CN1122082C - 阻燃的聚碳酸酯/abs模塑组合物 - Google Patents
阻燃的聚碳酸酯/abs模塑组合物 Download PDFInfo
- Publication number
- CN1122082C CN1122082C CN98808057A CN98808057A CN1122082C CN 1122082 C CN1122082 C CN 1122082C CN 98808057 A CN98808057 A CN 98808057A CN 98808057 A CN98808057 A CN 98808057A CN 1122082 C CN1122082 C CN 1122082C
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- China
- Prior art keywords
- component
- moulding compound
- compound
- methyl
- preferred
- Prior art date
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- Expired - Lifetime
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 36
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title abstract description 7
- 238000000465 moulding Methods 0.000 title abstract description 3
- -1 ethylene, propylene, vinyl Chemical group 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 9
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000206 moulding compound Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 17
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003063 flame retardant Substances 0.000 claims description 16
- 150000001721 carbon Chemical group 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 11
- 239000011707 mineral Substances 0.000 claims description 11
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- 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 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical group CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 5
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- KWQPWOQUXSQDNN-UHFFFAOYSA-N (2,3,4-trimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C(C)=C1C KWQPWOQUXSQDNN-UHFFFAOYSA-N 0.000 claims description 2
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- QCENBAIVVIEPCT-UHFFFAOYSA-N C1(=C(C=CC=C1)CC)C.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=C(C=CC=C1)CC)C.C1(=CC=CC=C1)C1=CC=CC=C1 QCENBAIVVIEPCT-UHFFFAOYSA-N 0.000 claims description 2
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 claims description 2
- NHIGHVRZSNLMEB-UHFFFAOYSA-N P(=O)(OCCCCCCCC)(O)O.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound P(=O)(OCCCCCCCC)(O)O.C1(=CC=CC=C1)C1=CC=CC=C1 NHIGHVRZSNLMEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229920006355 Tefzel Polymers 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- ILFXTQPXQOZOBB-UHFFFAOYSA-N [H]C([H])([H])OP(O)(OC([H])([H])[H])C([H])([H])[H] Chemical class [H]C([H])([H])OP(O)(OC([H])([H])[H])C([H])([H])[H] ILFXTQPXQOZOBB-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 claims description 2
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 2
- NYGNEXMYFRZEKZ-UHFFFAOYSA-N CC1=C(C(=C(C=C1)[PH2]=O)C)C Chemical compound CC1=C(C(=C(C=C1)[PH2]=O)C)C NYGNEXMYFRZEKZ-UHFFFAOYSA-N 0.000 claims 1
- 229920003244 diene elastomer Polymers 0.000 claims 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 229920000578 graft copolymer Polymers 0.000 abstract description 5
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 238000009757 thermoplastic moulding Methods 0.000 abstract description 2
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 229920006163 vinyl copolymer Polymers 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 12
