CN1159374C - 阻燃聚碳酸酯/abs模塑组合物 - Google Patents
阻燃聚碳酸酯/abs模塑组合物 Download PDFInfo
- Publication number
- CN1159374C CN1159374C CNB998079308A CN99807930A CN1159374C CN 1159374 C CN1159374 C CN 1159374C CN B998079308 A CNB998079308 A CN B998079308A CN 99807930 A CN99807930 A CN 99807930A CN 1159374 C CN1159374 C CN 1159374C
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- China
- Prior art keywords
- weight part
- alkyl
- moulding compound
- preferred
- component
- 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.)
- Expired - Lifetime
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 23
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title abstract description 6
- 238000000465 moulding Methods 0.000 title abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- -1 poly terephthalic acid alkane diol ester Chemical class 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 239000000206 moulding compound Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 229920001169 thermoplastic Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 239000005060 rubber Substances 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920002943 EPDM rubber Polymers 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 229920001084 poly(chloroprene) Polymers 0.000 claims 1
- 239000004945 silicone rubber Substances 0.000 claims 1
- 150000003673 urethanes Chemical class 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 25
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 150000001263 acyl chlorides Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 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 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- 238000012662 bulk polymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical group 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical class O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 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
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical class COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-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
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-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
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- KYGLCUAXJICESS-UHFFFAOYSA-N 2-[2,3-di(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC=CC(C=2C(=CC=CC=2)O)=C1C(C)C KYGLCUAXJICESS-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
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- 230000005501 phase interface Effects 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
