene ether, C) from 0.1 to 8 % by weight of a metal sulfide and, in addition, D) from 0 to 40 ~ by weight of a fibrous or particulate filler or a mixture thereof, E) from 0 to 25 % by weight of an impact-modifying rubber and F) from 0 to 25 % by weight of a flameproofing agent.
The present invention furthermore relates to the use of these molding materials for the production of molding~, and to moldings obtainable using these molding materials as e~sential componentq.
Blends of modified polyphenylene ether3 and polyamide~, containing or not containing fillers, are di~closed in WO 85/05 372, EP-A-260 123, WO 87~05 304, EP-A-46 040 and WO 86/02 986.
US 4,255,321 disclose~ mixture~ of polyphenylene ethers and high impact poly tyrene which contain metal sulfide~ as oxygen stabilizers for the polymers.
In addition, DE-A-34 43 154, EP-A 221 341 and WO
83/03 834 disclose thermoplastic molding materials which are ba~ed on unmodified polyphenylene ether~ and poly-amides and may contain small amounts of metal -~ulfides.
Although the mechanical properties of the blends known hitherto have been improved in pointQ, it must, however, be accepted that other mechanical properties have at the 3ame time worsened. In particular, a balanced mechanical property profile is essential in moldings for motor vehicle since high toughness is required, for example, in the ca~e of multiaxial load.
2~2 -~ 72~
- 2 - O.Z. 0050/41085 In addition, the processability of these blends is inadequate.
It was therefore an object of the present inven-tion to provide thermoplastic molding materials which have good free-flowing properties and multiaxial touqh-ness.
We have found tha~ this ob~ect is achieved by the molding materials defined at the outset.
The subclaims deal with preferred materials of this type and their ~se.
The polyamides present in the material~ as component A) are known per se and include partially crystalline and amorphous resins having molecular weights (weight averages) of S000 or more, usually known as nylon. Polyamides of this type are de~cribed, for ex-ample, in US Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210.
The polyamides can be prepared, for example, by condensing equimolar amounts of a saturated or aromatic dicarboxylic acid having from 4 to 12 carbon atom~ with a saturated or aromatic diamine having up to 14 carbon atom~ or by conden~ing ~-aminocarboxylic acids or by polyaddition of lactam~.
Example~ of polyamides are polyhexamethyleneadip-amide (nylon 66), polyhexamethyleneazelaamide (nylon 69),polyhexamethylene~ebacamide (nylon 610), polyhexamethyl-enedodecanediamide (nylon 612), the polyamide~ obtained by ring opening of lactam~, such as polycaprolactam and polylaurolactam, and poly-ll-aminoundecanoic acid and polyamide~ made from di(p aminocyclohexyl)methane and dodecanedioic acid.
It is also possible to use, ccording to the invention, polyamides prepared by copolycondensation of two or more of the abovementioned polymers or their component~, eg. copolymers made from adipic acid, i~ophthalic acid or terephthslic acid and hexamethylene-diamine or copolymer~ made from caprolactam, terephthalic 2~2~72~
_ 3 _ o.z. 0050/41085 acid and hexamethylenediamine. Partially aromatic copolyamides of this type contain, as component al), from 40 to 90 % by weight of units clerived from terephthalic acid and hexamethylenediamine. A small proportion of the S terephthalic acid, preferably not more than lO ~ by weight of all the aromatic dicarboxylic acids employed, may be replaced by .isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the car-boxyl is in the para-position.
In addition to the units derived from tereph-thalic acid and hexamethylenediamine, the partially aromatic copolyamides contain units derived from ~-caprolactam (a2) and/or units derived from adipic acid and hexamethylenediamine (a3).
lS The proportion of units derived from ~-caprolac-tam is up to 50 % by weight, preferably from 20 to S0 %
by weight, in particular from 25 to 40 ~ by weight, while the proportion of unit~ derived from adipic acid and hexamethylenediamine is up to 60 % by weight, preferably from 30 to 60 ~ by weight, in particular from 3S to 55 %
by weight.
The copolyamide~ may contain both units derived from ~-caprolactam and those derived from adipic acid and hexamethylenediamine; in this case, it must be ensured 2S that the proportion of units which are free from aromatic groups is lO ~ by weight or more, preferably 20 % by weight or more, but the ratio of units derived from ~-caprolactam to tho~e derived from adipic acid and hexa-methylenediaminQ is not sub~ect to any particular limitation.
It has proven particularly advantageous for many applications to use polyamides containing from 50 to 80 %
by weight, in particular from 60 to 75 % by weight~ of units derived from terephthalic acid and hexamethylene-diamine (units al)) and from 20 to 50 % by weight, preferably from 25 to 40 ~ by weight, of unit~ derived from ~-caprolactam (units az)).
'7 2 9 _ 4 _ o.z. 0050/41085 -The partially aromatic copolyamides can be prepared, for example, by the process described in EP-A-129 195 and EP 129 196.
Preference is given to linear polyamides having a melting point of above 200C.
Preferred polyamides are polyhexamethyleneadip-amide, polyhexamethylenesebacamide, polycaprolactam, nylon 6/6T and nylon 66/6T. The polyamides generally have a relative viscosity of from 2.0 to 5, determined in 1 ~
strength by weight solution in 96 ~ sulfuric acid at 23C, corresponding to a molecular weight of from about 15,000 to 45,000. Preference is given to polyamide~
having a relative viscosity of from 2.4 to 3.5, in particular from 2.5 to 3.4.
Other examples of polyamides are those obtain-able, for example, by condensing 1,4-diaminobutane with adipic acid at elevated temperature (nylon 4,6). Prepar-ation processes for polyamides of this structure are described, for example, in EP-A 38 094~ EP-A-38 582 and EP-A-39 524.
~he proportion of polyamides A) in the molding materials according to the invention is from 10 to 89.9~
by weight, preferably from 25 to 71.8 % by weight, in particular from 20 to 50 ~ by weight.
The molding materials according to the invention contain, as componen~ B), from 10 to 89.9 ~ by weight, preferably from 25 to 71.8 ~ by weight, in particular from 20 to 50 % by weight, of a modified polyphenylene ether.
Polyphenylene ethers generally have a moleculax wei~ht (weight average) in the range from 10,000 to 80,000, preferably from 20,000 to 60,000.
This correspond~ to a reduced specific viscosity ~r~d of from 0.2 to 0.9 dl/g, preferably from 0.35 to 0.8 dl/g, in particular from 0.45 to 0.6 dl/g, measured in 1 ~ strength by weight solution in chloroform at 25C
in accordance with DIN 53 726.
2 ~ 2 ~ r~ 2 ~
_ 5 _ O. Z . 0050/41085 The unmodified polypheny:Lene ethers bl) are known per se and are preferably prepared by oxidative coupling of o-disubsti~uted phenols.
Examples of substituents are halogen atom~, such as chlorine or bromine, and alkyl radicals having from 1 to 4 carbon atoms and preferably containing no ~-tertiary hydrogen, eg. methyl, ethyl, propyl or butyl. The alkyl radicals m~y in turn be substituted by halogen, such a~
chlorine or bromine, or by hydroxyl. Further examples of po~sible substituents are alkoxy, preferably having up to 4 carbon atoms, or phenyl which is unsubstituted or substituted by halogen and/or alkyl. Copolymers of different phenols, for example copolymer~ of 2,6-dLme-thylphenol and 2,3,6-trimethylphenol, are also ~uitable.
It is of course also possible to employ mixtures of different polyphenylene ethers.
Preferred polyphenylene ethers are those which are compatible with vinyl-aromatic polymers, ie. are fully or substantially soluble therein (cf. A. Noshay, Block Copolymer~, pages 8 to 10, Academic Pre s, 1977, and O. Olabisi, Polymer-Polymer Miscibility, 1979, pages 117 t~ 189).
Examples of polyphenylene ethers are poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6-diethoxy-1,4 polyphenylene) ether, poly(2-methoxy-6-ethoxy-1,4-phenylene) ether, poly(2-ethyl-6-~tearyloxy-1,4-phenylene) ether, polyt2,6-dichloro-1,4-phenylene)ether,poly(2-methyl-6-phenylene-1,4-phenylene) ether, poly~2,6-dibenzyl-1,4-phenylene) ether, poly(2-ethoxy-1,4-phenylene) ether, poly(2-chloro-1,4-phenylene) ether and poly(2,5-dibromo-1,4-phenylene) ether. Preference is given to polyphenylene ethers in which the sub tituents ara alkyl having from 1 to 4 carbon atoms, such a~ poly(2,6-dimet~yl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-2~ 7~
- 6 - O.Z. 0050/41085 methyl-6-propyl-1,4~phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether and poly(2-ethyl-6-propyl-1,4-phenylene) ether.
Graft polymers made from polyphenylene ethers and vinyl-aromatic polymers such as styrene, ~-methylstyrene, vinyltoluene and chlorostyrene are also suitable.
Functionalized or modified polyphenylene ethers B) are known per se, for example from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 116 and EP-A-254 048.
The polyphenylene ether bl) is usually modified by incorporating one or more carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups, ~hus ensur-ing adequate compatibility with the 2nd polymer of the mixture, the polyamide.
The modification is generally carried out by reacting a polyphenylene ether bl) with a modifier con-taining one or more of the abovementioned groups, insolution (WO-A 86/2086), in aqueous dispersion, in the gas phase (EP-A-25 200) or in the melt, if desired in the presence of suitable vinyl-aroma~ic polymer~ or impact modifier~, it al~o being po~sible for free-radical initiators to be present.
Examples of suitable modifiers (b3) are maleic acid, methyl maleic acid, itaconic acid, tetrahydro-phthalic acid, the anhydrides and imides thereof, fumaric acid, the monoesters and diester~ of the e acid~, for example of C~- and C2-C8-alkanols (monomer b3~), the monoamidos and diamides of these acids, such as N-phenyl-maleimide (monomers b32), maleic hydrazide, the acyl chloride of trimellitic anhydrid~, ben~ene-1,2-(dicar-boxylic anhydride)-4-(carboxylic acetic anhydride), chloroethanoylsuccinaldehyde, chloroformylsuccinaldehyde, citric acid And hydroxysuccinic acid. Example~ of monomer~ b33~ are N-vinylpyrrolidone and 2 ~
- 7 - O.Z~ 0050/41085 ~meth)acryloylcaprolactam.
