WO2002094534A1 - Method for the production of castings from polyamide nanocomposites - Google Patents
Method for the production of castings from polyamide nanocomposites Download PDFInfo
- Publication number
- WO2002094534A1 WO2002094534A1 PCT/EP2002/005472 EP0205472W WO02094534A1 WO 2002094534 A1 WO2002094534 A1 WO 2002094534A1 EP 0205472 W EP0205472 W EP 0205472W WO 02094534 A1 WO02094534 A1 WO 02094534A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- melt
- polyamide
- injection molding
- acid
- molded parts
- Prior art date
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 84
- 229920002647 polyamide Polymers 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000005266 casting Methods 0.000 title 1
- 239000000155 melt Substances 0.000 claims abstract description 70
- 238000001746 injection moulding Methods 0.000 claims abstract description 54
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 31
- 229920002292 Nylon 6 Polymers 0.000 claims description 13
- 235000012216 bentonite Nutrition 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 abstract description 8
- 239000007924 injection Substances 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 37
- 238000000465 moulding Methods 0.000 description 34
- 239000000203 mixture Substances 0.000 description 31
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 26
- 229920001971 elastomer Polymers 0.000 description 26
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 150000004760 silicates Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000000806 elastomer Substances 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000009757 thermoplastic moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004908 Emulsion polymer Substances 0.000 description 4
- 229920002614 Polyether block amide Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 150000003951 lactams Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229940092782 bentonite Drugs 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000005677 ethinylene group Chemical class [*:2]C#C[*:1] 0.000 description 3
- 239000012765 fibrous filler Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 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
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920001007 Nylon 4 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006097 Ultramide® Polymers 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- JZCKBEPITCOOMD-UHFFFAOYSA-N bis(2-hydroxyethyl)-nonadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCC[NH+](CCO)CCO JZCKBEPITCOOMD-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009830 intercalation Methods 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
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- 239000002244 precipitate Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920006024 semi-aromatic copolyamide Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 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
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical class CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- CKFRJFUTYHQHCA-UHFFFAOYSA-N 2-phosphanylethanol Chemical compound OCCP CKFRJFUTYHQHCA-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
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- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical compound [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 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
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BPSKTAWBYDTMAN-UHFFFAOYSA-N tridecane-1,13-diamine Chemical compound NCCCCCCCCCCCCCN BPSKTAWBYDTMAN-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
- B29C70/62—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler being oriented during moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
- B29C45/2701—Details not specific to hot or cold runner channels
- B29C45/2708—Gates
- B29C2045/2714—Gates elongated, e.g. film-like, annular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
Definitions
- the invention relates to a method for producing molded parts from polyamide nanocomposites, containing
- the invention relates to the moldings obtainable by the process, and to a process for increasing the toughness of moldings made of polyamide nanocomposites containing at least one polyamide A) and at least one delaminated layered silicate B).
- Polyamide nanocomposites are thermoplastic molding compounds containing polyamide and layered silicates delaminated as fillers and reinforcing materials.
- Such materials and molded parts made therefrom are, for. B. from the documents WO-A 94/11430, WO-A 93/04118, WO-A 93/04117, WO-A 99/41299 and EP-A 940430 known.
- moldings have from those described there molding compositions for some applications adequate mechanical properties, but they are for specific applications too brittle, ie the total fracture energy W tot according to DIN 53443 in the multiaxial impact test is comparatively small and the toughness is too low.
- the task was to remedy the disadvantages described.
- the object was to provide a process for the production of moldings from polyamide nanocomosites, which provides moldings with improved toughness (reduced brittleness), in particular improved multiaxial toughness.
- the task was to provide a method that delivers such molded parts with a higher total damage work W g e S (according to DIN 53443).
- the process defined at the outset was found. It is characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved, and that the high orientation of the melt is frozen when the melt solidifies.
- the moldings obtainable by the process were found, as well as a process for increasing the toughness of moldings made of polyamide nanocomposites, containing at least one polyamide A) and at least one delaminated layered silicate B).
- Preferred embodiments of the invention can be found in the subclaims.
- the polyamide nanocomposites contain at least one polyamide A).
- Polyamides with an aliphatic semi-crystalline or partially aromatic and amorphous structure of any kind and their 25 blends, including polyether amides such as polyether block amides, are suitable.
- polyamides should be understood to mean all known polyamides.
- Such polyamides generally have a viscosity number of 30 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 ,
- Semi-crystalline or amorphous resins with a molecular weight 35 (weight average) of at least 5,000 are preferred.
- Examples include polyamides derived from lactams with 7 to 13 ring members, 40 such as polycaprolactam, polycapryllactam and polylaurine lactam, and polyamides obtained by reacting dicarboxylic acids with diamines.
- Alkanedicarboxylic acids with 6 to 12, in particular 45, 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids.
- adipic acid, azelaic acid, sebacin Suitable promoters are potassium, sodium, manganese, chromium, cobalt, tungsten, molybdenum, nickel, iron, magnesium, calcium or mixtures thereof, preferably potassium, manganese, chromium, molybdenum or mixtures thereof, particularly preferably potassium, chromium, molybdenum or their mixtures mixtures.
- the shape and shape of the catalysts according to the invention can be selected as desired, such as tablets, rings, stars, wagon wheels, extrudates such as cylinders, pellets or strands, ring tablets or tablets are preferred.
- the ethylene to be cleaned can be processed in a two-step process
- the catalysts of the invention have a higher resistance to acetylenes than those catalysts which have not undergone inventive post-treatment by post-calcining the shaped bodies.
- the catalysts of the invention can be operated with a content of up to 200 [ppm] acetylenes in ethylene to be purified.
- This two-stage process can be preceded by a hydrogenation stage, which conducts the ethylene to be purified in the presence of a sufficient amount of hydrogen over a hydrogenation catalyst, for example a noble metal hydrogenation catalyst, for example 0.3% by weight of Pd on an Al 0 3 support .
- a hydrogenation catalyst for example a noble metal hydrogenation catalyst, for example 0.3% by weight of Pd on an Al 0 3 support .
- the invention relates to a process for the production of molded parts from polyamide nanocomposites containing
- the invention relates to the moldings obtainable by the process, and to a process for increasing the toughness of moldings made of polyamide nanocomposites containing at least one polyamide A) and at least one delaminated layered silicate B).
- Polyamide nanocomposites are thermoplastic molding compounds containing polyamide and layered silicates delaminated as fillers and reinforcing materials.
- Such materials and molded parts made therefrom are, for. B. from the documents WO-A 94/11430, WO-A 93/04118, WO-A 93/04117, WO-A 99/41299 and EP-A 940430 known.
- moldings have from those described there molding compositions for many applications sufficient mechanical natural sheep s, but they are brittle for certain applications, the total fracture energy W tot ie according to DIN 53443 in the multiaxial impact test is comparatively small and the toughness is too low.
- the task was to remedy the disadvantages described.
- the object was to provide a process for the production of moldings from polyamide nanocomosites, which provides moldings with improved toughness (reduced brittleness), in particular improved multiaxial toughness.
- the object was to provide a method which such molded parts having a higher overall fracture energy W tot (according to DIN 53443) provides.
- the process defined at the outset was found. It is characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved, and that the high orientation of the melt is frozen when the melt solidifies.
- the moldings obtainable by the process were found, as well as a process for increasing the toughness of moldings made of polyamide nanocomposites, containing at least one polyamide A) and at least one delaminated layered silicate B).
- Preferred embodiments of the invention can be found in the subclaims.
- the polyamide nanocomposites contain at least one polyamide A).
- Polyamides with an aliphatic semi-crystalline or partially aromatic and amorphous structure of any kind and their 25 blends, including polyether amides such as polyether block amides, are suitable.
- polyamides should be understood to mean all known polyamides.
- Such polyamides generally have a viscosity number of 30 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 ,
- Semi-crystalline or amorphous resins with a molecular weight 35 (weight average) of at least 5,000 are preferred.
- Examples include polyamides derived from lactams with 7 to 13 ring members, 40 such as polycaprolactam, polycapryllactam and polylaurine lactam, and polyamides obtained by reacting dicarboxylic acids with diamines.
- Alkanedicarboxylic acids with 6 to 12, in particular 45, 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids.
- Particularly suitable diamines are alkanediaes having 6 to 12, in particular 6 to 8, carbon atoms and -xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di- (4 -aminophenyl) propane or 2,2-di- (4-aminocyclohexyl) propane.
- Preferred polyamides are polyhexamethylene adipic acid amide (PA 66) and polyhexa ethylene sebacic acid id (PA 610), polycaprolactam (PA 6) and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.
- PA 6 PA 66 and copolyamides 6/66 are particularly preferred.
- Polyamide 6 (PA 6) is very particularly preferred.
- Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
- polyamides which are obtainable by copolymerizing two or more of the aforementioned monomers, or mixtures of two or more polyamides, the mixing ratio being arbitrary.
- partially aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T have proven particularly advantageous, the triamine content of which is less than 0.5, preferably less than 0.3% by weight (see EP-A 299 444).
- the partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196.
- PA 46 (tetramethylene diamine, adipic acid)
- PA 66 (hexamethylene diamine, adipic acid)
- PA 69 (hexamethylene diamine, azelaic acid).
- PA 610 (hexamethylene diamine, sebacic acid)
- PA 612 (hexamethylene diamine, decanedicarboxylic acid)
- PA 613 (hexamethylene diamine, undecanedicarboxylic acid)
- PA 1212 (1,12-dodecanediamine, decanedicarboxylic acid)
- PA 1313 (1, 13-diaminotridecane, undecanedicarboxylic acid)
- PA MXD6 m-xylylenediamine, adipic acid
- PA TMDT Tri ethylhexamethylene diamine, terephthalic acid
- PA 4 (pyrrolidone)
- PA 6 ( ⁇ -caprolactam)
- PA 8 (caprylic lactam)
- PA 9 (9-aminopelargonic acid)
- PA 11 (11-aminoundecanoic acid)
- PA 12 ((laurolactam)
- the polymerization or polycondensation of the starting monomers is preferably carried out by the customary processes.
- the polymerization of caprolactam can be carried out by the continuous processes described in DE-A 14 95 198 and DE-A 25 58 480.
- the polymerization of AH salt to produce PA 66 can be carried out by the customary batch process (see: Polymerization Processes pp. 424-467, in particular pp. 444-446, Interscience, New York, 1977) or by a continuous process , e.g. according to EP-A 129 196.
- chain regulators can also be used in the polymerization.
- Suitable chain regulators are, for example, triacetone diamine compounds (see WO-A 95/28443), monocarboxylic acids such as acetic acid, propionic acid and benzoic acid, and bases such as hexamethylene diamine, benzylamine and 1,4-cyclohexyl diamine.
- C 4 -C ⁇ dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid; C 5 -C 8 cycloalkane dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid; Benzene and naphthalenedicarboxylic acids such as isophthalic acid, terephthalic acid and naphthalene-2, 6-dicarboxylic acid are suitable as chain regulators.
- the polymer melt obtained is discharged from the reactor, cooled and granulated.
- the granules obtained are subjected to post-polymerization. This is done in a manner known per se Way by heating the granules to a temperature T- below the melting temperature T s or crystallite melting temperature T k of the polyamide.
- the final molecular weight of the polyamide (measurable as a viscosity number VZ, see details on the VZ above) is established by the post-polymerization.
- Postpolymerization usually lasts from 2 to 24 hours, in particular from 12 to 24 hours. When the desired molecular weight is reached, the granules are cooled in the usual way.
- the molding compositions contain at least one delaminated layered silicate B).
- Layered silicates are also called phyllosilicates.
- Layered silicate is generally understood to mean silicates in which the SiO 4 tetrahedra are connected to form two-dimensional infinite networks (layered grids).
- the empirical formula for the anion is (Si ⁇ 5 2 ") n >
- the individual layers are connected to each other by the cations lying between them, whereby in the naturally occurring layered silicates mostly as cations Na, K, Mg, Al or / and Approx.
- the layer thicknesses of such silicates before delamination are usually from 5 to 100 ⁇ , preferably 5 to 50 ⁇ and in particular 8 to 20 ⁇ . 1 angstrom corresponds to 0.1 nanometer 0 (nm).
- Examples of synthetic and natural layered silicates are montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, fluorhectorite, saponite, beidellite, talc, nontronite, steimmerite, vermiculite, bentonite, bentonite Fluoromiculite, halloysite and fluorine-containing synthetic mica types called.
- a delaminated layered silicate in the sense of the invention 0 is to be understood as meaning layered silicates in which the layer spacings are initially increased by reaction with so-called hydrophobizing agents and, if appropriate, subsequent addition of monomers (so-called swelling e.g. with so-called AH salts).
- the layered silicates are reacted with so-called hydrophobizing agents, which are often also referred to as onium ions or onium salts, before the molding compositions are produced.
- the cations of the layered silicates are replaced by organic water repellents, the desired layer spacings being able to be set by the type (size) of the organic residue.
- the layer spacing depends on the type of monomer or polymer in which the layered silicate is to be incorporated.
- the metal ions can be exchanged completely or partially. A complete exchange of the metal ions is preferred.
- the amount of exchangeable metal ions is usually given in milliequivalents (meq) per 100 g of layered silicate and referred to as the ion exchange capacity.
- Layered silicates with a cation exchange capacity of at least 50, preferably 80 to 130 meq / 100 g are preferred.
- Suitable organic water repellents are derived from oxonium, ammonium, phosphonium and sulfonium ions, which can carry one or more organic radicals.
- Suitable hydrophobicizing agents are those of the general formula I and / or II:
- R 2 , R 3 , R 4 independently of one another are hydrogen, a straight-chain branched, saturated or unsaturated hydrocarbon radical having 1 to 40, preferably 1 to 25, carbon atoms, which optionally carry at least one functional group or 2 of the radicals are connected to one another, in particular to form a heterocyclic radical having 5 to 10 carbon atoms,
- n is an integer from 1 to 5, preferably 1 to 3 and
- Suitable functional groups in R 1 to R 4 are hydroxyl
- Carboxyl, nitro or sulfo groups, carboxyl groups being particularly preferred, since such functional groups improve the bond to the end groups of the polyamide.
- Suitable anions Z are derived from proton-providing acids, in particular mineral acids, with halide anions such as chloride, bromide, fluoride and iodide, and sulfate, sulfonate, phosphate, phosphonate, phosphite and carboxylate, in particular acetate, being preferred.
- the layered silicates used as starting materials are generally reacted in the form of a suspension or solution.
- the preferred suspending agent or solvent is water, optionally in a mixture with alcohols, in particular lower alcohols with 1 to 3 carbon atoms. It can be advantageous to use a hydrocarbon, for example heptane, together with the aqueous medium, since the hydrophobized phyllosilicates are usually more compatible with hydrocarbons than with water.
- suspending agents are ketones and hydrocarbons.
- a water-miscible solvent is usually preferred.
- the metal salt formed as a by-product of the ion exchange is preferably water-soluble, so that the hydrophobized layered silicate can be separated off as a crystalline solid by, for example, filtering off.
- the ion exchange is largely independent of the reaction temperature.
- the temperature is preferably above the crystallization point of the suspension or solvent and below its boiling point. In aqueous systems the temperature is between 0 and 100 ° C, preferably between 20 and 80 ° C.
- alkylammonium ions are preferred, which are obtained in particular by reacting suitable ⁇ -aminocarboxylic acids such as ⁇ -aminododecanoic acid, ⁇ -aminoundecanoic acid, ⁇ -aminobutyric acid, ⁇ -aminocaprylic acid or ⁇ -aminocaproic acid with customary mineral acids, for example hydrochloric acid, sulfuric acid or phosphoric acid or methylating agents how to get methyl iodide.
- suitable ⁇ -aminocarboxylic acids such as ⁇ -aminododecanoic acid, ⁇ -aminoundecanoic acid, ⁇ -aminobutyric acid, ⁇ -aminocaprylic acid or ⁇ -aminocaproic acid
- customary mineral acids for example hydrochloric acid, sulfuric acid or phosphoric acid or methylating agents how to get methyl iodide.
- alkylammonium ions are laurylammonium, myristylammonium, palmitylammonium, stearylammonium, pyridinium, octadecylammonium, monomethyloctadecylammonium and dimethyloctadecylammonium ions, and the derivatives of these ions substituted with alkyl and / or hydroxyalkyl.
- Quaternary ammonium compounds e.g. Di (2-hydroxyethyl) methylstearylammonium chloride, dimethylstearylbenzylammonium chloride, and trimethylstrearylammonium chloride.
- Suitable phosphonium methyltri- nonylphosphonium, Ethyltrihexadecylphosphonium, Dimethyldidecyl- phosphonium, Diethyldio ⁇ tadecylphosphonium, Octadecyldiethylal- lylphosphonium, Trioctylvinylbenzylphosphonium, Dioctydecylethyl- include for example Docosyltrime- thylphosphonium, Hexatriacontyltricyclohexylphosphoniu, octadecyl cyltriethylphosphonium, Dicosyltriisobutylphosphonium, hydroxyethylphosphonium, Docosyldiethyldichlorbenzylphosphonium, Octylnonyldecylpropargylphosphonium, Triisobutylperfluordecyl - phosphonium, Eicosyl
- hydrophobizing agents are attributed, inter alia, in WO-A 93/4118, WO-A 93/4117, EP-A 398 551 and DE-A 36 32 865 be ⁇ .
- the layered silicates After the hydrophobization, the layered silicates have a layer spacing of 10 to 40 ⁇ , preferably of 13 to 20 ⁇ .
- the layer spacing usually means the distance from the lower layer edge of the upper layer to the upper layer edge of the lower layer.
- the length of the leaflets is usually up to 2000 ⁇ , preferably up to 1500 ⁇ .
- Hydrophobized bentonites for example hydrophobized montmorillonite, are particularly preferably used as delaminated layered silicate B).
- the polyamide nanocomposites can be produced, for example, by the in-situ or melt-intercalation method.
- In-situ method The layered silicate which has been rendered hydrophobic in the above manner is then mixed in suspension or as a solid 10 with the polyamide monomers or prepolymers and the polycondensation is carried out in the customary manner.
- the polycondensation is then carried out in the customary manner.
- the polycondensation is carried out particularly advantageously with simultaneous shear, preferably under shear stresses in accordance with DIN 11443 of 10 to 10 5 Pa, in particular 10 2 to 10 4 Pa.
- Any additives C) used can be added to the monomers or to the prepolymer melt (degassing extruder).