- 229960001553 phloroglucinol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000004713 phosphodiesters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- GFKSKVCFBACPGK-UHFFFAOYSA-N terephthalic acid;hydrochloride Chemical compound Cl.OC(=O)C1=CC=C(C(O)=O)C=C1 GFKSKVCFBACPGK-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical compound C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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Abstract
本发明涉及加入了磷腈和磷化合物的聚碳酸酯/ABS模塑材料,它们具有优异防火保护品质以及非常好的机械性能,如熔合线强度或冲击强度。
Description
技术领域
本发明涉及加入了磷腈和磷化合物的聚碳酸酯/ABS模塑组合物,该组合物表现出优异防燃以及非常好的机械性能,如熔合线强度或缺口冲击强度。
背景技术
DE-A 196 16 968描述了一种可聚合的磷腈衍生物、其生产方法及其作为可固化基料用于清漆、涂料、填料、敷面组合物、胶粘剂、模塑件或薄膜方面的应用。
WO 97/400 92描述了一种防燃模塑组合物,由热塑性聚合物和未取代的磷腈(PNn-xH1-y型)制成。
EP-A 728 811描述了一种热塑性共混物,由芳族聚碳酸酯、接枝共聚物、共聚物和磷腈组成,表现出优良防燃性能、冲击强度以及耐热。
无论WO 97400 92抑或EP-A 728 811均未描述磷腈和磷化合物的组合。
发明内容
本发明的目的是提供一种聚碳酸酯/ABS模塑组合物,它具有优异防燃及熔合线强度以及极佳机械性能,如缺口冲击强度及耐应力龟裂。此种等级的性能乃是数据处理用途特别要求的,例如制作显示器、打印机、复印机之类的外壳。
现已发现,PC/ABS模塑组合物,当包含磷腈与磷化合物和/或磷酸盐化合物的组合时,将显示所希望的性能。
因此,本发明提供一种热塑性模塑组合物,包含:
A)40~99,优选60~98.5重量份芳族聚碳酸酯和/或聚酯碳酸酯
B)0.5~60,优选1~40,尤其是2~25重量份接枝聚合物,由下列组成,
B.1)5~95,优选30~80wt%1种或多种乙烯基单体,接枝到
B.2)95~5,优选20~70wt%1种或多种接枝主链上,该主链的玻璃化转变温度小于10℃,优选小于0℃,尤其优选小于-20℃,
C)0~45,优选0~30,尤其优选2~25重量份至少1种热塑性聚合物,选自乙烯基(共)聚合物和聚对苯二甲酸链烷二醇酯,
D)0.1~50,优选2~35,尤其是5~25重量份至少1种下列通式磷腈的组分
其中
R每种情况可相同或不同,代表氨基,每种情况下任选被卤化、优选被氟所卤化的C1~C8烷基或C1~C8烷氧基,每种情况下任选地被烷基,优选C1~C4烷基和/或卤素,优选氯和/或溴取代的C5~C6环烷基、C6~C20芳基,优选苯基或萘基,C6~C20芳氧基,优选苯氧基、萘氧基,或者C7~C12芳烷基,优选苯基-C1~C4-烷基,
k代表0或者1~15的数,优选1~10的数,
E)0.5~20重量份,优选1~18重量份,尤其优选2~15重量份至少1种选自通式(IIa)、(IIb)、(IIc)和(IId)的磷化合物,
其中R1、R2、R3和R4彼此独立地代表每种情况下任选地被卤化的C1~C8烷基,每种情况任选地被烷基,优选C1~C4烷基和/或卤素,优选氯、溴取代的C5~C6环烷基,C6~C20芳基或C7~C12芳烷基,
n彼此独立地代表0或1,
N代表0~30,以及
X代表单-或多环6~30个碳原子的芳族残基,
其中
R5及R6彼此独立地代表任选卤代的C1~C24烷基,每种情况任选被卤素和/或C1~C10烷基取代的C5~C6环烷基、C6~C20芳基或C7~C12芳烷基,
R5和R6在通式(IId)的情况下构成烷基链,优选具有最多6,尤其是2或3个碳原子,
Me代表金属,选自周期表主族1~3及副族VIII、1B及2B,以及
q取决于金属离子的化合价,
F)0~5,优选0.1~1,尤其优选0.1~0.5重量份氟化聚烯烃。
组分A
适合本发明的组分A芳族聚碳酸酯和/或芳族聚酯碳酸酯在文献中是已知的,或者可采用由文献已知的方法制备(关于芳族聚碳酸酯的制备可参见,例如Schnell,《聚碳酸酯化学及物理》,国际科学出版社,1964,以及DE-AS 1 495 626、DE-OS 2 232 877、DE-OS 2 703376、DE-OS 2 714 544、DE-OS 3 000 610、DE-OS 3 832 396;关于芳族聚酯碳酸酯的制备,例如参见DE-OS 3 077 934)。
芳族聚碳酸酯的制备例如可通过二酚与碳酰卤,优选光气,和/或与芳族二羧酸二酰卤,优选苯二羧酸的二酰卤,按照相界面法,任选地采用链终止剂,例如一元酚,并任选地采用三官能或三官能以上的支化剂,例如三酚或四酚,来实施。
用于制备芳族聚碳酸酯和/或芳族聚酯碳酸酯的二酚优选是通式(III)的那些:
其中
A代表单键、C1~C5亚烷基、C2~C5-(1,1-)亚烷基、C5~C6环-(1,1-)亚烷基、-O-、-SO-、-CO-、-S-、-SO2-、C6~C12亚芳基,其上还可进一步稠合任选包含杂原子的芳环,
或者通式(IV)或(V)的残基
B每种情况代表C1~C12烷基,优选甲基、卤素,优选氯和/或溴
x每种情况彼此独立地代表0、1或2,
p代表1或0,以及
R7和R8,就每个X1而言可彼此独立、单独地选择,代表氢或C1~C6烷基,优选氢、甲基或乙基,
