CA2137428A1 - Three-stage graft copolymers and thermoplastic molding materials containing said copolymers and having great toughness - Google Patents
Three-stage graft copolymers and thermoplastic molding materials containing said copolymers and having great toughnessInfo
- Publication number
- CA2137428A1 CA2137428A1 CA 2137428 CA2137428A CA2137428A1 CA 2137428 A1 CA2137428 A1 CA 2137428A1 CA 2137428 CA2137428 CA 2137428 CA 2137428 A CA2137428 A CA 2137428A CA 2137428 A1 CA2137428 A1 CA 2137428A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- alkyl
- acrylic acid
- graft copolymer
- methacrylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 38
- 239000012778 molding material Substances 0.000 title claims description 29
- 238000009757 thermoplastic moulding Methods 0.000 title claims description 23
- 229920001577 copolymer Polymers 0.000 title claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 35
- -1 styrene compound Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004945 silicone rubber Substances 0.000 claims abstract description 11
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001567 vinyl ester resin Chemical group 0.000 claims abstract description 9
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims abstract description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 16
- 239000004417 polycarbonate Substances 0.000 claims description 13
- 229920000515 polycarbonate Polymers 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229940117913 acrylamide Drugs 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000306 component Substances 0.000 description 33
- 229940044603 styrene Drugs 0.000 description 21
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 229940048053 acrylate Drugs 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229940063557 methacrylate Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000007957 coemulsifier Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical group CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- KAIRTVANLJFYQS-UHFFFAOYSA-N 2-(3,5-dimethylheptyl)phenol Chemical compound CCC(C)CC(C)CCC1=CC=CC=C1O KAIRTVANLJFYQS-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HPSGLFKWHYAKSF-UHFFFAOYSA-N 2-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1=CC=CC=C1 HPSGLFKWHYAKSF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZDWSNKPLZUXBPE-UHFFFAOYSA-N 3,5-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1 ZDWSNKPLZUXBPE-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- PKBZUGSITIBLFK-UHFFFAOYSA-N 3-phenylpropyl prop-2-enoate Chemical compound C=CC(=O)OCCCC1=CC=CC=C1 PKBZUGSITIBLFK-UHFFFAOYSA-N 0.000 description 1
- CUAUDSWILJWDOD-UHFFFAOYSA-N 4-(3,5-dimethylheptyl)phenol Chemical compound CCC(C)CC(C)CCC1=CC=C(O)C=C1 CUAUDSWILJWDOD-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- NIRYBKWMEWFDPM-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-methylbutyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)CCC1=CC=C(O)C=C1 NIRYBKWMEWFDPM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- VRFCNQCFVJBFMC-UHFFFAOYSA-N cyclooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCCCC1 VRFCNQCFVJBFMC-UHFFFAOYSA-N 0.000 description 1
- JXVKENWQKWGKOL-UHFFFAOYSA-N cyclooctyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCCCC1 JXVKENWQKWGKOL-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
Abstract
Graft copolymers are obtainable by (A) polymerization of from 25 to 60% by weight of a mixture con-sisting essentially of (a1)from 70 to 99.9% by weight of a C1-C18-alkyl ester of acrylic acid, where the alkyl radical may be monosubsti-tuted by phenyl or phenoxy, (a2)from 0.1 to 10% by weight of a polyfunctional monomer and (a3)from 0 to 29.9% by weight of an ethylenically unsaturated monomer which differs from (a1) and (a2) and is copoly-merizable therewith in the presence of from 5 to 25% by weight of a cross-linked silicone rubber and (B) polymerization of from 30 to 50% by weight of a mixture con-sisting essentially of (b1)from 50 to 100% by weight of a styrene compound of the general formula (I) I
where R1 and R2 independently of one another are each hydro-gen, C1-C8-alkyl or C1-C4-alkyl-monosubstituted, C1-C4-alkyl-disubstituted or C1-C4-alkyl-trisubstituted phenyl, and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, malei-mide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, in the presence of the graft copolymer (A).
where R1 and R2 independently of one another are each hydro-gen, C1-C8-alkyl or C1-C4-alkyl-monosubstituted, C1-C4-alkyl-disubstituted or C1-C4-alkyl-trisubstituted phenyl, and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, malei-mide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, in the presence of the graft copolymer (A).
Description
BASF AXtiengesellschaft 920673 O.Z. 0050/44505 - 213742~
Three-stage graft copolymers and thermoplastic molding materials containing said copolymers and having great toughness 5 The present invention relates to graft copolymers obtainable by (A) polymerization of from 25 to 60% by weight of a mixture con-sisting essentially of (al)from 70 to 99.9% by weight of a Cl-Cl8-alkyl ester of acrylic acid, where the alkyl radical may be monosubsti-tuted by phenyl or phenoxy, (a2)from 0.1 to 10% by weight of a polyfunctional monomer and (a3)from 0 to 29.9% by weight of an ethylenically unsaturated monomer which differs from (al) and (a2) and is copoly-merizable therewith in the presence of from 5 to 25% by weight of a crosslinked silicone rubber and (B) polymerization of from 30 to 50% by weight of a mixture con-sisting essentially of (bl)from 50 to 100% by weight of a styrene compound of the general formula (I) RlC = CH2 ~ I
where Rl and R2 independently of one another are each hydro-gen, Cl-C8-alkyl or Cl-C4-alkyl-monosubstituted, Cl-C4-alkyl-disubstituted or Cl-C4-alkyl-trisubstituted phenyl, and/or of a Cl-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, malei-mide N-substituted by Cl-C4-alkyl, vinyl esters of BASF Aktiengesellschaft 920673 O.Z. 0050/44505 aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, in the presence of the graft copolymer (A).
The present invention furthermore relates to thermoplastic mold-ing materials contA;n;ng the novel graft copolymers, processes for the preparation of the novel graft copolymers and thermoplas-tic molding materials, the use of the novel graft copolymers for 10 the preparation of thermoplastic molding materials and moldings, the use of the novel molding materials for the production of moldings, and moldings obtainable from the novel graft copolymers and thermoplastic molding materials.
15 Graft copolymers cont~in;ng essentially a core of a silicone rub-ber, a first shell based on an alkyl ester and an outer shell based on a resin-forming monomer are disclosed, for example, in EP-A 246,537. A disadvantage, however, is the fact that the low-temperature toughness of molding materials and moldings prepared 20 therefrom is unsatisfactory.
The high proportion of silicone rubber in the graft rubbers, stated in the examples, presents problems since silicone rubber has a relatively high price compared with the other starting 25 materials.
Since the silicone rubber used has a very low glass transition temperature Tg of -120 C (cf. DE 25 39 572; in contrast to buta-diene rubber with -80 C or acrylate rubber with -40 C, cf.
30 European Patent 62901), it was expected that the low-temperature toughness would increase with increasing proportion of silicone rubber.
It is an object of the present invention to provide graft copoly-35 mers which can be processed to give thermoplastic molding mater-ials and/or moldings, the thermoplastic molding materials and moldings which can be prepared therefrom having good low-temperature toughness in conjunction with a low content of sili-cone rubber.
We have found that this object is achieved by the graft copoly-mers defined at the outset.
We have also found thermoplastic molding materials cont~;n;ng the 45 novel graft copolymers, processes for the preparation of the novel graft copolymers and thermoplastic molding materials, the use of the novel graft copolymers for the preparation of BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~1~8 thermoplastic molding materials and moldings and the use of the novel molding materials for the production of moldings, obtain-able from the novel graft copolymers and thermoplastic molding materials.
Suitable crosslinked silicone rubbers for the formation of the novel core are in general crosslinked silicone rubbers comprising units of the general formulae R2Sio~ RSiO3/2, R3Siol/2 and SiO2/4, where R is a monovalent radical and, in the case of R3SiOl/2, may lO furthermore be OH. The amounts of the individual siloxane units are usually such that there are from 0 to 10 molar units of the formula RSio3/2~ from 0 to 1.5 molar units of R3Siol/2 and from 0 to 3 molar units of SiO2/4 per 100 units of the formula R2Sio.
15 R is in general Cl-Clg-alkyl, preferably Cl-Cl2-alkyl, particularly preferably Cl-C6-alkyl, such as methyl, ethyl, n-propyl, isoprop-yl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, in particular methyl or ethyl, or C6-Cl0-aryl, such as phenyl or naphthyl, in particular phenyl, or Cl-Cl0-alkoxy or aryloxy, such 20 as methoxy, ethoxy or phenoxy, preferably methoxy, or groups which can be attacked by free radicals, such as vinyl, allyl, acryloyl, acryloyloxy, methacryloyl, methacryloyloxyalkyl, halo-gen or mercapto, preferably vinyl or mercapto-Cl-Cl0-alkyl, in particular mercaptopropyl, vinyl or methacryloyloxypropyl.