The preferred component B) in the molding materials according to the invention is a modified pol~phenylene ether obtainable by reacting bl) from 9.g4 to 99.94 ~ by weight of Pn unmodified polyphenylene ether, b2) from 0 to 90 ~ by weight of a vinyl-aromatic polymer, b3) from 0.05 to 10 % by weight of one or more compound~
from the group formed by b31) an l,~-unsaturated dicarbonyl compound, b32~ an amide-containing monomer having a polymeriz-able double bond and b33) a lactam-containing monomer having a polymeriz-able double bond, b4) from 0 to 80 ~ by weight of other graft-active monomers and b5) from 0.01 to 0.09 % by weight of a free-radical initiator, 20 the percentages by weight being based on the ~um of bl) to b5), for from 0.5 to 15 minutes at from 240 to 375C
in a suitable mixer and kneader, such as a twin-screw extruder.
The vinyl-aromatic polymer ~b2) should preferably 25 be compatible with the polyphenylene ether employed.
The molecular weight of these conventional polymers i8 generally in the range from 1500 to 2,000,000, preferably in the range from 70,000 to 1,000,000.
Example-~ of preferred vinyl-aromatic polymers which are compatible with polyphenylene ethers are given in the abovementioned monograph by Olabisi, pages 224 to 230 and 245. A~ representatives only, vinyl-aromatic polymers made from styrene~ chlorostyrene, ~-methyl-35 styrene and p-m~thylstyrene are mentioned here; in minor amounts (preferably not more than 20 % by weight, in particular not more than 8 % by weight), comonomer~
2~ ~ 72~
- 8 - O.Z. 0050/41085 such as (meth)acrylonitrile or (meth)acrylates may also participate in the synthesis. Particularly preferred vinyl-aromatic polymers are polystyrene and Lmpact-modified polystyrene. :[t is of course also possible to employ mixtures of these polymers. The preparation is preferably carried out by the process described in EP-A-302 485.
If desired, further comonomers b4) which react with or graft onto components bl and, if used, b2) under the preparation conditions can also be employed in the preparation of the modified polyphenylene ether B.
Examples which may be mentioned are acrylic acid, meth-acrylic acid, acrylates, methacrylates and vinyl-aromatic monomers such as styrene, ~-methylstyrene and vinyl-toluene, to mention but a few.
The proportion of component b4) is from 0 to 80 %by weight, preferably from 0 to 45 % by weight, in particular not more than 20 % by weight, based on the sum of components b1) to b5). Particularly preferred molding materials contain no component b4).
Examples of free-radical initiators (b5) are:
di(2,4-dichlorobenzoyl) peroxide, tert.-butyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroylperoxide, didecanoyl peroxide, dipropionyl peroxide, dibenzoyl peroxide, tert.-butyl peroxy-2-ethylhexanoate, tert.-butyl peroxydiethylacetate, tert.-butyl peroxyisobutyr-ate, 1,1-di-tert.-butylperoxy-3,3,5-trimethylcyclohexane, tert.-butyl peroxyi~opropylcarbonate, tert.-butylperoxy-3,3,5-trimeth.ylhexanoate, tert.-butyl peracetate, tert.-butyl perbenzoate, butyl 4,4-di-tert.-butyl peroxyvaler-ate, 2,2-di-tert.-butylperoxybutane, dicumyl peroxide, tert.-butylcumyl peroxide, 1,3-di(tert.-butylperoxyiso-propyl)benzene and di-tert.-butyl peroxide. Organic hydroperoxides, such a~ diisopropylbenzene monohydro-peroxide, cumene hydroperoxide, tert.-butyl hydroperox-ide, p-menthyl hydroperoxide and pinane hydroperoxide, and highly branched alkanes of the general structure 2~2~29 - 9 - O.Z. 0050/41085 R4 Rl where Rl to R6 are alkyl ha~ing from 1 to 8 carbon atoms, alkoxy having from 1 to 8 carbon atoms, aryl, such as phenyl or naphthyl, or 5- or 6-membered heterocyclic rings having a ~-electron system and nitrogen, oxygen or sulfur as heteroatoms, are also suitable. The substitu-ent3 R1 to R5 may themselves contain functional groups as sub~tituents, such as carboxyl, carboxyl derivatives, hydroxyl, amino, thiol or epoxide groups. Examples are 2,3-dLmethyl-2,3-diphenylbutane, 3,4-dLmethyl-3,4-di-phenylhexane and 2,2,3,3-tetraphenylbutane.
The molding materials according to the invention contain, as component C), from 0.1 to 8 % by weight, preferably from 0.2 to 4 ~ by weigh~, in particular from 0.25 to 3 ~ by weight, of a metal ~ulfide.
Suitable sulfides are alkali metal and alkaline earth metal sulfides, e.g. sodium sulfide, potassium sulfide, calcium sulfide and barium sulfide, and metal sulfides from the sub-group~ of the Periodic Table, such as manganese sulfide, iron sulfide, nickel sulfide, copper sulfide and cadmium sulfide, and particularly preferably zinc sulfide.
Commercially available zinc sulfide generally contains 97 % by weight or more of zinc sulfide in addition to small amounts of barium sulfate and zinc oxide.
It u~ually ha~ a zinc blende or wurzite structure and a den~ity, in general, of from 2 to 5 g/cm3, in particular from 4 to 5 g/cm3.
It i8 also possible to use mixtures of metal sulfides with oxideq in a mixing ratio of, in general, from 8:2 to 2:8.
In general, the metal sulfides in powder form can easily be incorporated into the molding materials according to the in~ention. Preference is given to 2 ~ r~ 2 ~
- lO - O.Z. 0050/41085 concentrates of the metal sulfide, for example in a polyamide, since this allow~ better dispersion of the pigment to be achieved.
The molding materials according to the invention contain, as component D), from 0 to 40 ~ by weight, preferably from 10 to 35 % by weight, of fibrous or particulate fillers or mixtures thereof. Examples of fillers are carbon or glass fibers in the form of woven glass fabrics, glass mats or glass rovings, glass beads, and wollastonite.
Preferred fibrous reinforcing materials (com-ponent C) are carbon fibers, potassium titanate whiskers, aramid fibers and, particularly preferably, glass fibers.
When gla~s fiberY are used, they may be provided with a size and coupling agent in order to impart better com-patibi~ity with the thermoplastic polyamide (A) or the polyphenylene ether (B). In general, the carbon fiber~
and glass fibers used have a diameter in the range from 6 to 20 ~m.
These glass fibers can be incorporated either in the form of short glass fiber~ or continuous extrudates (rovings). In the finished injection molding, the mean length of the glass fibers is preferably in the range from 0.08 to 0.5 mm.
~5 Suitable particulate fillers are amorphouq silica, asbesto3, magne#ium carbonate, chalk , powdered quartz, mica, talc, feldspar and, in particular, calcium ~ilicate~ such a~ wollastonite and kaolin (in particular calcined kaolin).
Examples of preferred combinations of fillers are 20 ~ by weight of glass fibers with 15 % by weight of wollastonite and 15 % by weight of glas~ fiber~ with 15 %
by waight of wollastonite.
In addition to the es~ential component~ A), B) and C), the molding materials according to the invention can contain from 0 to 25 % by weight, preferably from 3 to 20 % by weight, of an impact-modifying rubber. Con-~ O.Z. 0050/41085 ventional impact modifiers E) which are suitable for polyamides (component A) and rubbers E) which are usually used for the impact modification of polyphenylene ether~
B) can be used.
The preferred rubber-ela~tic polymers E) for polyamides A) are those which have reactive group~ at the surface.
Examples of groups of this type are epoxy, carboxyl, latent carboxyl, amino or amide groups, and functional groups which can be introduced by carrying out the polymerization in the presence of monomerq of the general formula R10 Rll CH 2=C--X~C--R12 ll where the substituent can have the following meanings:
Rl~ is hydrogen or C~-C4-alkyl, Rll is hydrogen, Cl-C8-alkyl or aryl, in particular phenyl, Rl2 is hydrogen, C1-C10-alkyl, C6-C12-aryl or oR13, Rl3 is Cl-C~-alkyl or C6-Cl2-aryl, which is unsubstituted or substituted by O~ or N containing groups, X i8 a chemical bond, C1-C10-alkylene, C6-Cl2-arylene or R
_c--Y
Y i8 O-Z or NH-Z and Z i~ C1-C10-alkylene or Cs-Cl2-arylene.
The graft monomer~ described in EP-A 208 187 are also suitable for introducing reactive groups at the surface.
Examples of monomers using which the abovemen-tioned functional groups can be introduced are glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl e~her, glycidyl itaconate, acrylic acid, methacrylic acid and the metal, in partlcular alkali metal, and ammonium salts thereof, maleic acid, fumaric 2~7~
- 12 - O.Z. 0050/41085 acid, itaconic acid, vinylbenzoic acid, vinylphthalic acid, monoesters of these acids with alcohols ROH where R has up to 29 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, stearyl, methoxy-ethyl, ethoxyethyl or hydroxyethyl. Although maleic anhydride and esters of acrylic acid or methacrylic acid with tertiary alcohols, for example tert.-butyl acrylate, do not have any free carboxyl groups, they behave in a similar manner to the free acids and are therefore regarded as monomers having latent acid groups.
Further examples are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (N-t-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and (N,N-diethylamino)ethyl acrylate.
The proportion of groups derived from the above-mentioned monomers is generally from 0.5 to 40 % by weight, preferably from 0.5 to 25 ~ by weight, based on the total weight of the rubber.
These monomers can either be copolym~rized with the other monomers during preparation of the rubber or grafted onto a pre-exi~ting, unmodified rubber (if necessary in the presence of initiator~, for example free-radical initiators).
The rubbers are generally polymers preferably built up from two or more of the following monomer~ as the principal component~: ethylene, propylene, butadiene, isobutene, i30prene, chloroprene, vinyl acetate, styrene, acrylonitrile, methacrylic acid, acrylic acid and acrylate~ and methacrylates having from 1 ~o 18 carbon atoms in the alcohol component.
A first preferred group comprises the ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers, which preferably h~ve an ethylene:
propylene ratio in the range from 40:60 to 90:10.
The Mooney viRcositie~ (MLl+4flQ0C) of uncro~s-2~7~
- 13 - O.Z. 0050/4108S
linXed EPM and EPDM rubbers of this type (gel contents generally less than I % by weigh~) are preferably in the range from 25 to 100, in particular from 35 to 90 (meas-ured in accordance with DIN 53 523 on the large rotor after a running time of 4 minutes at 100C).