- 238000005336 cracking Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 230000002180 anti-stress Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- 239000004033 plastic Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 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 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 125000001118 alkylidene group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-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
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- FUQAGKYWAUZSEJ-UHFFFAOYSA-N 2,3,4,5-tetrabromo-6-(2-hydroxyphenyl)phenol Chemical compound OC1=CC=CC=C1C1=C(O)C(Br)=C(Br)C(Br)=C1Br FUQAGKYWAUZSEJ-UHFFFAOYSA-N 0.000 description 1
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
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- PBTXWTNXVCYRJA-UHFFFAOYSA-N 4-hept-2-enylphenol Chemical compound CCCCC=CCC1=CC=C(O)C=C1 PBTXWTNXVCYRJA-UHFFFAOYSA-N 0.000 description 1
- KNDDEFBFJLKPFE-UHFFFAOYSA-N 4-n-Heptylphenol Chemical compound CCCCCCCC1=CC=C(O)C=C1 KNDDEFBFJLKPFE-UHFFFAOYSA-N 0.000 description 1
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
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- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
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- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
本发明涉及阻燃热塑性模塑材料,该材料包含下列化合物:具有不同溶液粘度的两种聚碳酸酯A.1和A.2的混合物;由一种或至少两种烯键式不饱和单体制成的乙烯基(共)聚合物;通过接枝共聚选自氯丁二烯、1,3-丁二烯、异戊二烯、苯乙烯、丙烯腈、乙烯、丙烯、乙酸乙烯酯和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯的至少两种单体而获得的接枝聚合物。本发明的模塑材料还包含:磷化合物;氟代聚烯烃;以及平均颗粒直径最多为200nm的无机化合物。
Description
本发明涉及用有机磷化合物赋予阻燃性的聚碳酸酯/ABS模塑组合物,该组合物具有一系列卓越的机械性能,特别是卓越的抗应力开裂性,并且是阻燃的。
EP-A-0 174 493描述了由芳族聚碳酸酯、含苯乙烯的接枝共聚物、单磷酸酯和特殊的聚四氟乙烯配方组成的阻燃的含卤聚合物混合物。尽管这些混合物就阻燃性和机械性能而言是足够的,但当使用高加工温度时模塑物品的表面性质被削弱了。模塑物品在抗应力开裂性方面也显示了一些缺点。
EP-A 0 363 608描述了由芳族聚碳酸酯、含苯乙烯的共聚物或接枝共聚物和作为阻燃添加剂的低聚磷酸酯组成的聚合物混合物。这些混合物的抗应力开裂性通常不足以生产薄壁居室部件。
EP-A 771 851描述了包括芳族聚碳酸酯、基于二烯橡胶的接枝共聚物、SAN共聚物、磷酸酯和四氟乙烯聚合物的模塑组合物,其中聚碳酸酯具有各种分子量。但是,没有描述非常精细的无机化合物作为模塑组合物的组分。
本发明的目的是提供具有卓越的抗应力开裂性及非常好的加工性能并且特别适于生产薄壁居室部件的阻燃性聚碳酸酯/ABS模塑组合物。
已令人惊讶地发现通过使用各具有明显不同溶液粘度的聚碳酸酯的特殊的混合物结合非常精细的无机化合物可以生产抗应力开裂性显著改进了的聚碳酸酯/ABS模塑组合物。
因此,本发明提供了阻燃热塑性模塑组合物,包含
A.5-95,优选10-90,特别优选20-80重量份的具有不同溶液粘度的两种芳族聚碳酸酯A.1和A.2的混合物,其中
1.A.1的相对溶液粘度为1.18-1.24,
2.A.2的相对溶液粘度为1.24-1.34并且
3.A.1和A.2的相对溶液粘度的差等于或大于0.06,
其中可向A.1和A.2的混合物中加入一种或多种另外的聚碳酸酯,
B.0-50,优选1-30,特别优选2-25重量份由一种或至少两种烯键式不饱和单体组成的(共)聚合物,
C.0.5-60,优选1-40,特别优选2-30重量份接枝聚合物,可通过接枝聚合选自氯丁二烯、丁二烯、异戊二烯、苯乙烯、丙烯腈、乙烯、丙烯、乙酸乙烯酯和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯的至少两种单体而获得,
其中
R1、R2、R3和R4彼此独立地代表任选卤代的C1-C8-烷基,或C5-C6-环烷基、C6-C20-芳基或C7-C12-芳烷基,每个基团任选被卤素和/或C1-C4-烷基取代,
n彼此独立地代表0或1,
N为0-30且
X代表含有6-30个碳原子的单或多核芳族基团,
E.0.05-5重量份,优选0.1-1重量份,特别优选0.1-0.5重量份氟代聚烯烃,
F.0.01-50重量份,优选0.1-10重量份(就每100重量份A-E而言)平均颗粒直径小于或等于200nm,优选小于或等于150nm,特别是小于或等于100nm的非常精细的无机化合物。
所有重量份A+B+C+D+E+F的和为100。
由于其优异的阻燃性、抗应力开裂性和非常好的加工性能,本发明的模塑组合物特别适于制备其中高加工温度和压力在所用材料上造成显著的应变的薄壁模塑制品(用于数据处理元件的居室部件)。
组分A
根据本发明适于用作组分A的热塑性芳族聚碳酸酯为基于式(II)的双酚,或式(III)的烷基取代的二羟基苯基环烷烃,
在式(II)中
A代表单键或C1-C5-亚烷基、C2-C5-(1,1-)亚烷基、C5-C6-环(1,1-)亚烷基、-S-、-SO2-、-O-、-CO-或C6-C12-亚芳基,
B代表氯或溴,
x为0、1或2并且
p为1或0,
在式(III)中