In a particular embodiment, silicone rubbers in which at least 80% of all radicals R are methyl are used. Silicone rubbers in which R is methyl or ethyl are also preferred.
30 In a further embodiment, silicone rubbers which contain the abovementioned groups which can be attacked by free radicals, in amounts of from 0.01 to 10, preferably from 0.2 to 2, mol%, based on all radicals R, are used. Such silicone rubbers are described in, for example, EP-A 260 558 and EP A 492 376.
It is also possible to use the silicone rubbers described in DE-A 25 39 572 or those disclosed in EP-A 370 347 as resins.
According to the invention, the core is used in an amount of from 40 5 to 25, preferably from 6 to 20, particularly preferably from 10 to 15, % by weight, based on the total amount of graft copolymer.
According to the invention, the component (A) is a mixture of es-sentially BASF Aktiengesellschaft 920673 O.Z. 0050/44505 (al) from 70 to 99.9, preferably from 75 to 99.5, particularly preferably from 80 to 99, % by weight of a C1-C18-alkyl ester of acrylic acid, where the alkyl radical may be monosubstituted by phenyl or phenoxy, (a2) from 0.1 to 10, preferably from 0.5 to 5, particularly preferably from 1 to 4, % by weight of a polyfunctional monomer and (a3) from 0 to 29.9, preferably from 0 to 24.5, particularly preferably from 0 to 19, % by weight of an ethylenically unsaturated monomer which differs from (al) and (a2) and is copolymerizable therewith.
Preferably used C1-C18-alkyl esters of acrylic acid (com-ponent (al)) are the C2-C8-alkyl esters, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, 20 hexyl, heptyl, n-octyl or 2-ethylhexyl acrylate, particularly preferably ethyl, n-propyl, n-butyl or 2-ethylhexyl acrylate.
Furthermore, the C1-C18-alkyl esters may be substituted by phenyl or phenoxy, phenyl-C1-C4-alkyl esters, such as benzyl acrylate, phenylethyl acrylate, phenylpropyl acrylate or phenoxy ethyl 25 acrylate, being preferred. The substituted C1-Cl8-alkyl esters may also be used as a mixture with unsubstituted C1-C18-alkyl esters of acrylic acid, at least one C1-C18-alkyl ester of acrylic acid preferably being used.
30 Examples of suitable polyfunctional monomers (component (a2)) are vinylically unsaturated compounds having at least two double bonds, such as vinylbenzenes, such as divinylbenzene and trivinylbenzene, 35 triallyl cyanurate and triallyl isocyanurate, diallyl maleate, diallyl fumarate and diallyl phthalate, .
which usually have a crosslinking action.
40 Observations to date have shown that graft-linking unsaturated monomers which may have a crosslinking action and carry epoxy, hydroxyl, carboxyl, amino or anhydride groups, such as hydroxy-C1-C6-alkyl methacrylates and hydroxy-C1-C6-alkyl acrylates, pre-ferably hydroxyethyl methacrylate, hydroxyethyl acrylate, 45 hydroxypropyl methacrylate and hydroxypropyl acrylate, are also suitable.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~137~28 The tricyclodecenyl acrylates Ia and Ib ~ o-c-CH = CH2 Ia 10 ~ ~ o-c-CH = CH2 Ib have proven particularly suitable monomers for component (a2) 15 (cf. DE-A 1,260,135).
Preferably used ethylenically unsaturated monomers (com-ponent (a3)) which differ from components (al) and (a2) but are copolymerizable with these components are vinylaromatic monomers, 20 such as styrene, ~-methylstyrene, p-methylstyrene, tert-butyl-styrene, l,l-diphenylethylene, monochlorostyrene and vinyl-toluene, particularly preferably styrene;
acrylonitrile and methacrylonitrile, preferably acrylonitrile;
Cl-C4-esters of acrylic and methacrylic acid, such as methyl 25 methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacry-late, sec-butyl methacrylate and tert-butyl methacrylate, methyl methacrylate being particularly preferred, as well as mixtures of these monomers;
methyl acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and tert-butyl acrylate, methyl acrylate being particularly preferred, as well as mixtures of these monomers;
C5 -C8-cycloalkyl esters of acrylic and methacrylic acid, such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl acrylate and cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl methacrylate, preferably cyclohexyl methacrylate;
isobornyl methacrylate;
maleimides which are substituted at the imide nitrogen atom by C1-C6-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 45 isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably N-methylmaleimide, and N-C6-C10-aryl- or N-C6-C20-aryl-Cl-C4-alkyl-substituted maleimides, where the aryl groups may be mono-BASF Aktiengesellschaft 920673 O.Z. OO50/44505 213742g substituted, disubstituted or trisubstituted by C1-C4-alkyl, such as N-phenylmaleimide and N-tolylmaleimide, preferably N-phenyl-maleimide;
5 maleic anhydride and Cl-C6-alkyl maleates and di-C1-C6-alkyl mal-eates, preferably maleic anhydride; and dienes, such as butadiene and isoprene, preferably butadiene.
lO The glass transition temperature of the 1st shell (A) is usually below 0 C, preferably below -20 C, particularly preferably below -30 C (the glass transition temperature is determined, for exam-ple, with the aid of DSC; K.H. Illers, Makromol. Chem. 127 (1969), 1).
The 1st shell (A) is prepared, as a rule, by known polymerization methods, such as emulsion, mass, solution or suspension polymer-ization, preferably in aqueous emulsion in the presence of an aqueous emulsion of the silicone rubber core (cf. German 20 Patent 1,260,135).
The conventional emulsifiers, such as the alkali metal salts of alkyl- or alkylarylsulfonic acids, alkylsulfates, fatty alcohol sulfonates, salts of higher fatty acids of 10 to 30 carbon atoms 25 or resin soaps, may be used for the preparation of the grafting base by emulsion polymerization. Sodium salts of alkylsulfonates or of fatty acids of 10 to 18 carbon atoms are preferably used.
In general, emulsifiers are used in amounts of from 0.1 to 5, preferably from 0.5 to 2, % by weight, based on the total weight 30 of the monomers used for the preparation of the 1st shell (A).
If desired, nonionic or anionic surfactants may be used as co-emulsifiers. Nonionic coemulsifiers are, for example, polyoxy-ethylene derivatives of fatty alcohols or fatty acids. Examples 35 are POE (3)-lauryl alcohol (POE = polyoxyethylene (x) where x is the degree of polymerization), POE (20)-oleyl alcohol, POE (7)-nonylphenol and POE (10) stearate. In general, a water/monomer ratio of from 10 : 1 to 0.7 : 1 is used.
40 The polymerization initiators used are customary hydroperoxides, the conventional persulfates and redox systems, such as hydroper-oxide and ascorbic acid, if desired, with the addition of Fe2~
salts and complexing agents. The conventional redox systems are known to a person skilled in the art. The amount of initiators 45 depends as a rule in a known manner on the desired molecular BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~28 weight and is usually from 0.01 to 1, preferably from 0.05 to 0.5, % by weight, based on the total weight of the monomers.
The polymerization assistants used are in general the conven-5 tional buffer substances, such as sodium bicarbonate or sodium pyrophosphate (with which a pH of from 6 to 9 can be estab-lished), and molecular weight regulators, such as mercaptans, terpinols or dimeric a-methylstyrene.
10 The exact polymerization conditions, in particular the type, rate of addition and amount of the emulsifier, are usually determined specifically within the abovementioned ranges so that the result-ing latex of the crosslinked polymer has a d50 value of from 40 to 2000 nm, preferably from 60 to 1000 nm, particularly preferably 15 from 80 to 800 nm.
For the preparation of the 1st shell (A) in aqueous emulsion, temperatures of from 20 to 100 C, preferably from 40 to 80 C, are usually employed.
According to the invention, the component (A) is used in an amount of from 25 to 60, preferably from 30 to 55, particularly preferably from 35 to 45, % by weight, based on the total amount of graft copolymer.
According to the invention, the component (B), the 2nd shell, is a mixture of essentially (bl)from 50 to 100, preferably from 55 to 100, particularly pre-ferably from 60 to 90, % by weight of a styrene compound of the general formula I
RlC = CH2 ~ I
~X2 where Rl and R2 independently of one another are each hydro-gen, Cl-C8-alkyl or Cl-C4-alkyl-monosubstituted, Cl-C4-alkyl-disubstituted or Cl-C4-alkyl-trisubstituted phenyl, and/or of a Cl-C8-alkyl ester of methacrylic or acrylic acid and/or BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~28 (b2)from 0 to 50, preferably from 0 to 40, particularly prefer-ably from 10 to 40, % by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by Cl-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether.
