CN106084718A - High-temp resistant fire-retarding polycarbonate compositions and preparation method thereof - Google Patents
High-temp resistant fire-retarding polycarbonate compositions and preparation method thereof Download PDFInfo
- Publication number
- CN106084718A CN106084718A CN201610423112.7A CN201610423112A CN106084718A CN 106084718 A CN106084718 A CN 106084718A CN 201610423112 A CN201610423112 A CN 201610423112A CN 106084718 A CN106084718 A CN 106084718A
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- CN
- China
- Prior art keywords
- polycarbonate
- flame retardant
- flame
- parts
- brominated
- Prior art date
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 109
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 110
- 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 claims abstract description 96
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 phosphate ester Chemical class 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 27
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 18
- 238000005809 transesterification reaction Methods 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000012695 Interfacial polymerization Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 7
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 claims description 3
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 239000013034 phenoxy resin Substances 0.000 claims description 3
- 229920006287 phenoxy resin Polymers 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- RDCRXUNDTLZUJN-UHFFFAOYSA-N phenyl butane-1-sulfonate Chemical compound CCCCS(=O)(=O)OC1=CC=CC=C1 RDCRXUNDTLZUJN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 7
- 239000010452 phosphate Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 18
- 239000004431 polycarbonate resin Substances 0.000 description 17
- 229920005668 polycarbonate resin Polymers 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 150000004650 carbonic acid diesters Chemical class 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical class [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XVMJVOYXXOQPHK-UHFFFAOYSA-N 2-(2-hydroxy-6-methylphenyl)acetic acid Chemical compound CC1=CC=CC(O)=C1CC(O)=O XVMJVOYXXOQPHK-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 229920000426 Microplastic Polymers 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
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- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 description 1
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- 239000012965 benzophenone Substances 0.000 description 1
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- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
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- OXDOANYFRLHSML-UHFFFAOYSA-N dimethoxyphosphorylbenzene Chemical compound COP(=O)(OC)C1=CC=CC=C1 OXDOANYFRLHSML-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 description 1
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- 150000002357 guanidines Chemical class 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
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- FEDFHMISXKDOJI-UHFFFAOYSA-M lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FEDFHMISXKDOJI-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LHTGBZMVHWJBQB-UHFFFAOYSA-N n,2-diethylaniline Chemical compound CCNC1=CC=CC=C1CC LHTGBZMVHWJBQB-UHFFFAOYSA-N 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KAVGMUDTWQVPDF-UHFFFAOYSA-N perflubutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 description 1
- 229950003332 perflubutane Drugs 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- PUBULWSNPHKIFY-UHFFFAOYSA-M potassium;1,1,2,2,2-pentafluoroethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)F PUBULWSNPHKIFY-UHFFFAOYSA-M 0.000 description 1
- BLVKDXZGNZXMBZ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,3-heptafluoropropane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F BLVKDXZGNZXMBZ-UHFFFAOYSA-M 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- YJLVKRVGSARISS-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphite Chemical compound CC1=CC=CC(C)=C1OP(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C YJLVKRVGSARISS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high-temp resistant fire-retarding polycarbonate compositions and preparation method thereof, by weight, there is following composition of raw materials: Merlon 70～99 parts, phosphoric acid Copolycarbonate 0.01～25 parts, fire retardant 0.01～5 parts, other auxiliary agent 0～10 parts；The weight portion sum of each component is 100 parts；Compared to prior art, the present invention adds phosphate ester Copolycarbonate in composition of raw materials, it is capable of in the case of not affecting Merlon toughness and thermostability, also greatly improve the flame retardant rating of polycarbonate compositions and fire-retardant stability, be particularly well-suited to the occasion using environmental requirement higher.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a high-heat-resistance flame-retardant polycarbonate composition and a preparation method thereof.
Background
Polycarbonate PC has the characteristics of high impact resistance, heat resistance, good dimensional stability, electric insulation performance and the like, and when the polycarbonate PC is applied to the fields of electronics, electric appliances, buildings, office equipment and the like, special requirements are usually put forward on the flame retardant performance of materials. Polycarbonate PC itself has a certain flame resistance (oxygen index of 25%), but in order to meet the high requirements for flame resistance in certain fields of application, it must be modified in a flame-retardant manner.