R11和R12是彼此独立的,各代表氢;卤素,优选氯或溴;或C1-C8-烷基,优选C1-C4-烷基;C5-C6-环烷基;C6-C10-芳基,优选苯基;或C7-C12-芳烷基,优选苯基-C1-C4-烷基,特别是苄基,
m为4-7的整数,优选4或5,
对于每一个Z,R13和R14可分别选择并且彼此独立地代表氢或C1-C6-烷基,优选氢、甲基或乙基,并且
Z代表碳,条件是在至少一个原子Z上R13和R14同时代表烷基。
式(II)的适宜双酚为例如氢醌、间苯二酚、4,4’-二羟基联苯、2,2-二-(4-羟基苯基)-丙烷、2,4-二-(4-羟基苯基)-2-甲基丁烷、1,1-二-(4-羟基苯基)-环己烷、2,2-二-(3-氯-4-羟基苯基)-丙烷、2,2-二-(3,5-二溴-4-羟基苯基)-丙烷。
优选的式(II)双酚为2,2-二-(4-羟基苯基)-丙烷、2,2-二-(3,5-二溴-4-羟基苯基)-丙烷和1,1-二-(4-羟基苯基)-环己烷。
其中1,1-二-(4-羟基苯基)-3,3,5-三甲基环己烷(式(IIIa))是特别优选的。
适于用作本发明组分A的聚碳酸酯可用已知方法支化,即优选通过引入相对所用双酚之和0.05-2.0mol%的三或三个以上官能团的化合物,如带有三个或三个以上酚基团者,例如间苯三酚、4,6-二甲基-2,4,6-三(4-羟基苯基)-庚-2-烯、4,6-二甲基-2,4,6-三(4-羟基苯基)-庚烷、1,3,4-三-(4-羟基苯基)-苯、1,1,1-三-(4-羟基苯基)-乙烷、三-(4-羟基苯基)-苯基甲烷、2,2-二-(4,4-二-(4-羟基苯基)-环己基)-丙烷、2,4-二-(4,4-二-4-羟基苯基)-异丙基)-苯酚、2,6-二-(2-羟基-5’-甲基苄基)-4-甲基苯酚、2-(4-羟基苯基)-2-(2,4-二羟基苯基)-丙烷、六-(4-(4-羟基苯基-异丙基)-苯基)-邻苯二甲酸酯、四-(4-羟基苯基)-甲烷、四-(4-(4-羟基苯基-异丙基)-苯氧基)-甲烷和1,4-二-((4’,4”-二羟基三苯基)-甲基)-苯。
一些其它的三官能团化合物为2,4-二羟基苯甲酸、苯均三酸、氰尿酰氯和3,3-二-(3-甲基-4-羟基苯基)-2-氧代-2,3-二氢吲哚。
除了双酚A均聚碳酸酯外,优选的聚碳酸酯为含有相对双酚的摩尔数之和最多15mol%的2,2-二-(3,5-二溴-4-羟基苯基)-丙烷的双酚A共聚碳酸酯。
组分A的芳族聚碳酸酯可部分被芳族聚酯碳酸酯取代。
组分A的芳族聚碳酸酯也可含有聚硅氧烷嵌段。其生产方法描述于例如DE-OS 3 334 872和US-PS 3 821 325中。
根据组分A的芳族聚碳酸酯和/或芳族聚酯碳酸酯是文献中已知的或可用文献中已知的方法生产(芳族聚碳酸酯的生产方法见例如Schnell的“聚碳酸酯的化学和物理”,Interscience Publisher,1964和DE-AS 1 495 626、DE-OS 2 232 877、DE-OS 2 703 376、DE-OS 2 714 544、DE-OS 3 000 610、DE-OS 3 832 396;芳族聚酯碳酸酯的生产方法见例如DE-OS 3 077 934)。
芳族聚碳酸酯和/或芳族聚酯碳酸酯是例如通过相界面方法使双酚与碳酰卤,优选光气;以及/或者与芳族二羧酸二酰卤,优选苯二羧酸二酰卤反应而生产的,任选使用链终止剂并任选使用三官能团或三个以上官能团的支化剂。
聚碳酸酯A.1和A.2优选具有相同结构,即它们由相同的单体构成。
特别优选聚碳酸酯A.1和A.2以及任选另外加入的聚碳酸酯A由相同的单体构成,即它们具有相同的化学结构。
另外的聚碳酸酯优选以30wt%(相对A.1和A.2的量)的量加入。
相对于聚碳酸酯A.1和A.2的混合物,A.1的含量为5-95、优选10-75、特别为10-35wt%,而A.2的含量为95-5、优选90-25、特别为90-65wt%。
聚碳酸酯A.1和A.2的混合物以A.1的相对溶液粘度为1.181.24,A.2的相对溶液粘度为1.24-1.34,并且A.1和A.2相对溶液粘度之差大于或等于0.06,特别是大于或等于0.09,即A.2的相对溶液粘度减A.1的相对溶液粘度≥0.06,特别是≥0.09为特征。相对溶液粘度是以CH2Cl2为溶剂在25℃和浓度为0.5g/100ml时测定的。
混合物中一种或两种聚碳酸酯组分A.1或A.2可以是再生的聚碳酸酯。再生聚碳酸酯应理解为已经历了一次加工和使用周期并且通过特殊的后处理过程已从中基本除去附着的杂质,适于进一步使用的产物。
组分B
热塑性聚合物B包括一种或至少两种烯键式不饱和单体(乙烯基单体)的(共)聚合物,所述单体为例如苯乙烯、α-甲基苯乙烯、环取代苯乙烯(例如卤素和/或烷基环取代)、丙烯腈、甲基丙烯腈、甲基丙烯酸甲酯、马来酸酐、N-取代马来酰亚胺和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯。
组分B的(共)聚合物是类似树脂的、热塑性的且是不含橡胶的。模塑组合物也可包含不同(共)聚合物B。
优选的乙烯基(共)聚合物B为由苯乙烯、α-甲基苯乙烯、环取代苯乙烯和/或甲基丙烯酸甲酯系列(B.1)中至少一种单体与丙烯腈、甲基丙烯腈、甲基丙烯酸甲酯、马来酸酐和/或N-芳基取代的马来酰亚胺系列(B.2)中至少一种单体组成的(共)聚合物。
(共)聚合物中单体B.1的浓度优选为50-99,特别优选60-95wt%,单体B.2的浓度优选为1-50,特别优选40-5wt%。
特别优选的共聚物B为由苯乙烯与丙烯腈并任选与甲基丙烯酸甲酯,由α-甲基苯乙烯与丙烯腈并任选与甲基丙烯酸甲酯,或由苯乙烯和α-甲基苯乙烯与丙烯腈并任选与甲基丙烯酸甲酯组成的共聚物。
根据组分B的(共)聚合物是已知的并可由自由基聚合,特别是乳液、悬浮、溶液或本体聚合生产。根据组分B的(共)聚合物的分子量Mw(重均,由光散射或沉降法测定)优选为15,000-200,000。
根据本发明特别优选的(共)聚合物B也是由苯乙烯和马来酸酐构成的无规共聚物,优选通过连续本体或溶液聚合由相应的单体不完全转化而制备。
在根据本发明并且由苯乙烯和马来酸酐构成的适宜无规共聚物中两种组分的比例可以在很宽的范围内变化。优选的马来酸酐的浓度为5-25wt%。
聚合物还可包含环取代苯乙烯如对甲基苯乙烯、2,4-二甲基苯乙烯和其它取代的苯乙烯如α-甲基苯乙烯以替代苯乙烯。
根据本发明组分B由苯乙烯和马来酸酐构成的无规共聚物的分子量(数均Mn)可以在很宽的范围内变化。优选范围为60,000-200,000。这些产物的特性粘数优选为0.3-0.9(于25℃在二甲基甲酰胺中测定;见Hoffmann,Krmer,Kuhn,聚合物分析I,Stuttgart1977,316及其后各页).
组分C
根据本发明的组分C是接枝聚合物。它们包括具有橡胶弹性性能的接枝共聚物,基本可由下列单体中的至少两种获得:氯丁二烯、1,3-丁二烯、异戊二烯、苯乙烯、丙烯腈、乙烯、丙烯、乙酸乙烯酯和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯;即例如在“有机化学方法”(Houben-Weyl),14/1卷,Georg Thieme Verlag出版社,Stuttgart 1961,393-406页和在C.B.Bucknall的“增韧塑料”,应用科学出版社,伦敦1977中所述的聚合物。优选的聚合物C是部分交联的并且凝胶含量超过20wt%,优选超过40wt%,特别是超过60wt%。
优选的接枝聚合物C包括:
C.1 5-95,优选30-80重量份的混合物,包括:
C.1.1 50-99重量份苯乙烯、α-甲基苯乙烯、卤素或甲基环取代的苯乙烯、甲基丙烯酸甲酯或这些化合物的混合物和
C.1.2 1-50重量份丙烯腈、甲基丙烯腈、甲基丙烯酸甲酯、马来酸酐、C1-C4-烷基或苯基-N-取代马来酰亚胺或这些化合物的混合物,接枝在
C.2 5-95,优选20-70重量份玻璃化转变温度低于-10℃的基于二烯和/或烷基丙烯酸酯的聚合物。
优选的接枝聚合物C为例如用苯乙烯和/或丙烯腈和/或(甲基)丙烯酸烷基酯接枝的基体C.2如聚丁二烯、丁二烯/苯乙烯共聚物和丙烯酸酯橡胶,即DE-OS 1 694 173(=US-PS 3 564 077)所述类型的共聚物;或用丙烯酸烷基酯或甲基丙烯酸烷基酯、乙酸乙烯酯、丙烯腈、苯乙烯和/或其它烷基苯乙烯接枝的、聚丁二烯、丁二烯/苯乙烯或丁二烯/丙烯腈共聚物,聚异丁烯或聚异戊二烯,如DE-OS 2 348 377(=US-PS 3 919 353)中所述。
特别优选的聚合物C的实例为ABS聚合物,如例如DE-OS 2 035390(=US-PS 3 644 5 74)或DE-OS 2 248 242(=GB-PS 1 409 275)中所述。
特别优选的接枝聚合物C是通过下列化合物的接枝反应而获得的:
α相对于接枝聚合物C,10-70,优选15-50,特别是20-40wt%的至少一种(甲基)丙烯酸酯或10-70,优选15-50,特别是20-40wt%由10-50,优选20-35wt%(相对混合物)丙烯腈或(甲基)丙烯酸酯和50-90,优选65-80wt%(相对于混合物)苯乙烯组成的混合物,作为外枝物C.1,
β相对于接枝聚合物C,30-90,优选50-85,特别是60-80wt%的丁二烯聚合物(相对于β,含有至少50wt%丁二烯基团),作为接枝基体C.2,
其中接枝基体β的凝胶含量优选至少为70wt%(在甲苯中测定),接枝度G为0.15-0.55并且接枝聚合物C.2的平均颗粒直径d50为0.05-2μm,优选0.1-0.6μm。
(甲基)丙烯酸酯α为丙烯酸或甲基丙烯酸与含有1-18个碳原子的单羟基醇的酯。甲基丙烯酸甲酯、乙酯和丙酯、丙烯酸正丁酯、丙烯酸叔丁酯和甲基丙烯酸叔丁酯是特别优选的。
除了丁二烯基团,接枝基体β可含有相对β最多50wt%的其它烯键式不饱和单体如苯乙烯、丙烯腈、醇组分中含有1-4个碳原子的丙烯酸酯或甲基丙烯酸酯(如丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯)、乙烯基酯和/或乙烯基醚。优选的接枝基体β由纯聚丁二烯组成。
接枝度G为接枝的单体与接枝基体之间的重量比并且是无量纲的。
平均粒度d50为在该直径上下颗粒各占50wt%的直径。它可由超离心测量技术测定(W.Scholtan,H.Lange,Kolloid,Z.und Z.Polymere 250(1972),782-796)。
特别优选的聚合物C也为例如下列化合物的接枝聚合物:
τ.相对于组分C,20-90wt%玻璃化转变温度<-20℃的丙烯酸酯橡胶,作为接枝基体C.2和
δ.相对于组分C,10-80wt%至少一种可聚合的烯键式不饱和单体,作为接枝单体C.1。
聚合物C中的丙烯酸酯橡胶τ优选为丙烯酸烷基酯的聚合物,任选含有最多40wt%(相对于τ)的其它可聚合烯键式不饱和单体。优选的可聚合丙烯酸酯包括C1-C8-烷基酯,如甲基、乙基、丁基、正辛基和2-乙基己基酯;卤代烷基酯,优选卤代-C1-C8-烷基酯,如氯乙基丙烯酸酯,及这些单体的混合物。
为了将产物交联,可共聚带有一个以上可聚合双键的单体。交联单体的优选实例为含有3-8个碳原子的不饱和单羧酸与含有3-12个碳原子的不饱和单羟基醇或含有2-4个OH基团和2-20个碳原子的饱和多元醇的酯如乙二醇二甲基丙烯酸酯、烯丙基甲基丙烯酸酯;多不饱和杂环化合物如三乙烯基和三烯丙基氰尿酸酯;多官能团乙烯基化合物如二-和三-乙烯基苯;以及三烯丙基磷酸酯和二烯丙基邻苯二甲酸酯。
优选的交联单体为烯丙基甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、二烯丙基邻苯二甲酸酯和含有至少三个烯键式不饱和基团的杂环化合物。
特别优选的交联单体为环单体三烯丙基氰尿酸酯、三烯丙基异氰尿酸酯、三乙烯基氰尿酸酯、三丙烯酰基六氢均三嗪、三烯丙基苯。
相对于接枝基体τ,交联单体的量优选为0.02-5,特别为0.05-2wt%。
在含有至少三个烯键式不饱和基团的环交联单体的情况下,将接枝基体τ的量限定在1wt%以下是有利的。
除丙烯酸酯以外也可任选用来生产接枝基体τ的优选“其它”可聚合烯键式不饱和单体为例如丙烯腈、苯乙烯、α-甲基苯乙烯、丙烯酰胺、乙烯基-C1-C6-烷基醚、甲基丙烯酸甲酯、丁二烯。优选的作为接枝基体τ的丙烯酸酯橡胶为凝胶含量至少为60wt%的乳液聚合物。
根据C.2另外的适宜接枝基体为带有接枝活性点的硅橡胶,如DE-OS 3 704 657、DE-OS 3 704 655、DE-OS 3 631 540和DE-OS 3631 539中所述。
接枝基体C.2的凝胶含量是在25℃于二甲基甲酰胺中测定的(M.Hoffmann,H.Krmer,R.Kuhn,聚合物分析I和II,GeorgeThieme-Verlag出版社,Stuttgart 1977)。
接枝聚合物C可由已知的方法如本体、悬浮、乳液或本体-乳液法生产。
因为在接枝反应中,已知接枝单体不能完全彻底地接枝到接枝基体上,所以根据本发明接枝聚合物C也应理解为是指在接枝基体存在下通过聚合接枝单体而获得的产物。
组分D
本发明的模塑组合物包含至少一种式(I)的有机磷化合物或有机磷化合物的混合物作为阻燃剂
在该结构式中,R1、R2、R3和R4具有上述相同的含义。R1、R2、R3和R4优选代表C1-C4-烷基或苯基、萘基或苯基-C1-C4-烷基。对于芳族基团R1、R2、R3和R4来说,它们可以被卤素和/或烷基(优选C1-C4-烷基)取代。特别优选的芳基为甲苯基、苯基、二甲苯基、丙基苯基或丁基苯基及其相应的溴代或氯代衍生物。
在式(I)中,X代表含有6-30个碳原子的单或多核芳族基团。优选衍生自根据式(II)的双酚如双酚A、间苯二酚或氢醌或其氯代或溴代衍生物。
在式(I)中,n可以彼此独立地为0或1,优选n为1。
N可以是0-30的任意值。
在磷化合物的混合物的情况下,N可以取0-30的平均值,优选0.3-20的平均值,特别优选0.5-10,更特别优选0.5-6。在该混合物中也可以含有单磷化合物和/或低聚磷化合物。N=0时,式(I)描述的是单磷化合物。
式(I)的磷化合物优选为三丁基磷酸酯、三-(2-氯乙基)-磷酸酯、三-(2,3-二溴丙基)-磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、二苯基甲苯基磷酸酯、二苯基辛基磷酸酯、二苯基-2-乙基甲苯基磷酸酯、三-(异丙基苯基)-磷酸酯、卤素取代的芳基磷酸酯、甲基膦酸二甲基酯、甲基膦酸二苯基酯、苯基膦酸二乙基酯、三苯基氧化膦和/或间亚苯基-双(二苯基)磷酸酯。
N值为0.5-10,特别为0.5-6的式(I)的磷化合物的混合物是优选的。
在混合物中式(I)的单和低聚磷化合物优选以可获得协同效应的方式挑选。该混合物一般由10-90wt%的二聚和/或低聚物及90-10wt%单磷化合物,优选式(I)的单磷化合物组成。优选单磷化合物在12-50,优选14-40,特别是15-40wt%的范围内与补足量的低聚磷化合物混合。