X1代表碳,以及
m代表4~7的整数,优选4或5,条件是R7和R8在至少1个原子X1上同时是烷基。
优选的二酚是氢醌、间苯二酚、二羟基联苯酚、双(羟苯基)-C1~C5-链烷、双(羟苯基)-C5~C6-环烷、双(羟苯基)醚、双(羟苯基)亚砜、双(羟苯基)甲酮、双(羟苯基)砜以及α,α-双(羟苯基)二异丙基苯及其环上溴代和/或环上氯代的衍生物。
具体优选的二酚是4,4’-二羟基联苯、双酚A、2,4-双(4-羟苯基)-2-甲基丁烷、1,1-双(4-羟苯基)环己烷、1,1-双(4-羟苯基)-3,3,5-三甲基环己烷、4,4’-二羟基二苯硫醚、4,4’-二羟基二苯砜及其二-及四溴化或氯化衍生物,例如2,2-双(3-氯-4-羟苯基)丙烷、2,2-双(3,5-二氯-4-羟苯基)丙烷或2,2-双(3,5-二溴-4-羟苯基)丙烷。
2,2-双(4-羟苯基)丙烷(双酚A)是尤其优选的。
二酚可以单独地或者以任何希望的混合物形式使用。
该二酚系文献中已知的或者可采用文献中已知的方法制取。
适合制备热塑性芳族聚碳酸酯的链终止剂例如是苯酚、对氯酚、对叔丁基酚或2,4,6-三溴酚,以及长链烷基酚,例如按照DE-OS 2 842005公开的4-(1,3-四甲基丁基)-酚;或者是烷基取代基中总共有8~20个碳原子的单烷基酚或二烷基酚,例如,3,5-二叔丁基酚、对异辛基酚、对叔辛基酚、对十二烷基酚以及2-(3,5-二甲基庚基)酚以及4-(3,5-二甲基庚基)酚。链终止剂的用量,以每种情况使用的二酚总摩尔数为基准,一般介于0.5mol%~10mol%。
热塑性芳族聚碳酸酯的重均分子量(Mw,例如按超离心或光散射测定)介于10000~200000,优选20000~80000。
热塑性芳族聚碳酸酯可按照已知方式实现支化,尤其优选通过加入以使用的二酚总摩尔数为基准0.05~2.0mol%三官能或三官能以上的化合物,例如具有3或大于3个酚基团的那些。
均聚碳酸酯及共聚碳酸酯都适用。本发明组分A共聚碳酸酯的制备中还可使用1~25wt%,优选2.5~25wt%(相对于二酚总用量)具有羟基-芳氧端基的聚二有机硅氧烷。它们是已知的(例如参见美国专利3 419 634)或者可采用文献中已知的方法制备。含聚二有机硅氧烷的共聚碳酸酯的制备例如描述在DE-OS 3 334 782中。
除了双酚A均聚碳酸酯之外,优选的聚碳酸酯还有双酚A与最高15mol%,相对于二酚总摩尔数而言,其他作为优选或尤其优选的二酚,特别是与2,2-双(3,5-二溴-4-羟苯基)丙烷生成的共聚碳酸酯。
用于制备芳族聚酯碳酸酯的芳族二羧酸二酰卤优选是间苯二甲酸、对苯二甲酸、二苯醚4,4’-二羧酸以及2,6-萘二羧酸等的二酰氯。
间苯二甲酸的和对苯二甲酸的二酰氯按1∶20~20∶1比例的混合物是尤其优选的。
另外还使用碳酰卤,优选光气,作为聚酯碳酸酯制备中的二官能酸衍生物。
除了上面提到的一元酚之外,还可考虑用于制备芳族聚酯碳酸酯的链终止剂包括其氯代碳酸酯以及芳族单羧酸的酰氯,其上可任选地取代上C1~C22烷基基团或者卤素原子,还包括脂族C2~C22单羧酸的酰氯。
每种情况下链终止剂的用量均为0.1~10mol%,其中在酚类链终止剂的情况下以二酚摩尔数为基准,而在单羧酸酰氯链终止剂的情况下则以二羧酸二酰氯摩尔数为基准。
芳族聚酯碳酸酯还可包含结合的芳族羟基羧酸。
芳族聚酯碳酸酯可以是线型或者是按已知方法支化的(关于这一点还可参见DE-OS 2 940 024和DE-OS 3 007 934)。
可使用的支化剂例如是三-或多官能羧酸酰氯,例如1,3,5-苯三酸三酰氯、氰尿酸三酰氯、3,3’-,4,4’-二苯酮四羧酸四酰氯、1,4,5,8-萘四羧酸四酰氯或1,2,4,5-苯四酸四酰氯,其用量介于0.01~1.0mol%(相对于二羧酸二酰氯用量而言),或者三-或多官能酚,例如间苯三酚、4,6-二甲基-2,4,6-三(4-羟苯基)-2-庚烯、4,4-二甲基-2,4,6-三(4-羟苯基)庚烷、1,3,5-三(4-羟苯基)苯、1,1,1-三(4-羟苯基)乙烷、三(4-羟苯基)苯基甲烷、2,2-双[4,4-双(4-羟苯基)环己基]丙烷、2,4-双(4-羟苯基异丙基)苯酚、四(4-羟苯基)甲烷、2,6-双(2-羟基-5-甲基苄基)-4-甲基苯酚、2-(4-羟苯基)-2-(2,4-二羟基苯基)丙烷、四(4-[4-羟苯基异丙基]苯氧基)甲烷、1,4-双[4,4’-二羟基三苯基)甲基]苯,其用量介于0.01~1.0mol%,以二酚用量为基准。酚类支化剂可在开始时随同二酚一起引入;酰氯支化剂可随同二酰氯一起引入。
碳酸酯结构单元在热塑性芳族聚酯碳酸酯中的比例可任意改变。碳酸酯基团的比例优选最高100mol%,尤其是最高80mol%,尤其优选最高50mol%,以酯基团与碳酸酯基团总和为基准。芳族聚酯碳酸酯的酯及碳酸酯部分皆可以嵌段形式存在,或者无规地分布在该缩聚产物中。
芳族聚碳酸酯及聚酯碳酸酯的溶液相对粘度(ηrel)介于1.18~1.4,优选1.22~1.3(0.5g聚碳酸酯或聚酯碳酸酯在100mL二氯甲烷中的溶液,在25℃测定)。
热塑性芳族聚碳酸酯和聚酯碳酸酯可单独或者以任何希望的彼此混合物形式使用。
组分B
组分B包含1种或多种接枝共聚物,由下列构成:
B.1)5~95,优选30~80wt%至少1种乙烯基单体,接枝到
B.2)95~5,优选70~20wt%1种或多种接枝主链上,该主链玻璃化转变温度小于10℃,优选小于0℃,尤其优选小于-20℃。
接枝主链B.2的平均粒度(d50值)通常介于0.05~5μm,优选0.10~0.5μm,尤其优选0.20~0.40μm。
单体B.1优选是下列组分的混合物:
B.1.1 50~99重量份乙烯基芳烃和/或环上取代的乙烯基芳烃(例如苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯)和/或甲基丙烯酸(C1~C4)-烷基酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯),以及