It is known that the addition of aromatic phosphoric acid ester flame retardants can meet the high requirements for flame retardancy of materials, but its addition usually lowers the decomposition temperature of the mixture and often corrodes the processing machinery, and some also affects the impact strength and heat resistance of polycarbonate resins. In addition, the halogen flame retardant generates toxic and harmful substances such as dioxin and the like during the combustion process, and causes environmental pollution, so that the use of the halogen flame retardant is gradually limited. Metal diphenylsulfone organosulfonates (KSS) and potassium perfluorobutane sulfonate (PPFBS) are also the predominant flame retardants in industrial applications. The organic sulfonic acid metal salt flame retardant can obtain good flame retardant effect in thicker products (the thickness is more than or equal to 3.2mm), but when the organic sulfonic acid metal salt flame retardant is applied to thinner products (the thickness is more than or equal to 1.6mm and less than 3.2mm), the organic sulfonic acid metal salt flame retardant is difficult to be mixed uniformly and the like due to the influence of factors that the addition amount of the organic sulfonic acid metal salt flame retardant is usually less than or equal to 1, and the stable flame retardant effect can be difficult to ensure. However, in practical applications, the ultra-thin and heat-resistant product is the development direction of market demand. Therefore, the applications of the above two flame retardants are greatly limited.
Chinese patent CN104403293 discloses a method for preparing halogen-free flame-retardant polycarbonate, which comprises the steps of firstly blending and granulating polycarbonate PC, a flame retardant, an antioxidant and a lubricant to prepare flame-retardant master batches, then extruding and granulating the flame-retardant master batches and other components to prepare a final product, ensuring the stability of the product by using the method of improving the dispersion effect of a trace flame retardant through the flame-retardant master batches, wherein the flame-retardant grade can be 1.6mmV-0, but the method of firstly preparing the flame-retardant master batches and then preparing the final product is troublesome in operation, and increases the production cost, thereby generating a certain limitation on the wide application of the product.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to overcome the defects, the invention provides the high heat-resistant flame-retardant polycarbonate composition and the preparation method thereof, the preparation method is simple and safe to operate, and the polycarbonate composition prepared by the preparation method has excellent toughness, heat resistance, thin-wall flame-retardant grade and flame-retardant stability, and is particularly suitable for occasions with higher requirements on use environments.
The technical scheme adopted by the invention for solving the technical problem is as follows: the high heat-resistant flame-retardant polycarbonate composition comprises the following raw materials in parts by weight: 70-99 parts of polycarbonate, 0.01-25 parts of phosphoric acid copolycarbonate, 0.01-5 parts of flame retardant and 0-10 parts of other additives; and the sum of the parts by weight of the components is 100 parts.
As a further improvement of the present invention, the polycarbonate is at least one selected from polycarbonates produced by an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer.
In a further improvement of the present invention, the polycarbonate is at least one selected from the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, and a branched polycarbonate.
As a further improvement of the invention, the polycarbonate is aromatic polycarbonate with viscosity average molecular weight of 13000-40000.
As a further improvement of the invention, the polycarbonate is selected from aromatic polycarbonate with the viscosity average molecular weight of 17000-24000.
As a further improvement of the invention, the phosphoric acid copolycarbonate is a phosphate-carbonate copolymer with the weight-average molecular weight of 50000-70000.
As a further improvement of the present invention, the flame retardant is selected from at least one of nitrogen-containing flame retardants, phosphorus-containing flame retardants, metal salts of organic sulfonic acids flame retardants;
or the flame retardant is selected from at least one of brominated polystyrene, brominated polyphenylene oxide, brominated bisphenol A epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromo tricyclopentadecane and brominated aromatic cross-linked polymer.
As a further improvement of the invention, the flame retardant is selected from organic sulfonic acid metal salt flame retardants, and the organic sulfonic acid metal salt flame retardants are at least one of diphenyl sulfone organic sulfonic acid metal salts, potassium perfluorobutane sulfonate and potassium per phenyl butane sulfonate.
As a further improvement of the invention, the other auxiliary agent is at least one selected from the group consisting of heat stabilizers, antioxidants, anti-dripping agents, light stabilizers, plasticizers, fillers and colorants.