- additives C) are used, they can also be introduced into the mixing device and thus produce a mixture of A), B) 40 and C).
- the polyamide molding compositions can then be subjected to a further thermal treatment, ie a post-condensation in the solid phase.
- a further thermal treatment ie a post-condensation in the solid phase.
- tempering units such as a tumbler mixer or 5 continuously and discontinuously operated tempering tubes
- the molding compound present in the respective processing mold is tempered until the desired viscosity number VZ or relative Viscosity ⁇ rel of the polyamide is reached.
- the temperature range of the tempering depends on the melting point of the pure component A). Preferred temperature ranges are 5 to 50, preferably 20 to 30 ° C. below the respective melting point of the pure components A).
- the process is preferably carried out in an inert gas atmosphere, nitrogen and superheated water vapor being preferred as inert gases.
- the residence times are generally from 0.5 to 50, preferably from 4 to 20 hours.
- molded parts are produced from the molding compositions by means of injection molding.
- the polyamide nanocomposites from which the molded parts are produced by the process according to the invention preferably contain
- the polyamide nanocomposites can contain further additives and processing aids, preferably in proportions of 0 to 70, in particular 0 to 50,% by weight.
- Further additives are, for example, in amounts up to 40, preferably up to 30 wt .-% elastomeric polymers (often also termed as Schlagzähodifier, elastomers or rubbers ⁇ records).
- these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 C atoms in the alcohol component.
- EPM ethylene-propylene
- EPDM ethylene-propylene-diene
- EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
- diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1 , 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene as well as alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadiene or mixtures thereof.
- conjugated dienes such
- Hexa-1,5-diene-5-ethylidene-norbornene and dicyclopentadiene are preferred.
- the diene content of the EPDM rubber is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
- EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives.
- reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride.
- Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
- the rubbers can be
- Dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Contain esters and anhydrides, and / or monomers containing epoxy groups.
- These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers M containing dicarboxylic acid or epoxy groups to the monomer mixture.
- Preferred dicarboxylic acid or epoxy monomers M are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate, and the esters with tertiary alcohols, such as t-butyl acrylate no free carboxyl groups, However, their behavior is close to that of free acids and are therefore referred to as monomers with latent carboxyl groups.
- the copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
- esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
- vinyl esters and vinyl ethers can also be used as comonomers.
- the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
- Preferred elastomers are also emulsion polymers, the production of which e.g. in Blackley, Emulsion Polymerization, Applied Science Publishers, London 1975.
- the emulsifiers and catalysts that can be used are known per se.
- homogeneous elastomers or those with a shell structure can be used.
- the shell-like structure is determined by the order of addition of the individual monomers;
- the morphology of the polymers is also influenced by this order of addition.
- acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
- monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
- monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or meth acrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
- the soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two shells); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.
- one or more hard components are involved in the construction of the elastomer, these are generally obtained by polymerizing styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, Acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate are produced as the main monomers. In addition, smaller proportions of further comonomers can also be used here.
- emulsion polymers which have reactive groups on the surface.
- groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups by the use of monomers of the general formula
- CH 2 CXNCR 2 0
- R ⁇ o is hydrogen or a C 1 -C 4 -alkyl group
- Ri is hydrogen, a C 1 -C 6 -alkyl group or an aryl group, in particular phenyl,
- R12 is hydrogen, a C 1 -C 8 -alkyl, a C 6 - to C 12 -aryl group or -OR 13
- R 13 is a C ⁇ ⁇ to C 8 -alkyl or C 6 - may be substituted by C ⁇ 2 -aryl group which gege ⁇ appropriate, with 0- or N-containing groups,
- X is a chemical bond, a C ⁇ ⁇ to Cio alkylene or C 6 -C 2 arylene group or
- acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butyla ino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ) called ethyl acrylate.
- the particles of the rubber phase can also be crosslinked.
- Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
- So-called graft-linking monomers can also be used, ie monomers with two or more polymerizable double bonds which react at different rates during the polymerization.
- Compounds are preferably used in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or reactive groups) polymerizes (polymerizes), for example, significantly more slowly.
- the different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber.
- graft-crosslinking monomers examples include monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
- allyl groups in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
- graft-crosslinking monomers for further details, reference is made here, for example, to US Pat. No. 4,148,846.
- the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
- Some preferred emulsion polymers are listed below.
- graft polymers with a core and at least one outer shell are to be mentioned, which have the following structure:
- graft polymers with a multi-layer structure instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of Bu-ta-l, 3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.
- emulsion polymers examples include n-Butylacry ⁇ lat / (meth) acrylic acid-copoly ere, n-butyl acrylate / glycidyl acrylate or n-B utylacrylat / glycidyl methacrylate copolymers, graft - polymers with an inner core of n-butyl acrylate or based on butadiene and an outer shell of the above genann ⁇ th copolymers, and copolymers of ethylene with comonomers which provide reactive groups.
- the elastomers described may also be prepared by other conventional processes, eg by suspension polymerization ⁇ to. Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.
- the polyamide nanocomposites can contain stabilizers, oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
- oxidation retarders and heat stabilizers are sterically hindered phenols, hydroquinones, copper compounds, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
- UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition.
- Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can be added as colorants.
- Sodium phenylphosphinate, aluminum oxide or silicon dioxide can be used as nucleating agents.
- Lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and amide derivatives (for example ethylene-bis-stearylamide) ) montan waxes (mixtures of straight-ge ⁇ saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes, or.
- long-chain fatty acids for example stearic acid or behenic acid
- their salts for example Ca or Zn stearate
- amide derivatives for example ethylene-bis-stearylamide
- Fibrous or particulate fillers are also suitable as additives C), for example in amounts of 0 to 50, preferably 5 to 40 and in particular 10 to 30% by weight.
- Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, glass fibers made of E-glass being particularly preferred. These can be used as rovings or cut glass in the commercially available forms.
- the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the polyamide.
- Suitable silane compounds are those of the general formula III
- n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1
- Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
- the silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on C)) for the surface coating.
- Fibrous fillers are preferred having an average arith metic ⁇ fiber length of 150 to 300, preferably 200 to 270 and in particular to 220 to 250 to.
- the average diameter is generally from 3 up to 30 m, preferably from 8 to 20 microns to and from ⁇ particular 10 to 14.
- the desired fiber length can be adjusted by milling in a ball mill for example, wherein a fiber length distribution ⁇ formed.
- the average fiber length is ⁇ 200 ⁇ m, a further reduction in the fiber length leads to a free-flowing bulk material that can be mixed into the polymer like a powder. Due to the short fiber length, there is only a slight further shortening of the fiber length during incorporation.
- the fiber content is usually determined after the polymer has been incinerated. To determine the fiber length distribution, the ash residue is generally taken up in silicone oil and photographed at 20x magnification of the microscope. The length of at least 500 fibers can be measured on the pictures and the arithmetic mean (d 50 ) can be calculated from them.
- needle-shaped mineral fillers which are mineral fillers with a pronounced needle-like character.
- An example is needle-shaped wollastonite.
- the mineral preferably has an L / D (length / diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
- the mineral filler can optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.
- Amorphous silica, magnesium carbonate (chalk), kaolin (in particular calcined kaolin), powdered quartz, mica, talc, feldspar and in particular calcium silicates such as wollastonite are suitable as particulate fillers.
- the moldings according to the invention generally have an A - [- B-A - ⁇ B layer structure, that is to say layer sequence ABABAB ..., A being the thermoplastic matrix and layer B being the delaminated layered silicate.
- the molded parts are produced in an injection molding process by introducing a melt containing the polyamide A) and the delaminated layered silicate B) via a sprue into an injection molding tool.
- layered silicate B In contrast to polyamide A), layered silicate B) generally does not melt during the injection molding process. Accordingly, the claim wording "melt” is to be understood as a mixture of molten (plastic) polyamide A) and solid layered silicate B).
- the melt is introduced into the injection molding tool via a sprue in a manner known per se, for example by means of an injection molding machine (piston, screw or other injection molding machine).
- an injection molding machine priston, screw or other injection molding machine.
- the injection molding process for the production of plastic molded parts has been known for a long time and requires no further explanation.
- the person skilled in the art finds details, for example, in the following monographs: Skype et al. , Instructions for the construction of injection molding tools, 2nd edition, Hanser Verlag, Kunststoff 1983; Menges, introduction to plastics processing, Hanser Verlag, Kunststoff 1979; Sarholz, injection molding: process flow, process parameters, process control, Hanser Verlag, Kunststoff 1979.
- the process according to the invention is characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved and that the high orientation of the melt upon solidification of the Melt is frozen.
- An arbitrary point X of the melt flowing forward in the injection mold describes a flow path x
- an arbitrary point Y of the flowing melt describes a flow path y.
- the flow path is the path that the melt travels from the gate in the mold (the gate is the interface between the injection molded part and the sprue).
- the injection molding conditions are to be selected such that the two flow paths x and y are equidistant, and are therefore parallel in the case of straight lines.
- the flow front of the flowing melt is therefore not just about substantially curved and the front and flows we ⁇ sentlichen at all points at the same speed.
- the limitation "substantially” reflects the fact that a melt flows more slowly in the region directly adjoining the tool surface the edge region and directly on the work ⁇ imaging surface, the flow rate is zero, the flow front so that in this edge region is curved and possibly of the flow path is not parallel.
- the flow paths of the melt are to be optimized in a manner known per se in such a way that the melt flows essentially parallel in the injection molding tool.
- the person skilled in the art for example from the injection molding of glass fiber-containing thermoplastic molding compositions, knows how to choose the injection molding conditions so that the melt in the injection molding tool flows essentially in parallel.
- Design of the sprue in particular the location of the sprue (e.g. in or outside the parting plane of the tool); Gating geometry, e.g. B. shape, cross section, volume; Geometry of any existing distribution channels, e.g. Length, cross section, volume; Geometry of the gate, e.g. Shape, cross-section, mold temperature (mold surface temperature) - melt temperature (melt temperature) melt pressure (injection pressure) hold pressure cycle time injection time and screw advance speed - cooling time
- Gating geometry e.g. B. shape, cross section, volume
- Geometry of any existing distribution channels e.g. Length, cross section, volume
- Geometry of the gate e.g. Shape, cross-section, mold temperature (mold surface temperature) - melt temperature (melt temperature) melt pressure (injection pressure) hold pressure cycle time injection time and screw advance speed - cooling time
- the parameters referred to within the following Be ⁇ are rich:
- Tool surface temperature from 15 to 140 ° C - melt temperature (melt temperature): from 240 to 320 ° C
- Mass pressure from 250 to 2500 bar
- Screw advance speed from 20 to 1000 mm / s - holding time: from 0.5 to 60 s.
- the numerical values to be selected strongly depend on the molded part to be produced (size, geometry) and on the composition and properties of the molding compound.
- the melt is preferably distributed in the sprue system in such a way that it enters the cavity of the tool with an approximately parallel flow front. The sprue system must be selected accordingly.
- the sprue is designed as a tape gate (also referred to as a film gate or tape gate), i.e. the melt does not enter the tool at one point - as in the case of point sprue or rod or cone sprue - but at the same time on a surface. For example, you can spray directly into the parting surface of the tool during the gate.
- a tape gate also referred to as a film gate or tape gate
- the melt usually enters the mold on the whole side at the same time.
- the band gate can have different thicknesses.
- the gate in front of the gate should be significantly larger in cross-section so that the gate is evenly filled with the melt.
- a shield gate also referred to as mushroom, plate or disc gate
- ring gate is used in a preferred embodiment.
- Melt (containing polyamide A) and layered silicate B)) reached, i.e. Due to the parallel flow, highly ordered structures are present in the melt.
- shear profile is present.
- the flow rate of the melt is directly on the tool press ⁇ gober Diagram zero. If one assumes that the flow speed in the middle between the tool surfaces is maximum, then a speed graph is present when viewed over the melt cross section. This gradient causes the melt to be subject to shear forces which are maximum in the edge region of the melt (so-called shear profile). The shear forces lead to an orientation of the melt which is maximal in the edge areas.
- Edge area means the area of the melt (more precisely: the melt cross-section) that borders on the tool surface, i.e. the area near the surface of the later molded part.
- the injection molding conditions are to be selected so that the high orientation of the melt is frozen when the melt solidifies. This means that by solidifying the Melt to the finished solid molded part, the highly ordered structures made of polyamide and layered silicate are virtually "fixed".
- Injection molding conditions must be selected so that the high orientation of the melt is frozen when it solidifies.
- Important parameters for freezing the highly oriented melt are the temperatures of the melt and the tool surface.
- the temperatures and the other injection molding conditions should preferably be selected in a manner known per se such that the tool is filled well and the high orientation generated by the parallel flow of the melt is frozen during solidification.
- melt orientation can generally be better frozen than with thick melt layers.
- the method is therefore particularly suitable for the production of thin-walled moldings and in particular of moldings which essentially have a wall thickness of at most 2 mm, preferably at most 1 mm (so-called thin-walled moldings).
- substantially is meant that the mold parts in the areas that are exposed to a loading stung ⁇ , a wall thickness of not more than 2 mm have.
- Such thin-walled moldings with a wall thickness of at most 2 mm are shell-shaped moldings, for example for housing, in particular mobile phone housing, also bobbin, cable ties, Ge ⁇ housing for electrical installations and electrical or electronic devices.
- shell-shaped moldings for example for housing, in particular mobile phone housing, also bobbin, cable ties, Ge ⁇ housing for electrical installations and electrical or electronic devices.
- the method according to the invention can be used to produce moldings of all types with improved toughness, including semi-finished products, pipes, profiles, plates, injection-molded foils, etc.
- thin-walled moldings can be produced with improved toughness.
- These molded parts are also the subject of the invention.
- Toughness means especially multiaxial toughness.
- the invention also relates to molded parts, the molded part being produced by the process according to the invention and being a circular disc 60 mm in diameter and 1 mm thick, which is produced from 95% by weight of polyamide 6 and 5% by weight of hydrophobic bentonite, and the round disk in the puncture test according to DIN 53443 at 23 ° C has a total damage work W tot of at least 30 J / mm.
- the invention further relates to a process for increasing the toughness of molded parts made of polyamide nanocomposites containing at least one polyamide A) and at least one delaminated layered silicate B), characterized in that the molded parts are injection-molded by introducing a melt containing A) and B) via a sprue in an injection molding tool, and that the melt in the injection molding tool flows essentially in parallel, whereby a high orientation of the melt is achieved and that the high orientation of the melt is frozen when the melt solidifies.
- Polyamide 6 (polycaprolactam) having a viscosity number VN of 150 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% hydrochloric pivot ⁇ ric acid at 25 ° C according to ISO 307. It has been Ultramid® B3 of BASF uses.
- Delaminated hydrophobized layered silicate 1 kg of purified sodium bentonite with an ion exchange capacity of 95 meq / 100 g was mixed with enough water in a stirred kettle that a 2% by weight suspension was removed. was standing. 397 g of di ( 2-hydroxyethyl) methylstearylammonium chloride were added to the suspension at room temperature within 1 min. The precipitate which separated out was separated off by filtration, purified with water and spray-dried. •
- the product is also available as Cloisite® 30B from Southern Clay Products, Texas, USA.
- the polyamide nanocomposite granules were dried in a vacuum at 100 ° C. for 16 hours.
- the screw advance speed was selected so that the flow rate of the melt was identical at the point that corresponded to the tested point of the test specimen.
- Round disks with a thickness of 1 mm and a diameter of 60 mm were produced.
- the screw advance speed was 22 mm / s, the mold surface temperature 80 ° C and the melt temperature (melt temperature) 270 ° C.
- a simple tool was used as the injection molding tool.
- the sprue system consisted of a sprue with a sprue that lay in the parting plane of the tool. Due to this arrangement, the melt in the work ⁇ did not flow generating parallel but radially.
- Plates of 1 mm thickness and 100x100 mm edge length were produced on an Nestal Synergy 1200 injection molding machine with a 32 mm screw diameter.
- the screw advance speed was 50 mm / s, the tool surface temperature 80 ° C and
- Melt temperature 270 ° C.
- a double mold was used as the injection molding tool.
- the sprue system consisted of a bar sprue that was perpendicular to the two molded parts of the two-cavity mold, and a subsequent band gate for each molded part. The band cut caused the melt to flow essentially parallel in the tool. Round disks of 1 mm thickness and 60 mm diameter were machined from the plates.
- the total damage work W tot was determined on the round disks in the multiaxial puncture test according to DIN 53443 at 23 ° C. The fracture behavior was determined visually.
- the table shows that by choosing the injection molding conditions such that the melt flows in the mold in parallel (here: by changing from the point gate to the band gate) and that the melt orientation is frozen, the toughness of the thin-walled molded parts is significantly improved.
- the total damage capacity increases by more than half from 19.7 to 33.4 J / mm, and the fracture behavior is ductile-tough instead of brittle.
Abstract
The invention relates to a method for the production of moulded parts by injection moulding using polyamide nanocomposites. Said moulded parts contain A) at least one polyamide A) and B) at least one delaminated phyllosilicate B). The inventive method involves injecting a melt containing A) and B) via a gate into an injection mould. The invention is characterized by the selection of injection moulding conditions in a manner known per se, allowing the melt to flow inside the injection mould in a substantially parallel manner so that a high orientation can be obtained therefor, said orientation exhibiting transition.
Description
Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocompo- sitesProcess for the production of molded parts from polyamide nanocomposites
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocomposites, enthaltendThe invention relates to a method for producing molded parts from polyamide nanocomposites, containing
A) mindestens ein Polyamid A) , undA) at least one polyamide A), and
B) mindestens ein delaminiertes Schichtsilikat B)B) at least one delaminated layered silicate B)
im Spritzgußverfahren durch Einbringen einer Schmelze enthaltend A) und B) über einen Anguß in ein Spritzgußwerkzeug.in the injection molding process by introducing a melt containing A) and B) via a sprue into an injection molding tool.
Außerdem betrifft die Erfindung die nach dem Verfahren erhältlichen Formteile, sowie ein Verfahren zur Erhöhung der Zähigkeit von Formteilen aus Polyamid-Nanocomposites, enthaltend mindestens ein Polyamid A) , und mindestens ein delaminiertes Schichtsilikat B) .In addition, the invention relates to the moldings obtainable by the process, and to a process for increasing the toughness of moldings made of polyamide nanocomposites containing at least one polyamide A) and at least one delaminated layered silicate B).