Styrene, ~-methylstyrene, l,l-diphenylethylene and styrenes alky-lated in the nucleus with Cl-C8-alkyl, such as p-methylstyrene or 10 tert-butylstyrene, particularly preferably styrene or ~-methyl-styrene, are preferably used as the styrene compound of the gen-eral formula I ~component (bl)).
According to the invention, methyl methacrylate (MMA), ethyl 15 methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacryl-ate, tert-butyl methacrylate, pentyl methacrylate, hexyl meth-acrylate, heptyl methacrylate, octyl methacrylate or 2-ethylhexyl methacrylate, particularly preferably methyl methacrylate, as 20 well as mixtures of these monomers, methyl acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate or 2-ethylhexyl acryl-ate, particularly preferably n-butyl acrylate, as well as mix-25 tures of these monomers with one another as well as with themethacrylates and/or styrene compounds of the general formula I
are used as Cl-C8-alkyl esters of methacrylic or acrylic acid.
According to the invention, a monomer selected from the group 30 consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by Cl-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, such as vinyl acetate or vinyl propionate, acrylamide and vinyl methyl ether is, if desired, used as component (b2).
In a preferred embodiment, a mixture of styrene and acrylonitrile (molar ratio usually from 10 : 1 to 1 : 1, preferably from 5 : 1 to 1 : 1) or a-methylstyrene and acrylonitrile (molar ratio usu-ally from 10 : 1 to 1 : 1, preferably from 5 : 1 to 1 : 1) or 40 methyl methacrylate and styrene (molar ratio usually from 10 : 1 to 1 : 1, preferably from 5 : 1 to 1 : 1) or methyl methacrylate alone, ie. without component (b2), is used.
BASF Aktiengesellschaft 920673 O.Z. OOS0/44505 ` ~137428 The preparation of the 2nd shell (B) is carried out, as a rule, by a conventional polymerization method, such as emulsion, mass, solution or suspension polymerization, in the presence of the graft copolymer (A).
However, it is advantageous to carry out the graft copolymeriza-tion of component (B) on the polymer (A) serving as the grafting base likewise in aqueous emulsion. It can be carried out in the same system as the polymerization of the grafting base, and fur-10 ther emulsifier and initiator may be added. These need not beidentical to the emulsifiers and initiators used for the prepara-tion of the shell (A). The emulsifier, initiator and polymeriza-tion assistants, either alone or as a mixture, may be initially taken with the emulsion of the grafting base (A). Any possible 15 combination of initially taken material and feed on the one hand and initiator, emulsifier and polymerization assistants on the other hand is suitable. The preferred embodiments are known to a person skilled in the art. The monomer mixture to be grafted may be added to the reaction mixture all at once, batchwise in a 20 plurality of stages or continuously during the polymerization.
The novel graft copolymers preferably have a median particle size - of from 0.1 to 10 ~m, particularly preferably from 0.1 to 1 ~m.
25 According to the invention, the component (B) is used in an amount of from 30 to 50, preferably from 35 to 45, particularly preferably from 35 to 40, % by weight, based on the total amount of graft copolymer.
30 The novel graft copolymers thus prepared may be worked up by known methods, for example by coagulation of the latices with electrolytes (salts, acids or bases)~ by heating or freezing out, by ultrasonics, by shearing or by a combination of these methods.
35 The novel graft copolymers may be used by themselves as molding materials. For this purpose, they can be worked up, for example by spray drying. However, the novel graft copolymers are prefer-ably used for mixing with copolymer (C) in order to increase its low-temperature toughness. Copolymers (C) suitable for modifica-40 tion are obtainable, according to the invention, by polymeriza-tion of a mixture consisting essentially of (cl) from 50 to 100~ by weight of a styrene compound of the general formula I and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~137928 (c2) from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, 5 maleic anhydride, maleimide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, (c3) from 0 to 90% by weight of a polycarbonate and (c4) from 0 to 100% by weight of conventional additives.
The components (cl) and (c2) correspond to the components (bl) and (b2) stated further above.
According to the invention, component (cl) is used in an amount of from 50 to 100, preferably from 60 to 90, particularly prefer-ably from 65 to 81, % by weight and component (c2) in an amount of from 0 to 50, preferably from 10 to 40, particularly prefer-20 ably from 19 to 35, % by weight.
Examples of the components (cl) and (c2) are homo- and copolymers of a vinylaromatic monomer and a polar, copolymerizable, ethylen-ically unsaturated monomer, such as polystyrene, polymethyl 25 methacrylate, styrene/acrylonitrile copolymers, a-methylstyrene/
acrylonitrile copolymers, styrene/maleic anhydride copolymers, styrene/phenylmaleimide copolymers, styrene/methyl methacrylate copolymers, methyl methacrylate/acrylonitrile copolymers, styr-ene/acrylonitrile/maleic anhydride copolymers, styrene/acrylo-30 nitrile/phenylmaleimide copolymers, a-methylstyrene/acrylo-nitrile/methyl methacrylate copolymers, a-methylstyrene/acrylo-nitrile/tert-butyl methacrylate copolymers and styrene/acrylo-nitrile/tert-butyl methacrylate copolymers.
35 The stated copolymers are frequently formed as byproducts, for example in the graft polymerization for the preparation of the novel graft copolymers, particularly when large amounts of the component (B) are grafted onto small amounts of the compo-nent (A). The vinyl polymers and (meth)acrylate polymers can be 40 prepared by known free radical, anionic and cationic polymeriza-tion methods. The known redox polymerization or the known poly-merization with organometallic mixed catalysts may also be advan-tageous.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 213742g Polycarbonate (PC), alone or as a mixture with the other compo-nents (cl) and (c2) mentioned above, may be used as novel component (c3).
5 Preferred novel blend components are, for example, mixtures of polycarbonate with the novel graft copolymers described above and the components (cl) and (c2).
Usually, the amount of the novel graft copolymers is from 5 to lO 95, preferably from 10 to 90, particularly preferably from 20 to 80, % by weight, the amount of the components (cl) and (c2) (sum cl + c2) is from 5 to 95, preferably from 10 to 90, particularly preferably from 20 to 80, % by weight and the amount of component (c3) is from 0 to 90, preferably from 0 to 80, particularly pre-15 ferably from 0 to 70, % by weight.
Examples of suitable polycarbonates are those based on diphenolsof the general formula (II) HO-Ar-A-Ar-OH (II) where 25 A is phenyl which is unsubstituted or monosubstituted, disub-stituted or trisubstituted by Cl-C4-alkyl or by halogen and A is a single bond, Cl-C3-alkylene, C2-C3-alkylidene, C3-C6-cycloalkylidene, -S- or -SO2-.
Preferred diphenols of the general formula (II) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane and l,l-bis-(4-hydroxyphenyl)-cyclohexane. 2,2-bis-(4-Hydroxy-35 phenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane are particularly preferred.
The diphenols of the general formula (II) are known per se or can be prepared by known processes.
The diphenols of the general formula (II) may be used both indi-vidually and as a mixture for the preparation of the polycarbonates.
45 The suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional com-BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~28 12pounds, for example those having three or more phenolic OH
groups.
Polycarbonates which have proven particularly suitable are those 5 which have relative viscosities ~rel of from 1.10 to 1.50, in particular from 1.25 to 1.40 (measured as 0.5~ strength by weight solutions of the polymers in chloroform at 23 C). This corresponds to weight average molecular weights Mw or from 10,000 to 200,000, preferably from 20,000 to 80,000, g/mol.
The polycarbonates can be prepared, for example, by reacting the diphenols of the general formula (II) with phosgene by the phase boundary process or with phosgene by the process in the homogen-eous phase (ie. the pyridine process), the molecular weight to be 15 established in each case being achieved in a known manner by a corresponding amount of known chain terminators (with regard to polydiorganosiloxane-contA;n;ng polycarbonates, cf. for example German Laid-Open Application DOS 3,334,782).
20 Examples of suitable chain terminators are phenol and p-tert-butylphenol, as well as long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol, according to German Laid-Open Application DOS 2,842,005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, 25 according to DE-A 35 06 472, for example p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-di-methylheptyl)phenol and 4-(3,5-dimethylheptyl)-phenol.
For example, polycarbonate/polysiloxane block copolymers, poly-30 carbonate/polyether block copolymers and polycarbonate/polyester block copolymers may also serve as component (c3).
As a rule, aromatic polyesters and polyester carbonates may also be used as component (c3).
The novel thermoplastic molding materials may contain conven-tional additives as further constituents (component (c4)).
Examples of these are dyes and pigments, light stabilizers, heat 40 stabilizers, plasticizers, blowing agents and organic or inorgan-ic fillers in granular, powder or fibrous form.