B.1.2 1~50重量份乙烯基氰化物(不饱和腈,例如丙烯腈及甲基丙烯腈)和/或(甲基)丙烯酸(C1-C8)-烷基酯(例如,甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和/或不饱和羧酸衍生物(例如酸酐及酰亚胺)(例如马来酐及N-苯基马来酰亚胺)。
优选的单体B.1.1选自单体苯乙烯、α-甲基苯乙烯和甲基丙烯酸甲酯中的至少1种;优选的单体B.1.2选自单体丙烯腈、马来酐和甲基丙烯酸甲酯中的至少1种。
尤其优选的单体是B.1.1苯乙烯和B.1.2丙烯腈。
适合用于接枝聚合物B的接枝主链B.2例如是二烯橡胶,EP(D)M橡胶,即,以乙烯/丙烯为基础,任选加入二烯的橡胶;丙烯酸酯、聚氨酯、硅氧烷、氯丁二烯及乙烯/醋酸乙烯等橡胶。
优选的接枝主链B.2是二烯橡胶(例如以丁二烯、异戊二烯等为基础的橡胶)或二烯橡胶的混合物或二烯橡胶的共聚物或者它们与其他可共聚单体(例如,符合B.1.1及B.1.2的那些)的混合物,条件是,组分B.2的玻璃化转变温度小于10℃,优选小于0℃,尤其优选小于-10℃。
纯聚丁二烯橡胶尤其优选。
尤其优选的聚合物B例如是ABS聚合物(乳液、本体及悬浮ABS),例如描述在DE-OS 2 035 390(=US-PS 3 644 574)或者DE-OS 2 248242(=GB-PS 1 409 275)中,或者Ulmann著《技术化学大全》,卷19(1980),pp.280起。接枝主链B2的凝胶含量至少是30wt%,优选至少40wt%(在甲苯中测定)。
接枝共聚物B系采用自由基聚合制备的,例如采用乳液、悬浮、溶液或本体聚合,优选采用乳液聚合。
特别合适的的接枝橡胶是,按照US-P 4 937 285,采用包含有机氢过氧化物和抗坏血酸的引发剂体系通过氧化还原引发制备的ABS聚合物。
众所周知,鉴于接枝单体不一定在接枝反应期间全部接枝到接枝主链上,因此,接枝聚合物B,按照本发明也理解为,包括那些接枝单体在接枝主链存在下(共)聚合获得的、又经过在后加工期间分离出来的产物。
合适的聚合物B的丙烯酸酯橡胶B.2优选是由丙烯酸烷基酯,任选地与最高相当于B.2的40wt%其他可聚合的、烯键不饱和的单体制备的聚合物。优选的可聚合丙烯酸烷基酯包括C1~C8烷基酯,例如甲基、乙基、丁基、正辛基及2-乙基己基的酯,卤化烷基酯,优选卤代C1~C8-烷基酯,例如丙烯酸氯代乙基酯以及这些单体的混合物。
具有多于1个可聚合双键的单体也可参与共聚,以便产生交联。交联(作用)单体的优选例子是3~8个碳原子不饱和单羧酸的酯及3~12个碳原子的不饱和单羟基醇或者2~20个碳原子、有2~4羟基的饱和多元醇,例如二甲基丙烯酸乙二醇酯、甲基丙烯酸烯丙基酯;多不饱和杂环化合物,例如三乙烯基及三烯丙基的氰尿酸酯;多官能乙烯基化合物,例如二-及三乙烯基苯;以及磷酸三烯丙基酯和邻苯二甲酸二烯丙基酯。
优选的交联单体是甲基丙烯酸烯丙基酯、二甲基丙烯酸乙二醇酯、邻苯二甲酸二烯丙基酯及具有至少3个烯键不饱和基团的杂环化合物。
尤其优选的交联单体是环状单体氰尿酸三烯丙基酯、异氰尿酸三烯丙基酯、三丙烯酰六氢-s-三嗪、三烯丙基苯。交联单体的用量优选介于0.02~5,尤其0.05~2wt%,以接枝主链B.2为基准。
有利的是,将具有至少3个烯键不饱和基团的环状交联单体数量限制在低于接枝主链B.2的1wt%的水平。
除丙烯酸酯以外,可任选用于制备接枝主链B.2的“其他”优选的可聚合的烯键不饱和的单体例如是,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。优选作为接枝主链B.2的丙烯酸酯橡胶是凝胶含量至少为60wt%的乳液聚合物。
另一类合适的接枝主链B.2是具有活性交联部位的硅橡胶,例如描述在DE-OS 3 704 657、DE-OS 3 704 655、DE-OS 3 631 540及DE-OS 3 631 539中。
接枝主链B.2的凝胶含量,是在适当溶剂中于25℃测定的(M.Hoffmann,H.Krmer,R.Kuhn,《聚合物分析学》卷I和II,GeorgThieme出版社,斯图加特1977)。
平均粒度d50是这样一种颗粒直径,小于和大于该直径的颗粒各占50wt%。该数值可采用超离心法测定(W.Scholtan,H.Lange,《胶体及聚合物杂志》250(1972),782~1796)。
组分C
组分C包含1种或多种热塑性乙烯基(共)聚合物C.1和/或聚对苯二甲酸链烷二醇酯C.2。
合适的乙烯基(共)聚合物C.1是至少1种下列单体的聚合物:乙烯基芳烃、乙烯基氰化物(不饱和腈)、(甲基)丙烯酸(C1~C8)-烷基酯、不饱和羧酸及不饱和羧酸的衍生物(例如酸酐及酰亚胺)。尤其合适的(共)聚合物是由下列单体制备的那些:
C.1.1 50~99,优选60~80重量份乙烯基芳烃和/或环上取代的乙烯基芳烃(例如苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯)和/或甲基丙烯酸(C1~C8)-烷基酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯)以及
C.1.2 1~50,优选20~40重量份乙烯基氰化物(不饱和腈),例如丙烯腈及甲基丙烯腈,和/或(甲基)丙烯酸(C1~C8)-烷基酯(例如,甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和/或不饱和羧酸(例如马来酸)和/或不饱和羧酸的衍生物(例如酸酐及酰亚胺)(例如马来酐及N-苯基马来酰亚胺)。
(共)聚合物C.1是树脂状热塑性的且不含橡胶。
C.1.1苯乙烯和C.1.2丙烯腈的共聚物是尤其优选的。
(共)聚合物C.1是已知的,可通过自由基聚合,特别是乳液、悬浮、溶液或本体聚合来制备。该(共)聚合物的分子量Mw(重均,按光散射或沉降法测定)介于15000~200000。
组分C.2聚对苯二甲酸链烷二醇酯是芳族二羧酸或其活性衍生物如二甲酯或酸酐,与脂族、环脂族或芳脂族二醇的反应产物,乃至这类反应产物的混合物。