The invention also provides a preparation method for preparing the high heat-resistant flame-retardant polycarbonate composition, which comprises the following preparation steps: firstly, weighing polycarbonate, phosphoric acid copolycarbonate, a flame retardant and other additives according to the formula ratio, putting the polycarbonate, the phosphoric acid copolycarbonate, the flame retardant and other additives into a mixer for blending, after uniform mixing, putting the mixture into a double-screw extruder for melt mixing, and performing extrusion granulation to obtain the high heat-resistant flame-retardant polycarbonate composition; the diameter of a screw of the double-screw extruder is 40:1, the temperature of each section of screw cylinder is set to be 250-260 ℃, and the rotating speed of the screw is 400-500 rpm.
The invention has the beneficial effects that: compared with the prior art, the phosphate copolycarbonate is added into the raw material formula, and after the phosphate copolycarbonate and the organic sulfonate flame retardant are compounded for use, the performance of the flame retardant property of the organic sulfonate can be greatly improved, so that the polycarbonate composition has excellent thin-wall flame retardant grade and flame retardant stability; in addition, since the phosphoric acid copolycarbonate is a high molecular polymer, the compatibility with polycarbonate is excellent, the toughness and the impact strength of the polycarbonate composition are not influenced, and the heat resistance of the polycarbonate is slightly influenced; the fluidity of the phosphoric acid copolycarbonate in the system is relatively good, and the uniform dispersion of the organic sulfonic acid metal salt is facilitated; therefore, the invention can greatly improve the flame retardant grade and the flame retardant stability of the polycarbonate composition under the condition of not influencing the toughness and the heat resistance of the polycarbonate by adding the phosphate copolycarbonate into the raw material formula, and is particularly suitable for occasions with higher requirements on use environments.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to these examples.
As is well known, the selection of materials, the formulation of raw materials, and the preparation process are three major factors that determine the quality of the product, and the three factors affect each other. Therefore, in order to better illustrate the advantages and innovativeness of the high heat-resistant and flame-retardant polycarbonate composition product obtained in the invention, the materials, raw material formula and preparation method of the high heat-resistant and flame-retardant polycarbonate composition product obtained in the invention are described in detail below.
(1) The invention adopts the following materials:
the invention discloses a high heat-resistant flame-retardant polycarbonate composition, which mainly comprises polycarbonate, phosphoric acid copolycarbonate, a flame retardant and other auxiliary agents, wherein the selection conditions of the raw materials are as follows:
(1a) polycarbonate (C): in the present invention, the polycarbonate is at least one selected from polycarbonates produced by an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer. Particularly preferred methods thereof will be described in detail below:
first, a method for producing a polycarbonate resin by an interfacial polymerization method will be described: in the interfacial polymerization method, a dihydroxy compound and a carbonate precursor are reacted in the presence of an inert organic solvent and an aqueous alkali solution while generally maintaining a pH of 9 or more, and then interfacial polymerization is performed in the presence of a polymerization catalyst to obtain a polycarbonate resin; molecular weight regulators (chain terminators), and antioxidants to prevent oxidation of the dihydroxy compounds may also be present in the reaction system as desired.
Further, in the above-described process for preparing a polycarbonate resin by the interfacial polymerization method, the carbonate precursor may preferably be phosgene, and such a method using phosgene is also particularly referred to as a phosgene method. The inert organic solvent may preferably be a chlorinated hydrocarbon, for example, among dichloromethane, 1, 2-dichloroethane, chloroform, monochlorobenzene, dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene. And in actual practice, one kind of the inert organic solvent may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
Examples of the alkali compound contained in the aqueous alkali solution may include: alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogencarbonate (among which sodium hydroxide and potassium hydroxide are preferred); and an alkaline earth metal compound. And in actual practice, one kind of alkali compound may be used, or two or more kinds thereof may be used together in a desired combination and ratio. Although the concentration of the alkali compound in the aqueous alkali solution is not limited herein, the concentration of the alkali compound is usually controlled to be preferably 5 wt% to 10 wt% to control the pH of the aqueous alkali solution during the reaction to 10 to 12. Further, when phosgene is bubbled, the molar ratio of the bisphenol compound to the alkali compound is usually set to 1: 1.9 or more, and 1: 3.2 or less (more preferably 1: 2.0 or more and 1: 2.5 or less), and the pH of the aqueous phase is controlled to 10 to 12 (preferably 10 to 11).