EPM rubbers generally have virtually no double bonds, while EPDM rubbers may contain from 1 to 20 double bonds per 100 carbon atom3.
Examples of diene monomers for EPDM rubbers are conjugated dienes, such as isoprene and butadiene, non-con~ugated diene~ having from 5 to 25 carbon atoms, such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic diene~, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyltricyclo-[5.2.1Ø2.6]-3,8-decadiene, and mixtures thereof.
Preference is given to hexadiene-1,5,5-ethylidenenorbor-nene and dicyclopentadiene. The diene content of the EPDM
rubbers is generally from 0.5 to 50 ~ by weight, in particular from 3 to 15 % by weight, based on the total weight of the rubber.
EPM and EPDM rubbers are usually grafted with the - abovementioned monomers carrying reactive group~, of which only acrylic acid, methacrylic acid and derivatives thereof, and maleic anhydride are mentioned here.
A further group of rubbers comprise~ copolymer~
of ~-olefin , preferably ethylene, with ester~ of acrylic or methacrylic acid, for example with the methyl, ethyl, propyl, n-, i- or t-butyl and 2-ethylhexyl esters. In addition, the rubbers may also contain the abovementioned reactive gxoup~, for example in the form of dicarboxylic acids, derivatives of these aclds, vinyl esters and vinyl ether~.
The ethylene content of the copolymers i~ gener-2~2~2~
- 14 - O.Z. 5050/41085 ally in the range from 50 to 98 % by weight, and the proportions of epoxide-contain:ing monomers and of the acrylate and/or methacrylate are each in the range from 1 to 49 % by weight.
Preference is given to olefin polymers comprising from 50 to 98.9 ~ by weight, in particular from 60 to 95 ~ by weight, of ethylene, from 0.1 to 20 ~ by weight, in particular from 0.15 to 15 ~ by weight, of glycidyl acrylate and~or glycidyl methacrylate, acrylic acid and/or maleic anhydride, and from 1 to 45 ~ by weight, in particular fxom 10 to 35 % by weight, of n-butyl acrylate and/or 2-ethylhexyl acrylate.
The above-described ethylene copolymers can be prepared by conventional processes, preferably by random copolymerization under superatmospheric pressure and at elevated temperature. Appropriate processes are described in the literature.
The melt flow index of the ethylene copolymers is generally in the range from 1 to 80 g/10 min (measured at 190C under a load of 2.16 kg).
Suitable elastomers for the impact modification of polyamide are furthermore graft copolymers/ containing reactive group~, with butadiene, butadieneJ~tyrene, butadiene/acrylonitrile and acrylate rubbers aQ the graft base, as deQcribed, for example, in DE-A 16 9~ 173, DE-A 23 48 377, DE-A 24 44 584 and DE-A-27 26 256, in particular the ABS polymer~, as de~cribed in DE-A-20 35 390, DE-A-22 48 242 and EP-A-22 216.
The rubber E may be a graft polymer comprising from 25 to 98 % by weight of an acrylate rubber having a glass transition temperature of below -20C as the graft baQe ~base polymer) and ?~ ~ 2 ~
- 15 - O.Z. 0050/41085 from 2 to 75 ~ by weight of a copolymerizable, ~thylenically unsaturated monomer whose homopolymers and copolymers have a glass transition temperature of greater than 25C, as the graft shell.
The graft base is an acrylate or methacrylate rubber containing up to 40 ~ by weight of further co-monomers. The Cl-C3-e~ter~ of acrylic acid or methacrylic acid and the halogenated derivatives thereof, and aromatic acrylates and mixtures thereof are usually employed.
Specific exampleR of comonomers in the graft base are acrylonitrile, methacrylonitrile, styrene, ~-methylstyr-ene, ac~ylamide~, methacrylamides and vinyl Cl-C~-alkyl ethers.
The graft base may be uncrosslinked or partially or fully crosslinked, which is achieved, for example, by copolymerizing preferably from 0.02 to 5 ~ by weight, in particular from 0.05 to 2 % by weight, of a crosslinking monomer containing more than one double bond. Suitable crosslinking monomer~ are described, for example, in DE-A 27 2~ 256 and EP-A 50 265.
Preferred crosslinking monomers are triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
If ths crosslinking monomerR contain more than 2 polymerizable double bond~, it i~ advantageous to limit their amount to not more than 1 ~ by weight, based on the graft base.
Highly ~uitable graft bases are emulsion polymers having a gal content of grea~er than 60 ~ by weight (determined in dimethylformamide at 25C by the method of M. Hoffmann, H. Rr~mer, R. Kuhn, Polymeranalytik, Georg-Thieme-Verlag, Stuttgart, 1977).
Other ~uitable graft ba3e~ are acrylate rubbers 3S having a diene core, as described, for example, in EP-A 50 262.
Particularly sui~able graft monomer-~ are styrene, 2~2~ 1~2~
- 16 - O.Z. 0050/41085 ~-methylstyrene, acrylonitrile, methacrylonitrile and methyl methacrylate, or mixtures thereof, in particular those comprisiny styrene and acrylonitrile in the weight ratio from 1:1 to 9:1.
The reactive groups can be introduced into the graft copolymers by, for example, carrying out the preparation of the graft shell in the presence of the appropriate monomers. In this case, the proportion thereof in the graft monomer mixture is preferably from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight. It is also possible to apply the appropriate monomers separately as the final graft shell.
The graft yield, ie. the quotient of the amount of grafted-on monomers and the amount of graft monomers employed, is generally in the range from 20 to 90 ~.
Examples of rubbers are those which are used for the impact modification of polyphenylene ethers B).
Examples which may be mentioned are thermoplastic rubbers, such as polybutadiene, polybutene, polyisoprene, acrylonitrile-butadiene, ethylene-propylene, polyesteror ethylene rubbers, and elastomeric copolymers made from ethylene and esters of (meth)acrylic acid, for example ethylene-butyl acrylate copolymers, furthermore ionomers, polyoctenylenes, graft rubbers having a graft core made from butadiene or isoprene or alkyl ~meth)acrylates and a graft shell made from styrene and/or ~-methyl~tyrene, and preferably ~tyrene-butadiene block copolymer3, including A~, A~A and ~BAB block copolymer~, which may al~o have indi3tinct transitions, star block copolymers and the like, analogous isoprene block copolymers and (partially) hydrogenated block copolymers. These rubber~
can also be employed in the form of a graft with vinyl-aromatic monomers, such a~ styrene (EP-A 234 063 and US-A 4,681,915).
The rubber~ E preferably have a gla~ transition temperature of below ~30C, in particular below -40C. It is of course al~o possible to employ mixtures of the 2~ 72~3 - 17 - O.Z. 0050/41085 abovementioned types of rubber.
The molding materials according to the invention may furthermore contain flameproofing agents F) in amounts of from 0 to 25 ~ by weight, preferably up to 15 ~ by weight, based on the total weight of the molding materials.
All known flameproofing agents are suitable, eg.
polyhalobiphenyl, polyhalobiphenyl ether, polyhalo-phthalic acid and derivatives thereof, polyhalooligo-carbonates and polyhalopolycarbonates, the correspondingbromine compound~ being particularly effective.
Examples of these are polymer~ of 2,6,2',6'-tetrabromobisphenol A, of tetrabromophthalic acid, of 2,6-dibromophenol and of 2,4,6-tribromophenol and deriv-atives thereof.
A preferred flameproofing agent F~ is elementalred phosphorus, which can generally be phlegmatized or coated with, for example, polyurethanes or other amino plastic~. In addition, concentrates of red phosphorus in, for example, a polyamide, elastomer or polyolefin are also suitable.
Particular preference i~ given to 1,2,3,4,7,8,9,-10,13,13,14,14-dodecachloro-1,4,4a,5,6,6a,7,10,10a,11,-12,12a-dodecahydro-1,4:7,10-dimethanodibenzo(a,e)cyclo-octane (Dechlorane~ Plus, Occidental Chemical Corp.) and,if desired, a synergi~t, for example antimony trioxide.
Other cuitable phosphorus compounds are organo-phosphoru~ compound~, such a~ phosphonates, phosphinate~, phosphinites, phosphine oxides, phosphines, pho~phites or phosphates. A ~pecific example i triphenylpho~phine oxide, which can be used alone or mixed with hexabromo-benzene or a chlorinated biphenyl or red pho~phoru~ and, if desired, antimony oxide.
Typical preferred phosphorus compounds which can be u~ed according ~o the pre~ent invention are tho~e of the general formula 2~72~
- 18 - O.Z. 0050/~1085 ~o-I~OQ
o~
where Q is hydrogen or identical or different hydrocarbon radicals or halogenated hydrocarbon radicals, such a~
alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-substituted alkyl, with the proviso that one or more of the radicals Q is aryl. Example~ of suitable phosphate~
of this type are phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl ethylene hydrogen phos-phate, phenyl bis(3,5,5'-trLmethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethylhexyl) phenyl pho~phate, tri(nonylphenyl) phosphate, phenyl methyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl pho~phate, triphenyl phosphate, dibutyl phenyl phosphate and diphenyl hydrogen phosphate. The preferred phosphates are those in which each Q i aryl. The most preferred phosphate is triphenyl phosphate. The combin-ation of triphenyl pho~phate with hexabromobenzene and antimony trioxide is also preferred.
Other suitabls flameproofing agent~ are compounds which contain phosphorus-nitrogen bond~, such as phospho-nitrile chloride, phosphori~ acid e~ter amides, phoc-phoric acid ester amine~, phosphoric acid amides, phosphonic acid amides, pho~phinic acid amide~, tris-(aziridinyl) phosphine oxide and tetrakis(hydroxymethyl)-phosphonium chloride. The ma~ority of these flame-inhibiting additives are commercially available.
Other ~uitable halogen-containing flameproofing agents are tetrabromoben~ene, hexachlorobenzene, hexa-bromobenzene, and halogenated polystyrene~ and polyphenylene ethers.
It is also pos~iblo to use the halogenated phthalimides de cribed in DE-A-l9 46 924, of which N,N'-ethylenebistetrabromophthalimide, in pasticular, has - 19 - O.Z. 0050/41085 achieved Lmportance.
In addition to the essential components A), B) and C) and, if desired, D), E) and F), the molding mater-ials according to the invention can also contain conven-S tional additives and processing aids, whose proportion isgenerally up to 20 % by weight, preferably up to 10 % by weight, based on the total weight of components A) to F).