根据组分D的磷化合物是已知的(见例如EP-A 363 608、EP-A 640655)或可以类似的方式由已知的方法制备(例如见UllmannsEncyklopdie der Technischen Chemie,18卷,301及以后各页,1979;Houben-Weyl,Methoden der Organischen Chemie,12/1卷,43页;贝恩斯坦,6卷,177页)。
组分E
氟代聚烯烃E是高分子量的化合物且玻璃化转变温度超过-30℃,一般超过100℃。其氟含量优选为65-76,特别为70-76wt%,其平均颗粒直径d50为0.05-1000,优选0.08-20μm。一般而言氟代聚烯烃E的密度为1.2-2.3g/cm3。
优选的氟代聚烯烃E为聚四氟乙烯、聚偏二氟乙烯、四氟乙烯/六氟丙烯共聚物和乙烯/四氟乙烯共聚物。
氟代聚烯烃是已知的(参看Schildknecht的“乙烯基及相关聚合物”,John Wiley & Sons,Inc.,纽约,1962,484-494页;Wall的“氟聚合物”,Wiley Interscience,John Wiley & Sons,Inc.,纽约,13卷,1970,623-654页;“现代塑料百科全书”,1970-1971,47卷,10A期,1970年10月,McGraw-Hill,Inc.,纽约,134和774页;“现代塑料百科全书”,1975-1976,1975年10月,52卷,10A期,McGraw-Hill,Inc.,纽约,27、28和472页及US-PS3 671 487、3 723 373和3 838 092)。
它们可以由已知的方法生产,例如通过在水相介质中使用生成自由基的催化剂如钠、钾或铵过二硫酸盐在7-71 kg/cm2的压力和0-200℃,优选20-100℃的温度下聚合四氟乙烯。(进一步的细节见例如美国专利2 393 967)。取决于实际所用的形式,这些材料的密度可为1.2-2.3g/cm3,平均粒度为0.05-1000μm.
根据本发明的优选氟代聚烯烃E为四氟乙烯聚合物并且平均颗粒直径为0.05-20μm,优选0.08-10μm,密度为1.2-1.9g/cm3且优选以四氟乙烯聚合物E乳液与接枝聚合物C乳液的凝聚混合物形式使用。
适宜的四氟乙烯聚合物乳液为市售产品并且由例如杜邦公司以Teflon30N出售。
可以粉末形式使用的适宜氟代聚烯烃E为平均颗粒直径为100-1000μm且密度为2.0-2.3g/cm3的四氟乙烯聚合物。
为了制备C和E的凝聚混合物,首先将平均乳胶颗粒直径为0.05-2μm,特别是0.1-0.6μm的接枝聚合物C的水相乳液(乳胶)与平均颗粒直径为0.05-20μm,特别是0.08-10μm的四氟乙烯聚合物E在水中的精细乳液混合。适宜的四氟乙烯聚合物乳液通常的固体含量为30-70wt%,特别为50-60wt%。
接枝聚合物C的水相乳液的固体含量为25-60wt%,优选30-45wt%,特别为30-35wt%。
在描述组分C时所给出的量的数据不包括在接枝聚合物和氟代聚烯烃的凝聚混合物中接枝聚合物的含量。
在乳液混合物中接枝聚合物C对四氟乙烯聚合物E的重量比为95∶5-60∶40。乳液混合物是以已知方式凝聚的,例如通过喷雾干燥、冷冻干燥或通过加入无机或有机盐、酸、碱或与水混溶的有机溶剂如醇、酮凝聚,优选在20-150℃,特别是50-100℃进行。如果需要,可在50-200℃,优选70-100℃进行干燥。
组分F
根据组分F的非常精细的无机化合物由一种或多种门捷列夫元素周期表1-5主族和1-8副族、优选2-5主族或4-8副族、特别优选3-5主族或4-8副族的金属与至少一种选自氧、硫、硼、磷、碳、氮、氢或硅的元素的化合物组成。
优选的化合物为例如氧化物、氢氧化物、水合氧化物、硫酸盐、亚硫酸盐、硫化物、碳酸盐、碳化物、硝酸盐、亚硝酸盐、氮化物、硼酸盐、硅酸盐、磷酸盐、氢化物、亚磷酸盐或膦酸盐。
优选的非常精细的无机化合物为例如TiN,TiO2,SnO2,WC,Zn0,Al2O3,AlO(OH),ZrO2,Sb2O3,SiO2,氧化铁,Na2SO4,BaSO4,氧化钒,硼酸锌,硅酸盐如硅酸铝、硅酸镁,和一、二或三维硅酸盐。也可使用混合物及掺杂的化合物。而且可用有机分子对这些极小的颗粒进行表面改性以获得与基体更好的相容性。以这种方法可以得到疏水或亲水的有机表面。
平均颗粒直径小于或等于200nm,优选小于或等于150nm,特别为1-100nm。
粒度和颗粒直径始终是指平均颗粒直径d50,是根据W.Scholtan等人的Kolloid-Z.und Z.Polymere 250(1972),782-796页由超离心测量方法测定的。
无机化合物可以粉末、浆料、溶胶、分散体或悬浮体使用。粉末可通过沉淀由分散体、溶胶或悬浮体获得。
粉末可通过常规方法引入热塑性塑料中,例如通过直接混合或挤塑模塑组合物组分和非常精细的无机粉末。优选的方法为生产母料配料,例如组分B或C的分散体与非常精细的无机材料的分散体、悬浮体、浆料或溶胶在阻燃添加剂、其它添加剂、单体、溶剂或热塑性A中一起共沉淀。
根据本发明的模塑组合物可包括至少一种常规添加剂如润滑剂和脱模剂、成核剂、抗静电剂、稳定剂以及染料和颜料。
根据本发明的模塑组合物也可包含用量最多为20重量份的不同于式(I)化合物的阻燃化合物。具有协同效应的阻燃剂是优选的。下面列举作为另外阻燃剂的化合物:有机卤化物如十溴二苯醚、四溴二苯酚,无机卤化物如溴化铵,氮化合物如蜜胺、蜜胺甲醛树脂或硅氧烷化合物。根据本发明的模塑组合物可任选包含不同于无机化合物F的无机物质如无机氢氧化物如氢氧化镁和铝,无机化合物如氧化铝、氧化锑、偏硼酸钡、羟锑酸盐、氧化锆、氢氧化锆、氧化钼、钼酸铵、硼酸锌、硼酸铵和氧化锡。
根据本发明包含组分A-F和任选另外的已知添加剂如稳定剂、染料、颜料、润滑剂和脱模剂、成核剂及抗静电剂的模塑组合物是通过以已知的方法混合具体的组分并在200-300℃于常规设备如密炼机、挤出机和双螺杆挤出机中熔融配混或熔融挤塑而生产的,其中组分E优选以上述凝聚混合物的形式使用。
可以以已知的方法混合各个组分,事实上是在约20℃(室温)或更高的温度顺序或同时进行的。
本发明的模塑组合物可用来制备各种模塑物品。特别是可通过注塑来生产模塑物品。可生产的模塑物品的实例为:各种居室部件,例如家庭用品如果汁机、咖啡机、搅拌机,办公室机器如计算机、打印机、监视器或复印机或建筑部件的面板及机动车辆部件。它们也可用在电机工程部件中,因为它们具有非常好的电性能。
这些模塑组合物特别适于生产其中要求所用塑料满足涉及流动行为和抗应力开裂性的特别高的限制的薄壁模塑物品(例如用于数据处理元件的居室部件)。
另一种加工形式为通过热成型由先前制备的板材或薄膜生产模塑物品。
因此,本发明也提供了根据本发明的模塑组合物在制备任何类型的、优选是上面提到的模塑物品方面的应用,以及由本发明的模塑组合物制成的模塑物品。
实施例
组分A
A
相对溶液粘度为1.252的基于双酚A的线性聚碳酸酯,粘度是以CH2Cl2为溶剂在25℃和浓度为0.5g/100ml时测定的。
A.1
相对溶液粘度为1.284的基于双酚A的线性聚碳酸酯,粘度是以CH2Cl2为溶剂在25℃和浓度为0.5g/100ml时测定的。
A.2
相对溶液粘度为1.200的基于双酚A的线性聚碳酸酯,粘度是以CH2Cl2为溶剂在25℃和浓度为0.5g/100ml时测定的。
组分B
苯乙烯/丙烯腈比为72∶28且特性粘度为0.55dl/g(于20℃在二甲基甲酰胺中测定)的苯乙烯/丙烯腈共聚物。