Examples of the polymerization catalyst include: aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and the like; alicyclic tertiary amines such as N, N '-dimethylcyclohexylamine, N' -diethylcyclohexylamine and the like; aromatic tertiary amines such as N, N '-dimethylaniline and N, N' -diethylaniline, etc.; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride and the like; pyridine; guanine; and guanidine salts and the like. In actual practice, one polymerization catalyst may be used, or two or more thereof may be used together in a desired combination and ratio.
Examples of the molecular weight regulator include: aromatic phenols having monovalent phenolic hydroxyl groups; aliphatic alcohols such as methanol and butanol, etc.; a thiol; and phthalimides; and the like, and among the above materials, aromatic phenols are preferably used, and specific examples of the aromatic phenols include: alkyl-substituted phenols such as m-methylphenol, p-methylphenol, m-propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like; vinyl group-containing phenols such as isopropenylphenol; an epoxy-containing phenol; and carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid, and the like. In actual practice, one molecular weight modifier may be used, or two or more thereof may be used together in a desired combination and ratio. The amount of the molecular weight modifier used is usually 0.5 mol or more and 50 mol or less, and more preferably 1 mol or more and 30 mol or less per 100 mol of the dihydroxy compound; setting the amount of the molecular weight modifier within this range can improve the thermal stability and hydrolysis resistance of the polycarbonate resin composition.
The reaction substrate, reaction medium, catalyst, additives, and the like may be mixed together during the reaction in any desired order as long as the desired polycarbonate resin can be obtained, and a suitable order may be established as needed. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator may be added at any desired timing between the time of reaction (phosgenation) of the dihydroxy compound with phosgene and the time of initiation of the polymerization reaction. The reaction temperature is usually set to 0 to 40 ℃ and the reaction time is usually in the range of several minutes (e.g., 10min) to several hours (e.g., 6 h).
Next, a method for producing a polycarbonate resin by the melt transesterification method will be described: in the melt transesterification method, for example, an ester exchange reaction is carried out between a carbonic acid diester and a dihydroxy compound. Among them, examples of the carbonic acid diester include: dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl carbonate and the like. Of the above materials, diphenyl carbonate and substituted diphenyl carbonates are preferred, with diphenyl carbonate being particularly preferred. In addition, in actual practice, one carbonic acid diester may be used, or two or more thereof may be used together in a desired combination and ratio.
In order to obtain the objective polycarbonate resin, a dihydroxy compound and a carbonic acid diester may be used in desired proportions, but it is preferable to use the carbonic acid diester in an amount of 1 molar equivalent or more and 1.30 molar equivalents or less per 1 mole of the dihydroxy compound, and the amount of the carbonic acid diester may be more preferably 1.01 molar equivalents or more and 1.30 molar equivalents or less. The amount of the terminal hydroxyl group can be adjusted to a preferable range by setting the ratio of the two compounds within the above range.
The amount of terminal hydroxyl groups in the polycarbonate resin tends to greatly affect thermal stability, hydrolysis resistance, color tone, and the like. Therefore, the amount of the terminal hydroxyl group can be adjusted by any known desired method and as needed. In the transesterification reaction, the polycarbonate resin in which the amount of the terminal hydroxyl group is adjusted can be generally obtained by adjusting the mixing ratio between the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction, and the like during the reaction. In addition, the molecular weight of the resulting polycarbonate resin can also be adjusted by this procedure in general. The amount of terminal hydroxyl groups can also be adjusted more effectively by adding a chain terminator separately during the reaction, examples of which include: one kind of chain terminator may be used, or two or more kinds thereof may be used together in a desired combination and ratio, among monovalent phenol, monovalent carboxylic acid, and carbonic acid diester.
When the polycarbonate resin is produced by the melt transesterification method, a transesterification catalyst is generally used, and any desired transesterification catalyst may be used, although the use of an alkali metal compound and/or an alkaline earth metal compound is preferred. Further, as the auxiliary compound, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, basic amine compounds, and the like can be used. One kind of transesterification catalyst may be used, or two or more kinds thereof may be used together in a desired combination and ratio. The reaction temperature in the molten transesterification method is usually 100 to 320 ℃, and the reaction is usually carried out under reduced pressure of 2mmHg or less; the detailed process should be a process in which the melt polycondensation reaction is carried out under the above-mentioned conditions while removing by-products such as aromatic hydroxy compounds and the like.