Polyamid-Nanocomposites sind thermopplastische Formmassen, die Polyamid und als Füll- und Verstärkungsstoff delaminierte Schichtsilikate enthalten.Polyamide nanocomposites are thermoplastic molding compounds containing polyamide and layered silicates delaminated as fillers and reinforcing materials.
Derartige Werkstoffe und daraus hergestellte Formteile sind z. B. aus den Schriften WO-A 94/11430, WO-A 93/04118, WO-A 93/04117, WO-A 99/41299 und EP-A 940430 bekannt. Zwar haben Formteile aus den dort beschriebenen Formmassen für manche Anwendungen ausrei- chende mechanische Eigenschaften, jedoch sind sie für bestimmte Anwendungen zu spröde, d. h. die Gesamtschädigungsarbeit Wges nach DIN 53443 im multiaxialen Durchstoßtest ist vergleichsweise klein und die Zähigkeit zu gering.Such materials and molded parts made therefrom are, for. B. from the documents WO-A 94/11430, WO-A 93/04118, WO-A 93/04117, WO-A 99/41299 and EP-A 940430 known. Although moldings have from those described there molding compositions for some applications adequate mechanical properties, but they are for specific applications too brittle, ie the total fracture energy W tot according to DIN 53443 in the multiaxial impact test is comparatively small and the toughness is too low.
Es bestand die Aufgabe, den geschilderten Nachteilen abzuhelfen. Insbesondere bestand die Aufgabe, ein Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocomosites bereitzustellen, das Formteile mit verbesserter Zähigkeit (verminderter Sprödigkeit) , insbesondere verbesserter multiaxialer Zähigkeit, liefert.The task was to remedy the disadvantages described. In particular, the object was to provide a process for the production of moldings from polyamide nanocomosites, which provides moldings with improved toughness (reduced brittleness), in particular improved multiaxial toughness.
Insbesondere bestand die Aufgabe, ein Verfahren bereitzustellen, das solche Formteile mit einer höheren Gesamtschädigungsarbeit WgeS (nach DIN 53443) liefert.In particular, the task was to provide a method that delivers such molded parts with a higher total damage work W g e S (according to DIN 53443).
Demgemäß wurde das eingangs definierte Verfahren gefunden. Es ist dadurch gekennzeichnet, daß man die Spritzgußbedingungen in an sich bekannter Weise derart wählt,
daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt, wodurch eine hohe Orientierung der Schmelze erreicht wird, und daß die hohe Orientierung der Schmelze beim Erstarren der 5 Schmelze eingefroren wird.Accordingly, the process defined at the outset was found. It is characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved, and that the high orientation of the melt is frozen when the melt solidifies.
Weiterhin wurden die nach dem Verfahren erhältlichen Formteile gefunden, sowie ein Verfahren zur Erhöhung der Zähigkeit von Formteilen aus Polyamid-Nanocomposites, enthaltend mindestens ein 10 Polyamid A) , und mindestens ein delaminiertes Schichtsilikat B) . Bevorzugte Ausführungsformen der Erfindung sind den Unteransprüchen zu entnehmen.Furthermore, the moldings obtainable by the process were found, as well as a process for increasing the toughness of moldings made of polyamide nanocomposites, containing at least one polyamide A) and at least one delaminated layered silicate B). Preferred embodiments of the invention can be found in the subclaims.
Überraschenderweise erhält man Formteile mit deutlich verbesser- 15 ter Zähigkeit, insbesondere verbesserter Gesamtschädigungsarbeit Wges, wenn man besondere Spritzgußbedingungen einstellt.Surprisingly, molded parts with significantly improved toughness, in particular improved overall damage work W total , are obtained if special injection molding conditions are set.
Komponente A)Component A)
20 Als Komponente A) enthalten die Polyamid-Nanocomposites mindestens ein Polyamid A) .20 As component A), the polyamide nanocomposites contain at least one polyamide A).
Geeignet sind Polyamide mit aliphatischem teilkristallinem oder teilaromatischem sowie amorphem Aufbau jeglicher Art und deren 25 Blends, einschließlich Polyetheramiden wie Polyetherblockamiden. Unter Polyamiden im Sinne der vorliegenden Erfindung sollten alle bekannten Polyamide verstanden werden.Polyamides with an aliphatic semi-crystalline or partially aromatic and amorphous structure of any kind and their 25 blends, including polyether amides such as polyether block amides, are suitable. For the purposes of the present invention, polyamides should be understood to mean all known polyamides.
Solche Polyamide weisen im allgemeinen eine Viskositätszahl von 30 90 bis 350, vorzugsweise 110 bis 240 ml/g auf bestimmt in einer 0,5 gew.-%-igen Lösung in 96 gew.-%-iger Schwefelsäure bei 25°C gemäß ISO 307.Such polyamides generally have a viscosity number of 30 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 ,
Halbkristalline oder amorphe Harze mit einem Molekulargewicht 35 (Gewichtsmittelwert) von mindestens 5.000, wie sie z.B. in den amerikanischen Patentschriften 2 071 250, 2 071 251, 2 130 523, 2 130 948, 2 241 322, 2 312 966, 2 512 606 und 3 393 210 beschrieben werden, sind bevorzugt. Beispiele hierfür sind Polyamide, die sich von Lactamen mit 7 bis 13 Ringgliedern ableiten, 40 wie Polycaprolactam, Polycapryllactam und Polylaurinlactam, sowie Polyamide, die durch Umsetzung von Dicarbonsäuren mit Diaminen erhalten werden.Semi-crystalline or amorphous resins with a molecular weight 35 (weight average) of at least 5,000, e.g. U.S. 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 are preferred. Examples include polyamides derived from lactams with 7 to 13 ring members, 40 such as polycaprolactam, polycapryllactam and polylaurine lactam, and polyamides obtained by reacting dicarboxylic acids with diamines.
Als Dicarbonsäuren sind Alkandicarbonsäuren mit 6 bis 12, ins- 45 besondere 6 bis 10 Kohlenstoffatomen und aromatische Dicarbonsäuren einsetzbar. Hier seien Adipinsäure, Azelainsäure, Sebacin-
Als Promotoren eignen sich Kalium, Natrium, Mangan, Chrom, Cobalt, Wolfram, Molybdän, Nickel, Eisen, Magnesium, Calcium oder deren Gemische, bevorzugt Kalium, Mangan, Chrom, Molybdän oder deren Gemische, besonders bevorzugt Kalium, Chrom, Molybdän oder deren Gemische.Alkanedicarboxylic acids with 6 to 12, in particular 45, 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Here are adipic acid, azelaic acid, sebacin Suitable promoters are potassium, sodium, manganese, chromium, cobalt, tungsten, molybdenum, nickel, iron, magnesium, calcium or mixtures thereof, preferably potassium, manganese, chromium, molybdenum or mixtures thereof, particularly preferably potassium, chromium, molybdenum or their mixtures mixtures.
Die Form und Gestalt der erfindungsgemäßen Katalysatoren ist beliebig wählbar wie Tabletten, Ringe, Sterne, Wagenräder, Extrudate wie Zylinder, Pellets oder Stränge, bevorzugt sind Ringtabletten oder Tabletten.The shape and shape of the catalysts according to the invention can be selected as desired, such as tablets, rings, stars, wagon wheels, extrudates such as cylinders, pellets or strands, ring tablets or tablets are preferred.
Die Reinigung von Ethylen mit den erfindungsgemäßen Katalysatoren kan wie folgt durchgeführt werden:The purification of ethylene with the catalysts according to the invention can be carried out as follows:
Das zu reinigende Ethylen kann in einem zweistufigen ProzessThe ethylene to be cleaned can be processed in a two-step process
a) in Gegenwart von Wasserstoff an den erfindungsgemäßen Katalysatoren im reduzierten Zustand bei einer Temperatur von 70 bis 110°C, bevorzugt 75 bis 100°C, besonders bevorzugt 80 bis 95°C und einem Druck von 5 bis 80 bar, bevorzugt 10 bis 70 bar, besonders bevorzugt 20 bis 60 bar und anschließenda) in the presence of hydrogen on the catalysts of the invention in the reduced state at a temperature of 70 to 110 ° C, preferably 75 to 100 ° C, particularly preferably 80 to 95 ° C and a pressure of 5 to 80 bar, preferably 10 to 70 bar, particularly preferably 20 to 60 bar and then
b) an den erfindungsgemäßen Katalysatoren im oxidierten Zustand bei einer Temperatur von 70 bis 110°C, bevorzugt 75 bis 100°C, besonders bevorzugt 80 bis 95°C und einem Druck von 5 bis 80 bar, bevorzugt 10 bis 70 bar, besonders bevorzugt 20 bis 60 bar umgesetzt werden.b) on the catalysts according to the invention in the oxidized state at a temperature of 70 to 110 ° C., preferably 75 to 100 ° C., particularly preferably 80 to 95 ° C. and a pressure of 5 to 80 bar, preferably 10 to 70 bar, particularly preferably 20 to 60 bar can be implemented.
Die erfindungsgemäßen Katalysatoren haben eine höhere Resistenz gegenüber Acetylenen, als solche Katalysatoren, die keine erfinderische Nachbehandlung durch Nachcalcinierung der Formkörper erfahren haben. Die erfindungsgemäßen Katalysatoren können mit einen Gehalt von bis zu 200 [ppm] Acetylenen in zu reinigenden Ethylen betrieben werden.The catalysts of the invention have a higher resistance to acetylenes than those catalysts which have not undergone inventive post-treatment by post-calcining the shaped bodies. The catalysts of the invention can be operated with a content of up to 200 [ppm] acetylenes in ethylene to be purified.
Diesem zweistufigen Prozess kann eine Hydier-Stufe vorgeschaltet sein, die das zu reinigende Ethylen in Gegenwart einer ausreichenden Menge Wasserstoff über einen Hydrierkatalysator, z.B. einen Edelmetallhydrierkatalysator, beispielsweise 0,3 Gew.-% Pd auf einem Al 03-Träger, leitet. Dies ist in der Regel dann angezeigt, wenn im zu reinigenden Ethylen große Mengen Acetylene, also Mengen von mehr als 200 [ppm] enthalten sind.
Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocompo sitesThis two-stage process can be preceded by a hydrogenation stage, which conducts the ethylene to be purified in the presence of a sufficient amount of hydrogen over a hydrogenation catalyst, for example a noble metal hydrogenation catalyst, for example 0.3% by weight of Pd on an Al 0 3 support . This is usually indicated if the ethylene to be cleaned contains large amounts of acetylenes, ie amounts of more than 200 [ppm]. Process for the production of molded parts from polyamide nanocompo sites
Beschreibungdescription
Die Erfindung betriff t ein Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocomposites , enthaltendThe invention relates to a process for the production of molded parts from polyamide nanocomposites containing
A) mindestens ein Polyamid A) , undA) at least one polyamide A), and
B) mindestens ein delaminiertes Schichtsilikat B)B) at least one delaminated layered silicate B)
im Spritzgußverfahren durch Einbringen einer Schmelze enthaltend A) und B) über einen Anguß in ein Spritzgußwerkzeug .in the injection molding process by introducing a melt containing A) and B) via a sprue into an injection molding tool.
Außerdem betrifft die Erfindung die nach dem Verfahren erhältlichen Formteile, sowie ein Verfahren zur Erhöhung der Zähigkeit von Formteilen aus Polyamid-Nanocomposites, enthaltend mindestens ein Polyamid A) , und mindestens ein delaminiertes Schichtsilikat B) .In addition, the invention relates to the moldings obtainable by the process, and to a process for increasing the toughness of moldings made of polyamide nanocomposites containing at least one polyamide A) and at least one delaminated layered silicate B).
Polyamid-Nanocomposites sind thermopplas ische Formmassen, die Polyamid und als Füll- und VerstärkungsStoff delaminierte Schichtsilikate enthalten.Polyamide nanocomposites are thermoplastic molding compounds containing polyamide and layered silicates delaminated as fillers and reinforcing materials.
Derartige Werkstoffe und daraus hergestellte Formteile sind z. B. aus den Schriften WO-A 94/11430, WO-A 93/04118, WO-A 93/04117, WO-A 99/41299 und EP-A 940430 bekannt. Zwar haben Formteile aus den dort beschriebenen Formmassen für manche Anwendungen ausrei- chende mechanische Eigenschaf en, jedoch sind sie für bestimmte Anwendungen zu spröde, d. h. die Gesamtschädigungsarbeit Wges nach DIN 53443 im multiaxialen Durchstoßtest ist vergleichsweise klein und die Zähigkeit zu gering.Such materials and molded parts made therefrom are, for. B. from the documents WO-A 94/11430, WO-A 93/04118, WO-A 93/04117, WO-A 99/41299 and EP-A 940430 known. Although moldings have from those described there molding compositions for many applications sufficient mechanical natural sheep s, but they are brittle for certain applications, the total fracture energy W tot ie according to DIN 53443 in the multiaxial impact test is comparatively small and the toughness is too low.
Es bestand die Aufgabe, den geschilderten Nachteilen abzuhelfen. Insbesondere bestand die Aufgabe, ein Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocomosites bereitzustellen, das Formteile mit verbesserter Zähigkeit (verminderter Sprödigkeit) , insbesondere verbesserter multiaxialer Zähigkeit, liefert.The task was to remedy the disadvantages described. In particular, the object was to provide a process for the production of moldings from polyamide nanocomosites, which provides moldings with improved toughness (reduced brittleness), in particular improved multiaxial toughness.
Insbesondere bestand die Aufgabe, ein Verfahren bereitzustellen, das solche Formteile mit einer höheren Gesamtschädigungsarbeit Wges (nach DIN 53443) liefert.In particular, the object was to provide a method which such molded parts having a higher overall fracture energy W tot (according to DIN 53443) provides.
Demgemäß wurde das eingangs definierte Verfahren gefunden. Es ist dadurch gekennzeichnet, daß man die Spritzgußbedingungen in an sich bekannter Weise derart wählt,
daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt, wodurch eine hohe Orientierung der Schmelze erreicht wird, und daß die hohe Orientierung der Schmelze beim Erstarren der 5 Schmelze eingefroren wird.Accordingly, the process defined at the outset was found. It is characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved, and that the high orientation of the melt is frozen when the melt solidifies.
Weiterhin wurden die nach dem Verfahren erhältlichen Formteile gefunden, sowie ein Verfahren zur Erhöhung der Zähigkeit von Formteilen aus Polyamid-Nanocomposites, enthaltend mindestens ein 10 Polyamid A) , und mindestens ein delaminiertes Schichtsilikat B) . Bevorzugte Ausführungsformen der Erfindung sind den Unter- ansprüchen zu entnehmen.Furthermore, the moldings obtainable by the process were found, as well as a process for increasing the toughness of moldings made of polyamide nanocomposites, containing at least one polyamide A) and at least one delaminated layered silicate B). Preferred embodiments of the invention can be found in the subclaims.
Überraschenderweise erhält man Formteile mit deutlich verbesser- 15 ter Zähigkeit, insbesondere verbesserter Gesamtschädigungsarbeit Wges, wenn man besondere Spritzgußbedingungen einstellt.Surprisingly, molded parts with significantly improved 15 ter strength, especially improved overall fracture energy Wg it when setting specific injection molding conditions.
Komponente A)Component A)
20 Als Komponente A) enthalten die Polyamid-Nanocomposites mindestens ein Polyamid A) .20 As component A), the polyamide nanocomposites contain at least one polyamide A).
Geeignet sind Polyamide mit aliphatischem teilkristallinem oder teilaromatischem sowie amorphem Aufbau jeglicher Art und deren 25 Blends, einschließlich Polyetheramiden wie Polyetherblockamiden. Unter Polyamiden im Sinne der vorliegenden Erfindung sollten alle bekannten Polyamide verstanden werden.Polyamides with an aliphatic semi-crystalline or partially aromatic and amorphous structure of any kind and their 25 blends, including polyether amides such as polyether block amides, are suitable. For the purposes of the present invention, polyamides should be understood to mean all known polyamides.
Solche Polyamide weisen im allgemeinen eine Viskositätszahl von 30 90 bis 350, vorzugsweise 110 bis 240 ml/g auf bestimmt in einer 0,5 gew.-%-igen Lösung in 96 gew.-%-iger Schwefelsäure bei 25°C gemäß ISO 307.Such polyamides generally have a viscosity number of 30 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 ,
Halbkristalline oder amorphe Harze mit einem Molekulargewicht 35 (Gewichtsmittelwert) von mindestens 5.000, wie sie z.B. in den amerikanischen Patentschriften 2 071 250, 2 071 251, 2 130 523, 2 130 948, 2 241 322, 2 312 966, 2 512 606 und 3 393 210 beschrieben werden, sind bevorzugt. Beispiele hierfür sind Polyamide, die sich von Lactamen mit 7 bis 13 Ringgliedern ableiten, 40 wie Polycaprolactam, Polycapryllactam und Polylaurinlactam, sowie Polyamide, die durch Umsetzung von Dicarbonsäuren mit Diaminen erhalten werden.Semi-crystalline or amorphous resins with a molecular weight 35 (weight average) of at least 5,000, e.g. U.S. 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 are preferred. Examples include polyamides derived from lactams with 7 to 13 ring members, 40 such as polycaprolactam, polycapryllactam and polylaurine lactam, and polyamides obtained by reacting dicarboxylic acids with diamines.
Als Dicarbonsäuren sind Alkandicarbonsäuren mit 6 bis 12, ins- 45 besondere 6 bis 10 Kohlenstoffatomen und aromatische Dicarbonsäuren einsetzbar. Hier seien Adipinsäure, Azelainsäure, Sebacin-
säure, Dodecandisäure (= Decandicarbonsäure) und Terephthal- und/ oder Isophthalsäure als Säuren genannt.Alkanedicarboxylic acids with 6 to 12, in particular 45, 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Here are adipic acid, azelaic acid, sebacin Acid, dodecanedioic acid (= decanedicarboxylic acid) and terephthalic and / or isophthalic acid are mentioned as acids.
Als Diamine eignen sich besonders Alkandia ine mit 6 bis 12, ins- besondere 6 bis 8 Kohlenstoffatomen sowie -Xylylendiamin, Di- (4-aminophenyl)methan, Di- (4-aminocyclohexyl) -methan, 2,2-Di- (4-aminophenyl) -propan oder 2 , 2-Di- (4-aminocyclo- hexyl) -propan.Particularly suitable diamines are alkanediaes having 6 to 12, in particular 6 to 8, carbon atoms and -xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di- (4 -aminophenyl) propane or 2,2-di- (4-aminocyclohexyl) propane.
