WO2002094534A1 - Procede pour produire des pieces moulees a partir de nanocomposites de polyamide - Google Patents
Procede pour produire des pieces moulees a partir de nanocomposites de polyamide 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
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 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
L'invention concerne un procédé pour produire des pièces moulées, par moulage par injection, à partir de nanocomposites de polyamide. Ces pièces moulées contiennent A) au moins un polyamide A), et B) au moins un phyllosilicate B) dont les couches sont désolidarisées. Ce procédé consiste à introduire une matière fondue contenant A) et B) par l'intermédiaire d'un culot d'injection dans un moule à injection. L'invention est caractérisée en ce que l'on sélectionne les conditions de moulage par injection, de manière connue en soi, de sorte que la matière fondue s'écoule de façon sensiblement parallèle dans le moule à injection, ce qui permet d'obtenir une orientation élevée de la matière fondue, et de sorte que cette orientation élevée soit figée lors de la solidification de la matière fondue.
Applications Claiming Priority (2)
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DE10125560.8 | 2001-05-23 | ||
DE2001125560 DE10125560A1 (de) | 2001-05-23 | 2001-05-23 | Verfahren zur Herstellung von Formteilen aus Polyamid-Nanocomposites |
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PCT/EP2002/005472 WO2002094534A1 (fr) | 2001-05-23 | 2002-05-17 | Procede pour produire des pieces moulees a partir de nanocomposites de polyamide |
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WO2006027123A1 (fr) * | 2004-09-10 | 2006-03-16 | Lanxess Deutschland Gmbh | Utilisation de materiaux composites thermoplastiques a base de polyamide presentant des proprietes rheologiques ameliorees, servant a la production de pieces moulees a parois minces |
EP1770115A1 (fr) * | 2005-09-30 | 2007-04-04 | Quadrant Plastic Composites AG | Produit semi-fini de forme plane renforcé de fibres |
CN106832913A (zh) * | 2017-02-28 | 2017-06-13 | 苏州博利迈新材料科技有限公司 | 一种疏水性尼龙66复合材料及其制备方法 |
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DE10239326A1 (de) * | 2002-08-27 | 2004-03-18 | Ems-Chemie Ag | Hochviskose Formmassen mit nanoskaligen Füllstoffen |
EP1780241A1 (fr) * | 2005-10-17 | 2007-05-02 | EMS-Chemie AG | Utilisation de compositions à mouler de polyamide pour la fabrication d'articles moulés à carbonisation superficielle réduite |
CN102395453A (zh) * | 2009-09-25 | 2012-03-28 | 东海橡胶工业株式会社 | 树脂成形方法及树脂成形品 |
DE102013208605A1 (de) * | 2013-05-10 | 2014-11-13 | Robert Bosch Gmbh | Wärmeleitfähige Kunststoffbauteile mit erhöhter Wärmeleitung in Dickenrichtung |
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EP0747451A2 (fr) * | 1995-06-07 | 1996-12-11 | Amcol International Corporation | Produits d'insertion et d'exfoliation formés avec des oligomères et des polymères et matériaux composites les contenant |
DE19714900A1 (de) * | 1997-04-10 | 1998-10-15 | Basf Ag | Flammgeschützte thermoplastische Formmassen |
WO1998049235A1 (fr) * | 1997-04-25 | 1998-11-05 | Unitika Ltd. | Composition de resine polyamide et procede de production de cette derniere |
US6060549A (en) * | 1997-05-20 | 2000-05-09 | Exxon Chemical Patents, Inc. | Rubber toughened thermoplastic resin nano composites |
EP0952187A1 (fr) * | 1998-04-22 | 1999-10-27 | Rheox, Inc. | Compositions argile/chimiques organiques pour la fabrication des matériaux nanocomposites ainsi que nanocomposites contenant des telles compositions |
WO2000047657A2 (fr) * | 1999-02-12 | 2000-08-17 | The Dow Chemical Company | Objets nanocomposites et procede de fabrication associe |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2006027123A1 (fr) * | 2004-09-10 | 2006-03-16 | Lanxess Deutschland Gmbh | Utilisation de materiaux composites thermoplastiques a base de polyamide presentant des proprietes rheologiques ameliorees, servant a la production de pieces moulees a parois minces |
EP1770115A1 (fr) * | 2005-09-30 | 2007-04-04 | Quadrant Plastic Composites AG | Produit semi-fini de forme plane renforcé de fibres |
CN106832913A (zh) * | 2017-02-28 | 2017-06-13 | 苏州博利迈新材料科技有限公司 | 一种疏水性尼龙66复合材料及其制备方法 |
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