The melt polycondensation reaction may be carried out by a batch process or a continuous process. When the batch process is carried out, the reaction substrate, the reaction medium, the catalyst, the additive and the like may be mixed together in any desired order as long as the objective aromatic polycarbonate resin can be obtained, and a suitable order may be established as needed. However, in view of, for example, the stability of polycarbonate and polycarbonate resin compositions, it is preferable to carry out melt polycondensation by a continuous process. The catalyst deactivator may be used as needed in the melt transesterification process, and any desired compound which neutralizes the transesterification catalyst may be used as the catalyst deactivator, and examples include sulfur-containing organic compounds, derivatives thereof, and the like; one kind of catalyst deactivator may be used, or two or more kinds thereof may be used together in a desired combination and ratio. The amount of the catalyst deactivator to be used is usually 0.5 weight equivalent or more and 10 weight equivalents or less, more preferably 1 weight equivalent or more and 5 weight equivalents or less, based on the alkali metal or alkaline earth metal contained in the transesterification catalyst; the concentration thereof is usually 1ppm or more and 100ppm or less, more preferably 1ppm or more and 20ppm or less, based on the aromatic polycarbonate resin.
In the present invention, the polycarbonate is at least one selected from the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, and a branched polycarbonate produced by the above-described particularly preferred production method; preferably, the polycarbonate is an aromatic polycarbonate with a viscosity average molecular weight of 13000-40000, more preferably 17000-24000, and has good mechanical strength and excellent moldability when the viscosity average molecular weight of the aromatic polycarbonate is 17000-24000.
(1b) Phosphoric acid copolycarbonate: when a phosphoric acid copolycarbonate having a smaller weight average molecular weight is selected in the preparation of a polycarbonate composition, the heat resistance of the polycarbonate composition is lowered; on the other hand, when a phosphoric acid copolycarbonate having a large weight average molecular weight is used, problems such as poor compatibility with degradation and poor appearance of the polycarbonate composition may occur. The invention is repeatedly verified through a plurality of tests, and the phosphate-carbonate copolymer with the weight-average molecular weight of 50000-70000 is preferably used, so that the heat resistance, the compatibility and the appearance of the high-heat-resistant flame-retardant polycarbonate composition can be effectively improved.
The phosphate-carbonate copolymer used in the present invention is composed of a phosphate unit represented by the following chemical formula (1) and a bisphenol A unit represented by the chemical formula (2);
in the chemical formula (1), R is an alkyl group having 1 to 10 carbon atoms, and the branched chain may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably a methyl group, an ethyl group or a propyl group, among which the methyl group and the ethyl group are preferable, and the most preferable is the methyl group.
The molar ratio of the phosphate unit to the carbonate unit in the phosphate-carbonate copolymer is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and particularly preferably 30:70 to 70: 30.
(1c) Flame retardant: in the invention, the flame retardant is selected from at least one or more of nitrogen-containing flame retardant, phosphorus-containing flame retardant and organic sulfonic acid metal salt flame retardant (selected from halogen-free flame retardant); or the flame retardant is selected from at least one of brominated polystyrene, brominated polyphenylene oxide, brominated bisphenol A epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromo tricyclopentadecane and brominated aromatic cross-linked polymer (selected from halogen flame retardants, preferably brominated polystyrene).
In practice, the flame retardant is preferably an organic sulfonic acid metal salt flame retardant, and the introduction of the organic sulfonic acid metal salt flame retardant can promote the formation of a carbonized layer during the combustion of the polycarbonate resin, so that the flame retardancy of the polycarbonate can be improved well, and the properties possessed by the polycarbonate, such as electrical properties, heat resistance and impact resistance, can be maintained at an excellent level.
The metal in the organic sulfonic acid metal salt is not particularly limited, but is preferably a metal such as sodium, lithium, potassium or cesium, or an alkaline earth metal such as beryllium, magnesium, calcium, strontium, or barium. However, potassium is preferred in view of flame retardancy and hydrolysis resistance.