The additives and assistants are used in conventional amounts, preferably in amounts of up to 50~ by weight, based on the total 45 weight of the thermoplastic molding material. Compatible plastics may also account for a higher proportion.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 '~137428 _ 13 In addition to the polymers mentioned as matrices, the novel graft copolymers may also be mixed with the following polymers:
polyphenylene ethers, polyamides, polyesters, polyurethanes, polyethylene homo- and copolymers, polypropylene homo- and co-5 polymers, halogenated polyolefins, such as polyvinyl chloride, polytetrafluoroethylene and derivatives, as well as polyoxy-methylenes, polyether ketones, polyether sulfones and polysulfones.
lO In a further preferred embodiment, the novel graft copolymers are mixed with known rubber-modified plastics, eg. ABS or ASA. ABS
(based on butadiene graft rubbers with styrene/acrylonitrile co-polymer) and ASA molding materials (based on acrylate graft rub-bers with styrene/acrylonitrile copolymer) are known to a person 15 skilled in the art and are described in, inter alia, German Patent 1,260,135 and European Patent 62,901.
The novel thermoplastic molding materials are processed, as a rule, by known methods, such as extrusion, injection molding, 20 compression molding of the melt, kneading, etc. The mixtures melted in this manner are usually cooled and then processed to give moldings (as a rule by injection molding)~ after which the moldings are subjected to mechanical tests.
25 The novel thermoplastic molding materials can be processed by the methods usually used for processing thermoplastics, such as ex-trusion and injection molding, to give a very wide range of mold-ings, such as window profiles, garden furniture, boats, sign-boards, lamp coverings, automotive parts and toys. The novel 30 thermoplastic molding materials are particularly suitable for the production of moldings which are required to have good low-tem-perature toughness.
Examples The notched impact strength aK (injection molding temperature/test temperature) (in kJ/m2) was measured according to DIN 53 453, at test temperatures of 23 C, 0 C and -20 C, using standard bars in-jection molded at 220, 250 and 280 C.
The heat distortion resistance Vicat B 50 was determined accord-ing to DIN 54 460 (in C).
The melt volume index MVI (in ml/10 minutes) was determined ac-45 cording to DIN 53 735 at 200 C and under a load of 21.6 kg.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 The stated median particle sizes are in all cases the weight average of the particle sizes which were determined by means of an analytical ultracentrifuge by a method corresponding to that of W. Scholtan and H. Lange, Kolloid-Z. and Z.Polymere 250 5 (1972), 782 - 796. The ultracentrifuge measurement gives the in-tegral mass distribution of the particle diameter of a sample.
From this it is possible to determine the percentage by weight of the particles which have a diameter equal to or smaller than a certain size. The median particle diameter, which is also re-10 ferred to as a d50 value of the integral mass distribution, is de-fined as the particle diameter at which 50% by weight of the par-ticles have a diameter smaller than the diameter which corres-ponds to the d50 value. Likewise, 50% by weight of the particles then have a diameter greater than the d50 value.
1. Preparation of the graft copolymers A
1.1. The silicone emulsion (dispersion) A1 used was a cross-linked polydimethylsiloxane emulsion (prepared similarly to Example 1 in EP-A 492 376): solids content (SC):
17.4%; particle diameter 156 nm; viscosity 4.6 mPa-s;
pH 7; degree of crosslinking 3%; 0.5% of methacryloyloxy-propyl functions.
25 1.2. Preparation of the 1st shell A2 1.2.1. Initially taken mixture Dispersion A1 (cf. Table 1) and water were heated to 60 C
and potassium persulfate (KPS) was then added.
1.2.2. Feed A mixture of n-butyl acrylate (BA) and the acrylate of tricyclodecenyl alcohol (DCPA) was added dropwise in the course of 1.5 hours. At the same time, a mixture of water and the sodium salts of a mixture of Cl3- and C14-alkyl-sulfonic acids (soap) was added dropwise. The dispersion A2 obtained was not isolated.
40 1.3. Preparation of the 2nd shell 5.1 g of potassium persulfate were added to the dispersion A2, and 960 g of styrene and 320 g of acrylonitrile were added dropwise in the course of 3 hours. Stirring was carried out for a further 2 hours. Theoretical solids content: 40.0~.
~ BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~ 2137~28 Table 1 Preparation of siloxane/acrylate rubbers All stated amounts in g Experiment 1 2 3 Initially taken mixture 1839 3678 5517 - component A1 3086 1575 255 lO _ water 4.8 3.9 2.88 - KPS
Feed - water 212 206 - soap 8 4 Analysi~
20 Solids content 39.5 39.7 39.6 (%) LT value 43 53 64 Swelling 4.4 4.6 4.2 indexl) Gel contentl) 96.3 93.4 84.5 25 (%) ) The swelling index is the weight increase on swelling of the sample in tert-butyl methyl ether at 23 C in the course of 24 hours. The gel content is the insoluble fraction obtained after the above swelling, when the soluble fractions have been separated off.
The light transmittance (LT; DIN 5036) is defined as the ratio of the light transmitted by a sample to the intensity of the inci-35 dent light. It must be measured as a function of the wavelengthin a range from 400 to 900 nm using an aqueous solution having a solids content of 0.01% by weight, in a 3 cm thick quartz cell.
Three-stage graft copolymers and thermoplastic molding materials containing said copolymers and having great toughness 5 The present invention relates to graft copolymers obtainable by (A) polymerization of from 25 to 60% by weight of a mixture con-sisting essentially of (al)from 70 to 99.9% by weight of a Cl-Cl8-alkyl ester of acrylic acid, where the alkyl radical may be monosubsti-tuted by phenyl or phenoxy, (a2)from 0.1 to 10% by weight of a polyfunctional monomer and (a3)from 0 to 29.9% by weight of an ethylenically unsaturated monomer which differs from (al) and (a2) and is copoly-merizable therewith in the presence of from 5 to 25% by weight of a crosslinked silicone rubber and (B) polymerization of from 30 to 50% by weight of a mixture con-sisting essentially of (bl)from 50 to 100% by weight of a styrene compound of the general formula (I) RlC = CH2 ~ I
where Rl and R2 independently of one another are each hydro-gen, Cl-C8-alkyl or Cl-C4-alkyl-monosubstituted, Cl-C4-alkyl-disubstituted or Cl-C4-alkyl-trisubstituted phenyl, and/or of a Cl-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, malei-mide N-substituted by Cl-C4-alkyl, vinyl esters of BASF Aktiengesellschaft 920673 O.Z. 0050/44505 aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, in the presence of the graft copolymer (A).
The present invention furthermore relates to thermoplastic mold-ing materials contA;n;ng the novel graft copolymers, processes for the preparation of the novel graft copolymers and thermoplas-tic molding materials, the use of the novel graft copolymers for 10 the preparation of thermoplastic molding materials and moldings, the use of the novel molding materials for the production of moldings, and moldings obtainable from the novel graft copolymers and thermoplastic molding materials.
15 Graft copolymers cont~in;ng essentially a core of a silicone rub-ber, a first shell based on an alkyl ester and an outer shell based on a resin-forming monomer are disclosed, for example, in EP-A 246,537. A disadvantage, however, is the fact that the low-temperature toughness of molding materials and moldings prepared 20 therefrom is unsatisfactory.
The high proportion of silicone rubber in the graft rubbers, stated in the examples, presents problems since silicone rubber has a relatively high price compared with the other starting 25 materials.
Since the silicone rubber used has a very low glass transition temperature Tg of -120 C (cf. DE 25 39 572; in contrast to buta-diene rubber with -80 C or acrylate rubber with -40 C, cf.
30 European Patent 62901), it was expected that the low-temperature toughness would increase with increasing proportion of silicone rubber.
It is an object of the present invention to provide graft copoly-35 mers which can be processed to give thermoplastic molding mater-ials and/or moldings, the thermoplastic molding materials and moldings which can be prepared therefrom having good low-temperature toughness in conjunction with a low content of sili-cone rubber.
We have found that this object is achieved by the graft copoly-mers defined at the outset.
We have also found thermoplastic molding materials cont~;n;ng the 45 novel graft copolymers, processes for the preparation of the novel graft copolymers and thermoplastic molding materials, the use of the novel graft copolymers for the preparation of BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~1~8 thermoplastic molding materials and moldings and the use of the novel molding materials for the production of moldings, obtain-able from the novel graft copolymers and thermoplastic molding materials.
Suitable crosslinked silicone rubbers for the formation of the novel core are in general crosslinked silicone rubbers comprising units of the general formulae R2Sio~ RSiO3/2, R3Siol/2 and SiO2/4, where R is a monovalent radical and, in the case of R3SiOl/2, may lO furthermore be OH. The amounts of the individual siloxane units are usually such that there are from 0 to 10 molar units of the formula RSio3/2~ from 0 to 1.5 molar units of R3Siol/2 and from 0 to 3 molar units of SiO2/4 per 100 units of the formula R2Sio.