Bevorzugte Polyamide sind Polyhexamethylenadipinsäureamid (PA 66) und Polyhexa ethylensebacinsäurea id (PA 610) , Polycaprolactam (PA 6) sowie Copolyamide 6/66, insbesondere mit einem Anteil von 5 bis 95 Gew.-% an Caprolactam-Einheiten.Preferred polyamides are polyhexamethylene adipic acid amide (PA 66) and polyhexa ethylene sebacic acid id (PA 610), polycaprolactam (PA 6) and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.
PA 6, PA 66 und Copolyamide 6/66 sind besonders bevorzugt. Ganz besonders bevorzugt ist Polyamid 6 (PA 6) .PA 6, PA 66 and copolyamides 6/66 are particularly preferred. Polyamide 6 (PA 6) is very particularly preferred.
Außerdem seien auch noch Polyamide erwähnt, die z.B. durch Kondensation von 1, 4-Diaminobutan mit Adipinsäure unter erhöhter Temperatur erhältlich sind (Polyamid-4, 6) . Herstellungsverfahren für Polyamide dieser Struktur sind z.B. in den EP-A 38 094, EP-A 38 582 und EP-A 39 524 beschrieben.Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
Weitere Beispiele sind Polyamide, die durch Copolymerisation zweier oder mehrerer der vorgenannten Monomeren erhältlich sind, oder Mischungen mehrerer Polyamide geeignet, wobei das Mischungsverhältnis beliebig ist.Other examples are polyamides which are obtainable by copolymerizing two or more of the aforementioned monomers, or mixtures of two or more polyamides, the mixing ratio being arbitrary.
Weiterhin haben sich solche teilaromatischen Copolyamide wie PA 6/6T und PA 66/6T als besonders vorteilhaft erwiesen, deren Triamingehalt weniger als 0,5, vorzugsweise weniger als 0,3 Gew.-% beträgt (siehe EP-A 299 444). Die Herstellung der teilaromatischen Copolyamide mit niedrigem Triamingehalt kann nach den in den EP-A 129 195 und 129 196 beschriebenen Verfahren erfolgen.Furthermore, those partially aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T have proven particularly advantageous, the triamine content of which is less than 0.5, preferably less than 0.3% by weight (see EP-A 299 444). The partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196.
Die nachfolgende nicht abschließende Aufzählung enthält die genannten, so wie weitere Polyamide im Sinne der Erfindung (in Klammern sind die Monomeren angegeben) :The following non-exhaustive list contains the named ones, as well as further polyamides in the sense of the invention (the monomers are given in brackets):
PA 46 (Tetramethylendiamin, Adipinsäure) PA 66 (Hexamethylendiamin, Adipinsäure) PA 69 (Hexamethylendiamin, Azelainsäure) . PA 610 (Hexamethylendiamin, Sebacinsäure) PA 612 (Hexamethylendiamin, Decandicarbonsäure) PA 613 (Hexamethylendiamin, Undecandicarbonsäure) PA 1212 (1,12-Dodecandiamin, Decandicarbonsäure)
PA 1313 (1, 13-Diaminotridecan, Undecandicarbonsäure)PA 46 (tetramethylene diamine, adipic acid) PA 66 (hexamethylene diamine, adipic acid) PA 69 (hexamethylene diamine, azelaic acid). PA 610 (hexamethylene diamine, sebacic acid) PA 612 (hexamethylene diamine, decanedicarboxylic acid) PA 613 (hexamethylene diamine, undecanedicarboxylic acid) PA 1212 (1,12-dodecanediamine, decanedicarboxylic acid) PA 1313 (1, 13-diaminotridecane, undecanedicarboxylic acid)
PA MXD6 (m-Xylylendiamin, Adipinsäure)PA MXD6 (m-xylylenediamine, adipic acid)
PA TMDT (Tri ethylhexamethylendiamin, Terephthalsäure)PA TMDT (Tri ethylhexamethylene diamine, terephthalic acid)
PA 4 (Pyrrolidon) PA 6 (ε-Caprolactam)PA 4 (pyrrolidone) PA 6 (ε-caprolactam)
PA 7 (Ethanolactam)PA 7 (ethanolactam)
PA 8 (Capryllactam)PA 8 (caprylic lactam)
PA 9 (9-Aminopelargonsäure)PA 9 (9-aminopelargonic acid)
PA 11 (11-Aminoundecansäure) PA 12 ( (Laurinlactam)PA 11 (11-aminoundecanoic acid) PA 12 ((laurolactam)
Diese Polyamide und ihre Herstellung sind bekannt. Einzelheiten zu ihrer Herstellung findet der Fachmann in Ullmanns Encyklopädie der Technischen Chemie, 4. Auflage, Bd. 19, S. 39-54, Verlag Che- mie, Weinheim 1980, sowie Ullmanns Encyclopedia of IndustrialThese polyamides and their production are known. The person skilled in the art can find details on their production in Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 19, pp. 39-54, Verlag Chemie, Weinheim 1980, and Ullmann's Encyclopedia of Industrial
Chemistry, Vol. A21, S. 179-206, VCH Verlag, Weinheim 1992, sowie Stoeckhert, Kunststofflexikon, 8. Auflage, S. 425-428, Hanser Verlag München 1992 (Stichwort "Polyamide" und folgende) .Chemistry, Vol. A21, pp. 179-206, VCH Verlag, Weinheim 1992, and Stoeckhert, Kunststofflexikon, 8th edition, pp. 425-428, Hanser Verlag München 1992 (keyword "Polyamide" and the following).
Auf die Herstellung der bevorzugten Polyamide PA6, PA 66 und Copolyamid 6/66 wird nachfolgend kurz eingegangen.The production of the preferred polyamides PA6, PA 66 and copolyamide 6/66 is briefly discussed below.
Die Polymerisation bzw. Polykondensation der Ausgangsmonomere wird vorzugsweise nach den üblichen Verfahren durchgeführt. So kann die Polymerisation des Caprolactams beispielsweise nach den in der DE-A 14 95 198 und DE-A 25 58 480 beschriebenen kontinuierlichen Verfahren erfolgen. Die Polymerisation von AH-Salz zur Herstellung von PA 66 kann nach dem üblichen diskontinuierlichen Verfahren (siehe: Poly erization Processes S. 424-467, ins- besondere S. 444-446, Interscience, New York, 1977) oder nach einem kontinuierlichen Verfahren, z.B. gemäß EP-A 129 196, erfolgen.The polymerization or polycondensation of the starting monomers is preferably carried out by the customary processes. For example, the polymerization of caprolactam can be carried out by the continuous processes described in DE-A 14 95 198 and DE-A 25 58 480. The polymerization of AH salt to produce PA 66 can be carried out by the customary batch process (see: Polymerization Processes pp. 424-467, in particular pp. 444-446, Interscience, New York, 1977) or by a continuous process , e.g. according to EP-A 129 196.
Bei der Polymerisation können übliche Kettenregler mitverwendet werden. Geeignete Kettenregler sind z.B. Triacetondiaminverbin- dungen (siehe WO-A 95/28443) , Monocarbonsäuren wie Essigsäure, Propionsäure und Benzoesäure, sowie Basen wie Hexamethylendiamin, Benzylamin und 1, 4-Cyclohexyldiamin. Auch C4-Cιo~Dicarbonsäuren wie Adipinsäure, Azelainsäure, Sebacinsäure, Dodecandisäure; C5-C8-Cycloalkandicarbonsäuren wie Cyclohexan-1, 4-dicarbonsäure; Benzol- und Naphthalindicarbonsäuren wie Isophthalsäure, Terephthalsäure und Naphthalin-2, 6-dicarbonsäure, sind als Kettenregler geeignet.Conventional chain regulators can also be used in the polymerization. Suitable chain regulators are, for example, triacetone diamine compounds (see WO-A 95/28443), monocarboxylic acids such as acetic acid, propionic acid and benzoic acid, and bases such as hexamethylene diamine, benzylamine and 1,4-cyclohexyl diamine. Also C 4 -C ~ dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid; C 5 -C 8 cycloalkane dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid; Benzene and naphthalenedicarboxylic acids such as isophthalic acid, terephthalic acid and naphthalene-2, 6-dicarboxylic acid are suitable as chain regulators.
Die erhaltene Polymerschmelze wird aus dem Reaktor ausgetragen, gekühlt und granuliert. Das erhaltene Granulat wird einer Nach- polymerisation unterworfen. Dies geschieht in an sich bekannter
Weise durch Erwärmen des Granulats auf eine Temperatur T- unterhalb der Schmelztemperatur Ts bzw. Kristallitschmelztemperatur Tk des Polyamids. Durch die Nachpolymerisation stellt sich das endgültige Molekulargewicht des Polyamids (messbar als Viskositäts- 5 zahl VZ, siehe Angaben zur VZ weiter oben) ein. Üblicherweise dauert die Nachpolymerisation 2 bis 24 Stunden , insbesondere 12 bis 24 Stunden. Wenn das gewünschte Molekulargewicht erreicht ist, wird das Granulat in üblicher Weise abgekühlt.The polymer melt obtained is discharged from the reactor, cooled and granulated. The granules obtained are subjected to post-polymerization. This is done in a manner known per se Way by heating the granules to a temperature T- below the melting temperature T s or crystallite melting temperature T k of the polyamide. The final molecular weight of the polyamide (measurable as a viscosity number VZ, see details on the VZ above) is established by the post-polymerization. Postpolymerization usually lasts from 2 to 24 hours, in particular from 12 to 24 hours. When the desired molecular weight is reached, the granules are cooled in the usual way.
0 Entsprechende Polyamide sind unter dem Handelsnamen Ultramid® von BASF erhältlich.Corresponding polyamides are available under the trade name Ultramid® from BASF.
Komponente B)Component B)
5 Als Komponente B) enthalten die Formmassen mindestens ein delaminiertes Schichtsilikat B) . Schichtsilikate werden auch als Phyl- losilikate bezeichnet.5 As component B), the molding compositions contain at least one delaminated layered silicate B). Layered silicates are also called phyllosilicates.
Unter einem Schichtsilikat versteht man im allgemeinen Silikate, 0 in welchen die Si04-Tetraeder zu zweidimensionalen unendlichen Netzwerken (Schichtengitter) verbunden sind. Die empirische Formel für das Anion lautet (Siθ5 2")n> Die einzelnen Schichten sind durch die zwischen ihnen liegenden Kationen miteinander verbunden, wobei in den natürlich vorkommenden Schichtsilikaten ei- 5 stens als Kationen Na, K, Mg, AI oder/und Ca vorliegen.Layered silicate is generally understood to mean silicates in which the SiO 4 tetrahedra are connected to form two-dimensional infinite networks (layered grids). The empirical formula for the anion is (Siθ 5 2 ") n > The individual layers are connected to each other by the cations lying between them, whereby in the naturally occurring layered silicates mostly as cations Na, K, Mg, Al or / and Approx.
Die Schichtdicken derartiger Silikate vor der Delaminierung be- ■ tragen üblicherweise von 5 bis 100 Ä, vorzugsweise 5 bis 50 und insbesondere 8 bis 20 Ä. 1 Angström (Ä) entspricht 0,1 Nanometer 0 (nm) .The layer thicknesses of such silicates before delamination are usually from 5 to 100 Å, preferably 5 to 50 Å and in particular 8 to 20 Å. 1 angstrom corresponds to 0.1 nanometer 0 (nm).
Als Beispiele für synthetische und natürliche Schichtsilikate (Phyllosilikate) seien Montmorillonit, Smectit, Illit, Sepiolit, Palygorskit, Muscovit, Allevardit, Amesit, Hectorit, Fluorhecto- 5 rit, Saponit, Beidellit, Talkum, Nontronit, Stevensit, Bentonit, Glimmer, Vermiculit, Fluorvermiculit, Halloysit und Fluor enthaltende synthetische Mica-Typen genannt.Examples of synthetic and natural layered silicates (phyllosilicates) are montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, fluorhectorite, saponite, beidellite, talc, nontronite, steimmerite, vermiculite, bentonite, bentonite Fluoromiculite, halloysite and fluorine-containing synthetic mica types called.
Unter einem delaminierten Schichtsilikat im Sinne der Erfindung 0 sollen Schichtsilikate verstanden werden, bei welchen durch Umsetzung mit sogenannten Hydrophobierungsmitteln und gegebenenfalls anschließender Monomerzugabe (sog. Quellung z.B. mit sog. AH-Salzen) die Schichtabstände zunächst vergrößert werden.A delaminated layered silicate in the sense of the invention 0 is to be understood as meaning layered silicates in which the layer spacings are initially increased by reaction with so-called hydrophobizing agents and, if appropriate, subsequent addition of monomers (so-called swelling e.g. with so-called AH salts).
Durch anschließende Polykondensation oder Mischung (z.B. durch Konfektionierung) des hydrophobierten und gegebenenfalls gequol¬ lenen Schichtsilikates mit Polyamiden erfolgt die Delaminierung
der Schichten, welche im Formkörper vorzugsweise zu einem Schichtabstand von mindestens 40 Ä, vorzugsweise mindestens 50 Ä führen.By subsequent polycondensation or mixture (for example by preparation) of the hydrophobic and optionally gequol ¬ lenen phyllosilicate with polyamides delamination occurs of the layers which preferably lead to a layer spacing of at least 40 Å, preferably at least 50 Å in the molded body.
Zur Vergrößerung der Schichtabstände (Hydrophobierung) werden die Schichtsilikate vor der Herstellung der Formmassen mit sogenannten Hydrophobierungsmitteln umgesetzt, welche oft auch als Oniu- mionen oder Oniumsalze bezeichnet werden.To increase the layer spacing (hydrophobization), the layered silicates are reacted with so-called hydrophobizing agents, which are often also referred to as onium ions or onium salts, before the molding compositions are produced.
Dabei werden die Kationen der Schichtsilikate durch organische Hydrophobierungsmittel ersetzt, wobei durch die Art (Größe) des organischen Restes die gewünschten Schichtabstände eingestellt werden können. Die Schichtabstände richten sich nach der Art des jeweiligen Monomeren oder Polymeren, in welches das Schicht- silikat eingebaut werden soll.The cations of the layered silicates are replaced by organic water repellents, the desired layer spacings being able to be set by the type (size) of the organic residue. The layer spacing depends on the type of monomer or polymer in which the layered silicate is to be incorporated.
Der Austausch der Metallionen kann vollständig oder teilweise erfolgen. Bevorzugt ist ein vollständiger Austausch der Metall - ionen. Die Menge der austauschbaren Metallionen wird üblicher- weise in Milliäquivalenten (meq) pro 100 g Schichtsilikat angegeben und als Ionenaustauschkapazität bezeichnet.The metal ions can be exchanged completely or partially. A complete exchange of the metal ions is preferred. The amount of exchangeable metal ions is usually given in milliequivalents (meq) per 100 g of layered silicate and referred to as the ion exchange capacity.
Bevorzugt sind Schichtsilikate mit einer Kationenaus auschkapazi- tät von mindestens 50, vorzugsweise 80 bis 130 meq/100 g.Layered silicates with a cation exchange capacity of at least 50, preferably 80 to 130 meq / 100 g are preferred.
Geeignete organische Hydrophobierungsmittel leiten sich von Oxo- nium-, Ammonium-, Phosphonium- und Sulfoniumionen ab, welche einen oder mehrere organische Reste tragen können.Suitable organic water repellents are derived from oxonium, ammonium, phosphonium and sulfonium ions, which can carry one or more organic radicals.
Als geeignete Hydrophobierungsmittel seien solche der allgemeinen Formel I und/oder II genannt:Suitable hydrophobicizing agents are those of the general formula I and / or II:
IIII
wobei die Substituenten folgende Bedeutung haben:where the substituents have the following meaning:
Rl,. R2, R3, R4 unabhängig voneinander Wasserstoff, ein gerad- kettiger verzweigter, gesättigter oder ungesättigter Kohlenwasserstoffrest mit 1 bis 40, vorzugsweise 1 bis 25 C-Atomen, welcher gegebenenfalls mindestens eine funktioneile Gruppe tragen
kann oder 2 der Reste miteinander verbunden sind, insbesondere zu einem heterocyclischen Rest mit 5 bis 10 C-Atomen, Rl. R 2 , R 3 , R 4 independently of one another are hydrogen, a straight-chain branched, saturated or unsaturated hydrocarbon radical having 1 to 40, preferably 1 to 25, carbon atoms, which optionally carry at least one functional group or 2 of the radicals are connected to one another, in particular to form a heterocyclic radical having 5 to 10 carbon atoms,
X Phosphor oder Stickstoff,X phosphorus or nitrogen,
Y Sauerstoff oder Schwefel,Y oxygen or sulfur,
n eine ganze Zahl von 1 bis 5, vorzugsweise 1 bis 3 und n is an integer from 1 to 5, preferably 1 to 3 and
Z ein Anion.Z an anion.
Geeignete funktioneile Gruppen in R1 bis R4 sind Hydroxyl-,Suitable functional groups in R 1 to R 4 are hydroxyl,
Carboxyl-, Nitro- oder Sulfogruppen, wobei Carboxylgruppen besonders bevorzugt sind, da durch derartige funktioneile Gruppen eine verbesserte Anbindung an die Endgruppen des Polyamides erfolgt.Carboxyl, nitro or sulfo groups, carboxyl groups being particularly preferred, since such functional groups improve the bond to the end groups of the polyamide.
Geeignete Anionen Z leiten sich von Protonen liefernden Säuren, insbesondere Mineralsäuren ab, wobei Halogenidanionen wie Chlorid, Bromid, Fluorid und Iodid, sowie Sulfat, Sulfonat, Phosphat, Phosphonat, Phosphit und Carboxylat, insbesondere Acetat, bevorzugt sind.Suitable anions Z are derived from proton-providing acids, in particular mineral acids, with halide anions such as chloride, bromide, fluoride and iodide, and sulfate, sulfonate, phosphate, phosphonate, phosphite and carboxylate, in particular acetate, being preferred.