The metal salts of organic sulfonic acids include: metal salts of fluorine-containing aliphatic sulfonic acids, metal salts of fluorine-containing aromatic sulfonimides, metal salts of aromatic sulfonic acids, and metal salts of aromatic sulfonamides. Preferred are metal salts of fluoroaliphatic sulfonic acids and metal salts of aromatic sulfonic acids (e.g., metal diphenylsulfone organic sulfonates, potassium per-phenylbutanesulfonate), and particularly preferred are metal salts of fluoroaliphatic sulfonic acids. The metal salt of the fluorine-containing aliphatic sulfonic acid includes: alkali metal salts of fluorine-containing aliphatic sulfonic acids containing at least one C-F bond in the molecule, such as potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, cesium perfluorobutane converted, lithium trifluoromethane sulfonate, sodium trifluoromethane sulfonate, potassium pentafluoroethane sulfonate, potassium heptafluoropropane sulfonate, and potassium decafluoro-4- (pentafluoroethyl) cyclohexane sulfonate, and the like, and potassium perfluorobutane sulfonate is particularly preferable.
(1d) When the polycarbonate resin is mixed with the phosphoric acid copolycarbonate and the flame retardant, other additives selected from at least one of a heat stabilizer, an antioxidant, an anti-dripping agent, a light stabilizer, a plasticizer, a filler, and a colorant may be added as needed. Wherein,
suitable heat stabilizers include: organic phosphites such as triphenyl phosphite, tris- (2, 6-dimethylphenyl) phosphite, tris-nonylphenyl phosphite, dimethylbenzene phosphonate, trimethyl phosphate, and the like.
Suitable antioxidants include: organophosphites, alkylated monophenols or polyphenols, alkylated reaction products of polyphenols and dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters and the like.
Suitable anti-dripping agents are preferably fluorinated polyolefins, which are generally polymers or copolymers containing a fluorine-containing ethylene structure, and may be specifically exemplified by vinylidene fluoride resins, tetrafluoroethylene resins, and tetrafluoroethylene/hexafluoropropylene copolymer resins, with tetrafluoroethylene resins being preferred.
Suitable light stabilizers include at least one of benzotriazoles, benzophenones.
Suitable plasticizers are phthalates.
Suitable fillers include titanium dioxide, talc, mica, barium sulfate, and the like.
Suitable colorants include various pigments, dyes.
(2) Preparing the high heat-resistant flame-retardant polycarbonate composition
Examples 1 to 7 and comparative examples 1 to 2 were prepared according to the following preparation steps, based on the parts by weight of the raw materials shown in Table 1: firstly, weighing polycarbonate, phosphoric acid copolycarbonate, a flame retardant and other additives according to the formula ratio, putting the polycarbonate, the phosphoric acid copolycarbonate, the flame retardant and other additives into a mixer for blending, after being uniformly mixed, putting the mixture into a double-screw extruder for melt mixing, and performing extrusion granulation to obtain a polycarbonate composition; the diameter of a screw of the double-screw extruder is 40:1, the temperature of each section of screw cylinder is set to be 250-260 ℃, and the rotating speed of the screw is 400-500 rpm.
Table 1: unit: parts by weight
Note that polycarbonate PC S-2000F has a viscosity average molecular weight of 25000 (Mitsubishi, Japan), phosphoric acid copolycarbonate CO6000 has a weight average molecular weight of 65000(FRX), phosphoric acid copolycarbonate CO3000 has a weight average molecular weight of 53000(FRX), a flame retardant is Baywet C4 (Langsheng chemical), an antioxidant AO1076 is β - (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (CAS No.: 2082-79-3), an anti-dripping agent:30 N PTFE(DuPont)。
(3) product physical Property test
According to the industry standard, the nine polycarbonate compositions prepared in the above examples 1-7 and comparative examples 1-2 were subjected to a plurality of basic physical property tests. The test standards or methods for multiple basic physical property tests are as follows:
UL94 flame retardancy test method:
the flammability test was carried out according to the protocol "flammability test of plastic materials, UL 94". Flame retardant ratings were derived based on the burn rate, extinguishing time, ability to resist dripping, and whether dripping (drip) was burning. Samples used for the test: bars having dimensions of 125mm length x 13mm width x no greater than 13mm thickness, the thickness of the bars when tested according to the invention being selected to be 1.5 mm. According to the UL94 protocol, and based on the test results obtained for five samples, the material flame retardant rating can be classified as (UL 94-HB): v0, V1, V2, 5VA and/or 5 VB; in the present invention, however, only the flame retardant rating of the material is classified as: v0, V1 and V2, and the classification criteria for each flame retardant rating are:
v0: in a sample placed so that its long axis is 180 degrees with respect to the flame, the period of burning and/or smoldering does not exceed 10 seconds after the ignition flame is removed, and the vertically placed sample does not produce dripping of combustion particles that ignite cotton wool. The flame holding time for the fifth bar is the flame holding time for the five bars, each lit twice, wherein the sum of the flame holding time for the first light (t1) and the flame holding time for the second light (t2), i.e. the maximum flame holding time (t1+ t2), is less than or equal to 50 seconds.