15 R is in general Cl-Clg-alkyl, preferably Cl-Cl2-alkyl, particularly preferably Cl-C6-alkyl, such as methyl, ethyl, n-propyl, isoprop-yl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, in particular methyl or ethyl, or C6-Cl0-aryl, such as phenyl or naphthyl, in particular phenyl, or Cl-Cl0-alkoxy or aryloxy, such 20 as methoxy, ethoxy or phenoxy, preferably methoxy, or groups which can be attacked by free radicals, such as vinyl, allyl, acryloyl, acryloyloxy, methacryloyl, methacryloyloxyalkyl, halo-gen or mercapto, preferably vinyl or mercapto-Cl-Cl0-alkyl, in particular mercaptopropyl, vinyl or methacryloyloxypropyl.
In a particular embodiment, silicone rubbers in which at least 80% of all radicals R are methyl are used. Silicone rubbers in which R is methyl or ethyl are also preferred.
30 In a further embodiment, silicone rubbers which contain the abovementioned groups which can be attacked by free radicals, in amounts of from 0.01 to 10, preferably from 0.2 to 2, mol%, based on all radicals R, are used. Such silicone rubbers are described in, for example, EP-A 260 558 and EP A 492 376.
It is also possible to use the silicone rubbers described in DE-A 25 39 572 or those disclosed in EP-A 370 347 as resins.
According to the invention, the core is used in an amount of from 40 5 to 25, preferably from 6 to 20, particularly preferably from 10 to 15, % by weight, based on the total amount of graft copolymer.
According to the invention, the component (A) is a mixture of es-sentially BASF Aktiengesellschaft 920673 O.Z. 0050/44505 (al) from 70 to 99.9, preferably from 75 to 99.5, particularly preferably from 80 to 99, % by weight of a C1-C18-alkyl ester of acrylic acid, where the alkyl radical may be monosubstituted by phenyl or phenoxy, (a2) from 0.1 to 10, preferably from 0.5 to 5, particularly preferably from 1 to 4, % by weight of a polyfunctional monomer and (a3) from 0 to 29.9, preferably from 0 to 24.5, particularly preferably from 0 to 19, % by weight of an ethylenically unsaturated monomer which differs from (al) and (a2) and is copolymerizable therewith.
Preferably used C1-C18-alkyl esters of acrylic acid (com-ponent (al)) are the C2-C8-alkyl esters, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, 20 hexyl, heptyl, n-octyl or 2-ethylhexyl acrylate, particularly preferably ethyl, n-propyl, n-butyl or 2-ethylhexyl acrylate.
Furthermore, the C1-C18-alkyl esters may be substituted by phenyl or phenoxy, phenyl-C1-C4-alkyl esters, such as benzyl acrylate, phenylethyl acrylate, phenylpropyl acrylate or phenoxy ethyl 25 acrylate, being preferred. The substituted C1-Cl8-alkyl esters may also be used as a mixture with unsubstituted C1-C18-alkyl esters of acrylic acid, at least one C1-C18-alkyl ester of acrylic acid preferably being used.
30 Examples of suitable polyfunctional monomers (component (a2)) are vinylically unsaturated compounds having at least two double bonds, such as vinylbenzenes, such as divinylbenzene and trivinylbenzene, 35 triallyl cyanurate and triallyl isocyanurate, diallyl maleate, diallyl fumarate and diallyl phthalate, .
which usually have a crosslinking action.
40 Observations to date have shown that graft-linking unsaturated monomers which may have a crosslinking action and carry epoxy, hydroxyl, carboxyl, amino or anhydride groups, such as hydroxy-C1-C6-alkyl methacrylates and hydroxy-C1-C6-alkyl acrylates, pre-ferably hydroxyethyl methacrylate, hydroxyethyl acrylate, 45 hydroxypropyl methacrylate and hydroxypropyl acrylate, are also suitable.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~137~28 The tricyclodecenyl acrylates Ia and Ib ~ o-c-CH = CH2 Ia 10 ~ ~ o-c-CH = CH2 Ib have proven particularly suitable monomers for component (a2) 15 (cf. DE-A 1,260,135).
Preferably used ethylenically unsaturated monomers (com-ponent (a3)) which differ from components (al) and (a2) but are copolymerizable with these components are vinylaromatic monomers, 20 such as styrene, ~-methylstyrene, p-methylstyrene, tert-butyl-styrene, l,l-diphenylethylene, monochlorostyrene and vinyl-toluene, particularly preferably styrene;
acrylonitrile and methacrylonitrile, preferably acrylonitrile;
Cl-C4-esters of acrylic and methacrylic acid, such as methyl 25 methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacry-late, sec-butyl methacrylate and tert-butyl methacrylate, methyl methacrylate being particularly preferred, as well as mixtures of these monomers;
methyl acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and tert-butyl acrylate, methyl acrylate being particularly preferred, as well as mixtures of these monomers;
C5 -C8-cycloalkyl esters of acrylic and methacrylic acid, such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl acrylate and cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl methacrylate, preferably cyclohexyl methacrylate;
isobornyl methacrylate;
maleimides which are substituted at the imide nitrogen atom by C1-C6-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 45 isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably N-methylmaleimide, and N-C6-C10-aryl- or N-C6-C20-aryl-Cl-C4-alkyl-substituted maleimides, where the aryl groups may be mono-BASF Aktiengesellschaft 920673 O.Z. OO50/44505 213742g substituted, disubstituted or trisubstituted by C1-C4-alkyl, such as N-phenylmaleimide and N-tolylmaleimide, preferably N-phenyl-maleimide;
5 maleic anhydride and Cl-C6-alkyl maleates and di-C1-C6-alkyl mal-eates, preferably maleic anhydride; and dienes, such as butadiene and isoprene, preferably butadiene.
lO The glass transition temperature of the 1st shell (A) is usually below 0 C, preferably below -20 C, particularly preferably below -30 C (the glass transition temperature is determined, for exam-ple, with the aid of DSC; K.H. Illers, Makromol. Chem. 127 (1969), 1).
The 1st shell (A) is prepared, as a rule, by known polymerization methods, such as emulsion, mass, solution or suspension polymer-ization, preferably in aqueous emulsion in the presence of an aqueous emulsion of the silicone rubber core (cf. German 20 Patent 1,260,135).
The conventional emulsifiers, such as the alkali metal salts of alkyl- or alkylarylsulfonic acids, alkylsulfates, fatty alcohol sulfonates, salts of higher fatty acids of 10 to 30 carbon atoms 25 or resin soaps, may be used for the preparation of the grafting base by emulsion polymerization. Sodium salts of alkylsulfonates or of fatty acids of 10 to 18 carbon atoms are preferably used.
In general, emulsifiers are used in amounts of from 0.1 to 5, preferably from 0.5 to 2, % by weight, based on the total weight 30 of the monomers used for the preparation of the 1st shell (A).
If desired, nonionic or anionic surfactants may be used as co-emulsifiers. Nonionic coemulsifiers are, for example, polyoxy-ethylene derivatives of fatty alcohols or fatty acids. Examples 35 are POE (3)-lauryl alcohol (POE = polyoxyethylene (x) where x is the degree of polymerization), POE (20)-oleyl alcohol, POE (7)-nonylphenol and POE (10) stearate. In general, a water/monomer ratio of from 10 : 1 to 0.7 : 1 is used.
40 The polymerization initiators used are customary hydroperoxides, the conventional persulfates and redox systems, such as hydroper-oxide and ascorbic acid, if desired, with the addition of Fe2~
salts and complexing agents. The conventional redox systems are known to a person skilled in the art. The amount of initiators 45 depends as a rule in a known manner on the desired molecular BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~28 weight and is usually from 0.01 to 1, preferably from 0.05 to 0.5, % by weight, based on the total weight of the monomers.
The polymerization assistants used are in general the conven-5 tional buffer substances, such as sodium bicarbonate or sodium pyrophosphate (with which a pH of from 6 to 9 can be estab-lished), and molecular weight regulators, such as mercaptans, terpinols or dimeric a-methylstyrene.
10 The exact polymerization conditions, in particular the type, rate of addition and amount of the emulsifier, are usually determined specifically within the abovementioned ranges so that the result-ing latex of the crosslinked polymer has a d50 value of from 40 to 2000 nm, preferably from 60 to 1000 nm, particularly preferably 15 from 80 to 800 nm.
For the preparation of the 1st shell (A) in aqueous emulsion, temperatures of from 20 to 100 C, preferably from 40 to 80 C, are usually employed.