Die als Ausgangsstoffe verwendeten Schichtsilikate werden in der Regel in Form einer Suspension bzw. Lösung umgesetzt. Das bevorzugte Suspendiermittel bzw. Lösungsmittel ist Wasser, gegebenenfalls in Mischung mit Alkoholen, insbesondere niederen Alkoho- len mit 1 bis 3 Kohlenstoffatomen. Es kann vorteilhaft sein, zusammen mit dem wäßrigen Medium einen Kohlenwasserstoff, zum Beispiel Heptan, einzusetzen, da die hydrophobierten Schichtsilikate mit Kohlenwasserstoffen gewöhnlich verträglicher sind als mit Wasser.The layered silicates used as starting materials are generally reacted in the form of a suspension or solution. The preferred suspending agent or solvent is water, optionally in a mixture with alcohols, in particular lower alcohols with 1 to 3 carbon atoms. It can be advantageous to use a hydrocarbon, for example heptane, together with the aqueous medium, since the hydrophobized phyllosilicates are usually more compatible with hydrocarbons than with water.
Weitere geeignete Beispiele für Suspendiermittel sind Ketone und Kohlenwasserstoffe. Gewöhnlich wird ein mit Wasser mischbares Lösungsmittel bevorzugt.Other suitable examples of suspending agents are ketones and hydrocarbons. A water-miscible solvent is usually preferred.
Bei der Zugabe des Hydrophobierungsmittels zum Schichtsilikat tritt ein Ionenaustausch ein, wodurch das Schichtsilikat üblicherweise hydrophober wird und aus der Lösung ausfällt. Das als Nebenprodukt des Ionenaustausch entstehende Metallsalz ist vorzugsweise wasserlöslich, so daß das hydrophobierte Schicht- silikat als kristalliner Feststoff durch z.B. Abfiltrieren abgetrennt werden kann.
Der Ionenaustausch ist von der Reaktionstemperatur weitgehend unabhängig. Die Temperatur liegt vorzugsweise über dem Kristallisationspunkt des Suspendier- bzw. Lösungsmittels und unter seinem Siedepunkt. Bei wäßrigen Systemen liegt die Temperatur zwischen 0 und 100°C, vorzugsweise zwischen 20 und 80°C.When the hydrophobizing agent is added to the layered silicate, an ion exchange takes place, as a result of which the layered silicate usually becomes more hydrophobic and precipitates out of the solution. The metal salt formed as a by-product of the ion exchange is preferably water-soluble, so that the hydrophobized layered silicate can be separated off as a crystalline solid by, for example, filtering off. The ion exchange is largely independent of the reaction temperature. The temperature is preferably above the crystallization point of the suspension or solvent and below its boiling point. In aqueous systems the temperature is between 0 and 100 ° C, preferably between 20 and 80 ° C.
Für .Polyamide sind Alkylammoniumionen bevorzugt, welche insbesondere durch Umsetzung von geeigneten ω-Aminocarbonsäuren wie ω-Aminododecansäure, ω-Aminoundecansäure, ω-Aminobuttersäure, ω-Aminocaprylsäure oder ω-Aminocapronsäure mit üblichen Mineral - säuren, beispielsweise Salzsäure, Schwefelsäure oder Phosphorsäure oder Methylierungsmitteln wie Methyliodid erhältlich sind.For .polyamides, alkylammonium ions are preferred, which are obtained in particular by reacting suitable ω-aminocarboxylic acids such as ω-aminododecanoic acid, ω-aminoundecanoic acid, ω-aminobutyric acid, ω-aminocaprylic acid or ω-aminocaproic acid with customary mineral acids, for example hydrochloric acid, sulfuric acid or phosphoric acid or methylating agents how to get methyl iodide.
Weitere bevorzugte Alkylammoniumionen sind Laurylammonium-, Myri- stylammonium, Palmitylammonium-, Stearylammonium-, Pyridinium-, Octadecylammonium-, Monomethyloctadecylammonium- und Dimethyloc- tadecylammoniumionen, sowie die mit Alkyl und/oder Hydroxyalkyl substituierten Derivate dieser Ionen.Further preferred alkylammonium ions are laurylammonium, myristylammonium, palmitylammonium, stearylammonium, pyridinium, octadecylammonium, monomethyloctadecylammonium and dimethyloctadecylammonium ions, and the derivatives of these ions substituted with alkyl and / or hydroxyalkyl.
Besonders geeignet für Polyamide sind quaternäre Ammoniumverbindungen, z.B. Di (2-hydroxyethyl)methylstearylammoniumchlo- rid, Dimethylstearylbenzylammoniumchlorid, und Trimethylstreary- lam oniumchlorid.Quaternary ammonium compounds, e.g. Di (2-hydroxyethyl) methylstearylammonium chloride, dimethylstearylbenzylammonium chloride, and trimethylstrearylammonium chloride.
Als geeignete Phosphoniumionen seien beispielsweise Docosyltrime- thylphosphonium, Hexatriacontyltricyclohexylphosphoniu , Octade- cyltriethylphosphonium, Dicosyltriisobutylphosphonium, Methyltri- nonylphosphonium, Ethyltrihexadecylphosphonium, Dimethyldidecyl- phosphonium, Diethyldioσtadecylphosphonium, Octadecyldiethylal- lylphosphonium, Trioctylvinylbenzylphosphonium, Dioctydecylethyl- hydroxyethylphosphonium, Docosyldiethyldichlorbenzylphosphonium, Octylnonyldecylpropargylphosphonium, Triisobutylperfluordecyl - phosphonium, Eicosyltrihydroxymethylphosphonium, Triacontyltris- cyanethylphosphoniu und Bis-trioctylethylendiphosphonium ge- nannt.Suitable phosphonium methyltri- nonylphosphonium, Ethyltrihexadecylphosphonium, Dimethyldidecyl- phosphonium, Diethyldioσtadecylphosphonium, Octadecyldiethylal- lylphosphonium, Trioctylvinylbenzylphosphonium, Dioctydecylethyl- include for example Docosyltrime- thylphosphonium, Hexatriacontyltricyclohexylphosphoniu, octadecyl cyltriethylphosphonium, Dicosyltriisobutylphosphonium, hydroxyethylphosphonium, Docosyldiethyldichlorbenzylphosphonium, Octylnonyldecylpropargylphosphonium, Triisobutylperfluordecyl - phosphonium, Eicosyltrihydroxymethylphosphonium, Triacontyltris - called cyanethylphosphoniu and bis-trioctylethylenediphosphonium.
Weitere geeignete Hydrophobierungsmittel sind u.a. in der WO-A 93/4118, WO-A 93/4117, EP-A 398 551 und DE-A 36 32 865 be¬ schrieben.Another suitable hydrophobizing agents are attributed, inter alia, in WO-A 93/4118, WO-A 93/4117, EP-A 398 551 and DE-A 36 32 865 be ¬.
Nach der Hydrophobierung weisen die Schichtsilikate einen Schichtabstand von 10 bis 40 Ä, vorzugsweise von 13 bis 20 Ä auf. Der Schichtabstand bedeutet üblicherweise den Abstand von der Schichtunterkante der oberen Schicht zur Schichtoberkante der un- teren Schicht. Die Länge der Blättchen beträgt üblicherweise bis zu 2000 Ä, vorzugsweise bis zu 1500 Ä.
Besonders bevorzugt verwendet man als delaminiertes Schicht- silikat B) hydrophobierte Bentonite, z.B. hydrophobierten Mont- morillonit .After the hydrophobization, the layered silicates have a layer spacing of 10 to 40 Å, preferably of 13 to 20 Å. The layer spacing usually means the distance from the lower layer edge of the upper layer to the upper layer edge of the lower layer. The length of the leaflets is usually up to 2000 Å, preferably up to 1500 Å. Hydrophobized bentonites, for example hydrophobized montmorillonite, are particularly preferably used as delaminated layered silicate B).
5 Die Herstellung der Polyamid-Nanocomposites kann beispielsweise nach der in-situ- oder der melt-intercalation-Methode erfolgen.5 The polyamide nanocomposites can be produced, for example, by the in-situ or melt-intercalation method.
In-situ-methode: Das auf die vorstehende Weise hydrophobierte Schichtsilikat wird anschließend in Suspension oder als Feststoff 10 mit den Polyamid-Monomeren oder -Präpolymeren gemischt und die Polykondensation wird in üblicher Weise durchgeführt.In-situ method: The layered silicate which has been rendered hydrophobic in the above manner is then mixed in suspension or as a solid 10 with the polyamide monomers or prepolymers and the polycondensation is carried out in the customary manner.
Hierbei ist es möglich, den Schichtabstand weiter zu vergrößern, indem man das Schichtsilikat mit Polyamidmonomeren bzw. Prä-It is possible to further increase the layer spacing by using the layered silicate with polyamide monomers or pre-
15 polymeren bei Temperaturen von 25 bis 300, vorzugsweise von 100 bis 280 und insbesondere von 200 bis 260°C über eine Verweilzeit von 5 bis 120 Min, vorzugsweise von 10 bis 60 Min umsetzt (sog. Quellung) . Je nach Dauer der Verweilzeit und Art des gewählten Monomeren vergrößert sich der Schichtabstand zusätzlich um 10 bis15 polymers at temperatures of 25 to 300, preferably from 100 to 280 and in particular from 200 to 260 ° C over a residence time of 5 to 120 minutes, preferably from 10 to 60 minutes (so-called swelling). Depending on the duration of the residence time and the type of monomer chosen, the layer spacing increases by an additional 10 to
20 150, vorzugsweise um 20 bis 50 Ä. Anschließend führt man die Polykondensation in üblicher Weise durch. Besonders vorteilhaft wird die Polykondensation unter gleichzeitiger Scherung durchgeführt, wobei vorzugsweise Scherspannungen gemäß DIN 11443 von 10 bis 105 Pa, insbesondere 102 bis 104 Pa vorliegen.20 150, preferably around 20 to 50 Å. The polycondensation is then carried out in the customary manner. The polycondensation is carried out particularly advantageously with simultaneous shear, preferably under shear stresses in accordance with DIN 11443 of 10 to 10 5 Pa, in particular 10 2 to 10 4 Pa.
2525
Gegebenenf lls verwendete Zusatzstoffe C) können hierbei zu den Monomeren oder zur Präpolymerschmelze (Entgasungsextruder) hinzugegeben werden.Any additives C) used can be added to the monomers or to the prepolymer melt (degassing extruder).
30 Melt-inercalation-Methode: Das auf die vorstehende Weise hydrophobierte Schichtsilikat B) wird als Feststoff mit dem fertigen Polyamid-Polymeren A) in üblicher Weise auf bekannten Vorrichtungen gemischt, und die Mischung ausgetragen, gekühlt und zerkleinert. Beispielsweise kann man A) und B) in einem Extruder unter30 Melt-incalation method: The layered silicate B) hydrophobicized in the above manner is mixed as a solid with the finished polyamide polymer A) in a conventional manner on known devices, and the mixture is discharged, cooled and comminuted. For example, you can A) and B) in an extruder
35 Aufschmelzen des Polyamids innig vermischen, und das Extrudat austragen, kühlen und granulieren.35 Mix the melt of the polyamide intimately, and discharge the extrudate, cool and granulate.
Werden Zusatzstoffe C) mitverwendet, kann man sie ebenfalls in die Mischvorrichtung einbringen und so eine Mischung aus A) , B) 40 und C) herstellen.If additives C) are used, they can also be introduced into the mixing device and thus produce a mixture of A), B) 40 and C).
Die Polyamidformmassen kann man danach einer weiteren thermischen Behandlung, d.h. einer Nachkondensation in -fester Phase unterwerfen. In Temperaggregaten wie z.B. einem Taumler-Mischer oder 5 kontinuierlich sowie diskontinuierlich betriebenen Temperrohren tempert man die in der jeweiligen Bearbeitungsform vorliegende Formmasse, bis die gewünschte Viskositätszahl VZ oder relative
Viskosität ηrel des Polyamids erreicht wird. Der Temperaturbereich der Temperung hängt vom Schmelzpunkt der reinen Komponente A) ab. Bevorzugte Temperaturbereiche sind 5 bis 50, vorzugsweise 20 bis 30°C unterhalb des jeweiligen Schmelzpunktes der reinen Komponen- ten A) . Das Verfahren erfolgt vorzugsweise in einer Inertgas - at osphäre, wobei Stickstoff und überhitzter Wasserdampf als Inertgase bevorzugt sind. Die Verweilzeiten betragen im allgemeinen von 0,5 bis 50, vorzugsweise von 4 bis 20 Stunden. Anschließend werden aus den Formmassen mittels Spritzguß Formteile hergestellt.The polyamide molding compositions can then be subjected to a further thermal treatment, ie a post-condensation in the solid phase. In tempering units such as a tumbler mixer or 5 continuously and discontinuously operated tempering tubes, the molding compound present in the respective processing mold is tempered until the desired viscosity number VZ or relative Viscosity ηrel of the polyamide is reached. The temperature range of the tempering depends on the melting point of the pure component A). Preferred temperature ranges are 5 to 50, preferably 20 to 30 ° C. below the respective melting point of the pure components A). The process is preferably carried out in an inert gas atmosphere, nitrogen and superheated water vapor being preferred as inert gases. The residence times are generally from 0.5 to 50, preferably from 4 to 20 hours. Then molded parts are produced from the molding compositions by means of injection molding.
Die in-situ- und die melt-intercalation-Methode werden in der DE-A 198 54 170, auf die hiermit verwiesen wird, eingehend beschrieben.The in-situ and the melt intercalation method are described in detail in DE-A 198 54 170, to which reference is hereby made.
Mengenanteile von A) und B)Quantities of A) and B)
Bevorzugt enthalten die Polyamid-Nanocomposites, aus denen die Formteile nach dem erfindungsgemäßen Verfahren hergestellt wer- den,The polyamide nanocomposites from which the molded parts are produced by the process according to the invention preferably contain
A) 60 bis 99,9, bevorzugt 90 bis 99 und besonders bevorzugt 93 bis 97 Gew.-% mindestens eines Polyamids A) , undA) 60 to 99.9, preferably 90 to 99 and particularly preferably 93 to 97% by weight of at least one polyamide A), and
B) 0,1 bis 40, bevorzugt 1 bis 10 und besonders bevorzugt 3 bis 7 Gew.-% mindestens eines delaminierten Schichtsilikates B) .B) 0.1 to 40, preferably 1 to 10 and particularly preferably 3 to 7% by weight of at least one delaminated layered silicate B).
Zusatzstoffe C)Additives C)
Als optionale Komponente C) können die Polyamid-Nanocomposites weitere Zusatzstoffe und Verarbeitungshilfsmittel enthalten, bevorzugt in Anteilen von 0 bis 70, insbesondere 0 bis 50 Gew.-%.As optional component C), the polyamide nanocomposites can contain further additives and processing aids, preferably in proportions of 0 to 70, in particular 0 to 50,% by weight.
Weitere Zusatzstoffe sind beispielsweise in Mengen bis zu 40, vorzugsweise bis zu 30 Gew.-% kautschukelastische Polymerisate (oft auch als Schlagzähodifier, Elastomere oder Kautschuke be¬ zeichnet) .Further additives are, for example, in amounts up to 40, preferably up to 30 wt .-% elastomeric polymers (often also termed as Schlagzähodifier, elastomers or rubbers ¬ records).
Ganz allgemein handelt es sich dabei um Copolymerisate die bevor- zugt aus mindestens zwei der folgenden Monomeren aufgebaut sind: Ethylen, Propylen, Butadien, Isobuten, Isopren, Chloropren, Vinylacetat, Styrol, Acrylnitril und Acryl- bzw. Methacrylsäure- ester mit 1 bis 18 C-Atomen in der Alkoholkomponente.In general, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 C atoms in the alcohol component.
Derartige Polymere werden z.B. in Houben-Weyl, Methoden der organischen Chemie, Bd. 14/1 (Georg-Thie e-Verlag, Stuttgart, 1961) . Seiten 392 bis 406 und in der Monographie von C.B. Bucknall,
"Toughened Plastics" (Applied Science Publishers, London, 1977) beschrieben.Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg-Thie e-Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).
Im folgenden werden einige bevorzugte Arten solcher Elastomerer vorgestellt.Some preferred types of such elastomers are presented below.
Bevorzugte Arten von solchen Elastomeren sind die sog. Ethylen- Propylen (EPM) bzw. Ethylen-Propylen-Dien- (EPDM) -Kautschuke.Preferred types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.
EPM-Kautschuke haben im allgemeinen praktisch keine Doppelbindungen mehr, während EPDM-Kautschuke 1 bis 20 Doppelbindungen/100 C- Atome aufweisen können.EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
Als Dien-Monomere für EPDM-Kautschuke seien beispielsweise konju- gierte Diene wie Isopren und Butadien, nicht-konjugierte Diene mit 5 bis 25 C-Atomen wie Penta-1, 4-dien, Hexa-1, 4-dien, Hexa-1, 5-dien, 2, 5-Dimethylhexa-l, 5-dien und Octa-1, 4-dien, cy- clische Diene wie Cyclopentadien, Cyclohexadiene, Cyclooctadiene und Dicyclopentadien sowie Alkenylnorbornene wie 5-Ethyliden-2-norbornen, 5-Butyliden-2-norbornen, 2-Meth- allyl-5-norbornen, 2-Isopropenyl-5-norbornen und Tricyclodiene wie 3-Methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadien oder deren Mischungen genannt. Bevorzugt werden Hexa-1, 5-dien-5-ethyliden- norbornen und Dicyclopentadien. Der Diengehalt der EPDM-Kau- tschuke beträgt vorzugsweise 0,5 bis 50, insbesondere 1 bis 8 Gew.-%, bezogen auf das Gesamtgewicht des Kautschuks.Examples of diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1 , 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene as well as alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadiene or mixtures thereof. Hexa-1,5-diene-5-ethylidene-norbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubber is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
EPM- bzw. EPDM-Kautschuke können vorzugsweise auch mit reaktiven Carbonsäuren oder deren Derivaten gepfropft sein. Hier seien z.B. Acrylsäure, Methacrylsäure und deren Derivate, z.B. Glycidyl- (meth) acrylat, sowie Maleinsäureanhydrid genannt.EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride.
Eine weitere Gruppe bevorzugter Kautschuke sind Copolymere des Ethylens mit Acrylsäure und/oder Methacrylsäure und/oder den Estern dieser Säuren. Zusätzlich können die Kautschuke nochAnother group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers can
Dicarbonsäuren wie Maleinsäure und Fumarsäure oder Derivate dieser Säuren, z.B. Ester und Anhydride, und/oder Epoxy-Gruppen enthaltende Monomere enthalten. Diese Dicarbonsäurederivate bzw. Epoxygruppen enthaltende Monomere werden vorzugsweise durch Zu- gäbe von Dicarbonsäure- bzw. Epoxygruppen enthaltenden Monomeren M zum Monomerengemisch in den Kautschuk eingebaut.Dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Contain esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers M containing dicarboxylic acid or epoxy groups to the monomer mixture.