V1: in a sample placed so that its long axis is 180 degrees relative to the flame, the period of burning and/or smoldering does not exceed 30 seconds after the ignition flame is removed, and the vertically placed sample does not produce dripping of burning particles that ignite cotton wool. The flame holding time for the fifth bar is the flame holding time for the five bars, each lit twice, wherein the sum of the first lit flame holding time (t1) and the second lit flame holding time (t2), i.e. the maximum flame holding time (t1+ t2), is less than or equal to 250 seconds.
V2: in a sample placed so that its long axis is 180 degrees relative to the flame, the average period of burning and/or smoldering after removal of the ignition flame does not exceed 30 seconds, but a vertically placed sample produces dripping of burning particles that ignite cotton. The flame holding time for the fifth bar is the flame holding time for the five bars, each lit twice, wherein the sum of the first lit flame holding time (t1) and the second lit flame holding time (t2), i.e. the maximum flame holding time (t1+ t2), is less than or equal to 250 seconds.
Measurement method of Flame stability (Flame stability): taking 20 bars with the size of 125mm length multiplied by 13mm width multiplied by no more than 13mm thickness (the thickness of the bar is selected to be 1.5mm when the test is carried out in the invention), and testing the bars according to the UL94 protocol to obtain the number of the bars meeting the V0 grade in 20 bars, wherein, the flame retardant stability is n/20 (wherein, n is more than or equal to 0 and less than or equal to 20), obviously, the larger n is, the better the flame retardant stability of the material is.
Measuring method of Melt Flow Rate (MFR): the plastic pellets were allowed to melt into a plastic fluid over a period of time (10 minutes) at a temperature and pressure (different standards for each material) and the number of grams of plastic fluid that flowed through a 2.1mm diameter circular tube was measured. The larger the outflow gram value is, the better the processing flowability of the plastic material is, otherwise, the poorer the processing flowability is; the test standard used herein is ASTM D1238, unit: g/10 min. The test conditions were: melt Flow Rate (MFR) at 300 ℃ under a load of 1.2 kg.
(iv) method for measuring Heat Deflection Temperature (HDT): HDT is determined according to the test standard ASTM D648 under a load of 1.82MPa, lying flat on bars of 3.2mm and/or 6.4mm thickness, the results being recorded in ℃ C.
The method for measuring the cantilever beam impact strength comprises the following steps: notched Izod impact strength was measured using a 3.2mm thick molded notched Izod impact bar at a temperature of 23 ℃. Notched Izod impact strength was measured according to ASTM D256 and the results were recorded in joules/meter. The test was carried out at room temperature (23 ℃).
The nine polycarbonate compositions prepared in examples 1 to 7 of the present invention and comparative examples 1 to 2 were subjected to the above physical property tests, and the test results are shown in table 2, wherein the average values are obtained:
table 2: basic physical property test results of polycarbonate compositions prepared in examples 1 to 7 of the present invention and comparative examples 1 to 2
As can be seen from Table 2, the polycarbonate composition prepared in comparative example 2 has a slightly poor flame retardancy grade and unsatisfactory flame retardancy stability; the polycarbonate composition prepared in the comparative example 1 has poor flame retardant grade and poor flame retardant stability; the polycarbonate composition prepared by the embodiment of the invention not only has excellent toughness and heat resistance, but also has excellent thin-wall flame retardant grade and flame retardant stability, and is particularly suitable for occasions with higher requirements on use environments.