组分C
45重量份苯乙烯和丙烯腈以72∶28的比例的共聚物在55重量份颗粒状交联聚丁二烯橡胶(平均颗粒直径d50=0.4μm)上的接枝聚合物,通过乳液聚合生产。
组分D
组分E
作为由根据组分C的SAN接枝聚合物在水中的乳液和四氟乙烯聚合物在水中的乳液形成的凝聚混合物的四氟乙烯聚合物。混合物中接枝聚合物C与四氟乙烯聚合物E的重量比为90wt%比10wt%。四氟乙烯聚合物乳液的固体含量为60wt%,平均颗粒直径为0.05-0.5μm。SAN接枝聚合物乳液的固体含量为34wt%,平均乳胶颗粒直径为0.4μm。
E的制备
将四氟乙烯聚合物乳液(Teflon 30 N,杜邦公司)与SAN接枝聚合物C乳液混合并用占聚合物固体1.8wt%的酚类抗氧剂稳定。在85-95℃用MgSO4(泻盐)水溶液和乙酸在pH为4-5时凝聚混合物,过滤并洗涤直到基本不含电解质。然后离心除去大部分水并在100℃将混合物干燥为粉末。随后可将该粉末与另外的组分在上述设备中进行复配。
组分F
用Pural 200,一种氧化铝-氢氧化铝(Condea公司,Hamburg,德国)作为非常精细的无机化合物。产物的平均粒度为约50nm。
制备并试验本发明的模塑组合物
在3L密炼机中混合组分A-F。于260℃在Arburg 270E型注塑机中制备模塑物品。
根据ISO180 1A方法于室温在80×10×4mm3棒上测定缺口抗冲击性。
根据DIN 53 460测定Vicat B软化点。
本体温度为260℃时在80×10×4mm3棒上测试应力开裂特性。用60vol%甲苯和40vol%异丙醇的混合物作为测试介质。通过圆弧模板将试验体预拉伸并于室温存放在测试介质中5分钟,预拉伸度εx为0.2-2.4%。通过作为预拉伸度函数的断裂或裂纹形成来评价应力开裂特性。
试验材料的组成和所得数据归纳在下面的表1中。
从该表可见与不含任何非常精细的无机粉末(组分F)的模塑组合物相比,本发明的模塑组合物具有非常好的机械性能、特别是出人意料的抗应力开裂性的改进和阻燃性的组合。
表1 聚碳酸酯/ABS模塑组合物的组成和性能
实施例 | 1对比例 | 2对比例 | 3本发明 |
组分(重量份)AA1A2BCDEF脱模剂 | 79--555.53-0.5 | -4930555.53-0.5 | -4930555.531.00.5 |
ηrel | 1.252 | 1.252 | 1.252 |
性能:Vicat/B120(℃)缺口抗冲击性:(kJ/m2) | 11444 | 11546 | 11546 |
侯化龟裂筛选5min/1.0%侯化龟裂筛选5min/0.8%侯化龟裂筛选5min/0.6%侯化龟裂筛选5min/0.4% | BR3:14KR | BR5:00KR+OR | BR5∶00KR+OR |
MVI240℃/5kgml/10min | 16.0 | 16.4 | 16.6 |
燃烧性能UL 94V(1.6mm) | V-2 | nb* | V-0 |
*nb=不阻燃
Claims (15)
1.阻燃的热塑性模塑组合物,包含
A.5-95重量份的具有不同溶液粘度的两种芳族聚碳酸酯A.1和A.2的混合物,其中
1.A.1的相对溶液粘度为1.18-1.24,
2.A.2的相对溶液粘度为1.24-1.34并且
3.A.1和A.2的相对溶液粘度的差等于或大于0.06,A.1和A.2的粘度是以CH2Cl2为溶剂在25℃和浓度为0.5g/100ml时测定的,
B.0-50重量份由一种或至少两种烯键式不饱和单体组成的(共)聚合物,所述烯键式不饱和单体选自苯乙烯、α-甲基苯乙烯、环取代苯乙烯、丙烯腈、甲基丙烯腈、甲基丙烯酸甲酯、马来酸酐、N-取代马来酰亚胺和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯,
C.0.5-60重量份接枝聚合物,由选自氯丁二烯、1,3-丁二烯、异戊二烯、苯乙烯、丙烯腈、乙烯、丙烯、乙酸乙烯酯和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯的至少两种单体接枝聚合而获得,
其中
R1、R2、R3和R4彼此独立地代表任选卤代的C1-C8-烷基,或C5-C6-环烷基、C6-C20-芳基或C7-C12-芳烷基,每个基团任选可被卤素和/或C1-C4-烷基取代,
n彼此独立地代表0或1,
N为0-30且
X代表含有6-30个碳原子的单或多核芳族基团,
E.0.05-5重量份氟代聚烯烃,
F.就每100重量份A-E而言0.01-50重量份平均颗粒直径小于或等于200nm的无机化合物,该无机化合物选自SnO2,ZnO,Al2O3,AlO(OH),Sb2O3,SiO2,硼酸锌,Na2SO4,氧化钒和硅酸盐。
2.根据权利要求1的模塑组合物,其特征在于式(I)中N具有0.3-20的值。
3.根据权利要求1的模塑组合物,其中组分B为一种或至少两种选自苯乙烯、α-甲基苯乙烯、环取代苯乙烯、丙烯腈、甲基丙烯腈、甲基丙烯酸甲酯、马来酸酐、N-取代马来酰亚胺和醇组分中含有1-18个碳原子的(甲基)丙烯酸酯的烯键式不饱和单体的(共)聚合物。
4.根据权利要求1的模塑组合物,其中式(I)中R1、R2、R3和R4彼此独立地代表C1-C4-烷基或苯基、萘基或苯基-C1-C4-烷基,每个基团任选可被卤素和/或烷基取代,并且X衍生自任选是氯代或溴代的选自双酚A、间苯二酚或氢醌的双酚。
5.根据权利要求1的模塑组合物,其中式(I)中的磷化合物选自三丁基磷酸酯、三-(2-氯乙基)-磷酸酯、三-(2,3-二溴丙基)-磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、二苯基甲苯基磷酸酯、二苯基辛基磷酸酯、二苯基-2-乙基甲苯基磷酸酯、三-(异丙基苯基)-磷酸酯、卤素取代的芳基磷酸酯、甲基膦酸二甲基酯、甲基膦酸二苯基酯、苯基膦酸二乙基酯、三苯基氧化膦、三甲苯基氧化膦和/或间亚苯基-双(二苯基)磷酸酯。
6.根据权利要求1的模塑组合物,其中聚四氟乙烯、聚偏二氟乙烯、四氟乙烯/六氟乙烯和/或乙烯/四氟乙烯共聚物用作氟代聚烯烃E。
7.根据权利要求1的模塑组合物,该组合物包括元素周期表1-5主族和1-8副族的元素与至少一种选自氧、硫、硼、碳、磷、氮、氢或硅的元素的化合物作为组分F。
8.根据权利要求1的模塑组合物,其中组分F选自TiN,TiO2,SnO2,WC,ZnO,Al2O3,AlO(OH),ZrO2,Sb2O3,SiO2,硼酸锌,Na2SO4,BaSO4,氧化钒和/或硅酸盐。
9.根据权利要求1的模塑组合物,其中组分F的平均颗粒直径小于或等于150nm。
10.根据权利要求1-9中之一的模塑组合物,其特征在于相对于总模塑组合物,它们包含0.01-20wt%不同于组分D的至少一种另外的阻燃剂。
11.根据权利要求1-9之一的模塑组合物,该组合物包含10-90重量份组分A)、任选2-30重量份组分B)、1-40重量份组分C)和1-18重量份组分D)、0.1-1重量份组分E)和0.1-10重量份组分F)。
12.根据权利要求1-9之一的模塑组合物,该组合物包含二烯橡胶、丙烯酸酯橡胶、硅橡胶或乙烯/丙烯/二烯橡胶作为接枝基体。
13.根据权利要求1-9之一的模塑组合物,该组合物包含至少一种来自稳定剂、颜料、脱模剂、流动促进剂和/或抗静电剂的添加剂。
14.根据权利要求1-9之一的模塑组合物在生产模塑物品方面的应用。