Bevorzugte Dicarbonsäure- bzw. Epoxy-Monomere M sind Maleinsäure, Maleinsäureanhydrid und Epoxygruppen-enthaltende Ester der Acryl- säure und/oder Methacrylsäure, wie Glycidylacrylat, Glycidylmeth- acrylat und die Ester mit tertiären Alkoholen, wie t-Butylacry- lat. Letztere weisen zwar keine freien Carboxylgruppen auf, kom-
men in ihrem Verhalten aber den freien Säuren nahe und werden deshalb als Monomere mit latenten Carboxylgruppen bezeichnet.Preferred dicarboxylic acid or epoxy monomers M are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate, and the esters with tertiary alcohols, such as t-butyl acrylate no free carboxyl groups, However, their behavior is close to that of free acids and are therefore referred to as monomers with latent carboxyl groups.
Vorteilhaft bestehen die Copolymeren aus 50 bis 98 Gew.-% Ethylen, 0,1 bis 20 Gew.-% Epoxygruppen enthaltenden Monomeren und/oder Methacrylsäure und/oder Säureanhydridgruppen enthaltenden Monomeren sowie der restlichen Menge an (Meth) acryl - säureestern.The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
Weitere bevorzugte Ester der Acryl- und/oder Methacrylsäure sind die Methyl-, Ethyl-, Propyl- und i- bzw. t-Butylester. Daneben können auch Vinylester und Vinylether als Comono ere eingesetzt werden.Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters. In addition, vinyl esters and vinyl ethers can also be used as comonomers.
Die vorstehend beschriebenen Ethylencopolymeren können nach an sich bekannten Verfahren hergestellt werden, vorzugsweise durch statistische Copolymerisation unter hohem Druck und erhöhter Temperatur. Entsprechende Verfahren sind allgemein bekannt.The ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
Bevorzugte Elastomere sind auch Emulsionspolymerisate, deren Herstellung z.B. in Blackley, Emulsion Polymerisation, Applied Science Publishers, London 1975, beschrieben wird. Die verwendbaren Emulgatoren und Katalystoren sind an sich bekannt.Preferred elastomers are also emulsion polymers, the production of which e.g. in Blackley, Emulsion Polymerization, Applied Science Publishers, London 1975. The emulsifiers and catalysts that can be used are known per se.
Grundsätzlich können homogen aufgebaute Elastomere oder aber solche mit einem Schalenaufbau eingesetzt werden. Der schalenartige Aufbau wird durch die Zugabereihenfolge der einzelnen Monomeren bestimmt; auch die Morphologie der Polymeren wird von dieser Zugabereihenfolge beeinflußt.In principle, homogeneous elastomers or those with a shell structure can be used. The shell-like structure is determined by the order of addition of the individual monomers; The morphology of the polymers is also influenced by this order of addition.
Nur stellvertretend seien hier als Monomere für die Herstellung des Kautschukteils der Elastomeren Acrylate wie z.B. n-Butylacry- lat und 2-Ethylhexylacrylat, entsprechende Methacrylate, Butadien und Isopren sowie deren Mischungen genannt. Diese Monomeren kön- nen mit weiteren Monomeren wie z.B. Styrol, Acrylnitril, Vinyl- ethern und weiteren Acrylaten oder Met acrylaten wie Methylmeth- acrylat, Methylacrylat, Ethylacrylat und Propylacrylat copoly- merisiert werden.Representative here are as monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or meth acrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
Die Weich- oder Kautschukphase (mit einer Glasübergangstemperatur von unter 0°C) der Elastomeren kann den Kern, die äußere Hülle oder eine mittlere Schale (bei Elastomeren mit mehr als zwei- schaligem Aufbau) darstellen; bei mehrschaligen Elastomeren können auch mehrere Schalen aus einer Kautschukphase bestehen.
Sind neben der Kautschukphase noch eine oder mehrere Hart- komponenten (mit Glasübergangs emperaturen von mehr als 20°C) am Aufbau des Elastomeren beteiligt, so werden diese im allgemeinen durch Polymerisation von Styrol, Acrylnitril, Methacrylnitril, α -Methylstyrol, p-Methylstyrol, Acrylsäureestern und Methacryl- säureestern wie Methylacrylat, Ethylacrylat und Methylmethacrylat als Hauptmonomeren hergestellt. Daneben können auch hier geringere Anteile an weiteren Comonomeren eingesetzt werden.The soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two shells); in the case of multi-layer elastomers, several shells can also consist of a rubber phase. If, in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C) are involved in the construction of the elastomer, these are generally obtained by polymerizing styrene, acrylonitrile, methacrylonitrile, α -methylstyrene, p-methylstyrene, Acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate are produced as the main monomers. In addition, smaller proportions of further comonomers can also be used here.
In einigen Fällen hat es sich als vorteilhaft herausgestellt,In some cases, it has proven to be beneficial
Emulsionspolymerisate einzusetzen, die an der Oberfläche reaktive Gruppen aufweisen. Derartige Gruppen sind z.B. Epoxy-, Carboxyl-, latente Carboxyl-, Amino- oder Amidgruppen sowie funktionelle Gruppen, die durch Mitverwendung von Monomeren der allgemeinen FormelTo use emulsion polymers which have reactive groups on the surface. Such groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups by the use of monomers of the general formula
Rιo Rιι R ιo R ιι
CH2=C X N C R2 0 eingeführt werden können,CH 2 = CXNCR 2 0 can be introduced,
wobei die Substituenten folgende Bedeutung haben:where the substituents have the following meaning:
Rιo Wasserstoff oder eine Ci- bis C4-Alkylgruppe, R ιo is hydrogen or a C 1 -C 4 -alkyl group,
Ri Wasserstoff, eine Cι~ bis Cg-Alkylgruppe oder eine Arylgruppe, insbesondere Phenyl ,Ri is hydrogen, a C 1 -C 6 -alkyl group or an aryl group, in particular phenyl,
R12 Wasserstoff, eine Cι~ bis Cι0-Alkyl-, eine C6- bis C12-Aryl- gruppe oder -OR13 R12 is hydrogen, a C 1 -C 8 -alkyl, a C 6 - to C 12 -aryl group or -OR 13
R13 eine Cι~ bis C8-Alkyl- oder C6- bis Cι2-Arylgruppe, die gege¬ benenfalls mit 0- oder N-haltigen Gruppen substituiert sein können,R 13 is a Cι ~ to C 8 -alkyl or C 6 - may be substituted by Cι 2 -aryl group which gege ¬ appropriate, with 0- or N-containing groups,
X eine chemische Bindung, eine Cχ~ bis Cio-Alkylen- oder C6-Cι2-Arylengruppe oderX is a chemical bond, a Cχ ~ to Cio alkylene or C 6 -C 2 arylene group or
O-Z oder NH-Z undO-Z or NH-Z and
eine Cι~ bis Cι0-Alkylen- oder C6~ bis Ci2-Arylengruppe .
Auch die in der EP-A 208 187 beschriebenen Pfropfmonomeren sind zur Einführung reaktiver Gruppen an der Oberfläche geeignet.a Cι ~ to Cι 0 alkylene or C 6 ~ to C i2 arylene group. The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
Als weitere Beispiele seien noch Acrylamid, Methacrylamid und substituierte Ester der Acrylsäure oder Methacrylsäure wie (N-t- Butyla ino) -ethylmethacrylat, (N,N-Dimethylamino) ethylacrylat, (N,N-Dimethylamino) -methylacrylat und (N,N-Diethylamino) ethylacrylat genannt.Further examples include acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butyla ino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ) called ethyl acrylate.
Weiterhin können die Teilchen der Kautschukphase auch vernetzt sein. Als Vernetzer wirkende Monomere sind beispielsweise Buta-l,3-dien, Divinylbenzol, Diallylphthalat und Dihydrodicyclo- pentadienylacrylat sowie die in der EP-A 50 265 beschriebenen Verbindungen.The particles of the rubber phase can also be crosslinked. Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
Ferner können auch sogenannten pfropfvernetzende Monomere (graft- linking monomers) verwendet werden, d.h. Monomere mit zwei oder mehr polymerisierbaren Doppelbindungen, die bei der Polymerisation mit unterschiedlichen Geschwindigkeiten reagieren. Vorzugsweise werden solche Verbindungen verwendet, in denen mindestens eine reaktive Gruppe mit etwa gleicher Geschwindigkeit wie die übrigen Monomeren polymerisiert, während die andere reaktive Gruppe (oder reaktive Gruppen) z.B. deutlich langsamer polymerisiert (polymerisieren) . Die unterschiedlichen Polymerisa- tionsgeschwindigkeiten bringen einen bestimmten Anteil an ungesättigten Doppelbindungen im Kautschuk mit sich. Wird anschließend auf einen solchen Kautschuk eine weitere Phase aufgepfropft, so reagieren die im Kautschuk vorhandenen Doppelbindungen zumindest teilweise mit den Pfropfmonomeren unter Ausbildung von chemischen Bindungen, d.h. die aufgepfropfte Phase ist zumin¬ dest teilweise über chemische Bindungen mit der Pfropfgrundlage verknüpft.So-called graft-linking monomers can also be used, ie monomers with two or more polymerizable double bonds which react at different rates during the polymerization. Compounds are preferably used in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or reactive groups) polymerizes (polymerizes), for example, significantly more slowly. The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. Is then grafted onto a rubber of a further phase, present in the rubber double bonds react at least partially with the graft monomers to form chemical bonds, ie, the grafted phase is at ¬ least partly linked by chemical bonds with the graft base.
Beispiele für solche pfropfvernetzende Monomere sind Allylgruppen enthaltende Monomere, insbesondere Allylester von ethylenisch ungesättigten Carbonsäuren wie Allylacrylat, Allylmethacrylat, Diallylmaleat, Diallylfumarat, Diallylitaconat oder die entsprechenden Monoallyl erbindungen dieser Dicarbonsäuren. Daneben gibt es eine Vielzahl weiterer geeigneter pfropfvernetzender Monome - rer; für nähere Einzelheiten sei hier beispielsweise auf die US-PS 4 148 846 verwiesen.Examples of such graft-crosslinking monomers are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. There are also a large number of other suitable graft-crosslinking monomers; for further details, reference is made here, for example, to US Pat. No. 4,148,846.
Im allgemeinen beträgt der Anteil dieser vernetzenden Monomeren an dem schlagzäh modifizierenden Polymer bis zu 5 Gew.-%, vorzugsweise nicht mehr als 3 Gew.-%, bezogen auf das schlagzäh modifizierende Polymere.
Nachfolgend seien einige bevorzugte Emulsionspolymerisate aufgeführt. Zunächst sind hier Pfropfpolymerisate mit einem Kern und mindestens einer äußeren Schale zu nennen, die folgenden Aufbau haben:In general, the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer. Some preferred emulsion polymers are listed below. First of all, graft polymers with a core and at least one outer shell are to be mentioned, which have the following structure:
Anstelle von Pfropfpolymerisaten mit einem mehrschaligen Aufbau können auch homogene, d.h. einschalige Elastomere aus Bu-ta-l,3-dien, Isopren und n-Butylacrylat oder deren Copolymeren eingesetzt werden. Auch diese Produkte können durch Mitverwendung von vernetzenden Monomeren oder Monomeren mit reaktiven Gruppen hergestellt werden.Instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of Bu-ta-l, 3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.
Beispiele für bevorzugte Emulsionspolymerisate sind n-Butylacry¬ lat/ (Meth) acrylsäure-Copoly ere, n-Butylacrylat/Glycidylacrylat- oder n-Butylacrylat/Glycidylmethacrylat-Copolymere, Pfropf - Polymerisate mit einem inneren Kern aus n-Butylacrylat oder auf Butadienbasis und einer äußeren Hülle aus den vorstehend genann¬ ten Copolymeren und Copolymere von Ethylen mit Comonomeren, die reaktive Gruppen liefern.Examples of preferred emulsion polymers are n-Butylacry ¬ lat / (meth) acrylic acid-copoly ere, n-butyl acrylate / glycidyl acrylate or n-B utylacrylat / glycidyl methacrylate copolymers, graft - polymers with an inner core of n-butyl acrylate or based on butadiene and an outer shell of the above genann ¬ th copolymers, and copolymers of ethylene with comonomers which provide reactive groups.
Die beschriebenen Elastomere können auch nach anderen üblichen Verfahren, z.B. durch Suspensionspolymerisation, hergestellt wer¬ den.
Siliconkautschuke, wie in der DE-A 37 25 576, der EP-A 235 690, der DE-A 38 00 603 und der EP-A 319 290 beschrieben, sind ebenfalls bevorzugt.The elastomers described may also be prepared by other conventional processes, eg by suspension polymerization ¬ to. Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.
Selbstverständlich können auch Mischungen der vorstehend aufgeführten Ka tschu typen eingesetzt werden.Of course, mixtures of the types of cheeses listed above can also be used.
Weiterhin können die Polyamid-Nanocomposites Stabilisatoren, Oxidationsverzogerer, Mittel gegen Wärmezersetzung und Zersetzung durch ultraviolettes Licht, Gleit- und Entformungsmittel, Färbemittel wie Farbstoffe und Pigmente, Keimbildungsmittel, Weichmacher usw. enthalten.Furthermore, the polyamide nanocomposites can contain stabilizers, oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
Als Beispiele für Oxidationsverzogerer und Wärmestabilisatoren sind sterisch gehinderte Phenole, Hydrochinone, Kupferverbindungen aromatische sekundäre Amine wie Diphenylamine, verschiedene substituierte Vertreter dieser Gruppen und deren Mischungen in Konzentrationen bis zu 1 Gew.-%, bezogen auf das Gewicht der thermoplastischen Formmassen genannt.Examples of oxidation retarders and heat stabilizers are sterically hindered phenols, hydroquinones, copper compounds, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
Als UV-Stabilisatoren, die im allgemeinen in Mengen bis zu 2 Gew.-%, bezogen auf die Formmasse, verwendet werden, seien verschiedene substituierte Resorcine, Salicylate, Benzotriazole und Be zophenone genannt.Various substituted resorcinols, salicylates, benzotriazoles and Be zophenones may be mentioned as UV stabilizers, which are generally used in amounts of up to 2% by weight, based on the molding composition.
Es können anorganische Pigmente, wie Titandioxid, Ultramarinblau, Eisenoxid und Ruß, weiterhin organische Pigmente, wie Phthalo- cyanine, Chinacridone, Perylene sowie Farbstoffe, wie Nigrosin und Anthrachinone als Farbmittel zugesetzt werden.Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can be added as colorants.
Als Keimbildungsmittel können Natriumphenylphosphinat, Aluminiumoxid oder Siliziumdioxid eingesetzt werden.Sodium phenylphosphinate, aluminum oxide or silicon dioxide can be used as nucleating agents.
Gleit- und Entformungsmittel, welche üblicherweise in Mengen bis zu 1 Gew.-% eingesetzt werden, sind bevorzugt langkettige Fettsäuren (z.B. Stearinsäure oder Behensäure) , deren Salze (z.B. Ca- oder Zn-Stearat) sowie Amidderivate (z.B. Ethylen-bis- stearylamid) oder Montanwachse (Mischungen aus geradkettigen, ge¬ sättigten Carbonsäuren mit Kettenlängen von 28 bis 32 C-Atomen) sowie niedermolekulare Polyethylen- bzw. Polypropylenwachse.Lubricants and mold release agents, which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and amide derivatives (for example ethylene-bis-stearylamide) ) montan waxes (mixtures of straight-ge ¬ saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes, or.
Als Zusatzstoffe C) sind außerdem faser- oder teilchenförmige Füllstoffe geeignet, beispielsweise in Mengen von 0 bis 50, bevorzugt 5 bis 40 und insbesondere 10 bis 30 Gew.-%.
Als bevorzugte faserförmige Füllstoffe seien Kohlenstoffasern, Aramid-Fasern und Kaliumtitanat-Fasern genannt, wobei Glasfasern aus E-Glas besonders bevorzugt sind. Diese können als Rovings oder Schnittglas in den handelsüblichen Formen eingesetzt werden.Fibrous or particulate fillers are also suitable as additives C), for example in amounts of 0 to 50, preferably 5 to 40 and in particular 10 to 30% by weight. Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, glass fibers made of E-glass being particularly preferred. These can be used as rovings or cut glass in the commercially available forms.
Die faserförmigen Füllstoffe können zur besseren Verträglichkeit mit dem Polyamid mit einer Silanverbindung oberflächlich vorbehandelt sein.The fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the polyamide.
Geeignete Silanverbindungen sind solche der allgemeinen Formel IIISuitable silane compounds are those of the general formula III
(X- (CH2) n) k _Si- (0-CmHm+ι) 4_k χll (X- (CH 2 ) n ) k _ Si (0-C m H m + ι) 4 _ k χll
m• der die Substituenten folgende Bedeutung haben:m • the substituents have the following meaning:
n eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4 m eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2 k eine ganze Zahl von 1 bis 3, bevorzugt 1.n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1
Bevorzugte Silanverbindungen sind Aminopropyltrimethoxysilan, Aminobutyltrimethoxysilan, Aminopropyltriethoxysilan, Aminobutyl- triethoxysilan sowie die entsprechenden Silane, welche als Substituent X eine Glycidylgruppe enthalten.Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
Die Silanverbindungen werden im allgemeinen in Mengen von 0,05 bis 5, vorzugsweise 0,5 bis 1,5 und insbesondere 0,8 bis 1 Gew.-% (bezogen auf C) ) zur Oberflächenbeschichtung eingesetzt.The silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on C)) for the surface coating.
Bevorzugt sind faserförmige Füllstoffe mit einer mittleren arith¬ metischen Faserlänge von 150 bis 300 um, bevorzugt 200 bis 270 um und insbesondere 220 bis 250 um. Der mittlere Durchmesser beträgt im allgemeinen von 3 bis 30 m, bevorzugt von 8 bis 20 um und ins¬ besondere 10 bis 14 μm. Die gewünschte Faserlänge kann z.B. durch Mahlen in einer Kugelmühle eingestellt werden, wobei eine Faser¬ längenverteilung entsteht.Fibrous fillers are preferred having an average arith metic ¬ fiber length of 150 to 300, preferably 200 to 270 and in particular to 220 to 250 to. The average diameter is generally from 3 up to 30 m, preferably from 8 to 20 microns to and from ¬ particular 10 to 14. The desired fiber length can be adjusted by milling in a ball mill for example, wherein a fiber length distribution ¬ formed.