The polycarbonate composition prepared by the invention has advantages in toughness, heat resistance, flame retardant grade and flame retardant stability, and mainly benefits from the optimization and improvement of the raw material formula, which is specifically represented as follows: according to the invention, the phosphate ester copolycarbonate is added into the raw material formula, and after the phosphate ester copolycarbonate and the organic sulfonate flame retardant are compounded for use, the exertion of the flame retardant property of the organic sulfonate can be greatly improved, so that the polycarbonate composition has excellent thin-wall flame retardant grade and flame retardant stability; in addition, since the phosphoric acid copolycarbonate is a high molecular polymer, the compatibility with polycarbonate is excellent, the toughness and the impact strength of the polycarbonate composition are not influenced, and the heat resistance of the polycarbonate is slightly influenced; and the fluidity of the phosphoric acid copolycarbonate in the system is relatively good, which is beneficial to the uniform dispersion of the organic sulfonic acid metal salt. Therefore, the phosphate ester copolycarbonate is added into the raw material formula, so that the flame retardant grade and the flame retardant stability of the polycarbonate composition can be greatly improved under the condition of not influencing the toughness and the heat resistance of the polycarbonate.
The high heat-resistant flame-retardant polycarbonate composition product prepared by the invention can be widely applied to mobile phones, MP3 players, computers, notebook computers, cameras, video recorders, tablet computers, hand receivers, parts of kitchen appliances or electric shells, automobile parts, shells or covers in the building field, shells and frames of electric appliances, and the like; has wide market prospect and market benefit.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (10)
1. A high heat-resistant flame-retardant polycarbonate composition is characterized in that: the formula comprises the following raw materials in parts by weight: 70-99 parts of polycarbonate, 0.01-25 parts of phosphoric acid copolycarbonate, 0.01-5 parts of flame retardant and 0-10 parts of other additives; and the sum of the parts by weight of the components is 100 parts.
2. The highly heat resistant, flame retardant polycarbonate composition of claim 1, wherein: the polycarbonate is at least one selected from polycarbonates produced by an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer.
3. The highly heat resistant flame retardant polycarbonate composition according to claim 1 or 2, wherein: the polycarbonate is at least one selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate and branched polycarbonate.
4. The highly heat resistant flame retardant polycarbonate composition according to claim 3, wherein: the polycarbonate is aromatic polycarbonate with the viscosity average molecular weight of 13000-40000.
5. The highly heat resistant, flame retardant polycarbonate composition of claim 4, wherein: the polycarbonate is selected from aromatic polycarbonate with the viscosity average molecular weight of 17000-24000.
6. The highly heat resistant, flame retardant polycarbonate composition of claim 1, wherein: the phosphoric acid copolycarbonate is a phosphate-carbonate copolymer with the weight-average molecular weight of 50000-70000.
7. The highly heat resistant, flame retardant polycarbonate composition of claim 1, wherein: the flame retardant is selected from at least one of nitrogen-containing flame retardant, phosphorus-containing flame retardant and organic sulfonic acid metal salt flame retardant;
or the flame retardant is selected from at least one of brominated polystyrene, brominated polyphenylene oxide, brominated bisphenol A epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromo tricyclopentadecane and brominated aromatic cross-linked polymer.
8. The highly heat resistant, flame retardant polycarbonate composition of claim 7, wherein: the flame retardant is selected from organic sulfonic acid metal salt flame retardants, and the organic sulfonic acid metal salt flame retardants are at least one of diphenyl sulfone organic sulfonic acid metal salts, potassium perfluorobutane sulfonate and potassium per phenyl butane sulfonate.
9. The highly heat resistant, flame retardant polycarbonate composition of claim 1, wherein: the other auxiliary agent is selected from at least one of a heat stabilizer, an antioxidant, an anti-dripping agent, a light stabilizer, a plasticizer, a filler and a coloring agent.
10. The method for preparing a highly heat and flame resistant polycarbonate composition according to any of claims 1 to 9, wherein: the preparation method comprises the following preparation steps: firstly, weighing polycarbonate, phosphoric acid copolycarbonate, a flame retardant and other additives according to the formula ratio, putting the polycarbonate, the phosphoric acid copolycarbonate, the flame retardant and other additives into a mixer for blending, after uniform mixing, putting the mixture into a double-screw extruder for melt mixing, and performing extrusion granulation to obtain the high heat-resistant flame-retardant polycarbonate composition; the diameter of a screw of the double-screw extruder is 40:1, the temperature of each section of screw cylinder is set to be 250-260 ℃, and the rotating speed of the screw is 400-500 rpm.
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