优选的聚对苯二甲酸链烷二醇酯包含,相对于二羧酸组分至少80wt%,优选至少90wt%对苯二甲酸残基,以及相对于二醇组分至少80wt%,优选至少90wt%乙二醇和/或1,4-丁二醇残基。
除了对苯二甲酸残基之外,优选的聚对苯二甲酸链烷二醇酯可包含最高20mol%,优选最高10mol%8~14个碳原子的其他芳族或环脂族二羧酸或4~12个碳原子脂族二羧酸的残基,例如邻苯二甲酸、间苯二甲酸、2,6-萘二羧酸、4,4’-联苯二羧酸、琥珀酸、己二酸、癸二酸、壬二酸、环己烷二乙酸等的残基。
除了乙二醇或1,4-丁二醇残基之外,优选的聚对苯二甲酸链烷二醇酯还可包含最高20mol%,优选最高10mol%其他3~12个碳原子的脂族二醇或6~21个碳原子的环脂族二醇,例如下列的残基:1,3-丙二醇、2-乙基-1,3-丙二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、1,4-环己烷二甲醇、3-乙基-2,4-戊烷二醇、2-甲基-2,4-戊烷二醇、2,2,4-三甲基-1,3-戊烷二醇、2-乙基-1,3-己二醇、2,2-二乙基-1,3-丙二醇、2,5-己二醇、1,4-二(β-羟乙氧基)苯、2,2-双(4-羟基环己基)丙烷、2,4-二羟基-1,1,3,3-四甲基环丁烷、2,2-双(4-β-羟基乙氧基苯基)丙烷以及2,2-双(4-羟基丙氧基苯基)丙烷(DE-OS 2407 674、2 407 776、2 715 932)。
该聚对苯二甲酸链烷二醇酯可通过加入较少量三-或四羟基醇或三-或四元羧酸达到支化,例如按照DE-OS 1900 270及US-PS 3 692744的方法。另一些优选的支化剂是1,3,5-苯三酸、1,2,4-苯三酸、三羟甲基乙烷及三羟甲基丙烷以及季戊四醇。
尤其优选的聚对苯二甲酸链烷二醇酯是那些仅由对苯二甲酸及其活性衍生物(例如,其二烷基酯)与乙二醇和/或1,4-丁二醇制备的,以及此类聚对苯二甲酸链烷二醇酯的混合物。
聚对苯二甲酸链烷二醇酯的混合物包含1~50wt%,优选1~30wt%聚对苯二甲酸乙二醇酯以及50~99wt%,优选70~99wt%聚对苯二甲酸丁二醇酯。
优选使用的聚对苯二甲酸链烷二醇酯的特性粘度一般介于0.4~1.5dl/g,优选0.5~1.2dl/g,用乌氏粘度计在25℃苯酚/邻二氯苯(1∶1重量比)中测定。
聚对苯二甲酸链烷二醇酯可采用已知的方法制备(例如参见《塑料手册》卷VIII,pp.695起,Carl Hanser出版社,慕尼黑1973)。
组分D
本发明使用的组分D磷腈是通式(Ia)的线型磷腈及通式(Ib)的环状磷腈
其中k和R的含义与上面相同。
可举出如下例子:丙氧基磷腈、苯氧基磷腈、甲基苯氧基磷腈、氨基磷腈及氟代烷基磷腈。
苯氧基磷腈是优选的。
磷腈可单独地或者以混合物形式使用。通式(Ia)和(Ib)中的残基R可总是相同,或者2个或多个残基可彼此不同。
磷腈及其制备描述在,例如EP-A 728 811、DE-A 1 961 668及WO 97/40092中。
组分E
组分E包含1种或多种上述通式(IIa)、(IIb)、(IIc)和(IId)的磷化合物或者至少1种单体-与至少1种低聚磷化合物的混合物。
通式(IIa)中的R1、R2、R3及R4的含义与上述相同。R1、R2、R3及R4优选彼此独立地代表C1~C4烷基、苯基、萘基或苯基-C1~C4-烷基。这些芳族基团R1、R2、R3及R4又可被卤素和/或烷基基团,优选氯、溴和/或C1~C4-烷基取代。尤其优选的芳基残基是甲苯基、苯基、二甲苯基、丙苯基或丁苯基及其对应的溴代或氯代衍生物。
X在通式(IIa)中代表6~30个碳原子的单-或多环芳族残基。这些残基优选由通式(III)的二酚衍生而来,例如二苯基苯酚、双酚A,或者由间苯二酚或氢醌或其溴代或氯代衍生物衍生而来。
n在通式(IIa)中可彼此独立地代表0或1,n优选等于1。
N代表0~30的数值,优选其平均值介于0.3~20,尤其优选0.5~10,特别是0.5~6。
由,按磷化合物总量计,优选10~90wt%,优选12~40wt%至少1种单磷化合物和10~90wt%,优选60~88wt%至少1种通式(IIa)的低聚磷化合物或低聚磷化合物混合物制备的混合物,尤其用作本发明的组分E。
通式(IIa)的单磷化合物具体地说是磷酸三丁酯、磷酸三(2-氯乙基)酯、磷酸三(2,3-二溴丙基)酯、磷酸三苯酯、磷酸三甲苯酯、磷酸二苯基甲苯酯、磷酸二苯基辛酯、磷酸二苯基-2-乙基甲苯酯、磷酸三(异丙基苯基)酯、磷酸卤代芳基酯、甲基膦酸二甲酯、甲基氧次膦酸二苯酯、苯基膦酸二乙酯、氧化三苯基膦或氧化三甲苯基膦。
通式(I)单体和低聚磷化合物的混合物的平均N值介于0.3~20,优选0.5~10,尤其是0.5~6。
组分E磷化合物是已知的(例如参见EP-A 363 608、EP-A 640 655)或者可利用已知方法按类似的方式制备(例如,Ullmanns,《技术化学大全》卷18,pp.301起,1979;Houben-Weyl,《有机化学方法》,卷12/1,p.43;《Beilstein》卷6,p.177)。
本发明模塑组合物可包含通式(IIb)和/或(IIc)的磷酸单酯的金属化合物,
或者通式(IId)的磷酸二酯的金属化合物作为磷化合物,
其中R5和R6、Me及q具有与上面的磷化合物中相同的含义。
R5和R6优选彼此独立地代表任选卤化的(优选由氯和/或溴卤化的)C1~C15,尤其是C1~C10-烷基每种情况可任选地被卤素(优选氯和/或溴)和/或C1~C6、尤其是C1~C4烷基、特别是甲基、乙基、正-或异丙基取代的环戊基、环己基、苯基、萘基、苯基-C1~C4-烷基(例如苄基)。
R5和R6尤其优选彼此独立地代表甲苯基、苯基、二甲苯基、丙苯基或丁苯基及其对应的溴代及氯代衍生物。
(门捷列夫)周期表主族1~3及副族VIII、IB及IIB构成合适的一类金属,其中优选主族2和3以及副族II的金属。
金属镁、钙、钡、硼、铝和锌的化合物是尤其优选的。