Eine weitere Reduzierung der Faserlänge führt, wenn die mittlere Faserlänge <200 μm ist, zu einem rieselfähigen Schüttgut, das wie ein Pulver in das Polymer eingemischt werden kann. Aufgrund der geringen Faserlänge tritt beim Einarbeiten nur noch eine geringe weitere Verkürzung der Faserlänge ein.
Der Fasergehalt wird üblicherweise nach Veraschen des Polymeren bestimmt. Zur Bestimmung der Faserlängenverteilung wird im allgemeinen der Ascherückstand in Silikonöl aufgenommen und bei 20-f cher Vergrößerung des Mikroskops fotografiert. Auf den Bil- dern können bei mindestens 500 Fasern die Länge ausgemessen und der arithmetische Mittelwert (d50) daraus berechnet werden.If the average fiber length is <200 μm, a further reduction in the fiber length leads to a free-flowing bulk material that can be mixed into the polymer like a powder. Due to the short fiber length, there is only a slight further shortening of the fiber length during incorporation. The fiber content is usually determined after the polymer has been incinerated. To determine the fiber length distribution, the ash residue is generally taken up in silicone oil and photographed at 20x magnification of the microscope. The length of at least 500 fibers can be measured on the pictures and the arithmetic mean (d 50 ) can be calculated from them.
Geeignet sind weiterhin nadeiförmige mineralische Füllstoffe, unter welchen mineralische Füllstoffe mit stark ausgeprägtem na- delformigen Charakter verstanden werden sollen. Als Beispiel sei nadeiförmiger Wollastonit genannt. Vorzugsweise weist das Mineral ein L/D- (Länge/Durchmesser) -Verhältnis von 8 : 1 bis 35 : 1, bevorzugt von 8 : 1 bis 11 : 1 auf. Der mineralische Füllstoff kann gegebenenfalls mit den vorstehend genannten Silanver- bindungen vorbehandelt sein; die Vorbehandlung ist jedoch nicht unbedingt erforderlich.Also suitable are needle-shaped mineral fillers, which are mineral fillers with a pronounced needle-like character. An example is needle-shaped wollastonite. The mineral preferably has an L / D (length / diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler can optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.
Als teilchenförmige Füllstoffe eignen sich amorphe Kieselsäure, Magnesiumcarbonat (Kreide) , Kaolin (insbesondere kalzinierter Kaolin) , gepulverter Quarz, Glimmer, Talkum, Feldspat und insbesondere Calciumsilikate wie Wollastonit.Amorphous silica, magnesium carbonate (chalk), kaolin (in particular calcined kaolin), powdered quartz, mica, talc, feldspar and in particular calcium silicates such as wollastonite are suitable as particulate fillers.
Die erfindungsgemäßen Formkörper weisen in der Regel einen A—[--B-A--πB Schichtaufbau auf, also Schichtfolge ABABAB..., wobei A die Thermoplastmatrix darstellt und die Schicht B das delaminierte Schichtsilikat bedeutet.The moldings according to the invention generally have an A - [- B-A - πB layer structure, that is to say layer sequence ABABAB ..., A being the thermoplastic matrix and layer B being the delaminated layered silicate.
Spritzgußverfahreninjection molding
Bei dem erfindungsgemäßen Verfahren werden die Formteile im Spritzgußverfahren durch Einbringen einer Schmelze, enthaltend das Polyamid A) und das delaminierte Schichtsilikat B) , über einen Anguß in ein Spritzgußwerkzeug, hergestellt.In the process according to the invention, the molded parts are produced in an injection molding process by introducing a melt containing the polyamide A) and the delaminated layered silicate B) via a sprue into an injection molding tool.
Das Schichtsilikat B) schmilzt im Gegensatz zum Polyamid A) in der Regel während des Spritzgußvorganges nicht auf. Demnach ist der Anspruchswortlaut "Schmelze" zu verstehen als Mischung aus geschmolzenem (plastischem) Polyamid A) und festem Schichtsilikat B) .In contrast to polyamide A), layered silicate B) generally does not melt during the injection molding process. Accordingly, the claim wording "melt" is to be understood as a mixture of molten (plastic) polyamide A) and solid layered silicate B).
Das Einbringen der Schmelze über einen Anguß in das Spritzguß- Werkzeug geschieht in an sich bekannter Weise, z.B. mittels einer Spritzgußmaschine (Kolben-, Schnecken- oder andere Spritzgu - maschine) .
Das Spritzgußverfahren zur Herstellung von Kunststoff-Formteilen ist seit langem bekannt und bedarf keiner näheren Erläuterung. Einzelheiten findet der Fachmann z.B. in folgenden Monographien: Menges et al . , Anleitung für den Bau von Spritzgießwerkzeugen, 2. Aufl., Hanser Verlag, München 1983; Menges, Einführung in die Kunststoffverarbeitung, Hanser Verlag, München 1979; Sarholz, Spritzgießen: Verfahrensablauf, Verfahrensparameter, Prozeßführung, Hanser Verlag, München 1979.The melt is introduced into the injection molding tool via a sprue in a manner known per se, for example by means of an injection molding machine (piston, screw or other injection molding machine). The injection molding process for the production of plastic molded parts has been known for a long time and requires no further explanation. The person skilled in the art finds details, for example, in the following monographs: Menges et al. , Instructions for the construction of injection molding tools, 2nd edition, Hanser Verlag, Munich 1983; Menges, introduction to plastics processing, Hanser Verlag, Munich 1979; Sarholz, injection molding: process flow, process parameters, process control, Hanser Verlag, Munich 1979.
Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß man die Spritzgußbedingungen in an sich bekannter Weise derart wählt, daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt, wodurch eine hohe Orientierung der Schmelze er- reicht wird, und daß die hohe Orientierung der Schmelze beim Erstarren der Schmelze eingefroren wird.The process according to the invention is characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved and that the high orientation of the melt upon solidification of the Melt is frozen.
Den Anspruchswortlaut "daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt" wird nachfolgend erläutert.The wording of the claim "that the melt flows essentially parallel in the injection molding tool" is explained below.
Ein beliebiger Punkt X der im Spritzgußwerkzeug vorwärts fließenden Schmelze beschreibe einen Fließweg x, und ein beliebiger Punkt Y der fließenden Schmelze beschreibe einen Fließweg y. Da- bei ist der Fließweg der Weg, den die Schmelze vom Anschnitt ausgehend im Werkzeug zurücklegt (der Anschnitt ist die Grenzfläche zwischen dem Spritzgußformteil und dem Anguss) . Erfindungsgemäß sind die Spritzgußbedingungen derart zu wählen, daß die beiden Fließwege x und y äquidistant sind, im Falle von Geraden demnach parallel sind.An arbitrary point X of the melt flowing forward in the injection mold describes a flow path x, and an arbitrary point Y of the flowing melt describes a flow path y. The flow path is the path that the melt travels from the gate in the mold (the gate is the interface between the injection molded part and the sprue). According to the invention, the injection molding conditions are to be selected such that the two flow paths x and y are equidistant, and are therefore parallel in the case of straight lines.
Die Fließfront der fließenden Schmelze ist folglich im wesentlichen gerade und nicht etwa gekrümmt, und die Front fließt im we¬ sentlichen an allen Stellen mit gleicher Geschwindigkeit.The flow front of the flowing melt is therefore not just about substantially curved and the front and flows we ¬ sentlichen at all points at the same speed.
Die Einschränkung "im wesentlichen" trägt der Tatsache Rechnung, daß eine Schmelze im unmittelbar an die Werkzeugoberfläche angrenzenden Randbereich langsamer fließt und direkt an der Werk¬ zeugoberfläche die Fließgeschwindigkeit null ist, sodaß die Fließfront in diesem Randbereich gekrümmt und möglicherweise der Fließweg nicht parallel ist.The limitation "substantially" reflects the fact that a melt flows more slowly in the region directly adjoining the tool surface the edge region and directly on the work ¬ imaging surface, the flow rate is zero, the flow front so that in this edge region is curved and possibly of the flow path is not parallel.
Mit anderen Worten: Erfindungsgemäß sind die Fließwege der Schmelze in an sich bekannter Weise derart zu optimieren, daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt.
Dem Fachmann ist - beispielsweise vom Spritzgießen glasfaser- haltiger thermoplastischer Formmassen - bekannt, wie er die Spritzgußbedingungen wählen muss, damit die Schmelze im Spritz - gußwerkzeug im wesentlichen parallel fließt.In other words: According to the invention, the flow paths of the melt are to be optimized in a manner known per se in such a way that the melt flows essentially parallel in the injection molding tool. The person skilled in the art, for example from the injection molding of glass fiber-containing thermoplastic molding compositions, knows how to choose the injection molding conditions so that the melt in the injection molding tool flows essentially in parallel.
Als Spritzgußbedingungen sind beispielhaft zu nennen:The following are examples of injection molding conditions:
Ausgestaltung des Angusses, insbesondere Ort des Angusses (z.B. in oder außerhalb der Trennebene des Werkzeuges); Geo- metrie des Angusses, z. B. Form, Querschnitt, Volumen; Geometrie evtl. vorhandener Verteilerkanäle, z.B. Länge, Querschnitt, Volumen; Geometrie des Anschnitts, z.B. Form, Querschnitt, Werkzeug-Temperatur (Werkzeugoberflächentemperatur) - Massetemperatur (Schmelzetemperatur) Massedruck (Einspritzdruck) Nachdruck Zykluszeit Einspritzzeit und Schneckenvorlaufgeschwindigkeit - KühlzeitDesign of the sprue, in particular the location of the sprue (e.g. in or outside the parting plane of the tool); Gating geometry, e.g. B. shape, cross section, volume; Geometry of any existing distribution channels, e.g. Length, cross section, volume; Geometry of the gate, e.g. Shape, cross-section, mold temperature (mold surface temperature) - melt temperature (melt temperature) melt pressure (injection pressure) hold pressure cycle time injection time and screw advance speed - cooling time
Nachdruckzeitpressure time
Werkzeug-OffenzeitMold open time
Querschnittsfläche der WerkzeugkavitätCross-sectional area of the tool cavity
Spritzlingsvolumen (Formteilvolumen) - ZuhaltekraftInjection molding volume (molding volume) - locking force
Einspritzgeschwindigkeit.Injection speed.
Es wird ausdrücklich auf die Norm DIN EN ISO 294-1 (Oktober 1998) verwiesen, in der die vorgenannten Parameter definiert sind.Reference is expressly made to the standard DIN EN ISO 294-1 (October 1998), in which the aforementioned parameters are defined.
Bevorzugt liegen die genannten Parameter innerhalb folgender Be¬ reiche:Preferably, the parameters referred to within the following Be ¬ are rich:
Werkzeugoberflächentemperatur: von 15 bis 140°C - Massetemperatur (Schmelzetemperatur) : von 240 bis 320°CTool surface temperature: from 15 to 140 ° C - melt temperature (melt temperature): from 240 to 320 ° C
Massedruck (Einspritzdruck) : von 250 bis 2500 barMass pressure (injection pressure): from 250 to 2500 bar
Nachdruck: von 250 bis 1500 barHolding pressure: from 250 to 1500 bar
Zykluszeit: von 3 bis 300 sCycle time: from 3 to 300 s
Schneckenvorlaufgeschwindigkeit: von 20 bis 1000 mm/s - Nachdruckzeit: von 0,5 bis 60 s.Screw advance speed: from 20 to 1000 mm / s - holding time: from 0.5 to 60 s.
Es versteht sich, daß im Einzelfall die zu wählenden Zahlenwerte stark vom herzustellenden Formteil (Größe, .Geometrie) sowie der Zusammensetzung und den Eigenschaften der Formmasse abhängen.
Bevorzugt wird die Schmelze im Angußsystem so verteilt, daß sie mit annähernd paralleler Fließfront in die Kavität des Werkzeugs eintritt. Das Angußsystem ist entsprechend auszuwählen.It goes without saying that in individual cases the numerical values to be selected strongly depend on the molded part to be produced (size, geometry) and on the composition and properties of the molding compound. The melt is preferably distributed in the sprue system in such a way that it enters the cavity of the tool with an approximately parallel flow front. The sprue system must be selected accordingly.
In einer bevorzugten Ausführungsform ist der Anguß als Bandanguß (auch als Filmanguß oder Bandanschnitt bezeichnet) ausgebildet, d.h. die Schmelze tritt nicht - wie beim Punktanguß oder beim Stangen- oder Kegelanguß - an einem Punkt in das Werkzeug ein, sondern gleichzeitig an einer Fläche. Beispielsweise kann man beim Bandanguß direkt in die Trennfläche des Werkzeugs spritzen.In a preferred embodiment, the sprue is designed as a tape gate (also referred to as a film gate or tape gate), i.e. the melt does not enter the tool at one point - as in the case of point sprue or rod or cone sprue - but at the same time on a surface. For example, you can spray directly into the parting surface of the tool during the gate.
Beim Bandanguß tritt die Schmelze in der Regel an der ganzen Seite gleichzeitig in das Werkzeug ein. Der Bandanschnitt kann je nach Dicke des Formteils verschieden dick sein. Der vor dem An- schnitt liegende Anguß (Verteilerkanal, sog. Bandverteiler) sollte im Querschnitt deutlich größer sein, damit der Anschnitt gleichmäßig mit der Schmelze gefüllt ist.The melt usually enters the mold on the whole side at the same time. Depending on the thickness of the molded part, the band gate can have different thicknesses. The gate in front of the gate (distribution channel, so-called belt distributor) should be significantly larger in cross-section so that the gate is evenly filled with the melt.
Für das Spritzgießen rohrförmiger Teile (z.B. Rohre, Laufrollen) verwendet man in einer bevorzugten Ausführungsform einen Schirmanguß (auch als Pilz-, Teller- oder Scheibenanguß bezeichnet) oder Ringanguß .For the injection molding of tubular parts (e.g. pipes, rollers), a shield gate (also referred to as mushroom, plate or disc gate) or ring gate is used in a preferred embodiment.
Durch die Wahl der Spritzgußbedingungen derart, daß die Schmelze im Werkzeug parallel fließt, wird eine hohe Orientierung derThe choice of the injection molding conditions in such a way that the melt flows in parallel in the mold ensures that the orientation is high
Schmelze (enthaltend Polyamid A) und Schichtsilikat B) ) erreicht, d.h. durch das parallele Fließen liegen in der Schmelze hoch geordnete Strukturen vor.Melt (containing polyamide A) and layered silicate B)) reached, i.e. Due to the parallel flow, highly ordered structures are present in the melt.
Eine mögliche Erklärung für das Entstehen der hohen Orientierung ist, daß ein sog. Scherprofil vorliegt: Wie bereits erwähnt, ist die Fließgeschwindigkeit der Schmelze unmittelbar an der Werkzeu¬ goberfläche null. Nimmt man an, daß die Fließgeschwindigkeit in der Mitte zwischen den Werkzeugoberflächen maximal ist, so liegt über den Schmelzequerschnitt betrachtet ein Geschwindigkeitsgra¬ dient vor. Dieser Gradient bewirkt, daß die Schmelze Scherkräften unterliegt, die im Randbereich der Schmelze maximal sind (sog. Scherprofil) . Die Scherkräfte führen zu einer Orientierung der Schmelze, die in den Randbereichen maximal ist.One possible explanation for the emergence of high orientation, that a so-called shear profile is present. As mentioned above, the flow rate of the melt is directly on the tool press ¬ goberfläche zero. If one assumes that the flow speed in the middle between the tool surfaces is maximum, then a speed graph is present when viewed over the melt cross section. This gradient causes the melt to be subject to shear forces which are maximum in the edge region of the melt (so-called shear profile). The shear forces lead to an orientation of the melt which is maximal in the edge areas.
Randbereich meint den Bereich der Schmelze (genauer: des Schmelzequerschnitts) , der an die Werkzeugoberfläche angrenzt, also den oberflächennahen Bereich des späteren Formteils.Edge area means the area of the melt (more precisely: the melt cross-section) that borders on the tool surface, i.e. the area near the surface of the later molded part.
Erfindungsgemäß sind die Spritzgußbedingungen so zu wählen, daß die hohe Orientierung der Schmelze beim Erstarren der Schmelze eingefroren wird. Dies bedeutet, daß durch das Erstarren der
Schmelze zum fertigen festen Formteil die hoch geordneten Strukturen aus Polyamid und Schichtsilikat quasi "fixiert" werden.According to the invention, the injection molding conditions are to be selected so that the high orientation of the melt is frozen when the melt solidifies. This means that by solidifying the Melt to the finished solid molded part, the highly ordered structures made of polyamide and layered silicate are virtually "fixed".
Dem Fachmann ist - beispielsweise vom Spritzgießen glasfaser- haltiger thermoplastischer Formmassen - bekannt, wie er dieThe person skilled in the art knows, for example from the injection molding of glass fiber-containing thermoplastic molding compositions, how he uses the
Spritzgußbedingungen wählen muss, damit die hohe Orientierung der Schmelze beim Erstarren eingefroren wird.Injection molding conditions must be selected so that the high orientation of the melt is frozen when it solidifies.
Wichtige Parameter für das Einfrieren der hoch orientierten Schmelze sind die Temperaturen der Schmelze und der Werkzeugoberfläche.Important parameters for freezing the highly oriented melt are the temperatures of the melt and the tool surface.
Die Temperaturen und die anderen Spritzgußbedingungen sind bevorzugt in an sich bekannter Weise derart zu wählen, daß das Werk- zeug gut gefüllt und die durch das parallele Fließen der Schmelze erzeugte hohe Orientierung beim Erstarren eingefroren wird.The temperatures and the other injection molding conditions should preferably be selected in a manner known per se such that the tool is filled well and the high orientation generated by the parallel flow of the melt is frozen during solidification.
Ein weiterer wichtiger Paramter für das Einfrieren der hoch orientierten Schmelze ist die Dimensionierung der Werkzeugkavität und damit des Formteils: ist die zwischen den gegenüberliegenden Werkzeugoberflächen befindliche Schmelzeschicht dünn, so kann man in der Regel die Schmelzeorientierung besser einfrieren als bei dicken Schmelzeschichten.Another important parameter for freezing the highly oriented melt is the dimensioning of the mold cavity and thus the molded part: if the melt layer located between the opposite tool surfaces is thin, the melt orientation can generally be better frozen than with thick melt layers.