Examples of conventional additives are stabiliz-ers, antioxidants, thermal stabilizers, W stabilizers, lubricants, mold release agents, dyes, pigments and plasticizers.
Examples of antioxidants and thermal stabilizers which can be added to the thermoplastic materials accord-ing to the invention are halides of metals of group I of the Periodic Table, eg. ~odium halides, potassium halides and lithium halides, if desired in combination with copper(I) halides, eg. chlorides, bromides or iodides. It is also possible to use zinc fluoride, zinc chloride, sterically hindered phenols, hydroquinone~, substituted representa~ive~ of thi~ group, and mixtures of these compounds, preferably in concentration~ of up to 1 % by weight, based on the weight of the mixture.
Examples of W 4tabilizers are various substituted resorcinols, salicylates, benzotriazole~ and benzophe-nones, which are generally employed in amounts of up to2 % by weight.
Materials for increasing the screening against electromagnetic waves, such as metal flakes, metal powders, metal fibers and metal-coated fillers, can also be used.
Lubricants and mold release agents, which are generally added to the thermopla~tic material in amounts of up to 1 ~ by weight, are stearic acid, stearyl alcohol, alkyl stearates, alkyl ~tearamides and esters of pentaerythritol with long-chain fatty acid~.
The additiveY al~o include ~tabilizers which prevent decomposition of the red phosphorus (component F) 2~L~ ~ 2~
- 20 - O.Z. 0050/41085 in khe pre~ence of moisture and atmospheric oxysen.
Examples are compounds of cadmium, zinc, aluminum, silver, iron, copper, antimony, tin, magnesium, man-ganese, vanadium and boron. Examples of particularly suitable compounds are oxides of the metals mentioned, furthermore carbonates or o~ycarbonates, hydroxides and salts of organic or inorganic acids, such as acetates, pho~phates, hydrogen phosphates and sulfates.
The thermoplastic molding materials according to the invention can be prepared by conventional processes by mixing and subsequently extruding the starting com-ponents in conventional mixers, such as screw extruder~, preferably twin-screw extruders, Brabender mills or Banburry mills, and kneaders. After extrusion, the extrudate i~ cooled and comminuted.
In order to obtain the mo~t homogeneous molding material possible, vigorous mixing i~ necessary. To this end, mean mixing times of from 0.2 to 30 minute~ at from 280 to 380C are generally necessary. The ~equence of mixing of the components may be varied; for example, it is po~sible to pre-mix two or three components, or to mix all the components together. It may be advantageous to prepare the modified polyphenylene ether B2 in a first zone of an extruder and to mix it with the other com-ponents of the molding material according to the inven-tion in one or more ~ub~equent zones. A proces~ of this type i~ described in DE-A 37 02 5B2.
The molding materials according to the invention have good toughness, in particular multiaxial toughness, combined with good processability.
This property profile makes the moldings which can be produced from ~he molding materials according to the invention particularly suitable for motor vehicle part~, ~ports equipment, and electronic and electrical components.
2~24 729 - 21 - O.Z. 0050/41085 EXAMPLES
Component A1) Poly-~-caprolactam having a Fikentscher K value of 73, measured in l ~ strength by weight solution of 96 % by weight sulfuric acid at 25C, corresponding to ~rel f 2.7.
Component A2) Polyhexamethyleneadipamide having a R value of 76, corresponding to a relative viscosity ~r~l of 2.95.
Component A3) Polyhexamethyleneadipamide having a K value of 60, corresponding to qr~l Of 2.05.
Component (Bl) A modified polyphenylene ether comprising 90 g by weight of poly(2,6-dLmethyl-1,4-phenylene) ether (~r~d = ~ 59 dl/g, measured in 1 % strength by weight solution in chloroform at 25C), 8 ~ by weight of polystyrene (melt flow index MFI at 200~C and a load of 5 kg: 24 g/10 min), 1.95 % by weight of fumaric acid and 0.05 % by weight of 3,4-dimethyl-3,4-diphenylhexane (initiator) wa~ prepared by mixing the component~ at from 290 to 310C in a twin screw extruder with subsequent dega~sing.
The melt was p2s~ed through a water bath, granulated and dried.
Component (Bl*) (for comparison) An unmodified polyphenylene ether having a mean molecular weight (weight average) ~ of 30,000 and ~rad = 0.59 dl/g.
Component C1) Zinc sulfide having a density of 4.1 g/cm3.
Component C2) Zinc ~ulfide pigment having a mean particle size of 0.35 ~m.
2~2~72~
- 22 - O.Z. 0050/41085 Component E1) A styrene-butadiene-styrene three-blockcopolymer having a styrene content of 30 ~ by weight.
Component E2) A two-block copolymer of styrene and hydrogenated polybutadiene having a styrene content of 35 % by weight;
n~mber average molecular weight ~ = 95,000.
Component E3) An ethylene copolymer comprising:
70 % by weiqht of ethylene, 25 % by weight of n-butyl acrylate and 5 ~ by weight of acrylic acid.
MFI = 11 g/10 min (190C/2.16 kg) (DIN 53 735) Preparation of the molding materials Components A), B) and C) and, if desired, D) to F) were mixed in a twin-screw extruder at a barrel temperature of 290C. The melt wa~ passed through a water bath and granulated. The dried granules were in~ection-molded at 280C to form dumbbell te~t specimens and a~
300C to form circular di~ks (60 x 2 mm).
The penetration energy was determined on circular disk~ in accordance with DIN 53 443; the modulus of ela~ticity was determined on dumbbell te~t specLmens in accordance with DIN 53 437.
The melt flow index (MFI) wa~ determined in accordance with DIN 53 735 at 275C and a load of 10 kg.
Th~ compositions of the molding material~ and the results of the measurements are shown in the table.
As can be seen, the melt flow index and the penetration energy are clearly superior in the examples according to the invention compared with the comparative examples.
~2~72~
- 23 C). Z . 0050/41085 ~ I
~, H O I ~ 11~ ~7 t` ~ ~1 0 1 U~ U N I O C:~ O O O O O C~
a ~a z I
~ ~ I
I
~ ~ I
ll ~1 I ____,____~
I N ~--I
+ ~
__ --O
I ---- -- ----U U ~ e~
~ ~ I U U U I I U U u~ u7 ul u~
~ .C I _I ~ _I C'~l ~ O O O O
o ~ I __ mm-- * ~ m~ ~ ~
~dP I m m t~ u~ m m m u~ m m m I O U~ O~ O ~ n ~ o o o o I ~ ~
U
I _I ~ _I t'~l C~ N ~
* *
O I ~ ~ *~ O _~
202~ ~729 - 24 - O.Z. 0050/41085 Key to table:
***) in addition 0.3 % by weight of 2-(2-hydroxy-5-methylphenyl)benzotriazole **) for comparison Example 6 additionally contained, in accordance with DE-A-3 443 154, 5 ~ by weight of styrene-maleic anhydride copolymer (92/8~ and 10 % by weight of triphenylphosphine oxide Example 7 contained, in accordance with Example 10 of EP-A-221,341, 10.4 ~ by weight of a styrene-acrylamide copolymer (90/10) Example 8 contained, in accordance with WO 83/0 38 34, 20 ~ by weight of triphenyl phosphate.
Examples 9 to 11 contained, in accordance with US 4,255,321, impact-modified polystyrene containing 8 % by weight of polybutadiene rubber (VN = 70 ml/g of the matrix tyrene in accordance with DIN 53 726), 9 = 49.5 ~ by weight, 10 = 50 ~ by weight, 11 = 49 ~ by weight.
o.z. 0050/41085 Stabilized thermop~astic moldin~ material~ based on polyphenylene ether~ and polyamides The present invention xelate~ to thermopla~tic molding material~ containing, as essential components, S A) from 10 to 89.9 % by weight of a thermoplastic polyamide, B) from 10 to 89.9 ~ by weight of a modif_ed poly-phenylene ether, C) from 0.1 to 8 % by weight of a metal sulfide and, in addition, D) from 0 to 40 ~ by weight of a fibrous or particulate filler or a mixture thereof, E) from 0 to 25 % by weight of an impact-modifying rubber and F) from 0 to 25 % by weight of a flameproofing agent.
The present invention furthermore relates to the use of these molding materials for the production of molding~, and to moldings obtainable using these molding materials as e~sential componentq.
Blends of modified polyphenylene ether3 and polyamide~, containing or not containing fillers, are di~closed in WO 85/05 372, EP-A-260 123, WO 87~05 304, EP-A-46 040 and WO 86/02 986.
US 4,255,321 disclose~ mixture~ of polyphenylene ethers and high impact poly tyrene which contain metal sulfide~ as oxygen stabilizers for the polymers.
In addition, DE-A-34 43 154, EP-A 221 341 and WO
83/03 834 disclose thermoplastic molding materials which are ba~ed on unmodified polyphenylene ether~ and poly-amides and may contain small amounts of metal -~ulfides.
Although the mechanical properties of the blends known hitherto have been improved in pointQ, it must, however, be accepted that other mechanical properties have at the 3ame time worsened. In particular, a balanced mechanical property profile is essential in moldings for motor vehicle since high toughness is required, for example, in the ca~e of multiaxial load.
2~2 -~ 72~
- 2 - O.Z. 0050/41085 In addition, the processability of these blends is inadequate.
It was therefore an object of the present inven-tion to provide thermoplastic molding materials which have good free-flowing properties and multiaxial touqh-ness.
We have found tha~ this ob~ect is achieved by the molding materials defined at the outset.
The subclaims deal with preferred materials of this type and their ~se.
The polyamides present in the material~ as component A) are known per se and include partially crystalline and amorphous resins having molecular weights (weight averages) of S000 or more, usually known as nylon. Polyamides of this type are de~cribed, for ex-ample, in US Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210.
The polyamides can be prepared, for example, by condensing equimolar amounts of a saturated or aromatic dicarboxylic acid having from 4 to 12 carbon atom~ with a saturated or aromatic diamine having up to 14 carbon atom~ or by conden~ing ~-aminocarboxylic acids or by polyaddition of lactam~.
Example~ of polyamides are polyhexamethyleneadip-amide (nylon 66), polyhexamethyleneazelaamide (nylon 69),polyhexamethylene~ebacamide (nylon 610), polyhexamethyl-enedodecanediamide (nylon 612), the polyamide~ obtained by ring opening of lactam~, such as polycaprolactam and polylaurolactam, and poly-ll-aminoundecanoic acid and polyamide~ made from di(p aminocyclohexyl)methane and dodecanedioic acid.