本发明磷酸酯金属化合物的适宜制备方法在文献中是已知的那些,例如由磷酸三酯出发的酯交换法,以及由磷酰氯出发的酰卤法(EP-A 0 801 116;《有机化学杂志》1978,卷43,第1期,pp.24~31)。
该无机反应组分优选以超细分散形式用于制备本发明的磷酸酯。其平均颗粒直径小于或等于1μm,优选小于或等于200nm。
组分F
氟化聚烯烃F为高分子量的,其玻璃化转变温度高于--30℃,通常高于100℃,氟含量优选介于65~76,尤其是70~76wt%,平均颗粒直径d50介于0.05~1000,优选0.08~20μm。氟化聚烯烃F的密度通常介于1.2~2.3g/cm3。优选的氟化聚烯烃F是聚四氟乙烯、聚偏二氟乙烯、四氟乙烯/六氟丙烯以及乙烯/四氟乙烯等共聚物。氟化聚烯烃是已知的(参见,《乙烯基及相关聚合物》,Schildknecht著,John Wiley & Sons公司,纽约,1962,pp.484~494;《氟聚合物》,Wall著,Wiley-国际科学公司,John Wiley & Sons公司,纽约,卷13,1970,pp.623~654;《当代塑料大全》,1970~1971,卷47,no.10A,1970年10月,Mc Graw-Hill公司,纽约,pp.134和774;《当代塑料大全》,1975-1976,1975年10月,卷52,no.10A,Mc Graw-Hill公司,纽约,pp.27、28及472;以及US-PS 3671 487、3 723 373及3 838 092)。
它们可采用已知方法制备,例如通过四氟乙烯在水介质中在自由基生成催化剂如过二硫酸钠、钾或铵存在下、7~71kg/cm2的压力及0~200℃的温度,优选20~100℃的温度进行聚合(进一步细节例如参见,美国专利2 393 967)。视它们使用的形式而定,这些材料的密度可介于1.2~2.3g/cm3,平均粒度介于0.5~1000μm。
本发明的优选氟化聚烯烃F是四氟乙烯聚合物,平均颗粒直径0.05~20μm,优选0.08~10μm,密度1.2~1.9g/cm3,且优选以四氟乙烯聚合物F乳液与接枝聚合物B乳剂的凝聚混合物形式使用。
可以粉末形式使用的适宜氟化聚烯烃F是平均颗粒直径100~1000μm、密度介于2.0g/cm3~2.3g/cm3的四氟乙烯聚合物。
B与F的凝聚混合物的制备是,首先将接枝聚合物B的水乳液(胶乳)与精细分散的四氟乙烯聚合物F的乳液混合;适宜四氟乙烯聚合物乳液习惯上的固体含量介于30~70wt%,尤其是50~60wt%,优选30~35wt%。
本文所述有关组分B的用量可包括由接枝聚合物与氟化聚烯烃制备的凝聚混合物中接枝聚合物的比例。
接枝聚合物B与四氟乙烯聚合物F在乳液混合物中的重量比是95∶5~60∶40。乳液聚合物随后按已知方法进行凝聚,例如通过喷雾干燥、冷冻干燥或借助加入无机或有机盐、酸、碱或有机水混溶性溶剂如醇类,酮类实现凝聚,优选在20~150℃,尤其是50~100℃的温度。需要的话,可在50~200℃,优选70~100℃进行干燥。
合适的四氟乙烯聚合物乳液是传统市售产品,例如由杜邦公司按商品名Teflon 30 N销售。
本发明的模塑组合物可包含至少1种传统添加剂,例如润滑剂和脱模剂、成核剂、抗静电剂、稳定剂以及染料和颜料。
本发明的模塑组合物可包含,相对于总模塑组合物,最高35wt%另一种任选协同的阻燃剂。可举出的另一种阻燃剂的例子是有机卤化物,例如十溴二苯醚、四溴双酚,无机卤化物如溴化铵,氮化合物如蜜胺、蜜胺甲醛树脂,无机氢氧化物如氢氧化镁、氢氧化铝,无机化合物如氧化锑、偏硼酸钡、hydroxoantimonate(羟配位锑酸)、氧化锆、氢氧化锆、氧化钼、钼酸铵、硼酸锌、硼酸铵、偏硼酸钡、滑石粉、硅酸盐、氧化硅及氧化锡,以及硅氧烷化合物。
本发明模塑组合物,其中包含组分A~F以及任选地另一些已知添加剂如稳定剂、染料、颜料、润滑剂和脱模剂、成核剂以及抗静电剂者,可通过这些具体组分按已知方式混合,并将它们放在传统装置如密炼机、挤出机及双螺杆挤出机中在200℃~300℃的温度熔融混炼并挤出来制备,其中组分F优选以上述凝聚混合物形式使用。
各个组分按已知方式的混合可采取顺序或同时加入的方式并且可在大约20℃(室温)或者在较高温度进行。
因此,本发明还提供一种制备该模塑组合物的方法。
凭借其优异阻燃性和熔合线强度以及优良机械性能,本发明热塑性模塑组合物适用于生产各种类型模塑件,尤其是要求较高抗破裂的那些。
本发明模塑组合物可用于生成任何种类模塑件。该模塑件尤其可采用注塑法生产。可生产的模塑件例子是:各种外壳,例如用于家用电器,如榨果汁机、煮咖啡机、食物混合机;用于办公室设备,例如显示器、打印机、复印机;或者建筑行业及汽车零件用复合钢板。它们还可用于电气工程领域,因为它们具有非常好的电气性能。
再有,本发明模塑组合物还可用来生产例如以下模塑件和成形制品:
1.轨道车辆内部装饰(FR(阻燃))
2.轮毂盖子
3.内装小变压器的电器外壳
4.信息传播及发送装置外壳
5.医用外壳及包覆层
6.按摩装置及其外壳
7.儿重玩具车
8.墙板元件
9.安全设备外壳
10.掀背式(汽车)扰流器
11.隔热运输槽罐
12.小动物圈养设备
13.卫生及浴室设施模塑件
14.通风口格栅
15.避暑别墅及棚子用模塑件
16.园艺设备外壳。
另一种加工方法是通过对以前生产的片材或薄膜进行热成形来生产模塑件。
因此,本发明还提供本发明模塑组合物在生产各种模塑件,优选上面提到的那些方面的应用,以及由本发明模塑组合物制造的模塑件。
具体实施方式
实施例
组分A
线型的基于双酚A的聚碳酸酯,其相对溶液粘度1.252,其中粘度系按照0.5g/100mL在溶剂二氯甲烷中的溶液形式在25℃测定的。
组分B
接枝聚合物,包含:45重量份苯乙烯与丙烯腈按72∶28的比例制备的共聚物,接枝到55重量份乳液聚合制备的粒状、交联的聚丁二烯橡胶(平均颗粒直径d50=0.40μm)上。
组分C
苯乙烯/丙烯腈共聚物,包含苯乙烯/丙烯腈,按重量比72∶28,特性粘度0.55dl/g(20℃、在二甲基甲酰胺中测定)。