According to the invention, the component (A) is used in an amount of from 25 to 60, preferably from 30 to 55, particularly preferably from 35 to 45, % by weight, based on the total amount of graft copolymer.
According to the invention, the component (B), the 2nd shell, is a mixture of essentially (bl)from 50 to 100, preferably from 55 to 100, particularly pre-ferably from 60 to 90, % by weight of a styrene compound of the general formula I
RlC = CH2 ~ I
~X2 where Rl and R2 independently of one another are each hydro-gen, Cl-C8-alkyl or Cl-C4-alkyl-monosubstituted, Cl-C4-alkyl-disubstituted or Cl-C4-alkyl-trisubstituted phenyl, and/or of a Cl-C8-alkyl ester of methacrylic or acrylic acid and/or BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~28 (b2)from 0 to 50, preferably from 0 to 40, particularly prefer-ably from 10 to 40, % by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by Cl-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether.
Styrene, ~-methylstyrene, l,l-diphenylethylene and styrenes alky-lated in the nucleus with Cl-C8-alkyl, such as p-methylstyrene or 10 tert-butylstyrene, particularly preferably styrene or ~-methyl-styrene, are preferably used as the styrene compound of the gen-eral formula I ~component (bl)).
According to the invention, methyl methacrylate (MMA), ethyl 15 methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacryl-ate, tert-butyl methacrylate, pentyl methacrylate, hexyl meth-acrylate, heptyl methacrylate, octyl methacrylate or 2-ethylhexyl methacrylate, particularly preferably methyl methacrylate, as 20 well as mixtures of these monomers, methyl acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate or 2-ethylhexyl acryl-ate, particularly preferably n-butyl acrylate, as well as mix-25 tures of these monomers with one another as well as with themethacrylates and/or styrene compounds of the general formula I
are used as Cl-C8-alkyl esters of methacrylic or acrylic acid.
According to the invention, a monomer selected from the group 30 consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by Cl-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, such as vinyl acetate or vinyl propionate, acrylamide and vinyl methyl ether is, if desired, used as component (b2).
In a preferred embodiment, a mixture of styrene and acrylonitrile (molar ratio usually from 10 : 1 to 1 : 1, preferably from 5 : 1 to 1 : 1) or a-methylstyrene and acrylonitrile (molar ratio usu-ally from 10 : 1 to 1 : 1, preferably from 5 : 1 to 1 : 1) or 40 methyl methacrylate and styrene (molar ratio usually from 10 : 1 to 1 : 1, preferably from 5 : 1 to 1 : 1) or methyl methacrylate alone, ie. without component (b2), is used.
BASF Aktiengesellschaft 920673 O.Z. OOS0/44505 ` ~137428 The preparation of the 2nd shell (B) is carried out, as a rule, by a conventional polymerization method, such as emulsion, mass, solution or suspension polymerization, in the presence of the graft copolymer (A).
However, it is advantageous to carry out the graft copolymeriza-tion of component (B) on the polymer (A) serving as the grafting base likewise in aqueous emulsion. It can be carried out in the same system as the polymerization of the grafting base, and fur-10 ther emulsifier and initiator may be added. These need not beidentical to the emulsifiers and initiators used for the prepara-tion of the shell (A). The emulsifier, initiator and polymeriza-tion assistants, either alone or as a mixture, may be initially taken with the emulsion of the grafting base (A). Any possible 15 combination of initially taken material and feed on the one hand and initiator, emulsifier and polymerization assistants on the other hand is suitable. The preferred embodiments are known to a person skilled in the art. The monomer mixture to be grafted may be added to the reaction mixture all at once, batchwise in a 20 plurality of stages or continuously during the polymerization.
The novel graft copolymers preferably have a median particle size - of from 0.1 to 10 ~m, particularly preferably from 0.1 to 1 ~m.
25 According to the invention, the component (B) is used in an amount of from 30 to 50, preferably from 35 to 45, particularly preferably from 35 to 40, % by weight, based on the total amount of graft copolymer.
30 The novel graft copolymers thus prepared may be worked up by known methods, for example by coagulation of the latices with electrolytes (salts, acids or bases)~ by heating or freezing out, by ultrasonics, by shearing or by a combination of these methods.
35 The novel graft copolymers may be used by themselves as molding materials. For this purpose, they can be worked up, for example by spray drying. However, the novel graft copolymers are prefer-ably used for mixing with copolymer (C) in order to increase its low-temperature toughness. Copolymers (C) suitable for modifica-40 tion are obtainable, according to the invention, by polymeriza-tion of a mixture consisting essentially of (cl) from 50 to 100~ by weight of a styrene compound of the general formula I and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~137928 (c2) from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, 5 maleic anhydride, maleimide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, (c3) from 0 to 90% by weight of a polycarbonate and (c4) from 0 to 100% by weight of conventional additives.
The components (cl) and (c2) correspond to the components (bl) and (b2) stated further above.
According to the invention, component (cl) is used in an amount of from 50 to 100, preferably from 60 to 90, particularly prefer-ably from 65 to 81, % by weight and component (c2) in an amount of from 0 to 50, preferably from 10 to 40, particularly prefer-20 ably from 19 to 35, % by weight.
Examples of the components (cl) and (c2) are homo- and copolymers of a vinylaromatic monomer and a polar, copolymerizable, ethylen-ically unsaturated monomer, such as polystyrene, polymethyl 25 methacrylate, styrene/acrylonitrile copolymers, a-methylstyrene/
acrylonitrile copolymers, styrene/maleic anhydride copolymers, styrene/phenylmaleimide copolymers, styrene/methyl methacrylate copolymers, methyl methacrylate/acrylonitrile copolymers, styr-ene/acrylonitrile/maleic anhydride copolymers, styrene/acrylo-30 nitrile/phenylmaleimide copolymers, a-methylstyrene/acrylo-nitrile/methyl methacrylate copolymers, a-methylstyrene/acrylo-nitrile/tert-butyl methacrylate copolymers and styrene/acrylo-nitrile/tert-butyl methacrylate copolymers.
35 The stated copolymers are frequently formed as byproducts, for example in the graft polymerization for the preparation of the novel graft copolymers, particularly when large amounts of the component (B) are grafted onto small amounts of the compo-nent (A). The vinyl polymers and (meth)acrylate polymers can be 40 prepared by known free radical, anionic and cationic polymeriza-tion methods. The known redox polymerization or the known poly-merization with organometallic mixed catalysts may also be advan-tageous.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 213742g Polycarbonate (PC), alone or as a mixture with the other compo-nents (cl) and (c2) mentioned above, may be used as novel component (c3).
5 Preferred novel blend components are, for example, mixtures of polycarbonate with the novel graft copolymers described above and the components (cl) and (c2).
Usually, the amount of the novel graft copolymers is from 5 to lO 95, preferably from 10 to 90, particularly preferably from 20 to 80, % by weight, the amount of the components (cl) and (c2) (sum cl + c2) is from 5 to 95, preferably from 10 to 90, particularly preferably from 20 to 80, % by weight and the amount of component (c3) is from 0 to 90, preferably from 0 to 80, particularly pre-15 ferably from 0 to 70, % by weight.
Examples of suitable polycarbonates are those based on diphenolsof the general formula (II) HO-Ar-A-Ar-OH (II) where 25 A is phenyl which is unsubstituted or monosubstituted, disub-stituted or trisubstituted by Cl-C4-alkyl or by halogen and A is a single bond, Cl-C3-alkylene, C2-C3-alkylidene, C3-C6-cycloalkylidene, -S- or -SO2-.
Preferred diphenols of the general formula (II) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane and l,l-bis-(4-hydroxyphenyl)-cyclohexane. 2,2-bis-(4-Hydroxy-35 phenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane are particularly preferred.
The diphenols of the general formula (II) are known per se or can be prepared by known processes.
The diphenols of the general formula (II) may be used both indi-vidually and as a mixture for the preparation of the polycarbonates.
45 The suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional com-BASF Aktiengesellschaft 920673 O.Z. 0050/44505 2137~28 12pounds, for example those having three or more phenolic OH
groups.
Polycarbonates which have proven particularly suitable are those 5 which have relative viscosities ~rel of from 1.10 to 1.50, in particular from 1.25 to 1.40 (measured as 0.5~ strength by weight solutions of the polymers in chloroform at 23 C). This corresponds to weight average molecular weights Mw or from 10,000 to 200,000, preferably from 20,000 to 80,000, g/mol.