Anknüpfend an das oben beschriebene Scherprofil, besteht die Vorstellung, daß bei dünnen Schmelzeschichten - d.h. dünnwandigen Formteilen - die hoch orientierten Randbereiche (oberflächennna- hen Bereiche) groß sind im Vergleich zum weniger hoch orientierten Inneren der Schmelze bzw. des Formteils.Based on the shear profile described above, there is the idea that with thin layers of melt - i.e. thin-walled molded parts - the highly oriented edge areas (areas close to the surface) are large compared to the less highly oriented interior of the melt or the molded part.
Das Verfahren eignet sich daher besonders zur Herstellung von dünnwandigen Formteilen und insbesondere von Formteilen, die im wesentlichen eine Wanddicke von maximal 2 mm, bevorzugt maximal 1 mm, aufweisen (sog. dünnwandige Formteile) . Mit "im wesentlichen" ist gemeint, daß die Formteile in den Bereichen, die einer Bela¬ stung ausgesetzt sind, eine Wanddicke von maximal 2 mm haben.The method is therefore particularly suitable for the production of thin-walled moldings and in particular of moldings which essentially have a wall thickness of at most 2 mm, preferably at most 1 mm (so-called thin-walled moldings). By "substantially" is meant that the mold parts in the areas that are exposed to a loading stung ¬, a wall thickness of not more than 2 mm have.
Beispiele für derartige dünnwandige Formteile mit Wanddicken von maximal 2 mm sind schalenförmige Formteile z.B. für Gehäuse, ins- besondere Handygehäuse, außerdem Spulenkörper, Kabelbinder, Ge¬ häuse für Elektroinstallationen und elektrische bzw. elektronische Geräte.
Es besteht die Vorstellung, daß die im Formteil vorhandenen, eingefrorenen hoch orientierten Strukturen die Ursache für die verbesserte Zähigkeit und Gesamtschädigungsarbeit der Formteile • sind.Examples of such thin-walled moldings with a wall thickness of at most 2 mm are shell-shaped moldings, for example for housing, in particular mobile phone housing, also bobbin, cable ties, Ge ¬ housing for electrical installations and electrical or electronic devices. There is an idea that the frozen, highly oriented structures present in the molded part are the cause of the improved toughness and overall damage work of the molded parts.
Mit dem erfindungsgemä en Verfahren lassen sich Formteile aller Art mit verbesserter Zähigkeit herstellen, auch Halbzeuge, Rohre, Profile, Platten, spritzgegossene Folien usw. Insbesondere lassen such dünnwandige Formteile mit verbesserter Zähigkeit herstellen. Diese Formteile sind ebenfalls Gegenstand der Erfindung. Zähigkeit meint insbesondere multiaxiale Zähigkeit.The method according to the invention can be used to produce moldings of all types with improved toughness, including semi-finished products, pipes, profiles, plates, injection-molded foils, etc. In particular, thin-walled moldings can be produced with improved toughness. These molded parts are also the subject of the invention. Toughness means especially multiaxial toughness.
Gegenstand der Erfindung sind außerdem Formteile, wobei das Formteil nach dem erfindungsgemäßen Verfahren hergestellt wird und eine Rundscheibe von 60 mm Durchmesser und 1 mm Dicke ist, die aus 95 Gew.-% Polyamid 6 und 5 Gew.-% hydrophobiertem Bentonit hergestellt wird, und wobei die Rundscheibe im Durchstoßtest nach DIN 53443 bei 23°C eine Gesamtschädigungsarbeit Wges von mindestens 30 J/mm aufweist.The invention also relates to molded parts, the molded part being produced by the process according to the invention and being a circular disc 60 mm in diameter and 1 mm thick, which is produced from 95% by weight of polyamide 6 and 5% by weight of hydrophobic bentonite, and the round disk in the puncture test according to DIN 53443 at 23 ° C has a total damage work W tot of at least 30 J / mm.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Erhöhung der Zähigkeit von Formteilen aus Polyamid-Nanocomposites, enthaltend mindestens ein Polyamid A) , und mindestens ein delaminiertes Schichtsilikat B) , dadurch gekennzeichnet, daß man die Formteile im Spritzgußverfahren durch Einbringen einer Schmelze enthaltend A) und B) über einen Anguß in ein Spritzgußwerkzeug herstellt, und daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt, wodurch eine hohe Orientierung der Schmelze erreicht wird, und daß die hohe Orientierung der Schmelze beim Erstarren der Schmelze eingefroren wird.The invention further relates to a process for increasing the toughness of molded parts made of polyamide nanocomposites containing at least one polyamide A) and at least one delaminated layered silicate B), characterized in that the molded parts are injection-molded by introducing a melt containing A) and B) via a sprue in an injection molding tool, and that the melt in the injection molding tool flows essentially in parallel, whereby a high orientation of the melt is achieved and that the high orientation of the melt is frozen when the melt solidifies.
Die nachfolgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
BeispieleExamples
Es wurden folgende Einsatzstoffe verwendet.The following feedstocks were used.
Polyamid:Polyamide:
Polyamid 6 (Polycaprolactam) mit einer Viskositätszahl VZ von 150 ml/g, gemessen als 0,5 gew.-%ige Lösung in 96 gew.-%iger Schwe¬ felsäure bei 25°C nach ISO 307. Es wurde Ultramid® B3 von BASF verwendet .Polyamide 6 (polycaprolactam) having a viscosity number VN of 150 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% hydrochloric pivot ¬ ric acid at 25 ° C according to ISO 307. It has been Ultramid® B3 of BASF uses.
Delaminiertes hydrophobiertes Schichtsilikat: 1 kg gereinigter Natrium-Bentonit mit einer Ionenaus ausch- kapazität von 95 meq/100 g wurde in einem gerührten Kessel mit soviel Wasser vermischt, daß eine 2 gew.-%ige Suspension ent-
stand. Zu der Suspension wurden bei Raumtemperatur 397 g Di(2-hydroxyethyl)methylstearylammoniumchlorid innerhalb 1 min zugefügt. Der ausgefallene Niederschlag wurde durch Filtration abgetrennt, mit Wasser gereinigt und sprühgetrocknet. •Delaminated hydrophobized layered silicate: 1 kg of purified sodium bentonite with an ion exchange capacity of 95 meq / 100 g was mixed with enough water in a stirred kettle that a 2% by weight suspension was removed. was standing. 397 g of di ( 2-hydroxyethyl) methylstearylammonium chloride were added to the suspension at room temperature within 1 min. The precipitate which separated out was separated off by filtration, purified with water and spray-dried. •
Das Produkt ist auch als Cloisite® 30B von Fa. Southern Clay Products, Texas, USA, erhältlich.The product is also available as Cloisite® 30B from Southern Clay Products, Texas, USA.
Herstellung der FormmasseProduction of the molding compound
95 Gew. -Teile Polyamid und 5 Gew. -Teile delaminiertes hydro- phobiertes Schichtsilikat wurden auf einem ZweiSchneckenextruder bei 250°C, 250 Umdrehungen/min und 20 kg/h Durchsatz innig vermischt, die Mischung als Stränge ausgetragen, im Wasserbad ge- kühlt und granuliert. Man erhielt ein Polyamid-Nanocomposite-Gra- nulat.95 parts by weight of polyamide and 5 parts by weight of delaminated hydrophobic layered silicate were intimately mixed on a twin-screw extruder at 250 ° C., 250 revolutions / min and 20 kg / h throughput, the mixture was discharged as strands and cooled in a water bath and granulated. A polyamide nanocomposite granulate was obtained.
Herstellung der FormkörperProduction of the moldings
Vor der Spritzgußverarbeitung wurde das Polyamid-Nanocomposite- Granulat 16 Stunden bei 100°C im Vakuum getrocknet.Before the injection molding processing, the polyamide nanocomposite granules were dried in a vacuum at 100 ° C. for 16 hours.
In den nachfolgenden Beispielen wurde die Schneckenvorlaufgeschwindigkeit so gewählt, daß die Fließgeschwindigkeit der Schmelze an der Stelle, die der geprüften Stelle des Probekörpers entsprach, identisch war.In the following examples, the screw advance speed was selected so that the flow rate of the melt was identical at the point that corresponded to the tested point of the test specimen.
Beispiel 1 (zum Vergleich)Example 1 (for comparison)
Auf einer Spritzgußmaschine Arburg Allrounder 270S mit 25 mmOn an Arburg Allrounder 270S injection molding machine with 25 mm
Schneckendurchmesser wurden Rundscheiben von 1 mm Dicke und 60 mm Durchmesser hergestellt. Die Schneckenvorlaufgeschwindigkeit betrug 22 mm/s, die Werkzeugoberflächentemperatur 80°C und die Schmelzetemperatur (Massetemperatur) 270°C. Als Spritzgußwerkzeug wurde ein Einfachwerkzeug verwendet. Das Angußsystem bestand aus einem Angußkanal mit Punktanguß, der in der Trennebene des Wer- zeugs lag. Aufgrund dieser Anordnung floss die Schmelze im Werk¬ zeug nicht parallel, sondern radial.Round disks with a thickness of 1 mm and a diameter of 60 mm were produced. The screw advance speed was 22 mm / s, the mold surface temperature 80 ° C and the melt temperature (melt temperature) 270 ° C. A simple tool was used as the injection molding tool. The sprue system consisted of a sprue with a sprue that lay in the parting plane of the tool. Due to this arrangement, the melt in the work ¬ did not flow generating parallel but radially.
Beispiel 2 (erfindungsgemäß)Example 2
Auf einer Spritzgußmaschine Nestal Synergy 1200 mit 32 mm Schneckendurchmesser wurden Platten von 1 mm Dicke und 100x100 mm Kantenlänge hergestellt. Die Schneckenvorlaufgeschwindigkeit be- trug 50 mm/s, die Werkzeugoberflächentemperatur 80°C und diePlates of 1 mm thickness and 100x100 mm edge length were produced on an Nestal Synergy 1200 injection molding machine with a 32 mm screw diameter. The screw advance speed was 50 mm / s, the tool surface temperature 80 ° C and
Schmelzetemperatur (Massetemperatur) 270°C. Als Spritzgußwerkzeug wurde ein Zweifachwerkzeug verwendet. Das Angußsystem bestand aus
einem Stangenanguß, der senkrecht zu den beiden Formteilen des Zweifachwerkzeugs lag, und pro Formteil einem nachfolgenden Band- anschnitt. Der Bandanschnitt bewirkte, daß die Schmelze im Werkzeug im wesentlichen parallel floss. Aus den Platten wurden Rund- Scheiben von 1 mm Dicke und 60 mm Durchmesser spanabhebend herausgearbeitet .Melt temperature (melt temperature) 270 ° C. A double mold was used as the injection molding tool. The sprue system consisted of a bar sprue that was perpendicular to the two molded parts of the two-cavity mold, and a subsequent band gate for each molded part. The band cut caused the melt to flow essentially parallel in the tool. Round disks of 1 mm thickness and 60 mm diameter were machined from the plates.
Prüfung und Eigenschaften der ProbekörperTesting and properties of the test specimens
An den Rundscheiben wurden im multiaxialen Durchstoßtest nach DIN 53443 bei 23°C die Gesamtschädigungsarbeit Wges bestimmt. Das Bruchverhalten wurde visuell bestimmt.The total damage work W tot was determined on the round disks in the multiaxial puncture test according to DIN 53443 at 23 ° C. The fracture behavior was determined visually.
Die Tabelle fasst die Ergebnisse zusammen.The table summarizes the results.
Die Tabelle zeigt, daß sich durch Wahl der Spritzgußbedingungen derart, daß die Schmelze im Werkzeug parallel fließt (hier: durch Wechsel vom Punktanguß zum Bandanguß) und daß die Schmelzeorientierung eingefroren wird, die Zähigkeit der dünnwandigen Formteile deutlich verbessert. Die Gesamtschädigungsabeit nimmt um mehr als die Hälfte von 19,7 auf 33,4 J/mm zu, und das Bruchverhalten ist duktil-zäh statt spröde.
The table shows that by choosing the injection molding conditions such that the melt flows in the mold in parallel (here: by changing from the point gate to the band gate) and that the melt orientation is frozen, the toughness of the thin-walled molded parts is significantly improved. The total damage capacity increases by more than half from 19.7 to 33.4 J / mm, and the fracture behavior is ductile-tough instead of brittle.
Claims
1. Verfahren zur Herstellung von Formteilen aus Polyamid-Nano- composites, enthaltend1. Process for the production of molded parts from polyamide nanocomposites containing
A) mindestens ein Polyamid A) , undA) at least one polyamide A), and
B) mindestens ein delaminiertes Schichtsilikat B)B) at least one delaminated layered silicate B)
im Spritzgußverfahren durch Einbringen einer Schmelze enthaltend A) und B) über einen Anguß in ein Spritzgußwerkzeug, dadurch gekennzeichnet, daß man die Spritzgußbedingungen in an sich bekannter Weise derart wählt, daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt, wodurch eine hohe Orientierung der Schmelze erreicht wird, und daß die hohe Orientierung der Schmelze beim Erstarren der Schmelze eingefroren wird.in the injection molding process by introducing a melt containing A) and B) over a sprue into an injection molding tool, characterized in that the injection molding conditions are selected in a manner known per se such that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved, and that the high orientation of the melt is frozen when the melt solidifies.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Anguß als Bandanguß, Schirmanguß oder Ringanguß ausgestaltet ist.2. The method according to claim 1, characterized in that the sprue is designed as a band gate, umbrella gate or ring gate.
3. Verfahren nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß die Polyamid-Nanocomposites 60 bis 99,9 Gew.-% des Polyamids A) und 0,1 bis 40 Gew.-% des Schichtsilikats B) enthalten.3. Process according to claims 1 to 2, characterized in that the polyamide nanocomposites contain 60 to 99.9% by weight of the polyamide A) and 0.1 to 40% by weight of the layered silicate B).
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeich¬ net, daß man als Polyamid A) ein Polyamid 6 verwendet.4. The method according to claims 1 to 3, characterized in ¬ net in that polyamide A) is a polyamide 6 is used as.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeich¬ net, daß man als Schichtsilikat B) hydrophobierte Bentonite verwendet.5. The method according to claims 1 to 4, characterized in ¬ net that as phyllosilicate B) hydrophobicized bentonites used.
6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Formteile im wesentlichen eine Wanddicke von maximal 2 mm aufweisen.6. The method according to claims 1 to 5, characterized in that the molded parts essentially have a wall thickness of at most 2 mm.
7. Formteile, erhältlich nach dem Verfahren gemäß den Ansprüchen 1 bis 6.7. Molded parts, obtainable by the process according to claims 1 to 6.
8. Formteile nach Anspruch 7, wobei das Formteil eine Rundscheibe von 60 mm Durchmesser und 1 mm Dicke ist, die aus 95 Gew.-% Polyamid 6 und 5 Gew.-% hydrophobiertem Bentonit hergestellt wird, und wobei die Rundscheibe im Durchstoßtest nach DIN 53443 bei 23°C eine Gesamtschädigungsarbeit Wges von mindestens 30 J/mm aufweist.8. Shaped parts according to claim 7, wherein the shaped part is a round disc of 60 mm in diameter and 1 mm thick, which is made of 95 wt .-% polyamide 6 and 5 wt .-% hydrophobic bentonite, and wherein the round disc in the puncture test according to DIN 53443 at 23 ° C has a total damage work W tot of at least 30 J / mm.
9. Verfahren zur Erhöhung der Zähigkeit von Formteilen aus Poly- amid-Nanocomposites, enthaltend mindestens ein Polyamid A) , und mindestens ein delaminiertes Schichtsilikat B) ,9. Process for increasing the toughness of molded parts made of polyamide nanocomposites, containing at least one polyamide A) and at least one delaminated layered silicate B),
dadurch gekennzeichnet, daß man die Formteile im Spritzgußverfahren durch Einbringen einer Schmelze enthaltend A) und B) über einen Anguß in ein Spritzgußwerkzeug herstellt, und daß die Schmelze im Spritzgußwerkzeug im wesentlichen parallel fließt, wodurch eine hohe Orientierung der Schmelze erreicht wird, und daß die hohe Orientierung der Schmelze beim Erstarren der Schmelze eingefroren wird. characterized in that the molded parts are produced in an injection molding process by introducing a melt containing A) and B) via a sprue into an injection molding tool, and in that the melt in the injection molding tool flows essentially in parallel, as a result of which a high orientation of the melt is achieved and that high orientation of the melt is frozen when the melt solidifies.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10125560.8 | 2001-05-23 | ||
DE2001125560 DE10125560A1 (en) | 2001-05-23 | 2001-05-23 | Production of profiled parts of increased ductility from polyamide nanocomposites containing polyamide A and a delaminated silicate layer consisting of hydrophobized bentonite |
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WO2002094534A1 true WO2002094534A1 (en) | 2002-11-28 |
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PCT/EP2002/005472 WO2002094534A1 (en) | 2001-05-23 | 2002-05-17 | Method for the production of castings from polyamide nanocomposites |
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DE (1) | DE10125560A1 (en) |
WO (1) | WO2002094534A1 (en) |
Cited By (3)
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WO2006027123A1 (en) * | 2004-09-10 | 2006-03-16 | Lanxess Deutschland Gmbh | Use of thermoplastic polyamide composite materials having improved flow properties, for producing moulded parts according to thin wall technology |
EP1770115A1 (en) * | 2005-09-30 | 2007-04-04 | Quadrant Plastic Composites AG | Fibre-reinforced sheet-like semi-finished product |
CN106832913A (en) * | 2017-02-28 | 2017-06-13 | 苏州博利迈新材料科技有限公司 | A kind of hydrophobicity nylon 66 composite material and preparation method thereof |
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EP1780241A1 (en) * | 2005-10-17 | 2007-05-02 | EMS-Chemie AG | Use of polyamide moulding materials for the fabrication of moulded articles with reduced superficial charring |
DE10239326A1 (en) * | 2002-08-27 | 2004-03-18 | Ems-Chemie Ag | Highly viscous molding compounds with nanoscale fillers |
US20110268923A1 (en) * | 2009-09-25 | 2011-11-03 | Tokai Rubber Industries, Ltd. | Resin molding method and resin molding |
DE102013208605A1 (en) * | 2013-05-10 | 2014-11-13 | Robert Bosch Gmbh | Thermally conductive plastic components with increased heat conduction in the thickness direction |
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