It is also possible to use, ccording to the invention, polyamides prepared by copolycondensation of two or more of the abovementioned polymers or their component~, eg. copolymers made from adipic acid, i~ophthalic acid or terephthslic acid and hexamethylene-diamine or copolymer~ made from caprolactam, terephthalic 2~2~72~
_ 3 _ o.z. 0050/41085 acid and hexamethylenediamine. Partially aromatic copolyamides of this type contain, as component al), from 40 to 90 % by weight of units clerived from terephthalic acid and hexamethylenediamine. A small proportion of the S terephthalic acid, preferably not more than lO ~ by weight of all the aromatic dicarboxylic acids employed, may be replaced by .isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the car-boxyl is in the para-position.
In addition to the units derived from tereph-thalic acid and hexamethylenediamine, the partially aromatic copolyamides contain units derived from ~-caprolactam (a2) and/or units derived from adipic acid and hexamethylenediamine (a3).
lS The proportion of units derived from ~-caprolac-tam is up to 50 % by weight, preferably from 20 to S0 %
by weight, in particular from 25 to 40 ~ by weight, while the proportion of unit~ derived from adipic acid and hexamethylenediamine is up to 60 % by weight, preferably from 30 to 60 ~ by weight, in particular from 3S to 55 %
by weight.
The copolyamide~ may contain both units derived from ~-caprolactam and those derived from adipic acid and hexamethylenediamine; in this case, it must be ensured 2S that the proportion of units which are free from aromatic groups is lO ~ by weight or more, preferably 20 % by weight or more, but the ratio of units derived from ~-caprolactam to tho~e derived from adipic acid and hexa-methylenediaminQ is not sub~ect to any particular limitation.
It has proven particularly advantageous for many applications to use polyamides containing from 50 to 80 %
by weight, in particular from 60 to 75 % by weight~ of units derived from terephthalic acid and hexamethylene-diamine (units al)) and from 20 to 50 % by weight, preferably from 25 to 40 ~ by weight, of unit~ derived from ~-caprolactam (units az)).
'7 2 9 _ 4 _ o.z. 0050/41085 -The partially aromatic copolyamides can be prepared, for example, by the process described in EP-A-129 195 and EP 129 196.
Preference is given to linear polyamides having a melting point of above 200C.
Preferred polyamides are polyhexamethyleneadip-amide, polyhexamethylenesebacamide, polycaprolactam, nylon 6/6T and nylon 66/6T. The polyamides generally have a relative viscosity of from 2.0 to 5, determined in 1 ~
strength by weight solution in 96 ~ sulfuric acid at 23C, corresponding to a molecular weight of from about 15,000 to 45,000. Preference is given to polyamide~
having a relative viscosity of from 2.4 to 3.5, in particular from 2.5 to 3.4.
Other examples of polyamides are those obtain-able, for example, by condensing 1,4-diaminobutane with adipic acid at elevated temperature (nylon 4,6). Prepar-ation processes for polyamides of this structure are described, for example, in EP-A 38 094~ EP-A-38 582 and EP-A-39 524.
~he proportion of polyamides A) in the molding materials according to the invention is from 10 to 89.9~
by weight, preferably from 25 to 71.8 % by weight, in particular from 20 to 50 ~ by weight.
The molding materials according to the invention contain, as componen~ B), from 10 to 89.9 ~ by weight, preferably from 25 to 71.8 ~ by weight, in particular from 20 to 50 % by weight, of a modified polyphenylene ether.
Polyphenylene ethers generally have a moleculax wei~ht (weight average) in the range from 10,000 to 80,000, preferably from 20,000 to 60,000.
This correspond~ to a reduced specific viscosity ~r~d of from 0.2 to 0.9 dl/g, preferably from 0.35 to 0.8 dl/g, in particular from 0.45 to 0.6 dl/g, measured in 1 ~ strength by weight solution in chloroform at 25C
in accordance with DIN 53 726.
2 ~ 2 ~ r~ 2 ~
_ 5 _ O. Z . 0050/41085 The unmodified polypheny:Lene ethers bl) are known per se and are preferably prepared by oxidative coupling of o-disubsti~uted phenols.
Examples of substituents are halogen atom~, such as chlorine or bromine, and alkyl radicals having from 1 to 4 carbon atoms and preferably containing no ~-tertiary hydrogen, eg. methyl, ethyl, propyl or butyl. The alkyl radicals m~y in turn be substituted by halogen, such a~
chlorine or bromine, or by hydroxyl. Further examples of po~sible substituents are alkoxy, preferably having up to 4 carbon atoms, or phenyl which is unsubstituted or substituted by halogen and/or alkyl. Copolymers of different phenols, for example copolymer~ of 2,6-dLme-thylphenol and 2,3,6-trimethylphenol, are also ~uitable.
It is of course also possible to employ mixtures of different polyphenylene ethers.
Preferred polyphenylene ethers are those which are compatible with vinyl-aromatic polymers, ie. are fully or substantially soluble therein (cf. A. Noshay, Block Copolymer~, pages 8 to 10, Academic Pre s, 1977, and O. Olabisi, Polymer-Polymer Miscibility, 1979, pages 117 t~ 189).
Examples of polyphenylene ethers are poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6-diethoxy-1,4 polyphenylene) ether, poly(2-methoxy-6-ethoxy-1,4-phenylene) ether, poly(2-ethyl-6-~tearyloxy-1,4-phenylene) ether, polyt2,6-dichloro-1,4-phenylene)ether,poly(2-methyl-6-phenylene-1,4-phenylene) ether, poly~2,6-dibenzyl-1,4-phenylene) ether, poly(2-ethoxy-1,4-phenylene) ether, poly(2-chloro-1,4-phenylene) ether and poly(2,5-dibromo-1,4-phenylene) ether. Preference is given to polyphenylene ethers in which the sub tituents ara alkyl having from 1 to 4 carbon atoms, such a~ poly(2,6-dimet~yl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-2~ 7~
- 6 - O.Z. 0050/41085 methyl-6-propyl-1,4~phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether and poly(2-ethyl-6-propyl-1,4-phenylene) ether.
Graft polymers made from polyphenylene ethers and vinyl-aromatic polymers such as styrene, ~-methylstyrene, vinyltoluene and chlorostyrene are also suitable.
Functionalized or modified polyphenylene ethers B) are known per se, for example from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 116 and EP-A-254 048.
The polyphenylene ether bl) is usually modified by incorporating one or more carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups, ~hus ensur-ing adequate compatibility with the 2nd polymer of the mixture, the polyamide.
The modification is generally carried out by reacting a polyphenylene ether bl) with a modifier con-taining one or more of the abovementioned groups, insolution (WO-A 86/2086), in aqueous dispersion, in the gas phase (EP-A-25 200) or in the melt, if desired in the presence of suitable vinyl-aroma~ic polymer~ or impact modifier~, it al~o being po~sible for free-radical initiators to be present.
Examples of suitable modifiers (b3) are maleic acid, methyl maleic acid, itaconic acid, tetrahydro-phthalic acid, the anhydrides and imides thereof, fumaric acid, the monoesters and diester~ of the e acid~, for example of C~- and C2-C8-alkanols (monomer b3~), the monoamidos and diamides of these acids, such as N-phenyl-maleimide (monomers b32), maleic hydrazide, the acyl chloride of trimellitic anhydrid~, ben~ene-1,2-(dicar-boxylic anhydride)-4-(carboxylic acetic anhydride), chloroethanoylsuccinaldehyde, chloroformylsuccinaldehyde, citric acid And hydroxysuccinic acid. Example~ of monomer~ b33~ are N-vinylpyrrolidone and 2 ~
- 7 - O.Z~ 0050/41085 ~meth)acryloylcaprolactam.
The preferred component B) in the molding materials according to the invention is a modified pol~phenylene ether obtainable by reacting bl) from 9.g4 to 99.94 ~ by weight of Pn unmodified polyphenylene ether, b2) from 0 to 90 ~ by weight of a vinyl-aromatic polymer, b3) from 0.05 to 10 % by weight of one or more compound~
from the group formed by b31) an l,~-unsaturated dicarbonyl compound, b32~ an amide-containing monomer having a polymeriz-able double bond and b33) a lactam-containing monomer having a polymeriz-able double bond, b4) from 0 to 80 ~ by weight of other graft-active monomers and b5) from 0.01 to 0.09 % by weight of a free-radical initiator, 20 the percentages by weight being based on the ~um of bl) to b5), for from 0.5 to 15 minutes at from 240 to 375C
in a suitable mixer and kneader, such as a twin-screw extruder.
The vinyl-aromatic polymer ~b2) should preferably 25 be compatible with the polyphenylene ether employed.
The molecular weight of these conventional polymers i8 generally in the range from 1500 to 2,000,000, preferably in the range from 70,000 to 1,000,000.
Example-~ of preferred vinyl-aromatic polymers which are compatible with polyphenylene ethers are given in the abovementioned monograph by Olabisi, pages 224 to 230 and 245. A~ representatives only, vinyl-aromatic polymers made from styrene~ chlorostyrene, ~-methyl-35 styrene and p-m~thylstyrene are mentioned here; in minor amounts (preferably not more than 20 % by weight, in particular not more than 8 % by weight), comonomer~
2~ ~ 72~
- 8 - O.Z. 0050/41085 such as (meth)acrylonitrile or (meth)acrylates may also participate in the synthesis. Particularly preferred vinyl-aromatic polymers are polystyrene and Lmpact-modified polystyrene. :[t is of course also possible to employ mixtures of these polymers. The preparation is preferably carried out by the process described in EP-A-302 485.
If desired, further comonomers b4) which react with or graft onto components bl and, if used, b2) under the preparation conditions can also be employed in the preparation of the modified polyphenylene ether B.
Examples which may be mentioned are acrylic acid, meth-acrylic acid, acrylates, methacrylates and vinyl-aromatic monomers such as styrene, ~-methylstyrene and vinyl-toluene, to mention but a few.
The proportion of component b4) is from 0 to 80 %by weight, preferably from 0 to 45 % by weight, in particular not more than 20 % by weight, based on the sum of components b1) to b5). Particularly preferred molding materials contain no component b4).