The polycarbonates can be prepared, for example, by reacting the diphenols of the general formula (II) with phosgene by the phase boundary process or with phosgene by the process in the homogen-eous phase (ie. the pyridine process), the molecular weight to be 15 established in each case being achieved in a known manner by a corresponding amount of known chain terminators (with regard to polydiorganosiloxane-contA;n;ng polycarbonates, cf. for example German Laid-Open Application DOS 3,334,782).
20 Examples of suitable chain terminators are phenol and p-tert-butylphenol, as well as long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol, according to German Laid-Open Application DOS 2,842,005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, 25 according to DE-A 35 06 472, for example p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-di-methylheptyl)phenol and 4-(3,5-dimethylheptyl)-phenol.
For example, polycarbonate/polysiloxane block copolymers, poly-30 carbonate/polyether block copolymers and polycarbonate/polyester block copolymers may also serve as component (c3).
As a rule, aromatic polyesters and polyester carbonates may also be used as component (c3).
The novel thermoplastic molding materials may contain conven-tional additives as further constituents (component (c4)).
Examples of these are dyes and pigments, light stabilizers, heat 40 stabilizers, plasticizers, blowing agents and organic or inorgan-ic fillers in granular, powder or fibrous form.
The additives and assistants are used in conventional amounts, preferably in amounts of up to 50~ by weight, based on the total 45 weight of the thermoplastic molding material. Compatible plastics may also account for a higher proportion.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 '~137428 _ 13 In addition to the polymers mentioned as matrices, the novel graft copolymers may also be mixed with the following polymers:
polyphenylene ethers, polyamides, polyesters, polyurethanes, polyethylene homo- and copolymers, polypropylene homo- and co-5 polymers, halogenated polyolefins, such as polyvinyl chloride, polytetrafluoroethylene and derivatives, as well as polyoxy-methylenes, polyether ketones, polyether sulfones and polysulfones.
lO In a further preferred embodiment, the novel graft copolymers are mixed with known rubber-modified plastics, eg. ABS or ASA. ABS
(based on butadiene graft rubbers with styrene/acrylonitrile co-polymer) and ASA molding materials (based on acrylate graft rub-bers with styrene/acrylonitrile copolymer) are known to a person 15 skilled in the art and are described in, inter alia, German Patent 1,260,135 and European Patent 62,901.
The novel thermoplastic molding materials are processed, as a rule, by known methods, such as extrusion, injection molding, 20 compression molding of the melt, kneading, etc. The mixtures melted in this manner are usually cooled and then processed to give moldings (as a rule by injection molding)~ after which the moldings are subjected to mechanical tests.
25 The novel thermoplastic molding materials can be processed by the methods usually used for processing thermoplastics, such as ex-trusion and injection molding, to give a very wide range of mold-ings, such as window profiles, garden furniture, boats, sign-boards, lamp coverings, automotive parts and toys. The novel 30 thermoplastic molding materials are particularly suitable for the production of moldings which are required to have good low-tem-perature toughness.
Examples The notched impact strength aK (injection molding temperature/test temperature) (in kJ/m2) was measured according to DIN 53 453, at test temperatures of 23 C, 0 C and -20 C, using standard bars in-jection molded at 220, 250 and 280 C.
The heat distortion resistance Vicat B 50 was determined accord-ing to DIN 54 460 (in C).
The melt volume index MVI (in ml/10 minutes) was determined ac-45 cording to DIN 53 735 at 200 C and under a load of 21.6 kg.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 The stated median particle sizes are in all cases the weight average of the particle sizes which were determined by means of an analytical ultracentrifuge by a method corresponding to that of W. Scholtan and H. Lange, Kolloid-Z. and Z.Polymere 250 5 (1972), 782 - 796. The ultracentrifuge measurement gives the in-tegral mass distribution of the particle diameter of a sample.
From this it is possible to determine the percentage by weight of the particles which have a diameter equal to or smaller than a certain size. The median particle diameter, which is also re-10 ferred to as a d50 value of the integral mass distribution, is de-fined as the particle diameter at which 50% by weight of the par-ticles have a diameter smaller than the diameter which corres-ponds to the d50 value. Likewise, 50% by weight of the particles then have a diameter greater than the d50 value.
1. Preparation of the graft copolymers A
1.1. The silicone emulsion (dispersion) A1 used was a cross-linked polydimethylsiloxane emulsion (prepared similarly to Example 1 in EP-A 492 376): solids content (SC):
17.4%; particle diameter 156 nm; viscosity 4.6 mPa-s;
pH 7; degree of crosslinking 3%; 0.5% of methacryloyloxy-propyl functions.
25 1.2. Preparation of the 1st shell A2 1.2.1. Initially taken mixture Dispersion A1 (cf. Table 1) and water were heated to 60 C
and potassium persulfate (KPS) was then added.
1.2.2. Feed A mixture of n-butyl acrylate (BA) and the acrylate of tricyclodecenyl alcohol (DCPA) was added dropwise in the course of 1.5 hours. At the same time, a mixture of water and the sodium salts of a mixture of Cl3- and C14-alkyl-sulfonic acids (soap) was added dropwise. The dispersion A2 obtained was not isolated.
40 1.3. Preparation of the 2nd shell 5.1 g of potassium persulfate were added to the dispersion A2, and 960 g of styrene and 320 g of acrylonitrile were added dropwise in the course of 3 hours. Stirring was carried out for a further 2 hours. Theoretical solids content: 40.0~.
~ BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~ 2137~28 Table 1 Preparation of siloxane/acrylate rubbers All stated amounts in g Experiment 1 2 3 Initially taken mixture 1839 3678 5517 - component A1 3086 1575 255 lO _ water 4.8 3.9 2.88 - KPS
Feed - water 212 206 - soap 8 4 Analysi~
20 Solids content 39.5 39.7 39.6 (%) LT value 43 53 64 Swelling 4.4 4.6 4.2 indexl) Gel contentl) 96.3 93.4 84.5 25 (%) ) The swelling index is the weight increase on swelling of the sample in tert-butyl methyl ether at 23 C in the course of 24 hours. The gel content is the insoluble fraction obtained after the above swelling, when the soluble fractions have been separated off.
The light transmittance (LT; DIN 5036) is defined as the ratio of the light transmitted by a sample to the intensity of the inci-35 dent light. It must be measured as a function of the wavelengthin a range from 400 to 900 nm using an aqueous solution having a solids content of 0.01% by weight, in a 3 cm thick quartz cell.
2. Comparative Experiment 1 (V1, silicone graft rubber) In a glass flask, 8333 g of dispersion A1 were heated to 60 C, 3.9 g of potassium persulfate were added and a mixture of 725 g of styrene and 242 g of acrylonitrile was added dropwise in the course of 3 hours; the reaction was allowed to continue for a 45 further 2 hours.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~137~g Solids content SC: 25.7%
LT value: 79 Swelling index: 3.9 Gel content: 89.9%.
3. Comparative Experiment 2 (V2, acrylate graft rubber) Preparation according to EP-8 6503, column 12, line 54, to column 13, line 22.
The rubbers (Experiments 1 to 3, V1 and V2) were worked up as described in EP-8 6503, column 13, lines 16 to 22.
BASF Aktiengesellschaft 920673 O.Z. 0050/44505 ~137~g Solids content SC: 25.7%
LT value: 79 Swelling index: 3.9 Gel content: 89.9%.
3. Comparative Experiment 2 (V2, acrylate graft rubber) Preparation according to EP-8 6503, column 12, line 54, to column 13, line 22.
The rubbers (Experiments 1 to 3, V1 and V2) were worked up as described in EP-8 6503, column 13, lines 16 to 22.
4. Component B
A solution polymer of styrene and acrylonitrile in a weight ratio of 65 : 35, having a viscosity number of 80 ml/g (measured at 23 C
in a 0.5% strength by weight dimethylformamide (DMF) solution), was used.
A solution polymer of styrene and acrylonitrile in a weight ratio of 65 : 35, having a viscosity number of 80 ml/g (measured at 23 C
in a 0.5% strength by weight dimethylformamide (DMF) solution), was used.
5. Preparation of the mixtures First, the rubbers (Experiments 1, 2 and 3 and V1 and V2) were each mixed with the component 8 described in 4. in a weight ratio 25 of 1 : 1, the mixture was extruded at 250 C in a ZSK 30 twin-screw extruder from Werner & Pfleiderer and the extrudate was granu-lated. The granules were converted, at 220, 250 and 280 C, into moldings for the mechanical test (Table 2).