15.由根据权利要求1-9之一的模塑组合物制成的模塑物品。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19734666A DE19734666A1 (de) | 1997-08-11 | 1997-08-11 | Flammwidrige Polycarbonat-ABS-Formmassen |
DE19734666.9 | 1997-08-11 |
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CN1266454A CN1266454A (zh) | 2000-09-13 |
CN1122082C true CN1122082C (zh) | 2003-09-24 |
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CN98808057A Expired - Lifetime CN1122082C (zh) | 1997-08-11 | 1998-07-29 | 阻燃的聚碳酸酯/abs模塑组合物 |
Country Status (13)
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US (2) | US6254968B1 (zh) |
EP (1) | EP1003817B1 (zh) |
JP (1) | JP4221146B2 (zh) |
KR (1) | KR100560040B1 (zh) |
CN (1) | CN1122082C (zh) |
AU (1) | AU9255798A (zh) |
BR (1) | BR9811893A (zh) |
CA (1) | CA2300215C (zh) |
DE (2) | DE19734666A1 (zh) |
ES (1) | ES2238766T3 (zh) |
HK (1) | HK1030961A1 (zh) |
TW (1) | TW473500B (zh) |
WO (1) | WO1999007791A1 (zh) |
Families Citing this family (16)
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DE19828536A1 (de) * | 1998-06-26 | 1999-12-30 | Bayer Ag | Flammwidrige Polycarbonat/ABS-Formmassen |
DE19853105A1 (de) | 1998-11-18 | 2000-05-25 | Bayer Ag | Flammwidrige Polycarbonat-ABS-Formmassen |
DE19904392A1 (de) * | 1999-02-04 | 2000-08-10 | Bayer Ag | Polycarbonat-Formmassen mit verbesserten antistatischen Eigenschaften |
DE19907831A1 (de) * | 1999-02-24 | 2000-08-31 | Bayer Ag | Flammwidrige thermoplastische Formmasse |
AU5525000A (en) * | 1999-06-11 | 2001-01-02 | Dr. Ing H.C.F. Porsche Aktiengesellschaft | Wheel for a motor vehicle |
DE19941824A1 (de) * | 1999-09-02 | 2001-03-08 | Bayer Ag | Flammwidrige Polycarbonat-Blends |
KR100611448B1 (ko) * | 1999-12-30 | 2006-08-09 | 제일모직주식회사 | 폴리카보네이트/스티렌계 수지 조성물 |
KR100611441B1 (ko) * | 1999-12-30 | 2006-08-09 | 제일모직주식회사 | 폴리카보네이트/스티렌계 수지 조성물 |
AU2012206982B2 (en) * | 2003-01-16 | 2013-12-05 | Viva Healthcare Packaging Limited | Methods, compositions and blends for forming articles having improved environmental stress crack resistance |
JP4943835B2 (ja) * | 2003-01-16 | 2012-05-30 | オード マイケル ヤコブズ イアン | 優れた耐環境応力亀裂性を持つ物品を形成するための方法、組成物及びブレンド |
US20070149661A1 (en) * | 2005-12-23 | 2007-06-28 | Sanjay Gurbasappa Charati | Polycarbonate composition, method of manufacture thereof and articles comprising the same |
KR100722146B1 (ko) | 2005-12-30 | 2007-05-28 | 제일모직주식회사 | 압출가공성 및 내열습성이 우수한 난연성 폴리카보네이트계열가소성 수지 조성물 |
EP2147046B1 (de) * | 2007-05-04 | 2013-07-03 | Sachtleben Chemie GmbH | Bariumsulfat enthaltender kunststoff |
CN102936402A (zh) * | 2011-08-15 | 2013-02-20 | 上海金发科技发展有限公司 | 一种低烟耐热无卤阻燃聚碳酸脂/丙烯腈-丁二烯-苯乙烯树脂组合物及其制备方法 |
KR102464098B1 (ko) * | 2017-02-10 | 2022-11-07 | 이네오스 스티롤루션 그룹 게엠베하 | 높은 표면 에너지를 가진 아크릴로니트릴―부타디엔―스티렌 공중합체 조성물 |
US11732130B2 (en) * | 2019-12-04 | 2023-08-22 | Covestro Intellectual Property Gmbh & Co. Kg | Flame retardant impact-modified polycarbonate composition |
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US3166606A (en) * | 1960-12-28 | 1965-01-19 | Union Carbide Corp | Polycarbonate resins having improved flow properties |
DE2729763A1 (de) * | 1977-07-01 | 1979-01-18 | Bayer Ag | Thermoplastisch verarbeitbare polycarbonatmischungen |