Examples of free-radical initiators (b5) are:
di(2,4-dichlorobenzoyl) peroxide, tert.-butyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroylperoxide, didecanoyl peroxide, dipropionyl peroxide, dibenzoyl peroxide, tert.-butyl peroxy-2-ethylhexanoate, tert.-butyl peroxydiethylacetate, tert.-butyl peroxyisobutyr-ate, 1,1-di-tert.-butylperoxy-3,3,5-trimethylcyclohexane, tert.-butyl peroxyi~opropylcarbonate, tert.-butylperoxy-3,3,5-trimeth.ylhexanoate, tert.-butyl peracetate, tert.-butyl perbenzoate, butyl 4,4-di-tert.-butyl peroxyvaler-ate, 2,2-di-tert.-butylperoxybutane, dicumyl peroxide, tert.-butylcumyl peroxide, 1,3-di(tert.-butylperoxyiso-propyl)benzene and di-tert.-butyl peroxide. Organic hydroperoxides, such a~ diisopropylbenzene monohydro-peroxide, cumene hydroperoxide, tert.-butyl hydroperox-ide, p-menthyl hydroperoxide and pinane hydroperoxide, and highly branched alkanes of the general structure 2~2~29 - 9 - O.Z. 0050/41085 R4 Rl where Rl to R6 are alkyl ha~ing from 1 to 8 carbon atoms, alkoxy having from 1 to 8 carbon atoms, aryl, such as phenyl or naphthyl, or 5- or 6-membered heterocyclic rings having a ~-electron system and nitrogen, oxygen or sulfur as heteroatoms, are also suitable. The substitu-ent3 R1 to R5 may themselves contain functional groups as sub~tituents, such as carboxyl, carboxyl derivatives, hydroxyl, amino, thiol or epoxide groups. Examples are 2,3-dLmethyl-2,3-diphenylbutane, 3,4-dLmethyl-3,4-di-phenylhexane and 2,2,3,3-tetraphenylbutane.
The molding materials according to the invention contain, as component C), from 0.1 to 8 % by weight, preferably from 0.2 to 4 ~ by weigh~, in particular from 0.25 to 3 ~ by weight, of a metal ~ulfide.
Suitable sulfides are alkali metal and alkaline earth metal sulfides, e.g. sodium sulfide, potassium sulfide, calcium sulfide and barium sulfide, and metal sulfides from the sub-group~ of the Periodic Table, such as manganese sulfide, iron sulfide, nickel sulfide, copper sulfide and cadmium sulfide, and particularly preferably zinc sulfide.
Commercially available zinc sulfide generally contains 97 % by weight or more of zinc sulfide in addition to small amounts of barium sulfate and zinc oxide.
It u~ually ha~ a zinc blende or wurzite structure and a den~ity, in general, of from 2 to 5 g/cm3, in particular from 4 to 5 g/cm3.
It i8 also possible to use mixtures of metal sulfides with oxideq in a mixing ratio of, in general, from 8:2 to 2:8.
In general, the metal sulfides in powder form can easily be incorporated into the molding materials according to the in~ention. Preference is given to 2 ~ r~ 2 ~
- lO - O.Z. 0050/41085 concentrates of the metal sulfide, for example in a polyamide, since this allow~ better dispersion of the pigment to be achieved.
The molding materials according to the invention contain, as component D), from 0 to 40 ~ by weight, preferably from 10 to 35 % by weight, of fibrous or particulate fillers or mixtures thereof. Examples of fillers are carbon or glass fibers in the form of woven glass fabrics, glass mats or glass rovings, glass beads, and wollastonite.
Preferred fibrous reinforcing materials (com-ponent C) are carbon fibers, potassium titanate whiskers, aramid fibers and, particularly preferably, glass fibers.
When gla~s fiberY are used, they may be provided with a size and coupling agent in order to impart better com-patibi~ity with the thermoplastic polyamide (A) or the polyphenylene ether (B). In general, the carbon fiber~
and glass fibers used have a diameter in the range from 6 to 20 ~m.
These glass fibers can be incorporated either in the form of short glass fiber~ or continuous extrudates (rovings). In the finished injection molding, the mean length of the glass fibers is preferably in the range from 0.08 to 0.5 mm.
~5 Suitable particulate fillers are amorphouq silica, asbesto3, magne#ium carbonate, chalk , powdered quartz, mica, talc, feldspar and, in particular, calcium ~ilicate~ such a~ wollastonite and kaolin (in particular calcined kaolin).
Examples of preferred combinations of fillers are 20 ~ by weight of glass fibers with 15 % by weight of wollastonite and 15 % by weight of glas~ fiber~ with 15 %
by waight of wollastonite.
In addition to the es~ential component~ A), B) and C), the molding materials according to the invention can contain from 0 to 25 % by weight, preferably from 3 to 20 % by weight, of an impact-modifying rubber. Con-~ O.Z. 0050/41085 ventional impact modifiers E) which are suitable for polyamides (component A) and rubbers E) which are usually used for the impact modification of polyphenylene ether~
B) can be used.
The preferred rubber-ela~tic polymers E) for polyamides A) are those which have reactive group~ at the surface.
Examples of groups of this type are epoxy, carboxyl, latent carboxyl, amino or amide groups, and functional groups which can be introduced by carrying out the polymerization in the presence of monomerq of the general formula R10 Rll CH 2=C--X~C--R12 ll where the substituent can have the following meanings:
Rl~ is hydrogen or C~-C4-alkyl, Rll is hydrogen, Cl-C8-alkyl or aryl, in particular phenyl, Rl2 is hydrogen, C1-C10-alkyl, C6-C12-aryl or oR13, Rl3 is Cl-C~-alkyl or C6-Cl2-aryl, which is unsubstituted or substituted by O~ or N containing groups, X i8 a chemical bond, C1-C10-alkylene, C6-Cl2-arylene or R
_c--Y
Y i8 O-Z or NH-Z and Z i~ C1-C10-alkylene or Cs-Cl2-arylene.
The graft monomer~ described in EP-A 208 187 are also suitable for introducing reactive groups at the surface.
Examples of monomers using which the abovemen-tioned functional groups can be introduced are glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl e~her, glycidyl itaconate, acrylic acid, methacrylic acid and the metal, in partlcular alkali metal, and ammonium salts thereof, maleic acid, fumaric 2~7~
- 12 - O.Z. 0050/41085 acid, itaconic acid, vinylbenzoic acid, vinylphthalic acid, monoesters of these acids with alcohols ROH where R has up to 29 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, stearyl, methoxy-ethyl, ethoxyethyl or hydroxyethyl. Although maleic anhydride and esters of acrylic acid or methacrylic acid with tertiary alcohols, for example tert.-butyl acrylate, do not have any free carboxyl groups, they behave in a similar manner to the free acids and are therefore regarded as monomers having latent acid groups.
Further examples are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (N-t-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and (N,N-diethylamino)ethyl acrylate.
The proportion of groups derived from the above-mentioned monomers is generally from 0.5 to 40 % by weight, preferably from 0.5 to 25 ~ by weight, based on the total weight of the rubber.
These monomers can either be copolym~rized with the other monomers during preparation of the rubber or grafted onto a pre-exi~ting, unmodified rubber (if necessary in the presence of initiator~, for example free-radical initiators).
The rubbers are generally polymers preferably built up from two or more of the following monomer~ as the principal component~: ethylene, propylene, butadiene, isobutene, i30prene, chloroprene, vinyl acetate, styrene, acrylonitrile, methacrylic acid, acrylic acid and acrylate~ and methacrylates having from 1 ~o 18 carbon atoms in the alcohol component.
A first preferred group comprises the ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers, which preferably h~ve an ethylene:
propylene ratio in the range from 40:60 to 90:10.
The Mooney viRcositie~ (MLl+4flQ0C) of uncro~s-2~7~
- 13 - O.Z. 0050/4108S
linXed EPM and EPDM rubbers of this type (gel contents generally less than I % by weigh~) are preferably in the range from 25 to 100, in particular from 35 to 90 (meas-ured in accordance with DIN 53 523 on the large rotor after a running time of 4 minutes at 100C).
EPM rubbers generally have virtually no double bonds, while EPDM rubbers may contain from 1 to 20 double bonds per 100 carbon atom3.
Examples of diene monomers for EPDM rubbers are conjugated dienes, such as isoprene and butadiene, non-con~ugated diene~ having from 5 to 25 carbon atoms, such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic diene~, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyltricyclo-[5.2.1Ø2.6]-3,8-decadiene, and mixtures thereof.
Preference is given to hexadiene-1,5,5-ethylidenenorbor-nene and dicyclopentadiene. The diene content of the EPDM
rubbers is generally from 0.5 to 50 ~ by weight, in particular from 3 to 15 % by weight, based on the total weight of the rubber.
EPM and EPDM rubbers are usually grafted with the - abovementioned monomers carrying reactive group~, of which only acrylic acid, methacrylic acid and derivatives thereof, and maleic anhydride are mentioned here.
A further group of rubbers comprise~ copolymer~
of ~-olefin , preferably ethylene, with ester~ of acrylic or methacrylic acid, for example with the methyl, ethyl, propyl, n-, i- or t-butyl and 2-ethylhexyl esters. In addition, the rubbers may also contain the abovementioned reactive gxoup~, for example in the form of dicarboxylic acids, derivatives of these aclds, vinyl esters and vinyl ether~.
The ethylene content of the copolymers i~ gener-2~2~2~
- 14 - O.Z. 5050/41085 ally in the range from 50 to 98 % by weight, and the proportions of epoxide-contain:ing monomers and of the acrylate and/or methacrylate are each in the range from 1 to 49 % by weight.
Preference is given to olefin polymers comprising from 50 to 98.9 ~ by weight, in particular from 60 to 95 ~ by weight, of ethylene, from 0.1 to 20 ~ by weight, in particular from 0.15 to 15 ~ by weight, of glycidyl acrylate and~or glycidyl methacrylate, acrylic acid and/or maleic anhydride, and from 1 to 45 ~ by weight, in particular fxom 10 to 35 % by weight, of n-butyl acrylate and/or 2-ethylhexyl acrylate.
The above-described ethylene copolymers can be prepared by conventional processes, preferably by random copolymerization under superatmospheric pressure and at elevated temperature. Appropriate processes are described in the literature.
The melt flow index of the ethylene copolymers is generally in the range from 1 to 80 g/10 min (measured at 190C under a load of 2.16 kg).