组分D
通式如下的苯氧基磷腈
市售品P-3800,Nippon Sodo公司(日本)制造。
组分E
E.1磷酸三苯酯,Disflamoll TP,拜耳公司生产(Leverkusen,德国)
E.2间亚苯基双(磷酸二苯酯),Fyrolflex,AKZO Nobel化学公司,52349 Düren,德国。
E.3二苯基二1,1-亚异丙基双(磷酸二苯酯),CR 741,Daihachi化学工业公司生产(东京,日本)。
E.4二苯基磷酸镁
组分F
四氟乙烯聚合物的凝聚混合物形式,由对应于上述组分B的SAN接枝聚合物水乳液和一种四氟乙烯聚合物水乳液制成。该混合物中接枝聚合物B与四氟乙烯聚合物F的重量比是90wt%∶10wt%。四氟乙烯聚合物乳液的固体含量为60wt%;平均颗粒直径介于0.05~0.5μm。SAN接枝聚合物乳液的固体含量为34wt%;平均胶乳颗粒直径d50=0.28μm。
F的制备
四氟乙烯聚合物(Teflon 30N,杜邦公司提供)的乳液与SAN接枝聚合物B的乳液进行混合,并以相对于聚合物固体的1.8wt%酚类抗氧剂进行稳定化。在85~95℃,混合物利用硫酸镁(Epsom盐)水溶液和乙酸的作用、在pH等于4~5进行凝聚,过滤并洗涤至实际上不含电解质,然后,通过离心移出大部分水,然后物料在100℃干燥成粉末。该粉末可与其他组分在所描述的装置中进行混炼。
本发明模塑组合物的制备及试验
诸组分在3L密炼机中进行混合。在Arburg 270E型注塑机中,260℃制成模塑件。
对尺寸80×10×4mm的样品条按照DIN 53 460(ISO 306)测定维卡B软化点。
熔合线强度的测定方法是:按照DIN 53 453测定从两面注塑(加工温度260℃)而成的、尺寸170×10×4mm的试样在熔合线处的冲击强度。
耐应力龟裂行为(ESC行为)是针对尺寸80×10×4mm、加工温度260℃的样品条进行的。使用的试验介质是60%(体积)甲苯与40%(体积)异丙醇的混合物。试样贴先在圆弧形靠模上接受预应力处理(初始伸长,%),然后浸泡在室温的试验介质中。根据随初始伸长的增加而在试验介质中出现龟裂或破坏的情况,来评估应力龟裂行为。
表:模塑组合物及其性能
1(对比例) | 2 | 3 | 4 | 5 | 6 | 7 | |
组分ABCDE.1E.2E.3E.4F | 66.77.39.415.0----4.2 | 66.77.39.412.0-3.0--4.2 | 66.77.39.49.0-6.0--4.2 | 66.77.39.412.0--3.0-4.2 | 66.77.39.49.0--60-4.2 | 66.77.39.46.01.54.5--4.2 | 66.77 39 412.0---3.04.2 |
ak(ISO 180/1A)维卡B 120(ISO 306)UL 94 V 1.6mmESC行为,破坏,在εx[%]an(熔合线)(DIN 53 453) | 51103V01.614.0 | 5598V01.818.5 | 5595V01.81 5.9 | 58100V02.017.5 | 6097V02.019.5 | 5399V02.012.2 | 62104V02.4*15.3 |
*无破坏。
Claims (13)
1.一种热塑性模塑组合物,包含:
A)40~99重量份芳族聚碳酸酯和/或聚酯碳酸酯
B)0.5~60重量份接枝聚合物,由下列组成,
B.1)5~95wt%1种或多种乙烯基单体,接枝到
B.2)95~5wt%1种或多种接枝主链上,该主链玻璃化转变温度小于10℃,
C)0~45重量份至少1种热塑性聚合物,选自乙烯基聚合物,包括均聚物和共聚物,和聚对苯二甲酸链烷二醇酯,
D)0.1~50重量份至少1种选自下列通式磷腈的组分
其中
R每种情况可相同或不同,代表未取代的或者被烷基和/或卤素取代的C6~C20芳氧基,以及
k代表0或者1~15的数,
E)0.5~20重量份至少1种选自通式(IIa)、(IIb)、(IIc)和(IId)的磷化合物,
其中R1、R2、R3和R4彼此独立地代表每种情况下未卤化的或者被卤化的C1~C8烷基,每种情况下未取代的或者被烷基和/或卤素取代的C5~C6环烷基、C6~C20芳基或C7~C12芳烷基,
n彼此独立地代表0或1,
N代表0~30,以及
X代表单-或多环6~30个碳原子的芳族残基;
其中
R5及R6彼此独立地代表未卤代的或者卤代的C1~C24烷基,每种情况下未取代的或者被卤素和/或C1~C10烷基取代的C5~C6环烷基、C6~C20芳基或C7~C12芳烷基,
或者
R5和R6在通式(IId)的情况下构成烷基链,
Me代表金属,选自周期表主族1~3和副族VIII、1B和2B,以及
q取决于金属离子的化合价,
F)0~5重量份氟化聚烯烃,
其中乙烯基单体B.1是下列组分的混合物:
B.1.1 50~99重量份乙烯基芳烃和/或环上取代的乙烯基芳烃和/或甲基丙烯酸C1~C4烷基酯,和
B.1.2 1~50重量份乙烯基氰化物和/或甲基丙烯酸C1~C8烷基酯、丙烯酸C1~C8烷基酯和/或不饱和羧酸衍生物,和
接枝主链B.2是选自二烯橡胶、EPM橡胶、EPDM橡胶、丙烯酸酯橡胶、聚氨酯橡胶、硅氧烷橡胶、氯丁二烯橡胶和乙烯/醋酸乙烯橡胶中的至少1种橡胶。
2.权利要求1的模塑组合物,包含
60~98.5重量份A
1~40重量份B
0~30重量份C
2~35重量份D
1~18重量份E以及
0.1~1重量份F。
3.权利要求1的模塑组合物,包含
2~25重量份B
5~25重量份D
2~15重量份E
0.1~0.5重量份F。
4.权利要求1-3中任一项的模塑组合物,包含2~25重量份C。
5.权利要求1-3中任一项的模塑组合物,其中组分B的平均颗粒直径d50介于0.05~5μm。
6.权利要求1-3中任一项的模塑组合物,其中平均颗粒直径d50介于0.1~0.5μm。
7.权利要求1-3中任一项的模塑组合物,其中组分D选自丙氧基磷腈、苯氧基磷腈、甲基苯氧基磷腈、氨基磷腈和氟代烷基磷腈。