EP0174493B1 (de) * | 1984-08-17 | 1988-05-25 | Bayer Ag | Thermoplastische Formmassen mit flammwidrigen Eigenschaften |
US5204394A (en) * | 1988-09-22 | 1993-04-20 | General Electric Company | Polymer mixture having aromatic polycarbonate, styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
JPH0619007B2 (ja) * | 1989-03-27 | 1994-03-16 | 帝人化成株式会社 | 難燃性ポリカーボネート樹脂組成物 |
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DE19538892A1 (de) * | 1995-10-19 | 1997-04-24 | Bayer Ag | Flammgeschützte, spannungsrißbeständige Polycarbonat/ABS-Blends |
SG69988A1 (en) | 1995-11-01 | 2000-01-25 | Gen Electric | Flame retardant polycarbonate/graft blends exhibiting heat aging stability |
DE19545289A1 (de) * | 1995-12-05 | 1997-06-12 | Bayer Ag | Thermoplastische Massen mit verbessertem Röntgenkontrast |
FR2744947B1 (fr) | 1996-02-19 | 1998-04-03 | Allibert Ind | Procede d'habillage, par une feuille, d'une piece injectee, moule pour la mise en oeuvre du procede et piece obtenue |
DE19622499A1 (de) | 1996-06-05 | 1997-12-11 | Otto Deuschle Modell Und Forme | Kunststoff-Formteil mit mehreren Feldern sowie Verfahren und Vorrichtung zu dessen Herstellung |
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-
1997
- 1997-08-11 DE DE19734666A patent/DE19734666A1/de not_active Withdrawn
-
1998
- 1998-07-20 US US09/485,518 patent/US6254968B1/en not_active Expired - Fee Related
- 1998-07-27 TW TW087112205A patent/TW473500B/zh not_active IP Right Cessation
- 1998-07-29 BR BR9811893-5A patent/BR9811893A/pt not_active IP Right Cessation
- 1998-07-29 CN CN98808057A patent/CN1122082C/zh not_active Expired - Lifetime
- 1998-07-29 WO PCT/EP1998/004731 patent/WO1999007791A1/de active IP Right Grant
- 1998-07-29 JP JP2000506282A patent/JP4221146B2/ja not_active Expired - Fee Related
- 1998-07-29 ES ES98945108T patent/ES2238766T3/es not_active Expired - Lifetime
- 1998-07-29 CA CA2300215A patent/CA2300215C/en not_active Expired - Fee Related
- 1998-07-29 EP EP98945108A patent/EP1003817B1/de not_active Expired - Lifetime
- 1998-07-29 DE DE59812563T patent/DE59812563D1/de not_active Expired - Lifetime
- 1998-07-29 AU AU92557/98A patent/AU9255798A/en not_active Abandoned
- 1998-07-29 US US09/485,100 patent/US6444735B1/en not_active Expired - Lifetime
- 1998-07-29 KR KR1020007001364A patent/KR100560040B1/ko not_active IP Right Cessation
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2001
- 2001-03-12 HK HK01101776A patent/HK1030961A1/xx unknown
Also Published As
Publication number | Publication date |
---|---|
JP4221146B2 (ja) | 2009-02-12 |
AU9255798A (en) | 1999-03-01 |
TW473500B (en) | 2002-01-21 |
KR100560040B1 (ko) | 2006-03-13 |
BR9811893A (pt) | 2000-08-22 |
EP1003817B1 (de) | 2005-02-09 |
CN1266454A (zh) | 2000-09-13 |
HK1030961A1 (en) | 2001-05-25 |
WO1999007791A1 (de) | 1999-02-18 |
CA2300215C (en) | 2011-04-26 |
KR20010022764A (ko) | 2001-03-26 |
EP1003817A1 (de) | 2000-05-31 |
JP2001512774A (ja) | 2001-08-28 |
US6254968B1 (en) | 2001-07-03 |
ES2238766T3 (es) | 2005-09-01 |
DE19734666A1 (de) | 1999-02-18 |
CA2300215A1 (en) | 1999-02-18 |
US6444735B1 (en) | 2002-09-03 |
DE59812563D1 (de) | 2005-03-17 |
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