Suitable elastomers for the impact modification of polyamide are furthermore graft copolymers/ containing reactive group~, with butadiene, butadieneJ~tyrene, butadiene/acrylonitrile and acrylate rubbers aQ the graft base, as deQcribed, for example, in DE-A 16 9~ 173, DE-A 23 48 377, DE-A 24 44 584 and DE-A-27 26 256, in particular the ABS polymer~, as de~cribed in DE-A-20 35 390, DE-A-22 48 242 and EP-A-22 216.
The rubber E may be a graft polymer comprising from 25 to 98 % by weight of an acrylate rubber having a glass transition temperature of below -20C as the graft baQe ~base polymer) and ?~ ~ 2 ~
- 15 - O.Z. 0050/41085 from 2 to 75 ~ by weight of a copolymerizable, ~thylenically unsaturated monomer whose homopolymers and copolymers have a glass transition temperature of greater than 25C, as the graft shell.
The graft base is an acrylate or methacrylate rubber containing up to 40 ~ by weight of further co-monomers. The Cl-C3-e~ter~ of acrylic acid or methacrylic acid and the halogenated derivatives thereof, and aromatic acrylates and mixtures thereof are usually employed.
Specific exampleR of comonomers in the graft base are acrylonitrile, methacrylonitrile, styrene, ~-methylstyr-ene, ac~ylamide~, methacrylamides and vinyl Cl-C~-alkyl ethers.
The graft base may be uncrosslinked or partially or fully crosslinked, which is achieved, for example, by copolymerizing preferably from 0.02 to 5 ~ by weight, in particular from 0.05 to 2 % by weight, of a crosslinking monomer containing more than one double bond. Suitable crosslinking monomer~ are described, for example, in DE-A 27 2~ 256 and EP-A 50 265.
Preferred crosslinking monomers are triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
If ths crosslinking monomerR contain more than 2 polymerizable double bond~, it i~ advantageous to limit their amount to not more than 1 ~ by weight, based on the graft base.
Highly ~uitable graft bases are emulsion polymers having a gal content of grea~er than 60 ~ by weight (determined in dimethylformamide at 25C by the method of M. Hoffmann, H. Rr~mer, R. Kuhn, Polymeranalytik, Georg-Thieme-Verlag, Stuttgart, 1977).
Other ~uitable graft ba3e~ are acrylate rubbers 3S having a diene core, as described, for example, in EP-A 50 262.
Particularly sui~able graft monomer-~ are styrene, 2~2~ 1~2~
- 16 - O.Z. 0050/41085 ~-methylstyrene, acrylonitrile, methacrylonitrile and methyl methacrylate, or mixtures thereof, in particular those comprisiny styrene and acrylonitrile in the weight ratio from 1:1 to 9:1.
The reactive groups can be introduced into the graft copolymers by, for example, carrying out the preparation of the graft shell in the presence of the appropriate monomers. In this case, the proportion thereof in the graft monomer mixture is preferably from 0.5 to 30 % by weight, in particular from 1 to 25 % by weight. It is also possible to apply the appropriate monomers separately as the final graft shell.
The graft yield, ie. the quotient of the amount of grafted-on monomers and the amount of graft monomers employed, is generally in the range from 20 to 90 ~.
Examples of rubbers are those which are used for the impact modification of polyphenylene ethers B).
Examples which may be mentioned are thermoplastic rubbers, such as polybutadiene, polybutene, polyisoprene, acrylonitrile-butadiene, ethylene-propylene, polyesteror ethylene rubbers, and elastomeric copolymers made from ethylene and esters of (meth)acrylic acid, for example ethylene-butyl acrylate copolymers, furthermore ionomers, polyoctenylenes, graft rubbers having a graft core made from butadiene or isoprene or alkyl ~meth)acrylates and a graft shell made from styrene and/or ~-methyl~tyrene, and preferably ~tyrene-butadiene block copolymer3, including A~, A~A and ~BAB block copolymer~, which may al~o have indi3tinct transitions, star block copolymers and the like, analogous isoprene block copolymers and (partially) hydrogenated block copolymers. These rubber~
can also be employed in the form of a graft with vinyl-aromatic monomers, such a~ styrene (EP-A 234 063 and US-A 4,681,915).
The rubber~ E preferably have a gla~ transition temperature of below ~30C, in particular below -40C. It is of course al~o possible to employ mixtures of the 2~ 72~3 - 17 - O.Z. 0050/41085 abovementioned types of rubber.
The molding materials according to the invention may furthermore contain flameproofing agents F) in amounts of from 0 to 25 ~ by weight, preferably up to 15 ~ by weight, based on the total weight of the molding materials.
All known flameproofing agents are suitable, eg.
polyhalobiphenyl, polyhalobiphenyl ether, polyhalo-phthalic acid and derivatives thereof, polyhalooligo-carbonates and polyhalopolycarbonates, the correspondingbromine compound~ being particularly effective.
Examples of these are polymer~ of 2,6,2',6'-tetrabromobisphenol A, of tetrabromophthalic acid, of 2,6-dibromophenol and of 2,4,6-tribromophenol and deriv-atives thereof.
A preferred flameproofing agent F~ is elementalred phosphorus, which can generally be phlegmatized or coated with, for example, polyurethanes or other amino plastic~. In addition, concentrates of red phosphorus in, for example, a polyamide, elastomer or polyolefin are also suitable.
Particular preference i~ given to 1,2,3,4,7,8,9,-10,13,13,14,14-dodecachloro-1,4,4a,5,6,6a,7,10,10a,11,-12,12a-dodecahydro-1,4:7,10-dimethanodibenzo(a,e)cyclo-octane (Dechlorane~ Plus, Occidental Chemical Corp.) and,if desired, a synergi~t, for example antimony trioxide.
Other cuitable phosphorus compounds are organo-phosphoru~ compound~, such a~ phosphonates, phosphinate~, phosphinites, phosphine oxides, phosphines, pho~phites or phosphates. A ~pecific example i triphenylpho~phine oxide, which can be used alone or mixed with hexabromo-benzene or a chlorinated biphenyl or red pho~phoru~ and, if desired, antimony oxide.
Typical preferred phosphorus compounds which can be u~ed according ~o the pre~ent invention are tho~e of the general formula 2~72~
- 18 - O.Z. 0050/~1085 ~o-I~OQ
o~
where Q is hydrogen or identical or different hydrocarbon radicals or halogenated hydrocarbon radicals, such a~
alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-substituted alkyl, with the proviso that one or more of the radicals Q is aryl. Example~ of suitable phosphate~
of this type are phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl ethylene hydrogen phos-phate, phenyl bis(3,5,5'-trLmethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethylhexyl) phenyl pho~phate, tri(nonylphenyl) phosphate, phenyl methyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl pho~phate, triphenyl phosphate, dibutyl phenyl phosphate and diphenyl hydrogen phosphate. The preferred phosphates are those in which each Q i aryl. The most preferred phosphate is triphenyl phosphate. The combin-ation of triphenyl pho~phate with hexabromobenzene and antimony trioxide is also preferred.
Other suitabls flameproofing agent~ are compounds which contain phosphorus-nitrogen bond~, such as phospho-nitrile chloride, phosphori~ acid e~ter amides, phoc-phoric acid ester amine~, phosphoric acid amides, phosphonic acid amides, pho~phinic acid amide~, tris-(aziridinyl) phosphine oxide and tetrakis(hydroxymethyl)-phosphonium chloride. The ma~ority of these flame-inhibiting additives are commercially available.
Other ~uitable halogen-containing flameproofing agents are tetrabromoben~ene, hexachlorobenzene, hexa-bromobenzene, and halogenated polystyrene~ and polyphenylene ethers.
It is also pos~iblo to use the halogenated phthalimides de cribed in DE-A-l9 46 924, of which N,N'-ethylenebistetrabromophthalimide, in pasticular, has - 19 - O.Z. 0050/41085 achieved Lmportance.
In addition to the essential components A), B) and C) and, if desired, D), E) and F), the molding mater-ials according to the invention can also contain conven-S tional additives and processing aids, whose proportion isgenerally up to 20 % by weight, preferably up to 10 % by weight, based on the total weight of components A) to F).
Examples of conventional additives are stabiliz-ers, antioxidants, thermal stabilizers, W stabilizers, lubricants, mold release agents, dyes, pigments and plasticizers.
Examples of antioxidants and thermal stabilizers which can be added to the thermoplastic materials accord-ing to the invention are halides of metals of group I of the Periodic Table, eg. ~odium halides, potassium halides and lithium halides, if desired in combination with copper(I) halides, eg. chlorides, bromides or iodides. It is also possible to use zinc fluoride, zinc chloride, sterically hindered phenols, hydroquinone~, substituted representa~ive~ of thi~ group, and mixtures of these compounds, preferably in concentration~ of up to 1 % by weight, based on the weight of the mixture.
Examples of W 4tabilizers are various substituted resorcinols, salicylates, benzotriazole~ and benzophe-nones, which are generally employed in amounts of up to2 % by weight.
Materials for increasing the screening against electromagnetic waves, such as metal flakes, metal powders, metal fibers and metal-coated fillers, can also be used.
Lubricants and mold release agents, which are generally added to the thermopla~tic material in amounts of up to 1 ~ by weight, are stearic acid, stearyl alcohol, alkyl stearates, alkyl ~tearamides and esters of pentaerythritol with long-chain fatty acid~.
The additiveY al~o include ~tabilizers which prevent decomposition of the red phosphorus (component F) 2~L~ ~ 2~
- 20 - O.Z. 0050/41085 in khe pre~ence of moisture and atmospheric oxysen.
Examples are compounds of cadmium, zinc, aluminum, silver, iron, copper, antimony, tin, magnesium, man-ganese, vanadium and boron. Examples of particularly suitable compounds are oxides of the metals mentioned, furthermore carbonates or o~ycarbonates, hydroxides and salts of organic or inorganic acids, such as acetates, pho~phates, hydrogen phosphates and sulfates.
The thermoplastic molding materials according to the invention can be prepared by conventional processes by mixing and subsequently extruding the starting com-ponents in conventional mixers, such as screw extruder~, preferably twin-screw extruders, Brabender mills or Banburry mills, and kneaders. After extrusion, the extrudate i~ cooled and comminuted.