8.权利要求1-3中任一项的模塑组合物,包含至少1种添加剂,选自润滑剂、脱模剂、成核剂、抗静电剂、稳定剂、染料和颜料。
9.权利要求1-3中任一项的模塑组合物,还包含不同于组分D和E的阻燃剂。
10.生产权利要求1的模塑组合物的方法,其中组分A~F和任选地进一步的添加剂进行混合并熔融混炼。
11.权利要求1的模塑组合物用于生产模塑件的应用。
12.由权利要求1的模塑组合物生产的模塑件。
13.权利要求12的模塑件,其为外壳零件。
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DE19828535.3 | 1998-06-26 | ||
DE19828535A DE19828535A1 (de) | 1998-06-26 | 1998-06-26 | Flammwidrige Polycarbonat-ABS-Formmassen |
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EP (1) | EP1095099B1 (zh) |
JP (1) | JP4343439B2 (zh) |
KR (1) | KR100541309B1 (zh) |
CN (1) | CN1159374C (zh) |
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DE (2) | DE19828535A1 (zh) |
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-
1998
- 1998-06-26 DE DE19828535A patent/DE19828535A1/de not_active Withdrawn
-
1999
- 1999-06-12 DK DK99929193T patent/DK1095099T3/da active
- 1999-06-12 ES ES99929193T patent/ES2192059T3/es not_active Expired - Lifetime
- 1999-06-12 KR KR1020007014740A patent/KR100541309B1/ko not_active IP Right Cessation
- 1999-06-12 EP EP99929193A patent/EP1095099B1/de not_active Expired - Lifetime
- 1999-06-12 AU AU46092/99A patent/AU4609299A/en not_active Abandoned
- 1999-06-12 CA CA002335946A patent/CA2335946A1/en not_active Abandoned
- 1999-06-12 US US09/720,214 patent/US6613822B1/en not_active Expired - Lifetime
- 1999-06-12 CN CNB998079308A patent/CN1159374C/zh not_active Expired - Lifetime
- 1999-06-12 DE DE59904970T patent/DE59904970D1/de not_active Expired - Lifetime
- 1999-06-12 JP JP2000557302A patent/JP4343439B2/ja not_active Expired - Fee Related
- 1999-06-12 WO PCT/EP1999/004062 patent/WO2000000544A1/de active IP Right Grant
- 1999-06-12 BR BR9911577-8A patent/BR9911577A/pt not_active IP Right Cessation
- 1999-06-24 MY MYPI99002605A patent/MY133104A/en unknown
- 1999-06-25 AR ARP990103070A patent/AR016995A1/es not_active Application Discontinuation
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DK1095099T3 (da) | 2003-07-21 |
JP4343439B2 (ja) | 2009-10-14 |
AR016995A1 (es) | 2001-08-01 |
DE59904970D1 (de) | 2003-05-15 |
WO2000000544A1 (de) | 2000-01-06 |
MY133104A (en) | 2007-10-31 |
AU4609299A (en) | 2000-01-17 |
KR20010053165A (ko) | 2001-06-25 |
EP1095099A1 (de) | 2001-05-02 |
US6613822B1 (en) | 2003-09-02 |
DE19828535A1 (de) | 1999-12-30 |
HK1038936A1 (zh) | 2002-04-04 |
BR9911577A (pt) | 2001-03-20 |
ES2192059T3 (es) | 2003-09-16 |
CN1307610A (zh) | 2001-08-08 |
EP1095099B1 (de) | 2003-04-09 |
JP2002519464A (ja) | 2002-07-02 |
CA2335946A1 (en) | 2000-01-06 |
KR100541309B1 (ko) | 2006-01-16 |
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