30 Table 2 Mechanical data of the novel molding materials Experiment 1 2 3 V1 V2 35 Vicat 850 88 87 87 92 87 (oc) MVI 5.6 4.6 4.4 2.8 3.9 (200/21.6) (ml/lOmin) 40 ak (kJ/m2) 22 24 21 12 26 (280/0) 18 19 16 8 5 (280/-20) 17 17 14 8 3
30 Table 2 Mechanical data of the novel molding materials Experiment 1 2 3 V1 V2 35 Vicat 850 88 87 87 92 87 (oc) MVI 5.6 4.6 4.4 2.8 3.9 (200/21.6) (ml/lOmin) 40 ak (kJ/m2) 22 24 21 12 26 (280/0) 18 19 16 8 5 (280/-20) 17 17 14 8 3
Claims (9)
1. A graft copolymer obtainable by (A) polymerization of from 25 to 60% by weight of a mixture consisting essentially of (a1)from 70 to 99.9% by weight of a C1-C18-alkyl ester of acrylic acid, where the alkyl radical may be monosubsti-tuted by phenyl or phenoxy, (a2)from 0.1 to 10% by weight of a polyfunctional monomer and (a3)from 0 to 29.9% by weight of an ethylenically unsaturated monomer which differs from (a1) and (a2) and is copoly-merizable therewith in the presence of from 5 to 25% by weight of a crosslinked silicone rubber and (B) polymerization of from 30 to 50% by weight of a mixture consisting essentially of (b1)from 50 to 100% by weight of a styrene compound of the formula (I) I
where R1 and R2 independently of one another are each hy-drogen, C1-C8-alkyl or C1-C4-alkyl-monosubstituted, C1-C4-alkyl-disubstituted or C1-C4-alkyl-trisubstituted phenyl, or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, malei-mide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, in the presence of the graft copolymer (A).
where R1 and R2 independently of one another are each hy-drogen, C1-C8-alkyl or C1-C4-alkyl-monosubstituted, C1-C4-alkyl-disubstituted or C1-C4-alkyl-trisubstituted phenyl, or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, malei-mide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, in the presence of the graft copolymer (A).
2. A graft copolymer as claimed in claim 1, wherein the polymer particles have a median particle size of from 0.1 to 10 µm.
3. A thermoplastic molding material consisting essentially of from 5 to 95% by weight of a graft copolymer as claimed in claim 1 or 2 and from 95 to 5% by weight of a copolymer (C) obtainable by polymerization of a mixture consisting essen-tially of (c1) from 50 to 100% by weight of a styrene compound of the formula I or of a C1-C8-alkyl ester of methacrylic or acrylic acid, (c2) from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by C1-C4-al-kyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acryla-mide and vinyl methyl ether, (c3) from 0 to 90% by weight of a polycarbonate and (c4) from 0 to 100% by weight of conventional additives.
4. A process for the preparation of a graft copolymer as claimed in claim 1, wherein (A) from 25 to 60% by weight of a mixture consisting essen-tially of (a1) from 70 to 99.9% by weightof a C1-C18-alkyl ester of acrylic acid, where the alkyl radical may be monosubstituted by phenyl or phenoxy, (a2) from 0.1 to 10% by weight of a polyfunctional monomer and (a3) from 0 to 29.9% by weight of an ethylenically unsaturated monomer which differs from (a1) and (a2) and is copolymerizable therewith are polymerized in the presence of from 5 to 25% by weight of a crosslinked silicone rubber and (B) from 30 to 50% by weight of a mixture consisting essen-tially of (b1) from 50 to 100% by weight of a styrene compound of the formula (I) I
where R1 and R2 independently of one another are each hy-drogen, C1-C8-alkyl or C1-C4-alkyl-monosubstituted, C1-C4-alkyl-disubstituted or C1-C4-alkyl-trisubstituted phenyl, or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, me-thacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, are polymerized in the presence of the graft copolymer (A).
where R1 and R2 independently of one another are each hy-drogen, C1-C8-alkyl or C1-C4-alkyl-monosubstituted, C1-C4-alkyl-disubstituted or C1-C4-alkyl-trisubstituted phenyl, or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and (b2)from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, me-thacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C2-C8-carboxylic acids, acrylamide and vinyl methyl ether, are polymerized in the presence of the graft copolymer (A).
5. A process for the preparation of a thermoplastic molding material as claimed in claim 3, wherein from 5 to 95% by weight of a graft copolymer as claimed in claim 1 and from 95 to 5% by weight of a copolymer (C), obtainable by polymeriza-tion of a mixture consisting essentially of (c1) from 50 to 100% by weight of a styrene compound of the formula I or of a C1-C8-alkyl ester of methacrylic or acrylic acid, (c2) from 0 to 50% by weight of a monomer selected from the group consisting of methacrylonitrile, acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, maleimide N-substituted by C1-C4-alkyl, vinyl esters of aliphatic C1-C8-carboxylic acids, acrylamide and vinyl methyl ether, (c3) from 0 to 90% by weight of a polycarbonate and (c4) from 0 to 100% by weight of conventional additives, are mixed in a manner known per se.
6. Use of a graft copolymer as claimed in claim 1 for the prepa-ration of thermoplastic molding materials and moldings.
7. Use of a thermoplastic molding material as claimed in claim 3 for the production of moldings.
8. A molding obtainable from a graft copolymer as claimed in claim 1 or from a thermoplastic molding material as claimed in claim 3.
9. A molding obtainable from a thermoplastic molding material as claimed in claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934342048 DE4342048A1 (en) | 1993-12-09 | 1993-12-09 | Graft copolymer for moulding materials with high cold impact strength |
| DEP4342048.6 | 1993-12-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2137428A1 true CA2137428A1 (en) | 1995-06-10 |
Family
ID=6504606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2137428 Abandoned CA2137428A1 (en) | 1993-12-09 | 1994-12-06 | Three-stage graft copolymers and thermoplastic molding materials containing said copolymers and having great toughness |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0678532A1 (en) |
| JP (1) | JPH07216036A (en) |
| CA (1) | CA2137428A1 (en) |
| DE (1) | DE4342048A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6063854A (en) * | 1996-07-25 | 2000-05-16 | Basf Aktiengesellschaft | Moldings for sanitary and bathroom fittings |
| US6316527B1 (en) | 1999-09-16 | 2001-11-13 | Rohm And Haas Company | Modified SAN resin blend compositions and articles produced therefrom |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19630144A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Housings for devices for information processing and transmission |
| DE19630120A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Housings of small transformers containing electrical devices |
| DE19630142A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Massager and housing therefor |
| DE19630103A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Thermally insulated transport containers |
| DE19630116A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Rear spoiler |
| DE19630099A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Hubcaps |
| DE19630095A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Cover grille for fan openings |
| DE19630062A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Molded parts for garden and tool sheds |
| DE19630118A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Flat wall elements |
| DE19630063A1 (en) * | 1996-07-25 | 1998-01-29 | Basf Ag | Interior components for rail vehicles |
| DE10236240A1 (en) * | 2002-02-06 | 2003-08-14 | Roehm Gmbh | Silicone graft copolymers with core-shell structure, impact-modified molding compositions and moldings, and process for their preparation |
| KR100638434B1 (en) | 2004-10-25 | 2006-10-24 | 주식회사 엘지화학 | Silicone-Acrylic Impact Modifier Having Improved Colorability And Thermoplastic Resin Composition Comprising The Same |
| JP2008189860A (en) * | 2007-02-07 | 2008-08-21 | Gantsu Kasei Kk | Silicone rubber graft copolymer and its production method |
| EP4347675A1 (en) | 2021-05-25 | 2024-04-10 | INEOS Styrolution Group GmbH | Acrylic rubber for thermoplastic material with good low temperature impact strength |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3617267A1 (en) * | 1986-05-23 | 1987-11-26 | Bayer Ag | NOTCH IMPACT TOE GRAFT POLYMERISATE |
| DE3631539A1 (en) * | 1986-09-17 | 1988-03-24 | Bayer Ag | AGING RESISTANT THERMOPLASTIC MOLDS WITH GOOD TOUGHNESS |
| AU604179B2 (en) * | 1988-01-25 | 1990-12-06 | Mitsubishi Rayon Company Limited | Vinyl chloride resin composition |
-
1993
- 1993-12-09 DE DE19934342048 patent/DE4342048A1/en not_active Withdrawn
-
1994
- 1994-11-30 EP EP94118850A patent/EP0678532A1/en not_active Withdrawn
- 1994-12-06 CA CA 2137428 patent/CA2137428A1/en not_active Abandoned
- 1994-12-08 JP JP6304793A patent/JPH07216036A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6063854A (en) * | 1996-07-25 | 2000-05-16 | Basf Aktiengesellschaft | Moldings for sanitary and bathroom fittings |
| US6316527B1 (en) | 1999-09-16 | 2001-11-13 | Rohm And Haas Company | Modified SAN resin blend compositions and articles produced therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4342048A1 (en) | 1995-06-14 |
| JPH07216036A (en) | 1995-08-15 |
| EP0678532A1 (en) | 1995-10-25 |
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