In order to obtain the mo~t homogeneous molding material possible, vigorous mixing i~ necessary. To this end, mean mixing times of from 0.2 to 30 minute~ at from 280 to 380C are generally necessary. The ~equence of mixing of the components may be varied; for example, it is po~sible to pre-mix two or three components, or to mix all the components together. It may be advantageous to prepare the modified polyphenylene ether B2 in a first zone of an extruder and to mix it with the other com-ponents of the molding material according to the inven-tion in one or more ~ub~equent zones. A proces~ of this type i~ described in DE-A 37 02 5B2.
The molding materials according to the invention have good toughness, in particular multiaxial toughness, combined with good processability.
This property profile makes the moldings which can be produced from ~he molding materials according to the invention particularly suitable for motor vehicle part~, ~ports equipment, and electronic and electrical components.
2~24 729 - 21 - O.Z. 0050/41085 EXAMPLES
Component A1) Poly-~-caprolactam having a Fikentscher K value of 73, measured in l ~ strength by weight solution of 96 % by weight sulfuric acid at 25C, corresponding to ~rel f 2.7.
Component A2) Polyhexamethyleneadipamide having a R value of 76, corresponding to a relative viscosity ~r~l of 2.95.
Component A3) Polyhexamethyleneadipamide having a K value of 60, corresponding to qr~l Of 2.05.
Component (Bl) A modified polyphenylene ether comprising 90 g by weight of poly(2,6-dLmethyl-1,4-phenylene) ether (~r~d = ~ 59 dl/g, measured in 1 % strength by weight solution in chloroform at 25C), 8 ~ by weight of polystyrene (melt flow index MFI at 200~C and a load of 5 kg: 24 g/10 min), 1.95 % by weight of fumaric acid and 0.05 % by weight of 3,4-dimethyl-3,4-diphenylhexane (initiator) wa~ prepared by mixing the component~ at from 290 to 310C in a twin screw extruder with subsequent dega~sing.
The melt was p2s~ed through a water bath, granulated and dried.
Component (Bl*) (for comparison) An unmodified polyphenylene ether having a mean molecular weight (weight average) ~ of 30,000 and ~rad = 0.59 dl/g.
Component C1) Zinc sulfide having a density of 4.1 g/cm3.
Component C2) Zinc ~ulfide pigment having a mean particle size of 0.35 ~m.
2~2~72~
- 22 - O.Z. 0050/41085 Component E1) A styrene-butadiene-styrene three-blockcopolymer having a styrene content of 30 ~ by weight.
Component E2) A two-block copolymer of styrene and hydrogenated polybutadiene having a styrene content of 35 % by weight;
n~mber average molecular weight ~ = 95,000.
Component E3) An ethylene copolymer comprising:
70 % by weiqht of ethylene, 25 % by weight of n-butyl acrylate and 5 ~ by weight of acrylic acid.
MFI = 11 g/10 min (190C/2.16 kg) (DIN 53 735) Preparation of the molding materials Components A), B) and C) and, if desired, D) to F) were mixed in a twin-screw extruder at a barrel temperature of 290C. The melt wa~ passed through a water bath and granulated. The dried granules were in~ection-molded at 280C to form dumbbell te~t specimens and a~
300C to form circular di~ks (60 x 2 mm).
The penetration energy was determined on circular disk~ in accordance with DIN 53 443; the modulus of ela~ticity was determined on dumbbell te~t specLmens in accordance with DIN 53 437.
The melt flow index (MFI) wa~ determined in accordance with DIN 53 735 at 275C and a load of 10 kg.
Th~ compositions of the molding material~ and the results of the measurements are shown in the table.
As can be seen, the melt flow index and the penetration energy are clearly superior in the examples according to the invention compared with the comparative examples.
~2~72~
- 23 C). Z . 0050/41085 ~ I
~, H O I ~ 11~ ~7 t` ~ ~1 0 1 U~ U N I O C:~ O O O O O C~
a ~a z I
~ ~ I
I
~ ~ I
ll ~1 I ____,____~
I N ~--I
+ ~
__ --O
I ---- -- ----U U ~ e~
~ ~ I U U U I I U U u~ u7 ul u~
~ .C I _I ~ _I C'~l ~ O O O O
o ~ I __ mm-- * ~ m~ ~ ~
~dP I m m t~ u~ m m m u~ m m m I O U~ O~ O ~ n ~ o o o o I ~ ~
U
I _I ~ _I t'~l C~ N ~
* *
O I ~ ~ *~ O _~
202~ ~729 - 24 - O.Z. 0050/41085 Key to table:
***) in addition 0.3 % by weight of 2-(2-hydroxy-5-methylphenyl)benzotriazole **) for comparison Example 6 additionally contained, in accordance with DE-A-3 443 154, 5 ~ by weight of styrene-maleic anhydride copolymer (92/8~ and 10 % by weight of triphenylphosphine oxide Example 7 contained, in accordance with Example 10 of EP-A-221,341, 10.4 ~ by weight of a styrene-acrylamide copolymer (90/10) Example 8 contained, in accordance with WO 83/0 38 34, 20 ~ by weight of triphenyl phosphate.
Examples 9 to 11 contained, in accordance with US 4,255,321, impact-modified polystyrene containing 8 % by weight of polybutadiene rubber (VN = 70 ml/g of the matrix tyrene in accordance with DIN 53 726), 9 = 49.5 ~ by weight, 10 = 50 ~ by weight, 11 = 49 ~ by weight.
Claims (5)
1. A thermoplastic molding material containing, as essential components, A) from 10 to 89.9 % by weight of a thermoplastic polyamide, B) from 10 to 89.9 % by weight of a modified poly-phenylene ether, C) from 0.1 to 8 % by weight of a metal sulfide and, in addition, D) from 0 to 40 % by weight of a fibrous or particulate filler or a mixture thereof, E) from 0 to 25 % by weight of an impact-modifying rubber and F) from 0 to 25 % by weight of a flameproofing agent.
2. A thermoplastic molding material as claimed in claim 1, containing from 25 to 71.8 % by weight of A), from 25 to 71.8 % by weight of B), from 0.2 to 4 % by weight of C) and from 3 to 20 % by weight of E).
3. A thermoplastic molding material as claimed in claim 1, in which component C) is zinc sulfide.
4. A thermoplastic molding material as claimed in claim 1, in which component B) is a modified poly-phenylene ether prepared from b1) from 9.94 to 99.95 % by weight of a polyphenylene ether, b2) from 0 to 90 % by weight of a vinyl-aromatic polymer, b3) from 0.05 to 10 % by weight of one or more compounds from the group formed by b31) an .alpha.,.beta.-unsaturated dicarbonyl compound, b32) an amide-containing monomer having a polymeriz-able double bond and b33) a lactam-containing monomer having a polymeriz-able double bond, b4) from 0 to 80 % by weight of further graft-active - 26 - O.Z. 0050/41085 monomers and b5) from 0.01 to 0.09 % by weight of a free-radical initiator.
4. A filler-containing thermoplastic molding material as claimed in claim 1, in which the filler comprises glass fibers, wollastonite, carbon fibers or a mixture thereof.
4. A filler-containing thermoplastic molding material as claimed in claim 1, in which the filler comprises glass fibers, wollastonite, carbon fibers or a mixture thereof.
5. A molding obtainable from a thermoplastic molding material as claimed in claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3929686A DE3929686A1 (en) | 1989-09-07 | 1989-09-07 | STABILIZED THERMOPLASTIC MOLDING MATERIALS BASED ON POLYPHENYLENE ETHERS AND POLYAMIDES |
DEP3929686.5 | 1989-09-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2024729A1 true CA2024729A1 (en) | 1991-03-08 |
Family
ID=6388793
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002024729A Abandoned CA2024729A1 (en) | 1989-09-07 | 1990-09-06 | Stabilized thermoplastic molding materials based on polyphenylene ethers and polyamides |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0416435B1 (en) |
CA (1) | CA2024729A1 (en) |
DE (2) | DE3929686A1 (en) |
ES (1) | ES2059939T3 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5296563A (en) * | 1991-12-21 | 1994-03-22 | Basf Aktiengesellschaft | Preparation of polyphenylene ether/polyamide molding materials |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4113162A1 (en) * | 1991-04-23 | 1992-10-29 | Basf Ag | HIGH IMPACT TOOLS |
JP3251068B2 (en) * | 1991-10-02 | 2002-01-28 | 住友化学工業株式会社 | Thermoplastic resin composition and secondary processed product thereof |
US5459189A (en) * | 1991-10-02 | 1995-10-17 | Sumitomo Chemical Company, Ltd. | Thermoplastic resin composition |
JPH09124927A (en) * | 1995-06-07 | 1997-05-13 | General Electric Co <Ge> | Composition containing polyphenylene ether resin and polyamide resin and exhibiting improved impact strength |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2226932B2 (en) * | 1972-06-02 | 1976-03-18 | Basf Ag, 6700 Ludwigshafen | GLASS FIBER REINFORCED THERMOPLASTIC MOLDING COMPOUNDS PIGMENTED WITH INORGANIC PIGMENTS |
DE3535273A1 (en) * | 1985-10-03 | 1987-04-09 | Basf Ag | MIXTURES OF POLYPHENYLENETHER AND POLYAMIDE AND THE USE THEREOF FOR THE PRODUCTION OF THERMOPLASTIC MOLDS |
DE3780383T2 (en) * | 1986-09-10 | 1992-12-17 | Mitsubishi Gas Chemical Co | POLYPHENYLENEEAETHER RESIN COMPOSITION. |
DE3736853A1 (en) * | 1987-10-30 | 1989-05-11 | Basf Ag | THERMOPLASTIC MOLDS |
-
1989
- 1989-09-07 DE DE3929686A patent/DE3929686A1/en not_active Withdrawn
-
1990
- 1990-08-28 EP EP90116437A patent/EP0416435B1/en not_active Expired - Lifetime
- 1990-08-28 ES ES90116437T patent/ES2059939T3/en not_active Expired - Lifetime
- 1990-08-28 DE DE90116437T patent/DE59003322D1/en not_active Expired - Lifetime
- 1990-09-06 CA CA002024729A patent/CA2024729A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5296563A (en) * | 1991-12-21 | 1994-03-22 | Basf Aktiengesellschaft | Preparation of polyphenylene ether/polyamide molding materials |
Also Published As
Publication number | Publication date |
---|---|
DE59003322D1 (en) | 1993-12-09 |
EP0416435B1 (en) | 1993-11-03 |
DE3929686A1 (en) | 1991-03-14 |
ES2059939T3 (en) | 1994-11-16 |
EP0416435A1 (en) | 1991-03-13 |
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